JP5915707B2 - Tackifying resin emulsion and acrylic emulsion type adhesive / adhesive composition - Google Patents
Tackifying resin emulsion and acrylic emulsion type adhesive / adhesive composition Download PDFInfo
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- JP5915707B2 JP5915707B2 JP2014183879A JP2014183879A JP5915707B2 JP 5915707 B2 JP5915707 B2 JP 5915707B2 JP 2014183879 A JP2014183879 A JP 2014183879A JP 2014183879 A JP2014183879 A JP 2014183879A JP 5915707 B2 JP5915707 B2 JP 5915707B2
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- polymerized rosin
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- 230000001070 adhesive effect Effects 0.000 title claims description 51
- 239000000853 adhesive Substances 0.000 title claims description 49
- 239000000839 emulsion Substances 0.000 title claims description 48
- 229920005989 resin Polymers 0.000 title claims description 37
- 239000011347 resin Substances 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 13
- 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 97
- 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 83
- 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 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 150000002148 esters Chemical class 0.000 claims description 33
- 238000005886 esterification reaction Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 description 69
- 239000000178 monomer Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 38
- -1 lithium aluminum hydride Chemical compound 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- 239000003995 emulsifying agent Substances 0.000 description 18
- 230000032050 esterification Effects 0.000 description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 18
- 229920000058 polyacrylate Polymers 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- 229920005601 base polymer Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000012874 anionic emulsifier Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003918 potentiometric titration Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000001530 fumaric acid Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 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
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、粘着付与樹脂エマルジョンおよび当該粘着付与樹脂エマルジョンを含有するアクリルエマルジョン型粘・接着剤組成物に関し、より詳しくは、高温下における接着性（以下、耐熱保持力という）や、ウレタンフォームのような表面に凹凸を有する被着体に対する接着力（以下、粗面接着力という）などの接着性能に優れ、かつ、ベースポリマーとの相溶性が良好な粘着付与樹脂エマルジョンを含有する水系粘・接着剤組成物に関する。 The present invention relates to a tackifying resin emulsion and an acrylic emulsion-type adhesive / adhesive composition containing the tackifying resin emulsion. More specifically, the present invention relates to adhesiveness at high temperatures (hereinafter referred to as heat resistance holding force), urethane foam, Water-based adhesive / adhesive containing a tackifying resin emulsion that has excellent adhesion performance (such as rough surface adhesion) to adherends with irregularities on the surface, and that has good compatibility with the base polymer The agent composition.
近年、環境に対する配慮から、揮発性有機溶剤などの含有量が少ない粘・接着剤組成物が切望されている。具体的には、例えば、自動車用途や建材用途においては、シックカー問題やシックハウス問題が懸念されるため、エマルジョン型粘・接着剤組成物が広く用いられている。また、自動車用途においては、例えば内装部材の場合には、夏場に車内温度が非常に高くなり、一方、建材用途においては、夏の直射日光を浴びるような環境では高温に達するため、用いるエマルジョン型粘・接着剤組成物には、かかる高温下での耐熱保持力が要求される。また、最近では基材も多様化しており、自動車用途ではウレタンフォームのような表面に凹凸を有する難被着体への充分な接着力を有することなども求められるようになってきた。しかし、従来の有機溶剤系の粘・接着剤を水系に変更しようとすると、高温での接着力や、ウレタンフォームのような表面に凹凸を有する被着体に対する接着力が不十分になるという問題があった。 In recent years, an adhesive composition having a low content of a volatile organic solvent or the like has been eagerly desired in consideration of the environment. Specifically, for example, in automobile use and building material use, there is a concern about the thick car problem and the sick house problem, and therefore emulsion type adhesive / adhesive compositions are widely used. Also, in the case of automobiles, for example, in the case of interior members, the interior temperature becomes very high in the summer, while in the building materials application, it reaches a high temperature in an environment where it is exposed to direct sunlight in summer. The adhesive / adhesive composition is required to have a heat-resistant holding force at such a high temperature. In recent years, base materials have also been diversified, and in automobile applications, it has been required to have sufficient adhesion to difficult-to-adhere substrates having uneven surfaces such as urethane foam. However, if the conventional organic solvent-based adhesives / adhesives are changed to water-based adhesives, the adhesive strength at high temperatures and the adhesive strength to adherends with uneven surfaces such as urethane foam will be insufficient. was there.
そのため、例えば、重合ロジンをアクリル酸もしくはフマル酸で変性し、多価アルコールでエステル化し、軟化点１３５〜１８０℃の高軟化点樹脂をエマルジョン化したものを粘・接着剤組成物に添加する提案がなされている（特許文献１参照）が、樹脂の高軟化点化に従って、耐熱保持力が向上するものの、それに伴い、分子量が急激に増加し、ベースポリマーとの相溶性が著しく低下するため、バランスの良い粘着性能を得るには不十分であった。 Therefore, for example, a proposal that a polymerized rosin is modified with acrylic acid or fumaric acid, esterified with a polyhydric alcohol, and emulsified with a high softening point resin having a softening point of 135 to 180 ° C. is added to the adhesive / adhesive composition (Refer to Patent Document 1), although the heat-resistant holding power is improved as the resin has a higher softening point, the molecular weight is rapidly increased along with it, and the compatibility with the base polymer is significantly reduced. It was insufficient to obtain a well-balanced adhesive performance.
また、アクリル系粘着剤または水分散型粘着付与剤の分子量３００以下の成分の割合を４．２重量％以下とする提案がなされている（特許文献２参照）が、耐熱保持力や粗面接着力の改善は確実とは言えなかった。 Moreover, although the proposal which makes the ratio of the component of molecular weight 300 or less of an acrylic adhesive or a water dispersion-type tackifier into 4.2 weight% or less is made (refer patent document 2), heat-resistant retention strength and rough surface adhesive force are made | formed. The improvement was not certain.
なお、本出願人は樹脂酸ダイマーを６０％以上含有してなる樹脂酸および多価アルコールを反応させて得られる高軟化点樹脂の粘着付与樹脂エマルジョンを提案している（特許文献３参照）。本発明によれば、高軟化点にも拘らず、シャープな分子量分布と適度な軟化点（ＳＰ値）を有しているため、様々なアクリル系重合体のエマルジョンをベース樹脂として選択可能であり、一定の性能を有する幅広い種類の水性エマルジョン型の粘着剤組成物を得ることができるものであった。本手法によれば、高軟化点とすることで、耐熱保持力を向上させることはできたが、粗面接着力を自動車用途や建材用途で満足されるレベルまで向上させることは困難であった。 The present applicant has proposed a tackifying resin emulsion of a high softening point resin obtained by reacting a resin acid containing 60% or more of a resin acid dimer and a polyhydric alcohol (see Patent Document 3). According to the present invention, it has a sharp molecular weight distribution and an appropriate softening point (SP value) regardless of the high softening point, so that various acrylic polymer emulsions can be selected as the base resin. A wide variety of water-based emulsion-type pressure-sensitive adhesive compositions having a certain performance can be obtained. According to this method, the heat-resistant holding force could be improved by setting the softening point to be high, but it was difficult to improve the rough surface adhesive force to a level that was satisfactory for automobile use and building material use.
本発明は、高温環境下でも優れた接着力を付与し、かつポリウレタンフォームのような粗面に対する接着力が良好で、アクリル系重合体ベースポリマーとの相溶性が良好な粘着付与樹脂エマルジョンを提供することを課題とする。 The present invention provides a tackifying resin emulsion that provides excellent adhesion even under high temperature environments, has good adhesion to rough surfaces such as polyurethane foam, and has good compatibility with acrylic polymer base polymers. The task is to do.
本発明者らは、前記課題を解決するために、特に粘着付与樹脂について鋭意検討したところ、特定の重合ロジンエステルを用いた粘着付与樹脂エマルジョンを用いることで前記課題を解決しうることを見出した。 In order to solve the above problems, the present inventors have intensively studied particularly tackifying resins, and found that the above problems can be solved by using a tackifying resin emulsion using a specific polymerized rosin ester. .
