JP5524119B2 - Adhesive composition and method for producing the same - Google Patents
Adhesive composition and method for producing the same Download PDFInfo
- Publication number
- JP5524119B2 JP5524119B2 JP2011079794A JP2011079794A JP5524119B2 JP 5524119 B2 JP5524119 B2 JP 5524119B2 JP 2011079794 A JP2011079794 A JP 2011079794A JP 2011079794 A JP2011079794 A JP 2011079794A JP 5524119 B2 JP5524119 B2 JP 5524119B2
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- JP
- Japan
- Prior art keywords
- polymer
- water
- ethylenically unsaturated
- adhesive composition
- unsaturated monomer
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 66
- 239000000853 adhesive Substances 0.000 title description 62
- 230000001070 adhesive effect Effects 0.000 title description 62
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims description 88
- 239000000178 monomer Substances 0.000 claims description 82
- 239000004821 Contact adhesive Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- WBZPMFHFKXZDRZ-UHFFFAOYSA-N ethenyl 6,6-dimethylheptanoate Chemical compound CC(C)(C)CCCCC(=O)OC=C WBZPMFHFKXZDRZ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- -1 for example Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 238000000576 coating method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000011120 plywood Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 239000002516 radical scavenger Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004566 building material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical class [*:2]C([*:1])=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 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
- 229920001971 elastomer Polymers 0.000 description 2
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 2
- FHJUNZDWQYDDNJ-UHFFFAOYSA-N ethoxy ethyl sulfate Chemical compound CCOOS(=O)(=O)OCC FHJUNZDWQYDDNJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 208000008842 sick building syndrome Diseases 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-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
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- TURPNXCLLLFJAP-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl hydrogen sulfate Chemical compound OCCOCCOCCOS(O)(=O)=O TURPNXCLLLFJAP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- RESQVPCTJIALIE-UHFFFAOYSA-N 2-methylprop-2-enoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CC(=C)C(O)=O RESQVPCTJIALIE-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)(C(OC=C)=C)NC Chemical compound CC(*)(C(OC=C)=C)NC 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 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 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000003712 anti-aging effect Effects 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MAOSFLAYGYQLBB-UHFFFAOYSA-N butane-1,4-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCCCO MAOSFLAYGYQLBB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 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
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、水分散型接着剤組成物及びその製造方法に関する。具体的には、本発明は、環境への負荷の大きい揮発性有機溶剤や可塑剤などを含まず、耐水性、初期接着性、コンタクト接着性、常態接着強度、引張剪断強度及び耐熱クリープ性に優れた、木材から金属、各種プラスチックまで幅広く接着できる、例えば建築用途、工業用途及びコーティング用、特に化粧合板、複合パネルなどの建材用途に有用な水分散型接着剤組成物及びその製造方法に関する。 The present invention relates to a water-dispersed adhesive composition and a method for producing the same. Specifically, the present invention does not include volatile organic solvents or plasticizers that have a large environmental load, and is resistant to water resistance, initial adhesion, contact adhesion, normal adhesion strength, tensile shear strength, and heat resistance creep resistance. The present invention relates to an excellent water-dispersed adhesive composition that can be widely bonded from wood to metal and various plastics, and is useful for, for example, building applications, industrial applications and coatings, especially for building materials such as decorative plywood and composite panels, and a method for producing the same.
家具、洗面台、建築内装材の各所に使用される接着剤、例えば、これらの用途において主に使用されているクロロプレンゴム系接着剤などの有機溶剤系接着剤は、シックハウス症候群や環境問題を引き起こす可能性の高い揮発性有機溶媒や塩素を含んでいる。一方で、近年、健康や環境に対する関心がさらに高まっていることから、揮発性有機化合物の含有量が少ない、水を媒体とする接着剤の転換が強く望まれている。更に、同様に家具や洗面台、建築内装材の他に化粧合板、複合パネルなどの建材用途にも使用される反応型ホットメルト接着剤は、塗装時の加熱溶融時に反応が進行しゲル物が発生するため、反応の進行を軽減させるために塗装機内部全体を窒素ガスで置換させる必要があり、塗装機のメンテナンスなど多大な経費も必要となる。従って、より安全でハンドリング性に優れる水系接着剤への転換が強く要望されている。
このような要望に従い、水を媒体とする酢ビ系エマルションやエチレン−酢ビエマルションを用いた接着剤組成物が開発された。しかしながら、これらの接着剤は、初期接着力、コンタクト性、耐水性、乾燥性及び塗工性が劣ると言う問題を有していた。
接着剤組成物から有機溶媒や塩素を初めとするハロゲンを除き、且つ接着力等が優れた接着剤組成物を得るための検討がなされている。例えば、特許文献１、特許文献２及び特許文献３では、ドライラミネート用水性接着剤として、連鎖移動剤存在下でカルボニル基とジヒドラジドの架橋構造を導入した水性接着剤が提案されている。しかしながら、これらの接着剤は、接着性及びコンタクト性を向上させる為に連鎖移動剤を必須成分としている為に、耐熱クリープ性など耐熱性が充分ではない。特許文献４、特許文献５、特許文献６、特許文献７、特許文献８、特許文献９及び特許文献１０では、カルボニル基とジヒドラジドの架橋構造を導入した樹脂が提案されている。しかしながら、これらの樹脂を用いた接着剤は、接着剤として求められる凝集力が不十分であり、プラスチック材との接着性、水系接着剤で問題となりやすい初期接着力も不十分である。
特許文献１１及び特許文献１２において、初期接着力やコンタクト接着性を解決するために、低分子量脂肪族カルボン酸のビニルエステルを必須成分とする接着剤組成物が提案されている。しかし、酢酸ビニルやプロピオン酸ビニルなどの低分子の脂肪族カルボン酸ビニルエステルは耐水性を著しく低下させる。一方、特許文献１２において開示されている低分子量分岐型脂肪族カルボン酸のビニルエステルや高分子量直鎖脂肪族カルボン酸のビニルエステルは、一般的に（メタ）アクリル酸エステルとの反応性比が小さく、エチレンや酢酸ビニルを第３成分として加えなければ共重合させることが難しい。しかし、酢酸ビニルを第３成分として共重合した場合、前述の通り耐水性が低下し、エチレンは気密性の高い反応釜を必要とするなど、容易に合成できなかった。
Adhesives used in furniture, wash basins and building interior materials, for example, organic solvent adhesives such as chloroprene rubber adhesives mainly used in these applications cause sick house syndrome and environmental problems It contains highly volatile organic solvents and chlorine. On the other hand, in recent years, interest in health and the environment has further increased, and therefore, there is a strong demand for the conversion of an adhesive using water as a medium with a low content of volatile organic compounds. In addition, reactive hot-melt adhesives that are also used for building materials such as decorative plywood and composite panels as well as furniture, washstands, and building interior materials react when heated and melted during painting, and gel substances are generated. Therefore, in order to reduce the progress of the reaction, it is necessary to replace the entire interior of the coating machine with nitrogen gas, which requires a large expense such as maintenance of the coating machine. Therefore, there is a strong demand for switching to a water-based adhesive that is safer and has excellent handling properties.
In accordance with such demands, adhesive compositions using water-based vinyl acetate emulsions or ethylene-vinyl acetate emulsions have been developed. However, these adhesives have problems that initial adhesive strength, contact property, water resistance, drying property and coating property are inferior.
Studies have been conducted to remove an organic solvent and halogen such as chlorine from the adhesive composition, and to obtain an adhesive composition excellent in adhesive strength and the like. For example, Patent Literature 1, Patent Literature 2, and Patent Literature 3 propose an aqueous adhesive in which a crosslinked structure of a carbonyl group and a dihydrazide is introduced in the presence of a chain transfer agent as an aqueous adhesive for dry lamination. However, since these adhesives contain a chain transfer agent as an essential component in order to improve adhesion and contact properties, heat resistance such as heat resistance creep resistance is not sufficient. In Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, and Patent Literature 10, a resin in which a crosslinked structure of a carbonyl group and a dihydrazide is introduced is proposed. However, the adhesives using these resins are insufficient in cohesive force required as an adhesive, and are insufficient in adhesiveness with plastic materials and initial adhesive force that tends to be a problem with aqueous adhesives.
Patent Documents 11 and 12 propose an adhesive composition containing a low molecular weight aliphatic carboxylic acid vinyl ester as an essential component in order to solve the initial adhesive force and contact adhesiveness. However, low molecular weight aliphatic carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate significantly reduce water resistance. On the other hand, vinyl ester of low molecular weight branched aliphatic carboxylic acid and vinyl ester of high molecular weight linear aliphatic carboxylic acid disclosed in Patent Document 12 generally have a reactivity ratio with (meth) acrylic acid ester. It is small and difficult to copolymerize unless ethylene or vinyl acetate is added as a third component. However, when vinyl acetate was copolymerized as the third component, the water resistance was lowered as described above, and ethylene could not be easily synthesized, for example, requiring a highly airtight reaction kettle.