すなわち、本発明は、樹脂酸ダイマーの含有率が５０重量％以上の重合ロジンにアルコール類を加えてエステル化反応させてなる、重量平均分子量 （Ｍｗ）が２０００〜３５００、水酸基価が３５〜１００ｍｇＫＯＨ／ｇ、重量平均分子量 （Ｍｗ）が２６０以下の成分の含有量が１．５重量％以下であり、軟化点が１６０〜１８５℃、および酸価が１００ｍｇＫＯＨ／ｇ以下である重合ロジンエステル樹脂 （Ａ）を乳化して得られる粘着付与樹脂エマルジョン；当該粘着付与樹脂エマルジョンを含有するアクリルエマルジョン型粘・接着剤組成物に関する。 That is, the present invention provides a weight average molecular weight (Mw) of 2000 to 3500 and a hydroxyl value of 35 to 100 mgKOH formed by adding an alcohol to a polymerized rosin having a resin acid dimer content of 50% by weight or more. / G, Polymerized rosin ester resin having a content of components having a weight average molecular weight (Mw) of 260 or less, 1.5% by weight or less, a softening point of 160 to 185 ° C., and an acid value of 100 mgKOH / g or less ( A tackifying resin emulsion obtained by emulsifying A); relates to an acrylic emulsion-type adhesive / adhesive composition containing the tackifying resin emulsion.
本発明によれば、高温環境下で優れた接着力を有し、かつフォーム基材、とりわけポリウレタンフォームのような粗面に対しても良好な接着力を有し、ベースポリマーとの相溶性が良好なアクリルエマルジョン型粘・接着剤を提供することができる。 According to the present invention, it has an excellent adhesive force in a high temperature environment, and has a good adhesive force even on a rough surface such as a foam substrate, particularly polyurethane foam, and has compatibility with the base polymer. A good acrylic emulsion-type adhesive / adhesive can be provided.
本発明の粘着付与樹脂エマルジョンは、樹脂酸ダイマーの含有率が５０重量％以上の重合ロジンにアルコール類を加えてエステル化反応させてなる、重量平均分子量 （Ｍｗ）が２０００〜３５００、水酸基価が３５〜１００ｍｇＫＯＨ／ｇ、重量平均分子量 （Ｍｗ）が２６０以下の成分の含有量が１．５重量％以下であり、軟化点が１６０〜１８５℃、および酸価が１００ｍｇＫＯＨ／ｇ以下である重合ロジンエステル樹脂 （Ａ）（以下、成分（Ａ）という）を乳化して得られることを特徴とする。 The tackifying resin emulsion of the present invention has a weight average molecular weight (Mw) of 2000 to 3500 and a hydroxyl value of esterification by adding an alcohol to a polymerized rosin having a resin acid dimer content of 50% by weight or more. Polymerized rosin having a content of 35 to 100 mgKOH / g, a weight average molecular weight (Mw) of 260 or less, a content of 1.5% by weight or less, a softening point of 160 to 185 ° C., and an acid value of 100 mgKOH / g or less It is obtained by emulsifying ester resin (A) (hereinafter referred to as component (A)).
成分（Ａ）は、通常、樹脂酸ダイマーの含有率が５０重量％以上の重合ロジンにアルコール類を加えてエステル化反応させて、その重量平均分子量（Ｍｗ）を２０００〜３５００、水酸基価を３５〜１００ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）が２６０以下の成分の含有量を１．５重量％以下、軟化点を１６０〜１８５℃、および酸価を１００ｍｇＫＯＨ／ｇ以下としたものである。 The component (A) is usually an esterification reaction by adding an alcohol to a polymerized rosin having a resin acid dimer content of 50% by weight or more, and having a weight average molecular weight (Mw) of 2000 to 3500 and a hydroxyl value of 35. ˜100 mg KOH / g, content of components having a weight average molecular weight (Mw) of 260 or less is 1.5% by weight or less, softening point is 160 to 185 ° C., and acid value is 100 mg KOH / g or less.
成分（Ａ）の製造に用いる重合ロジンとは、得られる粘着付与剤の重量平均分子量（Ｍｗ）を２０００以上とするために、樹脂酸ダイマー（二量化された樹脂酸）の含有率を５０重量％以上としたロジン誘導体である。該重合ロジンを製造する方法としては、公知の方法を採用することができる。具体的には、例えば、原料として、ガムロジン、トール油ロジン、ウッドロジンといった原料ロジン類の樹脂酸モノマーを硫酸、フッ化水素、塩化アルミニウム、四塩化チタン等の触媒を含むトルエン、キシレン等の溶媒中、温度４０〜１６０℃程度で、１〜５時間程度反応させる方法等があげられる。得られる反応生成物中に占める樹脂酸ダイマーの割合は反応温度、反応時間等により異ならしめ得る。 The polymerized rosin used for the production of the component (A) means that the content of the resin acid dimer (dimerized resin acid) is 50% in order to make the obtained tackifier have a weight average molecular weight (Mw) of 2000 or more. % Rosin derivative. As a method for producing the polymerized rosin, a known method can be employed. Specifically, for example, as a raw material, a resin acid monomer of raw material rosins such as gum rosin, tall oil rosin, and wood rosin contains a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, and titanium tetrachloride in a solvent such as toluene and xylene. And a method of reacting at a temperature of about 40 to 160 ° C. for about 1 to 5 hours. The proportion of the resin acid dimer in the obtained reaction product can be varied depending on the reaction temperature, reaction time and the like.
重合ロジンの具体例としてはトール油系重合ロジン（例えば、商品名「シルバタック１４０」、アリゾナケミカル社製）、ウッド系重合ロジン（例えば、商品名「ダイマレックス」、ハーキュレス社製）、ガム系重合ロジン（例えば、商品名「重合ロジンＢ−１４０」、新洲（武平）林化有限公司製）等があげられる。 Specific examples of the polymerized rosin include tall oil-based polymerized rosin (for example, trade name “Silvatac 140”, manufactured by Arizona Chemical), wood-based polymerized rosin (for example, product name “Dimalex”, manufactured by Hercules), gum-based Polymerized rosin (for example, trade name “polymerized rosin B-140”, manufactured by Shinshu (Takehira) Hayashi Kasei Co., Ltd.) and the like.
また、重合ロジンとしては、重合ロジンに、変性、水素化、不均化等の各種処理をしたものを用いることもできる。なお、各種処理は、単独であっても２種以上を組み合わせて行ってもよい。重合ロジンの変性方法としては、特に限定されず、公知の方法を採用することができる。具体的には、重合ロジンを不飽和カルボン酸類で変性する方法、フェノールで変性する方法などが挙げられる。 As the polymerized rosin, a polymerized rosin that has been subjected to various treatments such as modification, hydrogenation, and disproportionation can be used. In addition, you may perform various processes individually or in combination of 2 or more types. The method for modifying the polymerized rosin is not particularly limited, and a known method can be employed. Specifically, a method of modifying the polymerized rosin with an unsaturated carboxylic acid, a method of modifying with a phenol, and the like can be mentioned.
重合ロジンを不飽和カルボン酸で変性する場合に用いられる不飽和カルボン酸類としては、例えば、（無水）マレイン酸、フマル酸、（無水）イタコン酸、（無水）シトラコン酸、（メタ）アクリル酸などが挙げられる。重合ロジンの不飽和カルボン酸変性物の製造は特に限定されず、公知の方法を採用すればよい。具体的には、例えば、重合ロジンと不飽和カルボン酸類を１５０〜３００℃程度で、１〜２４時間程度反応させれば良い。なお、各成分の使用量としては、特に限定されないが、例えば、重合ロジン１００重量部に対して、不飽和カルボン酸類０.１〜２０重量部程度である。 Examples of the unsaturated carboxylic acids used when the polymerized rosin is modified with an unsaturated carboxylic acid include (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, (meth) acrylic acid, etc. Is mentioned. The production of the unsaturated carboxylic acid modified product of polymerized rosin is not particularly limited, and a known method may be adopted. Specifically, for example, polymerized rosin and unsaturated carboxylic acids may be reacted at about 150 to 300 ° C. for about 1 to 24 hours. The amount of each component used is not particularly limited, but is, for example, about 0.1 to 20 parts by weight of unsaturated carboxylic acids with respect to 100 parts by weight of polymerized rosin.