本発明の課題は、環境への負荷の大きい揮発性有機溶剤や可塑剤などを含まず、耐水性、初期接着性、コンタクト接着性、常態接着強度、引張剪断強度及び耐熱クリープ性に優れた、木材から金属、各種プラスチックまで幅広く接着できる、例えば建築用途、工業用途及びコーティング用、特に化粧合板、複合パネルなどの建材用途に有用な水分散型接着剤組成物を提供することにある。 The subject of the present invention does not include volatile organic solvents or plasticizers that have a large environmental load, and is excellent in water resistance, initial adhesiveness, contact adhesiveness, normal adhesive strength, tensile shear strength, and heat-resistant creep resistance, An object of the present invention is to provide a water-dispersed adhesive composition that can be widely bonded from wood to metal and various plastics, and is useful for, for example, building applications, industrial applications and coatings, especially for building materials such as decorative plywood and composite panels.
本発明者らは前記の課題について鋭意研究を重ねた結果、特定の単量体を共重合して得られる重合体及び特定の成分を含む水分散型接着剤組成物により、上記課題が解決できることを見いだし、本発明をするに至った。すなわち、本発明は、
（Ａ）下記一般式（ａ）
で表されるエチレン性不飽和単量体；２〜１５質量％及び、
（Ｂ）ベンゼン環を有するエチレン性不飽和単量体；１０〜４０質量％、
（Ｃ）カルボキシル基を有するエチレン性不飽和単量体；１〜５質量％、
（Ｄ）前記（Ａ）〜（Ｃ）以外の単量体であって、且つエチレン、酢酸ビニル、プロピオン酸ビニル及び酪酸ビニルではない共重合可能なエチレン性不飽和単量体；４０〜８７質量％、
を共重合した重合体と、
ホルムアルデヒド捕捉剤として、硫酸ヒドロキシルアミン、ジシアンジアミド、塩酸ヒドロキシルアミン、アジピン酸ジヒドラジドから選ばれる少なくとも１種と、
を有する水分散型接着剤組成物に関する。
As a result of intensive studies on the above problems, the present inventors can solve the above problems by using a polymer obtained by copolymerizing a specific monomer and a water-dispersed adhesive composition containing a specific component. As a result, the present invention has been completed. That is, the present invention
(A) The following general formula (a)
An ethylenically unsaturated monomer represented by: 2 to 15% by mass and
(B) an ethylenically unsaturated monomer having a benzene ring;
(C) an ethylenically unsaturated monomer having a carboxyl group; 1 to 5% by mass,
(D) Copolymerizable ethylenically unsaturated monomer that is a monomer other than the above (A) to (C) and is not ethylene, vinyl acetate, vinyl propionate or vinyl butyrate; 40 to 87 mass %,
A polymer copolymerized with
As a formaldehyde scavenger, at least one selected from hydroxylamine sulfate, dicyandiamide, hydroxylamine hydrochloride, adipic acid dihydrazide,
The present invention relates to a water-dispersed adhesive composition having
本発明の水分散型接着剤組成物は、成膜助剤や可塑剤として揮発性有機溶剤を含まず、耐水性、初期接着性、コンタクト接着性、常態接着強度、引張剪断強度及び耐熱クリープ性に優れた、木材から金属、各種プラスチックまで幅広く接着でき、例えば、建築用途、工業用途、コーティング用の幅広い用途に使用できる。本発明の水分散型接着剤組成物は、特に、化粧合板、複合パネルなどの建材用途に有用である。 The water-dispersed adhesive composition of the present invention does not contain a volatile organic solvent as a film forming aid or plasticizer, and is water resistant, initial adhesive, contact adhesive, normal adhesive strength, tensile shear strength, and heat-resistant creep resistance. It can be used for a wide range of applications such as architectural, industrial and coating applications. The water-dispersed adhesive composition of the present invention is particularly useful for building materials such as decorative plywood and composite panels.
以下、本発明の実施形態について詳細に説明する。
本発明の水分散型接着剤組成物は、特定の単量体を共重合して得られる重合体及びホルムアルデヒド補足剤を含む。
Hereinafter, embodiments of the present invention will be described in detail.
The water-dispersed adhesive composition of the present invention contains a polymer obtained by copolymerizing a specific monomer and a formaldehyde scavenger.
その１．重合体を得るために使用する単量体
１．エチレン性不飽和単量体（Ａ）
エチレン性不飽和単量体（Ａ）は、下記一般式（ａ）
で示されるエチレン性不飽和単量体である。これらの単量体の１種単独で又は２種以上を組み合わせて使用できる。
前記、エチレン性不飽和単量体（Ａ）としては、具体的には、ネオデカン酸ビニルエステル及びその異性体、ネオノナン酸ビニルエステル及びその異性体等が挙げられる。
エチレン性不飽和単量体（Ａ）を使用することにより、耐水性を低下することなく、初期接着性及びコンタクト接着性（引張剪断強度）を向上させると言う効果が得られる。
エチレン性不飽和単量体（Ａ）は、重合体の２〜１５質量％、好ましくは５〜１５質量％、より好ましくは５〜１０質量％の量で使用することが好ましい。２質量％以上の量で使用することにより、優れた引張剪断強度及び初期接着性を得ることができる。一方１５質量％以下の量で使用することにより、重合反応がスムーズに進むことにより、未反応モノマーの残存量を低減できる。
No.1. Monomers used to obtain a polymer Ethylenically unsaturated monomer (A)
The ethylenically unsaturated monomer (A) has the following general formula (a)
Is an ethylenically unsaturated monomer. These monomers can be used alone or in combination of two or more.
Specific examples of the ethylenically unsaturated monomer (A) include neodecanoic acid vinyl ester and its isomer, neononanoic acid vinyl ester and its isomer, and the like.
By using the ethylenically unsaturated monomer (A), the effect of improving the initial adhesiveness and contact adhesiveness (tensile shear strength) can be obtained without lowering the water resistance.
The ethylenically unsaturated monomer (A) is preferably used in an amount of 2 to 15% by mass, preferably 5 to 15% by mass, more preferably 5 to 10% by mass of the polymer. By using it in an amount of 2% by mass or more, excellent tensile shear strength and initial adhesiveness can be obtained. On the other hand, by using it in an amount of 15% by mass or less, the polymerization reaction proceeds smoothly, whereby the remaining amount of unreacted monomer can be reduced.
２．ベンゼン環を有するエチレン性不飽和単量体（Ｂ）
分子中にベンゼン環を有するエチレン性不飽和単量体（Ｂ）の具体例としては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−アクリロイロキシエチルフタル酸、スチレン、α−メチルスチレン、ビニルトルエン、ジビニルベンゼン等が挙げられる。これらは１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらの中でも、ホモポリマーのガラス転移温度が高く、他の単量体との共重合性が良好であるという点から、スチレン及びベンジルメタクリレートが好ましい。これらベンゼン環を有するエチレン性不飽和単量体を使用することにより、ポリマー中のベンゼン環がスタッキングし、塗膜の凝集力が高まり、優れた引張剪断強度が得られる。更に被着体がプラスチック材の場合、接着強度を高めることができる。ベンゼン環を有するエチレン性不飽和単量体（Ｂ）は、該重合体の１０〜４０質量％、好ましくは２０〜４０質量％、より好ましくは２０〜３６質量％の量で使用することが好ましい。１０質量％以上の量で使用することにより、優れた引張剪断強度が得られ、プラスチック材への接着性も向上する。一方、４０質量％以下の量で使用することにより、適度な凝集力を得ることができ、優れたコンタクト接着性を得ることができる。
2. Ethylenically unsaturated monomer having a benzene ring (B)
Specific examples of the ethylenically unsaturated monomer (B) having a benzene ring in the molecule include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2 -Acryloyloxyethyl phthalic acid, styrene, (alpha) -methylstyrene, vinyl toluene, divinylbenzene, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, styrene and benzyl methacrylate are preferable because the homopolymer has a high glass transition temperature and good copolymerizability with other monomers. By using these ethylenically unsaturated monomers having a benzene ring, the benzene ring in the polymer is stacked, the cohesive strength of the coating film is increased, and an excellent tensile shear strength is obtained. Furthermore, when the adherend is a plastic material, the adhesive strength can be increased. The ethylenically unsaturated monomer (B) having a benzene ring is preferably used in an amount of 10 to 40% by mass, preferably 20 to 40% by mass, more preferably 20 to 36% by mass of the polymer. . By using it in an amount of 10% by mass or more, excellent tensile shear strength can be obtained, and adhesion to a plastic material can be improved. On the other hand, by using it in an amount of 40% by mass or less, an appropriate cohesive force can be obtained, and excellent contact adhesiveness can be obtained.
３．カルボキシル基を有するエチレン性不飽和単量体（Ｃ）
カルボキシル基を有するエチレン性不飽和単量体としては、具体的には、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸等が挙げられる。特に、乳化重合時における反応性の観点からアクリル酸、メタクリル酸が好適に使用することができる。
カルボキシル基を有するエチレン性不飽和単量体（Ｃ）は、該重合体の１〜５質量％、好ましくは１〜４質量％、より好ましくは１．５〜３質量％の量で使用することが好ましい。１質量％以上の量で使用することにより、重合体を製造する際に凝集物が発生することを防ぐことができ、しかも良好な機械的安定性及び塗装作業性が得られ、更に、アルミ材の様な非鉄金属を含め、金属類に対する接着性が向上する。５質量％以下の量で使用することにより、優れた耐水性が得られ、また重合体が高粘度化することを防ぐことにより優れた塗装作業性を得ることができる。
3. Ethylenically unsaturated monomer having a carboxyl group (C)
Specific examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like. In particular, acrylic acid and methacrylic acid can be suitably used from the viewpoint of reactivity during emulsion polymerization.
The ethylenically unsaturated monomer (C) having a carboxyl group is used in an amount of 1 to 5% by mass, preferably 1 to 4% by mass, more preferably 1.5 to 3% by mass of the polymer. Is preferred. By using it in an amount of 1% by mass or more, it is possible to prevent the formation of agglomerates when producing a polymer, and to obtain good mechanical stability and coating workability. Adhesion to metals including non-ferrous metals such as is improved. By using it in an amount of 5% by mass or less, excellent water resistance can be obtained, and excellent coating workability can be obtained by preventing the polymer from becoming highly viscous.
４．その他のエチレン性不飽和単量体（Ｄ）
本発明で使用するその他のエチレン性不飽和単量体（Ｄ）は、前記（Ａ）〜（Ｃ）以外の単量体であって、且つエチレン、酢酸ビニル、プロピオン酸ビニル及び酪酸ビニルではない共重合可能なエチレン性不飽和単量体である。
これらの単量体として、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−ブトキシエチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、アリル（メタ）アクリレート、グリシジル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、（メタ）アクリル酸ソーダ、トリメチロールプロパン（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等のアクリル酸エステルモノマーを挙げることができる。
更に、上記のアクリル酸エステルモノマーの他に、アクロレイン、ダイアセトン（メタ）アクリルアミド、ホルミルスチロール、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン等のカルボニル基を持つα，β−エチレン性不飽和モノマーやアクリルアミド、アクリロニトリル、スチレン等のビニルモノマーを使用できる。
更に、架橋構造を導入する目的で、前記ジビニルベンゼンや、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、アリル（メタ）アクリレート等の分子中に重合性不飽和二重結合を２個以上有する単量体、乳化重合反応時の温度にて相互に反応する官能基を持つ単量体を組合せ、例えば、カルボキシル基とグリシジル基や、水酸基とイソシアネート基等の組合せの官能基を持つエチレン性不飽和単量体、加水分解縮合反応する、（メタ）アクリロキシプロピルトリメトキシシラン、や（メタ）アクリロキシプロピルトリエトキシシラン、（メタ）アクリロキシプロピルメチルジメトキシシラン等のシリル基含有エチレン性不飽和単量体も使用できる。
上記単量体は、いずれも、１種単独で又は２種以上を組み合わせて使用できる。
前記不飽和単量体（Ｄ）は、重合体の４０〜８７質量％、好ましくは５０〜８５質量％の量で使用することが好ましい。４０〜８７質量％の量で使用することにより、重合体のガラス転移温度を−３０℃〜１０℃に調整することができる。なお、前記架橋構造を導入する目的で使用する単量体は、重合体の３質量％以下の量で使用することにより良好な接着力及び粘着力を得ることができる。
4). Other ethylenically unsaturated monomers (D)
The other ethylenically unsaturated monomer (D) used in the present invention is a monomer other than the above (A) to (C), and is not ethylene, vinyl acetate, vinyl propionate or vinyl butyrate. It is a copolymerizable ethylenically unsaturated monomer.
As these monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, -Butoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, sodium (meth) acrylate, trimethylolpropane (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and other acrylic ester monomers Can do.
In addition to the above acrylic ester monomers, α, β-ethylenically unsaturated monomers having a carbonyl group such as acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc. Vinyl monomers such as acrylamide, acrylonitrile, and styrene can be used.
Furthermore, for the purpose of introducing a crosslinked structure, a polymerizable unsaturated double bond is formed in the molecule such as divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate. Combine two or more monomers and monomers with functional groups that react with each other at the temperature during the emulsion polymerization reaction. For example, combine functional groups such as carboxyl and glycidyl groups or hydroxyl and isocyanate groups. Contains silyl groups such as (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, etc. Ethylenically unsaturated monomers can also be used.
Any of the above monomers can be used alone or in combination of two or more.
The unsaturated monomer (D) is preferably used in an amount of 40 to 87% by mass, preferably 50 to 85% by mass of the polymer. By using it in an amount of 40 to 87% by mass, the glass transition temperature of the polymer can be adjusted to -30 ° C to 10 ° C. In addition, the monomer used for the purpose of introducing the cross-linked structure can obtain good adhesive force and adhesive strength by using it in an amount of 3% by mass or less of the polymer.
その２．重合体の製造方法
本発明の接着剤組成物に使用される重合体は、上記エチレン性不飽和単量体（Ａ）〜（Ｄ）を共重合することにより得られる。なお、エチレン性不飽和単量体（Ａ）は、その他の単量体との反応性が低いため、共重合反応がスムーズに進まない場合がある。このような場合には、エチレン性不飽和単量体（Ａ）のみを重合し、エチレン性不飽和単量体のポリマー転化率が８０〜９８質量％になった後に、その他のエチレン性不飽和単量体（Ｂ）〜（Ｄ）を乳化重合することにより、効率良く重合体を得ることができる。
具体的な方法として、例えば以下の方法により重合体を製造することができる。攪拌機、還流冷却塔、温度計及び滴下装置を備えた４つ口フラスコ等の容器に水、アニオン性界面活性剤及び／又はノニオン性界面活性剤を添加し、エチレン性不飽和単量体（Ａ）及び重合開始剤を添加する。反応容器中の液体を攪拌しながら良く混合し、重合開始剤や分子量に適した温度まで加熱し、重合反応を開始する。次いで、エチレン性不飽和単量体（Ａ）のポリマー転化率が８０〜９８質量％になった時点で、ベンゼン環を有するエチレン性不飽和単量体（Ｂ）、カルボキシル基を有するエチレン性不飽和単量体（Ｃ）及び、その他のエチレン性不飽和単量体（Ｄ）の混合物及び必要に応じて追加の重合開始剤を従来から公知の１段階又は、多段階にて逐次投入する半回分乳化重合することによって得ることができる。
尚、上記ポリマー転化率は、
（加熱残分−アニオン性界面活性剤及び又はノニオン性界面活性剤の質量）÷（配合中の投入したエチレン性不飽和単量体（Ａ）の質量）×１００
の式によって算出する。
また、加熱残分は、ＪＩＳ Ｋ５６０１−１−２に従い、１４０℃に設定したオーブンにて３０分間乾燥させた後の重量より算出する。
No.2. Production Method of Polymer The polymer used in the adhesive composition of the present invention is obtained by copolymerizing the above ethylenically unsaturated monomers (A) to (D). In addition, since the ethylenically unsaturated monomer (A) has low reactivity with other monomers, the copolymerization reaction may not proceed smoothly. In such a case, only the ethylenically unsaturated monomer (A) is polymerized, and after the polymer conversion of the ethylenically unsaturated monomer reaches 80 to 98% by mass, other ethylenically unsaturated monomers are used. A polymer can be obtained efficiently by emulsion polymerization of the monomers (B) to (D).