重合ロジンをフェノールで変性する場合に用いられるフェノール類としては、例えば、フェノール、アルキルフェノール等が挙げられる。フェノール変性重合ロジンは、公知の方法により製造することができる。具体的には、例えば重合ロジンとフェノール類を１５０〜３００℃程度で、１〜２４時間程度反応させれば良い。なお、各成分の使用量としては、特に限定されないが、例えば、重合ロジン１００重量部に対して、フェノール類０．１〜５０重量部程度である。 Examples of the phenols used when the polymerized rosin is modified with phenol include phenol and alkylphenol. The phenol-modified polymerized rosin can be produced by a known method. Specifically, for example, polymerized rosin and phenols may be reacted at about 150 to 300 ° C. for about 1 to 24 hours. In addition, although it does not specifically limit as the usage-amount of each component, For example, it is about 0.1-50 weight part of phenols with respect to 100 weight part of superposition | polymerization rosins.
重合ロジンの水素化は、特に限定されず、公知の方法により行えば良いが、通常、公知水素源の存在下、必要に応じて水素化触媒を用い、０．１〜３０ＭＰａ程度で反応させればよい。水素源としては、水素ガスの他、リチウムアルミニウムハイドライドなどが挙げられ、水素化触媒としては、ラネーニッケル、パラジウム炭素等が挙げられる。 The hydrogenation of the polymerized rosin is not particularly limited and may be carried out by a known method. Usually, in the presence of a known hydrogen source, the reaction is carried out at about 0.1 to 30 MPa using a hydrogenation catalyst as necessary. That's fine. Examples of the hydrogen source include lithium aluminum hydride and the like in addition to hydrogen gas, and examples of the hydrogenation catalyst include Raney nickel and palladium carbon.
重合ロジンの不均化は公知の方法で行えばよく、例えば、通常、公知水素源の存在下、不均化触媒を使用し、常圧で反応させればよい。 The disproportionation of the polymerized rosin may be carried out by a known method. For example, the disproportionation catalyst is usually used in the presence of a known hydrogen source, and the reaction is carried out at normal pressure.
重合ロジンにアルコール類を加えてエステル化反応させる方法としては、重合ロジンおよびアルコール類を溶媒の存在下または不存在下に、必要により硫酸やパラトルエンスルホン酸等のエステル化触媒を加え、２５０〜２８０℃程度で、１〜８時間程度加熱脱水反応させる方法によればよい。使用する溶媒としては炭化水素系溶媒が好ましい。 As a method of adding an alcohol to the polymerized rosin to cause an esterification reaction, the polymerized rosin and the alcohol are added in the presence or absence of a solvent, and an esterification catalyst such as sulfuric acid or paratoluenesulfonic acid is added as necessary. A method of heating and dehydrating at about 280 ° C. for about 1 to 8 hours may be used. The solvent used is preferably a hydrocarbon solvent.
使用するアルコール類としては、メタノール、エタノール、プロパノール等の１価のアルコール類、エチレングリコール、ジエチレングリコール、プロピレングリコール、ネオペンチルグリコール等の２価のアルコール類、グリセリン、トリメチロールエタン、トリメチロールプロパンなどの３価のアルコール類、ペンタエリスリトール、ジグリセリンなどの４価のアルコール類、ジペンタエリスリトールなどの６価のアルコール類等が挙げられる。２つ以上の水酸基を有する多価アルコール類が好ましく、特にペンタエリスリトールを用いるのがよい。 Examples of alcohols used include monohydric alcohols such as methanol, ethanol, and propanol, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol, glycerin, trimethylolethane, and trimethylolpropane. Examples include trivalent alcohols, tetravalent alcohols such as pentaerythritol and diglycerin, and hexavalent alcohols such as dipentaerythritol. Polyhydric alcohols having two or more hydroxyl groups are preferable, and pentaerythritol is particularly preferable.
また、重合ロジンおよびアルコール類の仕込み比率は特に制限されず、得られる重合ロジンエステルの水酸基価が３５〜１００ｍｇＫＯＨ／ｇの範囲となるように調整すればよい。通常は重合ロジンのカルボキシル基当量に対し、１〜２倍当量程度の水酸基を有する量の多価アルコール類を使用することが好ましく、１．２〜１．８倍程度にするのがより好ましい。 The charging ratio of the polymerized rosin and the alcohol is not particularly limited, and may be adjusted so that the hydroxyl value of the polymerized rosin ester obtained is in the range of 35 to 100 mgKOH / g. Usually, it is preferable to use polyhydric alcohols having an amount of hydroxyl groups of about 1 to 2 times equivalent to the carboxyl group equivalents of polymerized rosin, more preferably about 1.2 to 1.8 times.
なお、重合反応とエステル化反応の順番は、上記に限定されず、エステル化反応の後に、重合反応を行ってもよい。 The order of the polymerization reaction and the esterification reaction is not limited to the above, and the polymerization reaction may be performed after the esterification reaction.
本発明の粘着付与樹脂として使用する成分（Ａ）は、以上のようにして得られるものであって、その重量平均分子量（Ｍｗ）が２０００〜３５００、水酸基価が３５〜１００ｍｇＫＯＨ／ｇであり、重量平均分子量が２６０以下の成分の含有量が１．５重量％以下、軟化点が１６０〜１８５℃、および酸価が１００ｍｇＫＯＨ／ｇ以下に調整されたものである。 The component (A) used as the tackifying resin of the present invention is obtained as described above, and has a weight average molecular weight (Mw) of 2000 to 3500 and a hydroxyl value of 35 to 100 mgKOH / g. The content of the component having a weight average molecular weight of 260 or less is adjusted to 1.5% by weight or less, the softening point is adjusted to 160 to 185 ° C., and the acid value is adjusted to 100 mgKOH / g or less.
成分（Ａ）の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、標準ポリスチレンの検量線に基づき算出することができる。成分（Ａ）の重量平均分子量が３５００を超える場合には、水性粘・接着剤とする際に用いられるアクリル系重合体との相溶性が著しく低下しタック、接着力、耐熱保持力などのバランスの良い接着性能が得られなくなる。２０００未満の場合には耐熱保持力が著しく低下するため好ましくない。通常、成分（Ａ）の重量平均分子量は、２０００〜３０００であることが好ましい。 The weight average molecular weight of the component (A) can be calculated based on a standard polystyrene calibration curve using gel permeation chromatography (GPC). When the weight average molecular weight of the component (A) exceeds 3500, the compatibility with the acrylic polymer used for forming an aqueous adhesive / adhesive is remarkably lowered, and the balance such as tack, adhesive strength, heat resistance retention, etc. Good adhesion performance cannot be obtained. If it is less than 2000, the heat resistant holding power is remarkably lowered, which is not preferable. Usually, it is preferable that the weight average molecular weights of a component (A) are 2000-3000.
水酸基価は、電位差滴定法（ＪＩＳ Ｋ００７０）により測定した値であり、水酸基価が３５ｍｇＫＯＨ／ｇ未満の場合には、アクリル系重合体との相溶性が十分でなく、タックや接着力が著しく低下するため好ましくない。１００ｍｇＫＯＨ／ｇを超える場合には、耐熱保持力が低下するため好ましくない。通常、成分（Ａ）の水酸基価は、３５〜７０ｍｇＫＯＨ／ｇであることが好ましい。 The hydroxyl value is a value measured by potentiometric titration (JIS K0070). When the hydroxyl value is less than 35 mgKOH / g, the compatibility with the acrylic polymer is not sufficient, and tack and adhesive strength are remarkably reduced. Therefore, it is not preferable. When it exceeds 100 mgKOH / g, the heat-resistant holding force is lowered, which is not preferable. Usually, it is preferable that the hydroxyl value of a component (A) is 35-70 mgKOH / g.
さらに、本発明に使用する成分（Ａ）は、成分（Ａ）中に含まれる重量平均分子量２６０以下の成分の含有量が１．５重量％以下とする必要がある。重量平均分子量２６０以下の低分子成分の含有量を１．５重量％以下に低減することによって、耐熱保持力や、粗面接着力の良好な水系粘・接着剤組成物を得ることができる。通常、成分（Ａ）中に含まれる重量平均分子量（Ｍｗ）２６０以下の成分の含有量は１．２％以下であることが好ましい。 Furthermore, in the component (A) used in the present invention, the content of the component having a weight average molecular weight of 260 or less contained in the component (A) needs to be 1.5% by weight or less. By reducing the content of the low molecular component having a weight average molecular weight of 260 or less to 1.5% by weight or less, a water-based adhesive / adhesive composition having good heat resistance and rough surface adhesion can be obtained. Usually, the content of a component having a weight average molecular weight (Mw) of 260 or less contained in the component (A) is preferably 1.2% or less.
成分（Ａ）中の分子量２６０以下の成分を除去する方法としては、特に限定されず、公知の方法を採用することができる。具体的には、例えば、加熱・減圧する減圧蒸留法や、蒸発面と凝縮面との距離を蒸気分子の平均自由行程以下に接近させることで蒸留を行う分子蒸留法、加熱・常圧または減圧下で加熱した水蒸気を系内に吹き込む水蒸気蒸留法、分子量２６０以下の低分子成分のみを溶解する溶媒にて抽出する方法等があげられる。 The method for removing the component having a molecular weight of 260 or less in the component (A) is not particularly limited, and a known method can be adopted. Specifically, for example, a vacuum distillation method for heating / depressurizing, a molecular distillation method for performing distillation by bringing the distance between the evaporation surface and the condensation surface close to the mean free path of vapor molecules, heating / normal pressure or reduced pressure Examples thereof include a steam distillation method in which steam heated below is blown into the system, and a method of extracting with a solvent that dissolves only a low molecular component having a molecular weight of 260 or less.
加熱・減圧により分子量２６０以下の成分を除去する際には、通常、温度を２２０〜３００℃程度、圧力を０．０１〜３ｋＰａ程度の条件で、分子量２６０以下の成分の含有量が１．５重量％以下となるまで、継続的に処理すればよい。 When removing a component having a molecular weight of 260 or less by heating / depressurization, the content of the component having a molecular weight of 260 or less is usually 1.5 under conditions of a temperature of about 220 to 300 ° C. and a pressure of about 0.01 to 3 kPa. What is necessary is just to process continuously until it becomes the weight% or less.
水蒸気蒸留により分子量２６０以下の低分子成分を除去する際には、通常、常圧下、温度を２２０〜３００℃程度にて０．１〜１ＭＰａに加熱・加圧した水蒸気を吹き込み、水蒸気蒸留を実施する。時間は温度・水蒸気吹き込み条件により異なるが、分子量２６０以下の成分の含有量が１．５重量％以下となるまで、継続的に処理すればよい。 When removing low molecular components having a molecular weight of 260 or less by steam distillation, steam steam heated and pressurized to 0.1 to 1 MPa at a temperature of about 220 to 300 ° C. under normal pressure is usually used for steam distillation. To do. Although the time varies depending on the temperature and steam blowing conditions, the treatment may be continued until the content of the component having a molecular weight of 260 or less is 1.5% by weight or less.
溶媒にて抽出する場合には、例えば、前記重合ロジンエステル樹脂を粉砕し、分子量２６０以下の成分のみを溶解する溶媒にて抽出する方法があげられる。使用する溶媒としては、例えば、ヘキサンやヘプタン等の脂肪族炭化水素、メタノールやエタノール等のアルコールなどがあげられる。 In the case of extraction with a solvent, for example, there is a method in which the polymerized rosin ester resin is pulverized and extracted with a solvent that dissolves only a component having a molecular weight of 260 or less. Examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, alcohols such as methanol and ethanol, and the like.
成分（Ａ）の軟化点は１６０〜１８５℃であり、特に１６０〜１８０℃とすることが好ましい。軟化点が１６０℃未満の場合には、耐熱保持力が低下する傾向にあり、１８５℃を超える場合には、粘着付与樹脂の分子量が増大し、アクリル系重合体との相溶性が低下するため、良好な接着力が得られない場合がある。なお、当該軟化点は、環球法（ＪＩＳ Ｋ５９０２）により測定した値である。 The softening point of a component (A) is 160-185 degreeC, and it is preferable to set it as 160-180 degreeC especially. When the softening point is less than 160 ° C., the heat-resistant holding force tends to decrease, and when it exceeds 185 ° C., the molecular weight of the tackifying resin increases and the compatibility with the acrylic polymer decreases. In some cases, good adhesive strength cannot be obtained. The softening point is a value measured by the ring and ball method (JIS K5902).
成分（Ａ）の酸価が、１００ｍｇＫＯＨ／ｇを超える場合には、耐熱保持力が低下する傾向にあるため、成分（Ａ）の酸価は１００ｍｇＫＯＨ／ｇ以下であることが好ましい。なお、成分（Ａ）の酸価は、電位差滴定法（ＪＩＳ Ｋ００７０）により測定した値である。 When the acid value of component (A) exceeds 100 mgKOH / g, the heat resistance retention tends to decrease. Therefore, the acid value of component (A) is preferably 100 mgKOH / g or less. The acid value of component (A) is a value measured by potentiometric titration (JIS K0070).
このようにして得られた成分（Ａ）を、必要に応じて乳化剤を用い、水中に分散させることにより本発明の粘着付与樹脂エマルジョンを得ることができる。 The tackifier resin emulsion of the present invention can be obtained by dispersing the component (A) thus obtained in water using an emulsifier as necessary.
使用する乳化剤としては、特に限定されず公知の乳化剤を使用することができる。具体的には、例えば、アニオン性乳化剤、ノニオン性乳化剤などを使用することができる。アニオン性乳化剤としては、例えば、ジアルキルスルホコハク酸塩、アルカンスルホン酸塩、α−オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ナフタリンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等を例示でき、ノニオン性乳化剤としてはポリオキシエチレンアルキルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、およびこれら乳化剤にビニル基またはアリル基、プロペニル基を導入した反応性乳化剤等を例示できる。これら乳化剤は１種または２種以上を適宜選択して使用することができる。 It does not specifically limit as an emulsifier to use, A well-known emulsifier can be used. Specifically, for example, an anionic emulsifier and a nonionic emulsifier can be used. Examples of the anionic emulsifier include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalene sulfonate formalin. Examples include condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc. Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene sorbitan fatty acid esters And reactive emulsifiers in which a vinyl group, an allyl group or a propenyl group is introduced into these emulsifiers. These emulsifiers can be used by appropriately selecting one kind or two or more kinds.
また、乳化剤としては、各種モノマーを重合して得られる高分子乳化剤を用いてもよい。高分子乳化剤の製造に使用するモノマーとしては、例えば、イオン性モノマー、疎水性モノマー、これら以外のモノマーなどが挙げられる。 As the emulsifier, a polymer emulsifier obtained by polymerizing various monomers may be used. Examples of the monomer used for the production of the polymer emulsifier include ionic monomers, hydrophobic monomers, and other monomers.