As a specific method, for example, a polymer can be produced by the following method. Water, an anionic surfactant and / or a nonionic surfactant are added to a container such as a four-necked flask equipped with a stirrer, a reflux cooling tower, a thermometer and a dropping device, and an ethylenically unsaturated monomer (A ) And a polymerization initiator. The liquid in the reaction vessel is mixed well with stirring and heated to a temperature suitable for the polymerization initiator and molecular weight to initiate the polymerization reaction. Next, when the polymer conversion of the ethylenically unsaturated monomer (A) reaches 80 to 98% by mass, the ethylenically unsaturated monomer (B) having a benzene ring and the ethylenically unsaturated monomer having a carboxyl group are obtained. A mixture of a saturated monomer (C) and another ethylenically unsaturated monomer (D) and, if necessary, an additional polymerization initiator are conventionally added in a known one-stage or multi-stage sequentially. It can be obtained by batch emulsion polymerization.
The polymer conversion rate is
(Mass of heating residue-anionic surfactant and / or nonionic surfactant) ÷ (mass of charged ethylenically unsaturated monomer (A) during compounding) × 100
It is calculated by the following formula.
The heating residue is calculated from the weight after drying for 30 minutes in an oven set at 140 ° C. in accordance with JIS K5601-1-2.
上記重合開始剤としては、従来から一般的にラジカル重合に使用されているものが使用可能であるが、中でも水溶性のものが好適であり、例えば、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩類；２，２’−アゾビス（２−アミノジプロパン）ハイドロクロライドや、４，４’−アゾビス−シアノバレリックアシッド、２，２’−アゾビス（２−メチルブタンアミドオキシム）ジハイドロクロライドテトラハイドレート等のアゾ系化合物；過酸化水素水、ｔ−ブチルハイドロパーオキサイド等の過酸化物等を挙げることができる。更に、Ｌ−アスコルビン酸、チオ硫酸ナトリウム等の還元剤と、硫酸第一鉄等とを組み合わせたレドックス系も使用できる。前記重合開始剤は、重合開始剤の種類や得られる重合体の分子量に合わせて適宜調整して使用する。
なお、連鎖移動剤については、ポリマーの分子量低下によって耐熱クリープ性、接着強度の低下をまねく為に使用しないことが好ましい。なお、使用しないことが好ましい連鎖移動剤としては、例えば、ｎ−ドデシルメルカプタン等の長鎖のアルキルメルカプタン類や、芳香族メルカプタン類、ハロゲン化炭化水素類等、α−メチルスチレンダイマー、アルコール類を挙げることができる。
As the polymerization initiator, those conventionally used for radical polymerization can be used, but water-soluble ones are preferred, for example, persulfates such as potassium persulfate and ammonium persulfate. 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis-cyanovaleric acid, 2,2′-azobis (2-methylbutanamidooxime) dihydrochloride tetrahydrate Azo compounds such as hydrogen peroxide, peroxides such as t-butyl hydroperoxide, and the like. Furthermore, a redox system in which a reducing agent such as L-ascorbic acid or sodium thiosulfate is combined with ferrous sulfate or the like can also be used. The polymerization initiator is appropriately adjusted according to the kind of the polymerization initiator and the molecular weight of the obtained polymer.
In addition, it is preferable not to use a chain transfer agent in order to reduce heat resistant creep resistance and adhesive strength due to a decrease in the molecular weight of the polymer. Examples of chain transfer agents that are preferably not used include, for example, long-chain alkyl mercaptans such as n-dodecyl mercaptan, aromatic mercaptans, halogenated hydrocarbons, α-methylstyrene dimer, and alcohols. Can be mentioned.
更に該重合体を合成するにあたり、一般的に乳化重合で用いられる界面活性剤については特に制限無く使用することができる。例えば、ラウリル硫酸ナトリウム等の脂肪酸塩や、高級アルコール硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシノニルフェニルエーテルスルホン酸アンモニウム、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩、等のアニオン性界面活性剤が挙げられる。更に、ポリオキシエチレンアルキルエーテルや、ポリオキシエチレンノニルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、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等のノニオン性界面活性剤も適宜組み合わせて使用することができる。その他、乳化安定化剤としてポリビニルアルコールや、ヒドロキシエチルセルロース、ポリビニルピロリドン等が好適に用いる事ができる。但し、上記界面活性剤及び乳化安定剤としては、接着剤塗布時に被着材と接着剤組成物との界面に配向する傾向があり、剥離の原因となる場合がある。その為、より好適には、分子中にエチレン性不飽和基を有する、α−スルホナト−ω−（１−（アリルオキシメチル−アルキルオキシポリオキシエチレンアンモニウム塩（第一工業製薬（株）製；アクアロンＫＨシリーズ）、
２−ポリオキシエチレン−４−ノニル−２−プロペニルフェニルエーテル（第一工業製薬（株）製；アクアロンＲＮシリーズ）、
［（｛α−［２−（アリルオキシ）−１−（｛［アルキル（Ｃ＝１０〜１４）］オキシ｝メチル）エチル］−ω−ヒドロキシポリ（ｎ＝１〜１００）（オキシエチレン）｝を主成分とする、｛アルカノール（Ｃ＝１０〜１４、分岐型）と１−（アリルオキシ）−２，３−エポキシプロパンの反応生成物｝のオキシラン重付加物）の硫酸エステル化物］のアンモニウム塩（ＡＤＥＫＡ（株）製；アデカリアソープＳＲシリーズ）、
α−スルホ−ω−（１−（ノニルフェノキシ）メチル−２−（２−プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル）アンモニウム塩（ＡＤＥＫＡ（株）製；アデカリアソープＳＥシリーズ）、
α−ヒドロ−ω−（１−アルコキシメチル−２−（２−プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル））（ＡＤＥＫＡ（株）製；アデカリアソープＥＲシリーズ）、
ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム（花王（株）製；ラテムルＰＤシリーズ）、
ビス（ポリオキシエチレン多環フェニルエーテル）メタクリレート硫酸エステル塩（日本乳化剤（株）製；アントックスＭＳ６０）、
ポリエチレングリコールモノメタクリレート（日本乳化剤（株）製；ＭＡ５０、日本油脂（株）製；ブレンマーＰＥ−３５０）、
ポリプロピレングリコールモノメタクリレート（日本油脂（株）製；ブレンマーＰＰ−１０００）、
ポリ（エチレングリコール−プロピレングリコール）モノメタクリレート（日本油脂（株）製；ブレンマーＰＥＰシリーズ）、
ポリ（エチレングリコール−プロピレングリコール）モノアクリレート（日本油脂（株）製；ブレンマーＡＥＰシリーズ）、
などを反応性界面活性剤として使用することが好ましい。
これら界面活性剤は、１種単独又は２種以上を組み合わせて使用できる。界面活性剤の量は、エチレン性不飽和単量体（Ａ）〜（Ｄ）の総量に対して、０．８〜３０質量％の量で使用される。
Furthermore, in synthesizing the polymer, surfactants generally used in emulsion polymerization can be used without any particular limitation. For example, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate esters, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxynonyl phenyl ether sulfonate ammonium, polyoxyethylene- Examples include anionic surfactants such as polyoxypropylene glycol ether sulfate. Furthermore, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer may be used in appropriate combination. it can. In addition, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, and the like can be suitably used as the emulsion stabilizer. However, the surfactant and the emulsion stabilizer tend to be oriented at the interface between the adherend and the adhesive composition when the adhesive is applied, and may cause peeling. Therefore, more preferably, α-sulfonato-ω- (1- (allyloxymethyl-alkyloxypolyoxyethyleneammonium salt (Daiichi Kogyo Seiyaku Co., Ltd.); having an ethylenically unsaturated group in the molecule; Aqualon KH series),
2-polyoxyethylene-4-nonyl-2-propenylphenyl ether (Daiichi Kogyo Seiyaku Co., Ltd .; Aqualon RN series),
[({Α- [2- (allyloxy) -1-({[alkyl (C = 10-14)] oxy} methyl) ethyl] -ω-hydroxypoly (n = 1-100) (oxyethylene)}. Ammonium salt of {sulfate esterified product of oxirane polyadduct of alkanol (C = 10-14, branched type) and 1- (allyloxy) -2,3-epoxypropane}) as a main component] ADEKA Co., Ltd .; ADEKA rear soap SR series),
α-sulfo-ω- (1- (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt (manufactured by ADEKA Corp .; ADEKA rear soap SE series ),
α-hydro-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl)) (manufactured by ADEKA Corporation; Adeka Soap ER Series),
Polyoxyalkylene alkenyl ether ammonium sulfate (manufactured by Kao Corporation; Latem PD series),
Bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate (manufactured by Nippon Emulsifier Co., Ltd .; Antox MS60),
Polyethylene glycol monomethacrylate (manufactured by Nippon Emulsifier Co., Ltd .; MA50, manufactured by Nippon Oil & Fats Co., Ltd .; Bremer PE-350),
Polypropylene glycol monomethacrylate (Nippon Yushi Co., Ltd .; Bremer PP-1000),
Poly (ethylene glycol-propylene glycol) monomethacrylate (manufactured by NOF Corporation; Bremer PEP series),
Poly (ethylene glycol-propylene glycol) monoacrylate (manufactured by NOF Corporation; Bremer AEP series),
Etc. are preferably used as reactive surfactants.