イオン性モノマーとしては、分子中にイオン性官能基を有するモノマーであれば特に限定されず公知のものを使用することができる。具体的には、例えば、アニオン性官能基を有するアニオン性モノマー、カチオン性官能基を有するカチオン性モノマーが挙げられる。アニオン性モノマーとしては、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸、無水マレイン酸等のカルボキシル基を有するビニルモノマー、ビニルスルホン酸、スチレンスルホン酸、（メタ）アクリル酸スルホエチル、（メタ）アクリル酸スルホプロピル、（メタ）アリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸などのスルホン酸基を有するモノマー、アシッドホスホオキシエチル（メタ）アクリレート、アシッドホスホオキシプロピル（メタ）アクリレート、アシッドホスホオキシポリエチレングリコール（メタ）アクリレート等のリン酸基を有するモノマーおよびこれらモノマーの塩（例えば、ナトリウム塩、カリウム塩、アミン塩等）などが挙げられる。カチオン性モノマーとしては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミド、トリアリルアミンなどの第三級アミノ基を有するビニルモノマーまたはそれらの塩酸、硫酸等の無機酸もしくは酢酸などの有機酸の塩類、または該第三級アミノ基含有ビニルモノマ−とメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリンなどの四級化剤との反応によって得られる第四級アンモニウム塩を含有するビニルモノマ−などがあげられる。これらアニオン性モノマー、カチオン性モノマーは一種を単独で用いても良く、２種以上を併用してもよい。粘・接着剤のベースポリマーがアニオン性である場合には、アニオン性モノマーをカチオン性モノマーより多く用いることが好ましく、ベースポリマーがカチオン性である場合には、カチオン性モノマーをアニオン性モノマーより多く用いることが好ましい。通常、ベースポリマーとして、アニオン性のものが用いられることが多いため、アニオン性モノマーを多く用いることが好ましい。 As an ionic monomer, if it is a monomer which has an ionic functional group in a molecule | numerator, it will not specifically limit, A well-known thing can be used. Specific examples include an anionic monomer having an anionic functional group and a cationic monomer having a cationic functional group. Examples of the anionic monomer include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, muconic acid, citraconic acid, maleic anhydride and other vinyl monomers having a carboxyl group, vinyl sulfonic acid, styrene sulfonic acid, (Meth) acrylic acid sulfoethyl, (meth) acrylic acid sulfopropyl, (meth) allylsulfonic acid, monomers having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl (meth) acrylate, Examples thereof include monomers having a phosphate group such as acid phosphooxypropyl (meth) acrylate and acid phosphooxypolyethylene glycol (meth) acrylate, and salts of these monomers (for example, sodium salt, potassium salt, amine salt, etc.). As the cationic monomer, a vinyl monomer having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, triallylamine, or the like Obtained by reaction of inorganic acid salts such as hydrochloric acid and sulfuric acid or organic acid salts such as acetic acid, or quaternizing agents such as methyl chloride, benzyl chloride, dimethyl sulfate, and epichlorohydrin with the tertiary amino group-containing vinyl monomers. And vinyl monomers containing a quaternary ammonium salt. These anionic monomers and cationic monomers may be used alone or in combination of two or more. When the base polymer of the adhesive / adhesive is anionic, it is preferable to use more anionic monomer than cationic monomer. When the base polymer is cationic, more cationic monomer than anionic monomer is used. It is preferable to use it. Usually, anionic polymers are often used as the base polymer, so that it is preferable to use a lot of anionic monomers.
疎水性モノマーとしては、具体的には、例えば、（メタ）アクリル酸エチル、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸アルキルエステル（アルキル基の炭素数が１〜２０であるものが好ましい）、スチレン、α−メチルスチレン等のスチレン類や、これらスチレン類の芳香環に炭素数１〜４のアルキル基を有するスチレン系化合物などのスチレン系単量体、酢酸ビニル、プロピオン酸ビニル等のカルボン酸ビニルエステル、炭素数６〜２２のα−オレフィン、炭素数１〜２２のアルキルビニルエーテル、ビニルピロリドン等を例示できる。これらのなかでも、特に（メタ）アクリル酸アルキルエステル、スチレン系単量体、カルボン酸ビニルエステル等が乳化性の点で好ましい。これらは１種を単独で用いてもよく２種以上を混合して用いてもよい。 Specific examples of the hydrophobic monomer include (meth) acrylic acid alkyl esters such as ethyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate ( Those having 1 to 20 carbon atoms in the alkyl group are preferred), styrenes such as styrene and α-methylstyrene, and styrene compounds having an alkyl group having 1 to 4 carbon atoms in the aromatic ring of these styrenes, etc. Examples thereof include styrene-based monomers, vinyl acetates such as vinyl acetate and vinyl propionate, α-olefins having 6 to 22 carbon atoms, alkyl vinyl ethers having 1 to 22 carbon atoms, and vinylpyrrolidone. Among these, (meth) acrylic acid alkyl ester, styrene monomer, carboxylic acid vinyl ester and the like are particularly preferable from the viewpoint of emulsification. These may be used alone or in combination of two or more.
イオン性モノマー、疎水性モノマー以外のモノマーとしては、例えば、（メタ）アクリルアミドなどが挙げられる。これらは１種を単独で用いてもよく２種以上を混合して用いてもよい。 Examples of the monomer other than the ionic monomer and the hydrophobic monomer include (meth) acrylamide. These may be used alone or in combination of two or more.
高分子乳化剤はこれらの成分を公知の方法で重合して得られる。各成分の使用量は特に限定されないが、通常、イオン性モノマー：疎水性モノマー：イオン性モノマーおよび疎水性モノマー以外のモノマーが、１〜８０モル％：１〜８０モル％：０〜９０モル％程度である。 The polymer emulsifier is obtained by polymerizing these components by a known method. Although the usage-amount of each component is not specifically limited, Usually, ionic monomer: hydrophobic monomer: monomers other than an ionic monomer and a hydrophobic monomer are 1-80 mol%: 1-80 mol%: 0-90 mol% Degree.
乳化方法としては特に限定されず公知の方法を採用することができる。具体的には、たとえば、（１）．成分（Ａ）をトルエン、キシレン、シクロヘキサン、メチルシクロヘキサン、ペンタン等の有機溶剤で溶解し、軟水および乳化剤を添加した後に、高圧乳化機を用いて乳化し、減圧下に有機溶剤を除去する方法、（２）．成分（Ａ）と少量の有機溶剤、乳化剤を混合し、熱水を徐々に添加してゆき、転相乳化させてエマルジョンとする方法（必要に応じてさらに、減圧下に該溶剤を除去してもよい）、（３）．加圧下または常圧下に、成分（Ａ）の軟化点以上の温度で、成分（Ａ）および乳化剤を混合し、さらに熱水を徐々に添加してゆき、転相乳化させる方法などが挙げられる。 It does not specifically limit as an emulsification method, A well-known method is employable. Specifically, for example, (1). A method of dissolving component (A) in an organic solvent such as toluene, xylene, cyclohexane, methylcyclohexane, pentane, etc., adding soft water and an emulsifier, emulsifying using a high-pressure emulsifier, and removing the organic solvent under reduced pressure, (2). Method of mixing component (A) with a small amount of organic solvent and emulsifier, gradually adding hot water, phase inversion emulsification to make an emulsion (if necessary, further removing the solvent under reduced pressure (3). Examples thereof include a method in which component (A) and an emulsifier are mixed at a temperature equal to or higher than the softening point of component (A) under pressure or normal pressure, and hot water is gradually added to perform phase inversion emulsification.
このようにして得られた粘着付与樹脂エマルジョンの固形分濃度は特に限定されないが、通常３５〜６５重量％程度となるように適宜調整して用いる。また、得られたエマルジョンの体積平均粒子径は、通常０．１〜２μｍ程度であり、大部分は１μｍ以下の粒子として均一に分散しているが、当該体積平均粒子径を０．７μｍ以下とすることが、貯蔵安定性の点から好ましい。また、該エマルジョンは白色ないし乳白色の外観を呈し、ｐＨは２〜１０程度で、粘度（Ｂ型粘度計）は通常１０〜１０００ｍＰａ・ｓ程度（２５℃、固形分濃度５０％において）である。 The solid content concentration of the tackifier resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately so as to be about 35 to 65% by weight. Moreover, the volume average particle diameter of the obtained emulsion is usually about 0.1 to 2 μm, and most of them are uniformly dispersed as particles of 1 μm or less, but the volume average particle diameter is 0.7 μm or less. It is preferable from the viewpoint of storage stability. The emulsion has a white to milky white appearance, has a pH of about 2 to 10, and a viscosity (B-type viscometer) is usually about 10 to 1000 mPa · s (at 25 ° C. and a solid content concentration of 50%).
本発明のアクリルエマルジョン型水系粘・接着剤組成物は、前記粘着付与樹脂エマルジョンおよびアクリル系重合体エマルジョンを含有するものである。なお、アクリルエマルジョン型水系粘・接着剤組成物は、カルボキシル基に反応性を有する架橋剤を含有していてもよい。 The acrylic emulsion type water-based adhesive / adhesive composition of the present invention contains the tackifying resin emulsion and the acrylic polymer emulsion. In addition, the acrylic emulsion type water-based adhesive / adhesive composition may contain a crosslinking agent having reactivity with a carboxyl group.
アクリル系重合体エマルジョンとしては、一般に各種アクリル系粘・接着剤に用いられている公知のものを使用でき、（メタ）アクリル酸エステル等のモノマーの一括仕込み重合法、モノマー逐次添加重合法、乳化モノマー逐次添加重合法、シード重合法等の公知の乳化重合法により容易に製造することができる。 As the acrylic polymer emulsion, known ones generally used for various acrylic adhesives and adhesives can be used, such as batch polymerization of monomers such as (meth) acrylic acid ester, monomer sequential addition polymerization method, emulsification It can be easily produced by a known emulsion polymerization method such as a monomer sequential addition polymerization method or a seed polymerization method.
アクリル系重合体の製造に用いられる（メタ）アクリル酸エステルとしては、たとえば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−ヒドロキシエチル等をあげることができ、これらを単独でまたは二種以上を混合して用いる。また、得られるアクリル系重合体エマルジョンに貯蔵安定性を付与するため前記（メタ）アクリル酸エステルと共に（メタ）アクリル酸を少量使用してもよい。さらに所望によりアクリル系重合体の接着特性を損なわない程度において、たとえば、酢酸ビニル、スチレン等の共重合可能なモノマーの他、高分子乳化剤に用いられる（メタ）アクリル酸以外のイオン性モノマーも併用できる。なお、アクリル系重合体エマルジョンに用いられる乳化剤にはアニオン系乳化剤、部分ケン化ポリビニルアルコール等を使用でき、その使用量は当該重合体１００重量部に対して通常０．１〜５重量部程度、好ましくは０．５〜３重量部である。 Examples of the (meth) acrylic acid ester used for the production of the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include glycidyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, and these are used alone or in admixture of two or more. Moreover, in order to provide storage stability to the obtained acrylic polymer emulsion, a small amount of (meth) acrylic acid may be used together with the (meth) acrylic acid ester. Furthermore, as long as it does not impair the adhesive properties of the acrylic polymer as desired, for example, in addition to a copolymerizable monomer such as vinyl acetate or styrene, an ionic monomer other than (meth) acrylic acid used in a polymer emulsifier is also used. it can. In addition, an anionic emulsifier, a partially saponified polyvinyl alcohol, or the like can be used as an emulsifier used in the acrylic polymer emulsion, and the amount used is usually about 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer. Preferably it is 0.5-3 weight part.
アクリル系重合体エマルジョンと粘着付与樹脂エマルジョンの使用割合は、特に限定されないが、粘着付与樹脂エマルジョンによる改質の効果が十分に発現でき、かつ、過剰使用による耐熱保持力、タック等の低下を引き起こさない適当な使用範囲としては、アクリル系重合体エマルジョン１００重量部（固形分換算）に対して、粘着付与樹脂エマルジョンを通常２〜４０重量部程度（固形分換算）とするのがよい。 The use ratio of the acrylic polymer emulsion and the tackifying resin emulsion is not particularly limited, but the effect of the modification by the tackifying resin emulsion can be sufficiently expressed, and the heat resistance holding force, tack, etc. are reduced due to excessive use. As an appropriate use range, the tackifier resin emulsion is usually about 2 to 40 parts by weight (in terms of solid content) with respect to 100 parts by weight of the acrylic polymer emulsion (in terms of solid content).
本発明のアクリルエマルジョン型水系粘・接着剤組成物には、さらに必要に応じて消泡剤、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤等の公知の各種添加剤を使用することもできる。なお、アクリルエマルジョン型水系粘・接着剤組成物の固形分濃度は通常４０〜７０重量％程度、好ましくは５５〜７０重量％である。 The acrylic emulsion type water-based adhesive / adhesive composition of the present invention may further include various known additions such as an antifoaming agent, a thickening agent, a filler, an antioxidant, a water-resistant agent, and a film-forming auxiliary as necessary. Agents can also be used. The solid content concentration of the acrylic emulsion type water-based adhesive / adhesive composition is usually about 40 to 70% by weight, preferably 55 to 70% by weight.
以下、製造例、実施例をあげて本発明を更に具体的に説明するが、本発明がこれら実施例に限定されることはない。なお、以下「部」、「％」はいずれも重量基準である。 Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to these examples. Hereinafter, “parts” and “%” are based on weight.
製造例１ [ベースポリマーエマルジョンの製造]
攪拌装置、温度計、還流冷却管、滴下ロートおよび窒素導入管を備えた反応容器に、窒素ガス気流下、水４３．４部およびポリオキシエチレンアルキルエーテル硫酸エステルナトリウム塩（アニオン性乳化剤：商品名「ハイテノール０７３」：第一工業製薬（株）製）０．９２部からなる水溶液を仕込み、７０℃に昇温した。
次いで、アクリル酸ブチル９０部、アクリル酸２−エチルヘキシル７部およびアクリル酸３部からなる混合物と、過硫酸カリウム（重合開始剤）０．２４部、ｐＨ調整剤（重曹）０．１１部および水８．８３部からなる開始剤水溶液の１／１０量を反応容器に添加し、窒素ガス気流下にて７０℃、３０分間予備重合反応を行った。次いで、前記混合物と前記開始剤水溶液の残りの９／１０量を２時間にわたり反応容器に添加して乳化重合を行い、その後７０℃で１時間保持して重合反応を完結させた。こうして得られたアクリル系重合体エマルジョンを室温まで冷却した後１００メッシュ金網を用いてろ過し、固形分４７．８％のアクリル系重合体エマルジョンを得た。
Production Example 1 [Production of base polymer emulsion]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 43.4 parts of water and polyoxyethylene alkyl ether sulfate sodium salt (anionic emulsifier: trade name) under nitrogen gas flow An aqueous solution consisting of 0.92 part of “Hitenol 073” (Daiichi Kogyo Seiyaku Co., Ltd.) was charged and the temperature was raised to 70 ° C.
Next, a mixture comprising 90 parts of butyl acrylate, 7 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid, 0.24 parts of potassium persulfate (polymerization initiator), 0.11 part of pH adjusting agent (bicarbonate) and water 1/10 amount of the initiator aqueous solution consisting of 8.83 parts was added to the reaction vessel, and a prepolymerization reaction was performed at 70 ° C. for 30 minutes under a nitrogen gas stream. Next, the remaining 9/10 amount of the mixture and the aqueous initiator solution was added to the reaction vessel over 2 hours to carry out emulsion polymerization, and then held at 70 ° C. for 1 hour to complete the polymerization reaction. The acrylic polymer emulsion thus obtained was cooled to room temperature and then filtered using a 100 mesh wire net to obtain an acrylic polymer emulsion having a solid content of 47.8%.