These surfactants can be used singly or in combination of two or more. The amount of the surfactant is used in an amount of 0.8 to 30% by mass with respect to the total amount of the ethylenically unsaturated monomers (A) to (D).
その３．重合体
前記方法によって得られる重合体は、−３０〜１０℃、好ましくは−２０〜１０℃、より好ましくは−１５〜５℃の範囲のガラス転移温度（以下、Ｔｇという）を有することが好ましい。−３０℃以上のガラス転移温度を有することにより、良好なコンタクト接着性や粘着性と共に、良好な引張剪断強度及び耐熱クリープ性を得ることができる。一方、１０℃以下のＴｇを有することにより、良好なコンタクト接着性及び造膜性を得ることができ、水分散型接着剤組成物に成膜助剤や可塑剤を添加する必要が無くなる。なお、Ｔｇは、上記エチレン性不飽和単量体（Ａ）〜（Ｄ）を適宜組み合わせることにより調整できる。
尚、本発明において、重合体組成物のＴｇは、次のＦＯＸ式を用いて計算されるものをいう。
１／Ｔｇ＝Ｗ1／Ｔｇ1＋Ｗ2／Ｔｇ2＋……＋Ｗi／Ｔｇi＋……Ｗn／Ｔｇn
［上記ＦＯＸ式は、ｎ種の単量体からなる重合体を構成する各モノマーのホモポリマーのガラス転移温度をＴｇi（Ｋ）とし、各モノマーの質量分率をＷiとしており、（Ｗ1＋Ｗ2＋・・・＋Ｗi＋・・・＋Ｗn＝１）である。］
また、最低成膜温度を下げる目的で、成膜助剤、凝集助剤として、エチレングリコールモノブチルエーテルやジエチレングリコールモノブチルエーテル、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートなど、一般的に使用されるものは特に制限無く使用することが出来るが、これらは揮発性有機溶剤である為、人体を始め環境への負荷が大きい為に、出来る限り使用しないことが好適である。
本発明で使用する重合体の重量平均分子量は、１００，０００〜１，０００，０００、好ましくは１５０，０００〜１，０００，０００、より好ましくは２００，０００〜１，０００，０００であることが好ましい。１００，０００以上の重量平均分子量であることにより、コンタクト接着性（引張剪断強度）及び耐熱クリープ性を向上すると言う効果が得られる。また、１，０００，０００以下の重量平均分子量であることにより、初期接着性の向上と言う効果が得られる。
3 Polymer The polymer obtained by the above method preferably has a glass transition temperature (hereinafter referred to as Tg) in the range of -30 to 10 ° C, preferably -20 to 10 ° C, more preferably -15 to 5 ° C. . By having a glass transition temperature of −30 ° C. or higher, it is possible to obtain good tensile shear strength and heat-resistant creep resistance as well as good contact adhesiveness and tackiness. On the other hand, by having a Tg of 10 ° C. or less, it is possible to obtain good contact adhesiveness and film-forming property, and it becomes unnecessary to add a film forming aid or a plasticizer to the water-dispersed adhesive composition. Tg can be adjusted by appropriately combining the ethylenically unsaturated monomers (A) to (D).
In the present invention, the Tg of the polymer composition is calculated using the following FOX equation.
1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 +... + W i / Tg i +... W n / Tg n
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tg i (K), the mass fraction of each monomer is W i, and (W 1 + W 2 +... + W i +... + W n = 1). ]
Further, for the purpose of lowering the minimum film forming temperature, as a film forming aid and a coagulant aid, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, etc. Generally used ones can be used without any particular limitation. However, since these are volatile organic solvents, it is preferable not to use them as much as possible because they have a heavy load on the human body and the environment.
The weight average molecular weight of the polymer used in the present invention is 100,000 to 1,000,000, preferably 150,000 to 1,000,000, more preferably 200,000 to 1,000,000. Is preferred. By having a weight average molecular weight of 100,000 or more, an effect of improving contact adhesiveness (tensile shear strength) and heat-resistant creep property can be obtained. Further, when the weight average molecular weight is 1,000,000 or less, an effect of improving initial adhesiveness can be obtained.
なお、本発明で使用する前記重合体にアンモニアやトリエチルアミン、ジメチルエタノールアミン等のアミン類、水酸化ナトリウムや水酸化カリウム等の水溶性無機塩類をｐＨ調整剤として添加してｐＨ７〜１０に調整しておくことで、得られた重合体の貯蔵時の安定性を更に改善できる。前記ｐＨ調整剤として、特にアンモニア、水酸化ナトリウムを好適に使用することができる。 The polymer used in the present invention is adjusted to pH 7 to 10 by adding amines such as ammonia, triethylamine and dimethylethanolamine, and water-soluble inorganic salts such as sodium hydroxide and potassium hydroxide as a pH adjuster. In this case, the stability of the obtained polymer during storage can be further improved. In particular, ammonia and sodium hydroxide can be suitably used as the pH adjuster.
その４．ホルムアルデヒド補足剤
ホルムアルデヒド捕捉剤は、例えば、硫酸ヒドロキシルアミン、ジシアンジアミド、塩酸ヒドロキシルアミン、アジピン酸ジヒドラジド等が挙げられる。これらホルムアルデヒド補足剤は、１種を単独で又は２種以上を組み合わせて使用できる。ホルムアルデヒド補足剤を使用することにより、接着剤を使用する対象である合板等が、シックハウス症候群などの主原因とも言われるホルムアルデヒドを含んでいる場合であっても、前記ホルムアルデヒド補足剤がホルムアルデヒドを吸着し、ホルムアルデヒドの大気中への放散を防止できる。
4 Formaldehyde scavenger Examples of the formaldehyde scavenger include hydroxylamine sulfate, dicyandiamide, hydroxylamine hydrochloride, adipic acid dihydrazide and the like. These formaldehyde supplements can be used singly or in combination of two or more. By using a formaldehyde supplement, the formaldehyde supplement adsorbs formaldehyde even when the plywood, etc., to which the adhesive is used, contains formaldehyde, which is said to be the main cause of sick house syndrome. , Can prevent the emission of formaldehyde into the atmosphere.
その５．水分散型接着剤組成物
本発明の水分散型接着剤組成物は、前記重合体及びホルムアルデヒド補足剤を含む。具体的には、本発明の水分散型接着剤組成物は、前記重合体及びホルムアルデヒド補足剤に、必要に応じて任意の成分を添加し、攪拌することにより得ることができる。なお、前記重合体の量は、乾燥質量により、水分散型接着剤組成物の６０〜９９．８質量％、好ましくは８０〜９９．８質量％、より好ましくは９０〜９９．８質量％の量で配合することが好ましい。重合体を６０質量％以上含むことにより、初期接着性やコンタクト接着性が向上すると言う効果が得られる。
ホルムアルデヒド補足剤は、水分散型接着剤組成物の０．２〜２０質量％、好ましくは１〜１５質量％、より好ましくは２〜１０質量％の量で使用することが好ましい。０．２質量％以上の量で使用することにより、接着対象物に含まれるホルムアルデヒドを大気中に放散させることを低減することができると言う効果が得られる。一方、２０質量％を超過する量を添加しても、ホルムアルデヒドの低減効果は一定以上の向上は見られない。
更に、必要に応じて前記重合体とは別の水分散型重合体又は水溶性重合体、消泡剤、防腐剤、増粘剤、レベリング剤、湿潤剤、炭酸カルシウムなどの充填材、更に劣化や老化を防止する目的で、ヒンダードアミン系光安定剤や酸化防止剤などの老化防止剤を任意で添加することができる。
水は、水分散型接着剤組成物の４０〜６０質量％、好ましくは４５〜５０質量％の量で含むことが好ましい。
上記のように得られた本発明の水分散型接着剤組成物は、常圧下で沸点が５０〜２６０℃である揮発性有機化合物（ＶＯＣ）を含まないことがより好ましい。
No.5. Water-dispersed adhesive composition The water-dispersed adhesive composition of the present invention includes the polymer and a formaldehyde supplement. Specifically, the water-dispersed adhesive composition of the present invention can be obtained by adding optional components to the polymer and the formaldehyde scavenger as necessary and stirring. The amount of the polymer is 60 to 99.8% by weight, preferably 80 to 99.8% by weight, more preferably 90 to 99.8% by weight of the water-dispersed adhesive composition, based on the dry weight. It is preferable to mix | blend in quantity. By including 60% by mass or more of the polymer, an effect that the initial adhesiveness and the contact adhesiveness are improved can be obtained.