製造例２[重合ロジンエステルの製造]
攪拌装置、コンデンサー、温度計および窒素導入管・水蒸気導入管を備えた反応容器に、重合ロジン１００部（樹脂酸ダイマー６５％、酸価１４５、軟化点１４０℃）、ペンタエリスリトール１４部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。得られた重合ロジンエステルの特性（重量平均分子量（Ｍｗ）、水酸基価、重量平均分子量（Ｍｗ）２６０以下の成分量、酸価、軟化点）を下記の方法により測定した。その結果を表１に示す。
Production Example 2 [Production of polymerized rosin ester]
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube / steam introduction tube was charged with 100 parts of polymerized rosin (resin acid dimer 65%, acid value 145, softening point 140 ° C.) and 14 parts of pentaerythritol. Then, after making it react at 250 degreeC under nitrogen gas stream for 2 hours, it heated up further to 280 degreeC and was made to react at the same temperature for 12 hours, and esterification was completed. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester. The properties (weight average molecular weight (Mw), hydroxyl value, component amount of weight average molecular weight (Mw) 260 or less, acid value, softening point) of the obtained polymerized rosin ester were measured by the following methods. The results are shown in Table 1.
（重量平均分子量（Ｍｗ））
重量平均分子量（Ｍｗ）はゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、標準ポリスチレンの検量線から求めた、ポリスチレン換算値として算出した。なお、ＧＰＣ法は以下の条件で測定した。
分析装置：ＨＬＣ−８１２０（東ソー（株）製）
カラム：ＴＳＫｇｅｌＳｕｐｅｒＨＭ−Ｌ×３本
溶離液：テトラヒドロフラン
注入試料濃度：５ｍｇ/ｍＬ
流量：０．６ｍＬ/ｍｉｎ
注入量：１００μＬ
カラム温度：４０℃
検出器：ＲＩ
(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) was calculated as a polystyrene conversion value obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC). The GPC method was measured under the following conditions.
Analyzer: HLC-8120 (manufactured by Tosoh Corporation)
Column: TSKgelSuperHM-L × 3 eluent: tetrahydrofuran injection Sample concentration: 5 mg / mL
Flow rate: 0.6mL / min
Injection volume: 100 μL
Column temperature: 40 ° C
Detector: RI
（水酸基価）
ＪＩＳ Ｋ ０７００に準ずる電位差滴定法で測定した。
(Hydroxyl value)
It measured by the potentiometric titration method according to JISK0700.
（重量平均分子量（Ｍｗ）２６０以下の成分の含有量）
重量平均分子基準で、ポリスチレン換算値を基に上記と同様にＧＰＣ法により、算出した。
(Content of components having a weight average molecular weight (Mw) of 260 or less)
On the basis of weight average molecular weight, it was calculated by the GPC method in the same manner as above based on the polystyrene conversion value.
（軟化点）
ＪＩＳ Ｋ ２５３１の環球法により測定した。
(Softening point)
It was measured by the ring and ball method of JIS K 2531.
（酸価）
ＪＩＳ Ｋ ０７００に準ずる電位差滴定法で測定した。
(Acid value)
It measured by the potentiometric titration method according to JISK0700.
製造例３[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１３部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 3 [Production of polymerized rosin ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 13 parts of pentaerythritol, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 12 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例４[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１１部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１０時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 4 [Production of polymerized rosin ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 11 parts of pentaerythritol, and reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 10 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例５[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１３部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１４時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 5 [Production of polymerized rosin ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 13 parts of pentaerythritol, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 14 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例６[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（樹脂酸ダイマー８３％、酸価１３８、軟化点１５８℃）１００部、ペンタエリスリトール１７部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１０時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 6 [Production of polymerized rosin ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (resin acid dimer 83%, acid value 138, softening point 158 ° C.) and 17 parts of pentaerythritol, and then at 250 ° C. for 2 hours under a nitrogen gas stream. After the reaction, the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 10 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例７[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１５．８部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１３時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 7 [Production of polymerized rosin ester]
In a reaction apparatus similar to Production Example 1, 100 parts of polymerized rosin (same as Production Example 2) and 15.8 parts of pentaerythritol were charged, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 13 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例８[重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール８．５部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で６時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 8 [Production of polymerized rosin ester]
In a reactor similar to Production Example 1, 100 parts of polymerized rosin (same as Production Example 2) and 8.5 parts of pentaerythritol were charged and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 6 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例９[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール７．２部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で６時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 9 [Production of Comparative Polymerized Rosin Ester]
In a reactor similar to Production Example 1, 100 parts of polymerized rosin (same as Production Example 2) and 7.2 parts of pentaerythritol were charged, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 6 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例１０[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１４．５部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１０時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 10 [Production of Comparative Polymerized Rosin Ester]
In a reactor similar to Production Example 1, 100 parts of polymerized rosin (same as Production Example 2) and 14.5 parts of pentaerythritol were charged, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 10 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例１１[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン１００部（樹脂酸ダイマー８３％、酸価１３８、軟化点１５８℃）、ペンタエリスリトール１３部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１４時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を４時間吹き込み、重合ロジンエステルを得た。
Production Example 11 [Production of Polymerized Rosin Ester for Comparison]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (resin acid dimer 83%, acid value 138, softening point 158 ° C.) and 13 parts of pentaerythritol, and then at 250 ° C. for 2 hours under a nitrogen gas stream. After the reaction, the temperature was further raised to 280 ° C. and the reaction was carried out at the same temperature for 14 hours to complete the esterification. Thereafter, 0.1 MPa water vapor was blown in for 4 hours to obtain a polymerized rosin ester.
製造例１２[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）８０部、ガムロジン２０部、ペンタエリスリトール１３部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 12 [Production of Comparative Polymerized Rosin Ester]
In a reactor similar to Production Example 1, 80 parts of polymerized rosin (same as Production Example 2), 20 parts of gum rosin, and 13 parts of pentaerythritol were charged and reacted at 250 ° C. for 2 hours in a nitrogen gas stream. Thereafter, the temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 12 hours to complete esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例１３[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１１部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 13 [Production of Comparative Polymerized Rosin Ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 11 parts of pentaerythritol, and reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 12 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例１４[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１３部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３０分吹き込み、重合ロジンエステルを得た。
Production Example 14 [Production of Polymerized Rosin Ester for Comparison]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 13 parts of pentaerythritol, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 12 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 30 minutes to obtain a polymerized rosin ester.
製造例１５[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン１００部（樹脂酸ダイマー８３％、酸価１３８、軟化点１５８℃）、ペンタエリスリトール１２．８部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１２時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 15 [Production of Comparative Polymerized Rosin Ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (83% resin acid dimer, acid value 138, softening point 158 ° C.) and 12.8 parts of pentaerythritol at 250 ° C. under a nitrogen gas stream. After reacting for 2 hours, the temperature was further raised to 280 ° C., and the reaction was performed at the same temperature for 12 hours to complete esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例１６[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール１８部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で１０時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 16 [Production of Comparative Polymerized Rosin Ester]
A reactor similar to Production Example 1 was charged with 100 parts of polymerized rosin (same as Production Example 2) and 18 parts of pentaerythritol, and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was raised to 0 ° C. and reacted at the same temperature for 10 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
製造例１７[比較用重合ロジンエステルの製造]
製造例１と同様の反応装置に、重合ロジン（製造例２と同一のもの）１００部、ペンタエリスリトール４．５部を仕込んだ後、窒素ガス気流下に２５０℃で２時間反応させた後、さらに２８０℃まで昇温し同温度で６時間反応させ、エステル化を完了させた。その後、０．１ＭＰａの水蒸気を３時間吹き込み、重合ロジンエステルを得た。
Production Example 17 [Production of Comparative Polymerized Rosin Ester]
In a reaction apparatus similar to Production Example 1, 100 parts of polymerized rosin (same as Production Example 2) and 4.5 parts of pentaerythritol were charged and then reacted at 250 ° C. for 2 hours under a nitrogen gas stream. The temperature was further raised to 280 ° C., and the reaction was carried out at the same temperature for 6 hours to complete the esterification. Thereafter, 0.1 MPa of water vapor was blown for 3 hours to obtain a polymerized rosin ester.