The formaldehyde scavenger is preferably used in an amount of 0.2 to 20% by mass, preferably 1 to 15% by mass, more preferably 2 to 10% by mass of the water-dispersed adhesive composition. By using it in an amount of 0.2% by mass or more, an effect is obtained that it is possible to reduce the emission of formaldehyde contained in the bonding object into the atmosphere. On the other hand, even when an amount exceeding 20% by mass is added, the reduction effect of formaldehyde is not improved beyond a certain level.
Further, if necessary, a water-dispersed polymer or a water-soluble polymer different from the polymer, an antifoaming agent, a preservative, a thickener, a leveling agent, a wetting agent, a filler such as calcium carbonate, and further deterioration Anti-aging agents such as hindered amine light stabilizers and antioxidants can be optionally added for the purpose of preventing aging.
It is preferable that water is contained in an amount of 40 to 60% by mass, preferably 45 to 50% by mass of the water-dispersed adhesive composition.
It is more preferable that the water-dispersed adhesive composition of the present invention obtained as described above does not contain a volatile organic compound (VOC) having a boiling point of 50 to 260 ° C. under normal pressure.
その６．水分散型接着剤組成物の使用方法
本発明の水分散型接着剤組成物は、接着する対象に塗布し、接着対象を密着させ、必要に応じて加熱することにより、接着対象を接着できる。
本発明の水分散型接着剤組成物を接着する対象に塗布する際には、例えば、刷毛やロール、スプレー等の方法により塗布することができる。塗布量は、例えば、乾燥質量により１０〜５００ｇ／ｍ2の量を塗布することができる。
一方又は両方の接着対象に本発明の水分散型接着剤組成物を塗布し、必要に応じて加熱を行うこともできる。加熱する場合には、例えば、６０〜１５０℃の温度で１〜１０分加熱することができる。
本発明の水分散型接着剤組成物を使用する接着対象に特に制限はなく、例えば、建築用途、工業用途及びコーティング用、特に化粧合板、複合パネルなどの建材用途に好適に使用される。
6. Method of using water-dispersed adhesive composition The water-dispersed adhesive composition of the present invention can be adhered to an object to be adhered by applying to the object to be adhered, bringing the object to be adhered into close contact, and heating as necessary.
When applying the water-dispersed adhesive composition of the present invention to an object to be bonded, it can be applied by a method such as a brush, a roll, or a spray. The coating amount can be applied in an amount of 10 to 500 g / m 2 by dry mass, for example.
The water-dispersed adhesive composition of the present invention can be applied to one or both objects to be bonded, and heated as necessary. In the case of heating, for example, it can be heated at a temperature of 60 to 150 ° C. for 1 to 10 minutes.
There is no restriction | limiting in particular in the adhesion | attachment object which uses the water-dispersed adhesive composition of this invention, For example, it uses suitably for building materials uses, such as a building use, an industrial use, and a coating use, especially a decorative plywood and a composite panel.
以下、本発明について、実施例により更に詳細に説明する。なお、実施例中「部」、「％」は、特に断らない限り質量基準で示す。 Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.
《重合体１の合成》
攪拌機、還流冷却管、温度計、滴下装置を備えた４つ口フラスコに、イオン交換水４０部及び、アンモニウム＝４−ノニル−２−（１−プロペニル）フェノキシポリ（ｎ＝０〜２９）エトキシエチル＝スルファート１５％水溶液（第一工業製薬製；アクアロンＢＣ０５１５）２．７部仕込み、反応器内を撹拌しながら窒素で置換し、８０℃まで昇温した。その後、ｐＨ調整剤として、炭酸水素ナトリウム０．１部、引き続き、開始剤として過硫酸カリウム０．４部をそれぞれ添加し、次いで予め別容器にて撹拌混合しておいた、表１に記載の単量体混合物を４時間かけて連続滴下した。その後、撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却後１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和し、重合体１を得た。
<< Synthesis of Polymer 1 >>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device, 40 parts of ion-exchanged water and ammonium = 4-nonyl-2- (1-propenyl) phenoxypoly (n = 0-29) ethoxy 2.7 parts of an ethyl sulfate 15% aqueous solution (Daiichi Kogyo Seiyaku; Aqualon BC0515) were charged, the inside of the reactor was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C. Thereafter, 0.1 parts of sodium hydrogen carbonate as a pH adjuster, and subsequently 0.4 parts of potassium persulfate as an initiator were added, respectively, and then stirred and mixed in a separate container in advance. The monomer mixture was continuously added dropwise over 4 hours. Thereafter, the mixture was aged at 80 ° C. for 3 hours while continuing to stir, and then cooled to room temperature and neutralized to pH 8 using a 10 mass% aqueous sodium hydroxide solution to obtain a polymer 1.
《重合体２の合成》
重合体１の合成と同様に４つ口フラスコに、イオン交換水４０部、ポリオキシエチレンスチリルフェニルエーテル硫酸エステルアンモニウム塩２５％水溶液（第一工業製薬製；ハイテノールＮＦ０８２５）１．６部及び、ネオノナン酸ビニルエステル１０部を仕込み、反応器内を撹拌しながら窒素で置換し、８０℃まで昇温した。炭酸水素ナトリウム０．１部、過硫酸カリウム０．４部を順次添加し、撹拌を続けながら８０℃で５０分間維持した。（この時点で反応器内の樹脂分散体をサンプリングし、ポリマー転化率を計算したところ９９％であった。）引き続き、予め別容器にて撹拌混合しておいた、表１に記載の単量体混合物を４時間かけて連続滴下した。更に撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却し、１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和し、重合体２を得た。
<< Synthesis of Polymer 2 >>
Similarly to the synthesis of polymer 1, in a four-necked flask, 40 parts of ion-exchanged water, 1.6 parts of 25% aqueous solution of polyoxyethylene styrylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku; Hytenol NF0825), and 10 parts of neononanoic acid vinyl ester was charged, the inside of the reactor was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C. Sodium hydrogen carbonate (0.1 part) and potassium persulfate (0.4 part) were sequentially added, and the mixture was maintained at 80 ° C. for 50 minutes while stirring was continued. (At this point, the resin dispersion in the reactor was sampled and the polymer conversion rate was calculated to be 99%.) Subsequently, the single amount shown in Table 1 previously stirred and mixed in a separate container. The body mixture was continuously added dropwise over 4 hours. Further, the mixture was aged at 80 ° C. for 3 hours while continuing to stir, then cooled to room temperature, and neutralized to pH 8 using a 10 mass% sodium hydroxide aqueous solution to obtain a polymer 2.
《重合体３の合成》
重合体２の合成と同様に過硫酸カリウム０．４部を添加後、撹拌を続けながら８０℃で１５分間維持した。（この時点で反応器内の樹脂分散体をサンプリングし、ポリマー転化率を計算したところ７５％であった。）引き続き、予め別容器にて撹拌混合しておいた表１に記載の単量体混合物を４時間かけて連続滴下した。更に撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却し、１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和し、重合体３を得た。
<< Synthesis of Polymer 3 >>
Similarly to the synthesis of Polymer 2, 0.4 part of potassium persulfate was added, and the mixture was maintained at 80 ° C. for 15 minutes while stirring was continued. (At this point, the resin dispersion in the reactor was sampled and the polymer conversion was calculated to be 75%.) Subsequently, the monomers listed in Table 1 that had been stirred and mixed in a separate container in advance. The mixture was continuously added dropwise over 4 hours. Further, the mixture was aged at 80 ° C. for 3 hours while continuing to stir, then cooled to room temperature, and neutralized to pH 8 using a 10 mass% aqueous sodium hydroxide solution to obtain a polymer 3.