実施例１ ［粘着付与樹脂エマルジョンの調製］
製造例２で得た、重合ロジンエステル１００重量部をトルエン７０部に８０℃にて３時間かけて溶解させた後、アニオン性乳化剤(ドデシルベンゼンスルホン酸ナトリウム)を固形分換算で３部および水１４０部を添加し、１時間攪拌した。次いで、高圧乳化機（マントンガウリン社製）により３０ＭＰａの圧力で高圧乳化して乳化物を得た。次いで、７０℃、２．９３×１０−２ＭＰａの条件下に６時間減圧蒸留を行い、固形分５０％の粘着付与樹脂エマルジョン１を得た。
Example 1 [Preparation of tackifying resin emulsion]
After dissolving 100 parts by weight of the polymerized rosin ester obtained in Production Example 2 in 70 parts of toluene at 80 ° C. over 3 hours, 3 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) and water 140 parts were added and stirred for 1 hour. Subsequently, high pressure emulsification was performed with a high pressure emulsifier (mantongaurin) at a pressure of 30 MPa to obtain an emulsion. Subsequently, vacuum distillation was performed for 6 hours under the conditions of 70 ° C. and 2.93 × 10 −2 MPa to obtain a tackifier resin emulsion 1 having a solid content of 50%.
実施例２〜７ ［粘着付与樹脂エマルジョンの調製］
実施例１において、重合ロジンエステルを表２の様に代えた他は実施例１と同様に行い、粘着付与樹脂エマルジョンを得た。
Examples 2 to 7 [Preparation of tackifying resin emulsion]
A tackifying resin emulsion was obtained in the same manner as in Example 1 except that the polymerized rosin ester was changed as shown in Table 2 in Example 1.
比較例１〜９ ［粘着付与樹脂エマルジョンの調製］
実施例１において、重合ロジンエステルを表２の様に代えた他は実施例１と同様に行い、粘着付与樹脂エマルジョンを得た。
Comparative Examples 1-9 [Preparation of tackifying resin emulsion]
A tackifying resin emulsion was obtained in the same manner as in Example 1 except that the polymerized rosin ester was changed as shown in Table 2 in Example 1.
実施例１〜７および比較例１〜９で得られた粘着付与樹脂エマルジョン１５部と製造例１で得られたアクリル系重合体のエマルジョン８５部（固形分換算）を混合し、増粘剤プライマルＡＳＥ−６０（ロームアンドハース社製）０．５部を添加し、アンモニア水を適量加え、増粘させて水系粘着剤組成物を得た。得られた水系粘着剤組成物について、以下の評価方法により耐熱保持力および粗面接着力を評価した。 A thickener primal was prepared by mixing 15 parts of the tackifier resin emulsion obtained in Examples 1 to 7 and Comparative Examples 1 to 9 and 85 parts (in terms of solid content) of the acrylic polymer emulsion obtained in Production Example 1. 0.5 part of ASE-60 (made by Rohm and Haas) was added, an appropriate amount of aqueous ammonia was added, and the mixture was thickened to obtain an aqueous pressure-sensitive adhesive composition. About the obtained water-based pressure-sensitive adhesive composition, the heat resistance holding force and the rough surface adhesive force were evaluated by the following evaluation methods.
（試験サンプルの作製）
上記水系粘着剤組成物を厚さ３８μｍのポリエステルフィルム（商品名「Ｓ−１００」、三菱化学ポリエステルフィルム（株）製）にサイコロ型アプリケーター（大佑機材（株）製）にて乾燥膜厚が６０μｍ程度となるように塗布し、次いで１０５℃の循風乾燥機中で５分間乾燥させて試料テープ用フィルムを作製した。以下の試験方法により粘着特性を評価した。評価結果は表２に示す。
(Preparation of test sample)
The above water-based pressure-sensitive adhesive composition is dried on a polyester film (trade name “S-100”, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) with a thickness of 38 μm using a dice-type applicator (manufactured by Otsugi Equipment Co., Ltd.). The film was applied to a certain degree, and then dried in a circulating drier at 105 ° C. for 5 minutes to produce a sample tape film. The adhesive properties were evaluated by the following test methods. The evaluation results are shown in Table 2.
（耐熱保持力）
前記試料テープ用フィルムをステンレス板に巾２５ｍｍ×長さ２５ｍｍで貼り付け、８０℃で１ｋｇの荷重をかけ、１２時間経過後のズレ距離（ｍｍ）もしくは１２時間経過前に落下した場合にはその落下までに要した時間を測定した。
(Heat resistant holding power)
The sample tape film is affixed to a stainless steel plate with a width of 25 mm and a length of 25 mm, a load of 1 kg is applied at 80 ° C., and when it is dropped before 12 hours, The time required to fall was measured.
（粗面接着力）
前記試料テープ用フィルムをＥＣＳ系ウレタンフォーム（巾２５ｍｍ×長さ１００ｍｍ）に１０ｋｇロールを１往復して張り合わせ、８０℃にて剥離速度３００ｍｍ/分で１８０°剥離を行い、粗面接着力を測定した。
(Rough surface adhesion)
The film for the sample tape was bonded to an ECS urethane foam (width 25 mm × length 100 mm) by reciprocating a 10 kg roll, peeled 180 ° at a peeling speed of 300 mm / min at 80 ° C., and measured the rough surface adhesive force. .
（相溶性）
分光光度計（（株）日立製作所製、商品名「Ｕ−３２１０形自記分光光度計」）を用い、５００ｎｍの光を前記試料テープ用フィルムに照射し、透過率を測定した。得られた透過率より相溶性を以下のように評価した。
○：透過率７０％以上 △：透過率５０％以上７０％未満 ×：透過率５０％未満
(Compatibility)
Using a spectrophotometer (trade name “U-3210 type self-recording spectrophotometer” manufactured by Hitachi, Ltd.), the film for sample tape was irradiated with light of 500 nm, and the transmittance was measured. From the obtained transmittance, the compatibility was evaluated as follows.
○: Transmittance of 70% or more Δ: Transmittance of 50% or more and less than 70% ×: Transmittance of less than 50%
Claims (3)
ルジョン。 The tackifying resin emulsion according to claim 1, which has a weight average molecular weight (Mw) of 2000 to 3000.
Claim 1 or acrylic emulsion type water-based tacky adhesive compositions containing 2 tackifier resin emulsion.
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| JPWO2006109441A1 (en) * | 2005-03-30 | 2008-10-16 | 荒川化学工業株式会社 | Tackifier and tackifier resin emulsion |
| JP5757606B2 (en) * | 2010-11-04 | 2015-07-29 | 日東電工株式会社 | Adhesive sheet |
| JP6003474B2 (en) * | 2011-09-27 | 2016-10-05 | 荒川化学工業株式会社 | Tackifier for water-based adhesive / adhesive, tackifier resin emulsion, water-based adhesive / adhesive composition, and method for bonding to rough surface |
| JP6061087B2 (en) * | 2013-03-13 | 2017-01-18 | 荒川化学工業株式会社 | Method for producing polymerized rosin ester and polymerized rosin ester obtained by the method |
| US10781344B2 (en) | 2015-11-30 | 2020-09-22 | Harima Chemicals, Incorporated | Tackifier resin and pressure-sensitive adhesive composition |
| JP7134984B2 (en) * | 2017-09-20 | 2022-09-12 | ハリマ化成株式会社 | Tackifying resin and adhesive composition |
| JP7115427B2 (en) | 2018-07-11 | 2022-08-09 | 荒川化学工業株式会社 | Tackifying resin emulsion, water-based adhesive/adhesive composition, and adhesive/adhesive sheet |
| CN110256980B (en) * | 2019-06-20 | 2021-09-17 | 江苏省人民医院 | Antibacterial polyurethane flexible foam adhesive material for preventing pressure sores of infants and preparation method thereof |
| JP7286434B2 (en) * | 2019-06-25 | 2023-06-05 | 三井化学株式会社 | (Co)polymers and tackifiers |
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