《重合体４の合成》
重合体２の合成と同様に４つ口フラスコに、イオン交換水４０部、アンモニウム＝４−ノニル−２−（１−プロペニル）フェノキシポリ（ｎ＝０〜２９）エトキシエチル＝スルファート１５％水溶液（第一工業製薬製；アクアロンＢＣ０５１５）２．７部及び、ネオノナン酸ビニルエステル５部、ネオデカン酸ビニルエステル５部を仕込み、反応器内を撹拌しながら窒素で置換し、８０℃まで昇温した。炭酸水素ナトリウム０．１部、過硫酸カリウム０．４部を順次添加し、撹拌を続けながら８０℃で３０分間維持した。（この時点で反応器内の樹脂分散体をサンプリングし、ポリマー転化率を計算したところ９２％であった。）引き続き、予め別容器にて撹拌混合しておいた、表１に記載の単量体混合物を４時間かけて連続滴下した。更に撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却し、１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和し、重合体４を得た。
<< Synthesis of Polymer 4 >>
Similarly to the synthesis of polymer 2, in a four-necked flask, 40 parts of ion-exchanged water, ammonium = 4-nonyl-2- (1-propenyl) phenoxypoly (n = 0-29) ethoxyethyl sulfate 15% aqueous solution ( Daiichi Kogyo Seiyaku Co., Ltd .; Aqualon BC0515) 2.7 parts, neononanoic acid vinyl ester 5 parts and neodecanoic acid vinyl ester 5 parts were charged, the inside of the reactor was replaced with nitrogen, and the temperature was raised to 80 ° C. Sodium hydrogen carbonate (0.1 part) and potassium persulfate (0.4 part) were sequentially added, and the mixture was maintained at 80 ° C. for 30 minutes while continuing stirring. (At this point, the resin dispersion in the reactor was sampled and the polymer conversion rate was calculated to be 92%.) Subsequently, the single amount shown in Table 1 previously stirred and mixed in a separate container. The body mixture was continuously added dropwise over 4 hours. The mixture was further aged at 80 ° C. for 3 hours while continuing to stir, and then cooled to room temperature and neutralized to pH 8 using a 10 mass% aqueous sodium hydroxide solution to obtain a polymer 4.
《重合体５の合成》
重合体２の合成と同様に４つ口フラスコに、イオン交換水４０部、ポリオキシエチレンスチリルフェニルエーテル硫酸エステルアンモニウム塩２５％水溶液（第一工業製薬製；ハイテノールＮＦ０８２５）１．６部及び、ネオデカン酸ビニルエステル５部を仕込み、反応器内を撹拌しながら窒素で置換し、８０℃まで昇温した。炭酸水素ナトリウム０．１部、過硫酸カリウム０．４部を順次添加し、撹拌を続けながら８０℃で３０分間維持した。（この時点で反応器内の樹脂分散体をサンプリングし、ポリマー転化率を計算したところ９５％であった。）引き続き、予め別容器にて撹拌混合しておいた、表１に記載の単量体混合物を４時間かけて連続滴下した。更に撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却し、１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和し、重合体５を得た。
<< Synthesis of Polymer 5 >>
Similarly to the synthesis of polymer 2, in a four-necked flask, 40 parts of ion-exchanged water, 1.6 parts of 25% aqueous solution of polyoxyethylene styrylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku; Hytenol NF0825), and 5 parts of neodecanoic acid vinyl ester was charged, the inside of the reactor was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C. Sodium hydrogen carbonate (0.1 part) and potassium persulfate (0.4 part) were sequentially added, and the mixture was maintained at 80 ° C. for 30 minutes while continuing stirring. (At this point, the resin dispersion in the reactor was sampled and the polymer conversion rate was calculated to be 95%.) Subsequently, the single amount shown in Table 1 previously stirred and mixed in a separate container. The body mixture was continuously added dropwise over 4 hours. Further, the mixture was aged at 80 ° C. for 3 hours while continuing to stir, then cooled to room temperature, and neutralized to pH 8 using a 10 mass% aqueous sodium hydroxide solution to obtain a polymer 5.
《重合体６の合成》
単量体の組成を表１のものに変更した以外は、重合体５の合成と同様に合成し、重合体６を得た。
<< Synthesis of Polymer 6 >>
A polymer 6 was obtained in the same manner as in the synthesis of the polymer 5 except that the monomer composition was changed to that shown in Table 1.
《重合体７の合成》
アニオン性界面活性剤を、ポリオキシエチレンスチリルフェニルエーテル硫酸エステルアンモニウム塩２５％水溶液から、アンモニウム＝４−ノニル−２−（１−プロペニル）フェノキシポリ（ｎ＝０〜２９）エトキシエチル＝スルファート１５％水溶液２．７部に変更した以外、重合体５と同様に合成することで重合体７を得た。尚、重合体７を東ソー製 ＨＬＣ−８２２０ＧＰＣにて重量平均分子量を測定したところ、約７０，０００ｇ／ｍｏｌ（ポリスチレン換算）であった。
<< Synthesis of Polymer 7 >>
Anionic surfactants were prepared from 25% aqueous solution of polyoxyethylene styryl phenyl ether sulfate ammonium salt, ammonium = 4-nonyl-2- (1-propenyl) phenoxypoly (n = 0-29) ethoxyethyl sulfate 15% The polymer 7 was obtained by synthesizing in the same manner as the polymer 5 except that the aqueous solution was changed to 2.7 parts. In addition, when the weight average molecular weight of the polymer 7 was measured by Tosoh HLC-8220GPC, it was about 70,000 g / mol (polystyrene conversion).
《重合体８の合成》
単量体の組成を表１のものに変更した以外は、重合体１と同様に合成することで重合体８を得た。
<< Synthesis of Polymer 8 >>
A polymer 8 was obtained by synthesizing in the same manner as the polymer 1 except that the monomer composition was changed to that of Table 1.
《重合体９の合成》
単量体の組成を表１のものに変更した以外は、重合体７と同様に合成することで重合体９を得た。
<< Synthesis of Polymer 9 >>
A polymer 9 was obtained by synthesizing in the same manner as the polymer 7 except that the monomer composition was changed to that of Table 1.
《重合体１０の合成》
攪拌機、還流冷却管、温度計、滴下装置を備えた４つ口フラスコに、イオン交換水４０部及び、ポリオキシエチレンスチリルフェニルエーテル硫酸エステルアンモニウム塩２５％水溶液（第一工業製薬製；ハイテノールＮＦ０８２５）１．６部仕込み、反応器内を撹拌しながら窒素で置換し、８０℃まで昇温した。その後、ｐＨ調整剤として、炭酸水素ナトリウム０．１部、引き続き、開始剤として過硫酸カリウム０．４部をそれぞれ添加し、次いで予め別容器にて撹拌混合しておいた、表１に記載の単量体混合物を４時間かけて連続滴下した。その後、撹拌を続けながら８０℃で３時間熟成した後、室温まで冷却後１０質量％水酸化ナトリウム水溶液を用いてｐＨ８まで中和した。但し、重合時の安定性は非常に悪く、凝集体が大量に発生した為、１５０メッシュのステンレスメッシュを用いて濾過し、濾液を重合体１０として得た。
<< Synthesis of Polymer 10 >>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping device, 40 parts of ion exchange water and 25% aqueous solution of polyoxyethylene styrylphenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku; Hytenol NF0825) ) 1.6 parts were charged, the inside of the reactor was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C. Thereafter, 0.1 parts of sodium hydrogen carbonate as a pH adjuster, and subsequently 0.4 parts of potassium persulfate as an initiator were added, respectively, and then stirred and mixed in a separate container in advance. The monomer mixture was continuously added dropwise over 4 hours. Thereafter, the mixture was aged at 80 ° C. for 3 hours while continuing to stir, then cooled to room temperature and neutralized to pH 8 using a 10 mass% aqueous sodium hydroxide solution. However, the stability at the time of polymerization was very poor and a large amount of aggregates were generated. Therefore, filtration was performed using a 150-mesh stainless steel mesh, and a filtrate was obtained as a polymer 10.
《重合体１１の合成》
単量体（Ａ）組成を、ネオノナン酸ビニルエステル１０部に変更した以外、重合体４と同様に合成し、重合体１１を得た。尚、表１記載の単量体混合物を滴下する直前の反応器内の重合率は、９１％であった。
<< Synthesis of Polymer 11 >>
A polymer 11 was obtained by synthesizing in the same manner as the polymer 4 except that the monomer (A) composition was changed to 10 parts of neononanoic acid vinyl ester. The polymerization rate in the reactor immediately before dropping the monomer mixture shown in Table 1 was 91%.
《重合体１２の合成》
単量体の組成を表１のものに変更した以外は、重合体１の合成と同様にして、重合体１２を得た。
<< Synthesis of Polymer 12 >>
A polymer 12 was obtained in the same manner as in the synthesis of the polymer 1 except that the monomer composition was changed to that shown in Table 1.
《重合体１３の合成》
単量体の組成を表１のものに変更した以外は、重合体５の合成と同様にして、重合体１３を得た。尚、表１記載の単量体混合物を滴下する直前の反応器内の重合率は、９６％であった。
<< Synthesis of Polymer 13 >>
A polymer 13 was obtained in the same manner as the synthesis of the polymer 5 except that the monomer composition was changed to that shown in Table 1. The polymerization rate in the reactor immediately before dropping the monomer mixture shown in Table 1 was 96%.
《重合体１４の合成》
単量体（Ａ）組成を、ネオデカン酸ビニルエステル１０部に変更した以外、重合体２と同様に合成し、重合体１４を得た。尚、表１記載の単量体混合物を滴下する直前の反応器内の重合率は９４％であった。
<< Synthesis of Polymer 14 >>
A polymer 14 was obtained by synthesizing in the same manner as the polymer 2 except that the monomer (A) composition was changed to 10 parts of neodecanoic acid vinyl ester. The polymerization rate in the reactor immediately before dropping the monomer mixture shown in Table 1 was 94%.
〔実施例１〜８及び比較例１〜８〕
上記の様にして得られた重合体１〜１４にホルムアルデヒド補足剤を添加し、更に、消泡剤としてアデカネートＢ−９４３（ＡＤＥＫＡ製）及び防腐剤としてデニサイドＥＦ（ナガセケムテックス製）を添加した。また、増粘剤としてアデカノールＵＨ４２０（ＡＤＥＫＡ製）を適宜添加し、接着剤組成物の粘度を２，０００ｍＰａ・ｓに調整した。但し、比較例８については、重合体１４の粘度が２，０００ｍＰａ・ｓ以上であった為、増粘剤は添加せず、そのまま用いた。また、実施例１については造膜助剤としてエチレングリコールモノブチルエーテルを添加した。
[Examples 1-8 and Comparative Examples 1-8]
A formaldehyde scavenger was added to the polymers 1 to 14 obtained as described above, and Adecanate B-943 (manufactured by ADEKA) was added as an antifoaming agent, and Denicide EF (manufactured by Nagase ChemteX) was added as a preservative. . Moreover, Adecanol UH420 (made by ADEKA) was added suitably as a thickener, and the viscosity of the adhesive composition was adjusted to 2,000 mPa * s. However, in Comparative Example 8, since the viscosity of the polymer 14 was 2,000 mPa · s or more, a thickener was not added and used as it was. In Example 1, ethylene glycol monobutyl ether was added as a film forming aid.
〔評価方法〕
［重合体の状態］
重合体１〜１４を合成後に１５０メッシュで濾過し、濾過残渣を乾燥後秤量する。その後以下の計算式にて、凝集物発生量を算出し、更に以下の規準にて重合体の状態を評価した。
凝集物発生量＝（乾燥後の濾過残渣の重量）／（単量体の総重量）
○；凝集物発生量が０．１％以下
×；凝集物発生量が０．１％を超過
〔Evaluation method〕
[Polymer state]
Polymers 1-14 are filtered through 150 mesh after synthesis, and the filter residue is dried and weighed. Thereafter, the aggregate generation amount was calculated by the following calculation formula, and the state of the polymer was evaluated by the following criteria.
Aggregate generation amount = (weight of filtration residue after drying) / (total weight of monomer)
○: Aggregate generation amount is 0.1% or less ×; Aggregate generation amount exceeds 0.1%
［臭気］
官能試験によって行い、以下の規準にて評価した。
○；弱いアクリル臭のみが感じられる。
△；やや未反応のモノマー臭又は、添加された造膜助剤臭が感じられる。
×；強いモノマー臭がする。
[Odor]
The sensory test was conducted and the following criteria were evaluated.
○: Only a weak acrylic odor is felt.
Δ: Slightly unreacted monomer odor or added film-forming aid odor is felt.
X: Strong monomer odor.
［コンタクト接着性］
ＪＩＳ Ｋ６８５０に準拠して行う。１５０ｍｍ×２５ｍｍ×５ｍｍの木板（栂材）、ポリスチレン板、塩化ビニル板、ＡＢＳ板、アルミ（アルマイト封孔処理）板それぞれに、乾燥後塗布重量５０ｇ／ｍ2となるように塗布し、６０℃オーブンにて３分間乾燥した後、同種材同士を２５ｍｍ×２５ｍｍとなる様に相互に塗布面を貼り合わせる。その後２３℃、５０％ＲＨにて７日間養生し、試験板を得た。
その後、島津製作所製オートグラフＡＧ−Ｉにて引張剪断強度試験を行い、以下の規準にて評価した。尚、引張の速度は５０ｍｍ／ｍｉｎで行った。
○；１．０Ｎ／ｍｍ2以上
△；０．５Ｎ／ｍｍ2以上、１．０Ｎ／ｍｍ2未満
×；０．５Ｎ／ｍｍ2未満
[Contact adhesiveness]
Performed in accordance with JIS K6850. 150 mm × 25 mm × 5 mm wood plate (wooden material), polystyrene plate, vinyl chloride plate, ABS plate, aluminum (anodized sealing treatment) plate each coated to a coating weight of 50 g / m 2 after drying, 60 ° C. After drying in an oven for 3 minutes, the coated surfaces are bonded to each other so that the same kind of materials become 25 mm × 25 mm. Thereafter, it was cured at 23 ° C. and 50% RH for 7 days to obtain a test plate.
Thereafter, a tensile shear strength test was performed using an autograph AG-I manufactured by Shimadzu Corporation, and the following criteria were evaluated. The tensile speed was 50 mm / min.
○: 1.0 N / mm 2 or more Δ: 0.5 N / mm 2 or more, less than 1.0 N / mm 2 ×: Less than 0.5 N / mm 2
［常態接着強度（１８０°剥離接着強度試験）］
ＪＩＳ Ｋ６８５４−２に準拠して行う。オレフィンシート（２００ｍｍ×２５ｍｍ×０．２５ｍｍ）に５０〜７５ｇ／ｍ2となるように塗布し、６０℃オーブンにて３分間乾燥した後、２３℃室温下にて１５０ｍｍ×２５ｍｍ×５ｍｍのポリスチレン板を貼り合わせ、ゴムローラーにて圧着した。その後２３℃、５０ＲＨにて７日間養生し、試験片を得た。
その後、２３℃下にて島津製作所製オートグラフＡＧ−Ｉにて１８０°剥離接着強度試験を行い、以下の規準にて評価した。尚、剥離速度は３００ｍｍ／ｍｉｎで行った。
○；２０Ｎ／２５ｍｍ以上
△；５Ｎ／２５ｍｍ以上、２０Ｎ／２５ｍｍ未満
×；５Ｎ／２５ｍｍ未満
[Normal adhesive strength (180 ° peel strength test)]
Performed in accordance with JIS K6854-2. It is applied to an olefin sheet (200 mm x 25 mm x 0.25 mm) so as to be 50 to 75 g / m 2 , dried in an oven at 60 ° C for 3 minutes, and then a polystyrene plate of 150 mm × 25 mm × 5 mm at 23 ° C at room temperature. And bonded with a rubber roller. Thereafter, it was cured at 23 ° C. and 50 RH for 7 days to obtain a test piece.
Thereafter, a 180 ° peel adhesion strength test was performed at 23 ° C. with an autograph AG-I manufactured by Shimadzu Corporation, and the following criteria were evaluated. The peeling rate was 300 mm / min.
○: 20 N / 25 mm or more Δ; 5 N / 25 mm or more, less than 20 N / 25 mm ×: less than 5 N / 25 mm
［初期接着性試験（クリープ試験）］
常態接着強度と同様に接着剤を塗布・乾燥させたポリオレフィンシートにポリスチレン板を貼り合わせ、２３℃室温下にてゴムローラーにて圧着させ、９０°剥離試験片を得た。その後速やかに９０°剥離試験片の一方のポリオレフィンシートの端部に５００ｇの錘を載せ、９０°剥離式のクリープ試験を行い、９０秒後の剥離距離に応じて以下の規準にて評価した。
○；剥離距離が０〜１０ｍｍ未満
△；剥離距離が１０ｍｍ以上、２０ｍｍ未満
×；２０ｍｍ以上剥離
[Initial adhesion test (creep test)]
A polystyrene plate was bonded to a polyolefin sheet coated and dried with an adhesive in the same manner as in the normal adhesive strength, and pressure-bonded with a rubber roller at 23 ° C. room temperature to obtain a 90 ° peel test piece. Immediately thereafter, a 500 g weight was placed on the end of one polyolefin sheet of a 90 ° peel test piece, a 90 ° peel-type creep test was performed, and the following criteria were evaluated according to the peel distance after 90 seconds.
○: Peeling distance of 0 to less than 10 mm Δ: Peeling distance of 10 mm or more and less than 20 mm ×: Peeling of 20 mm or more
［耐熱クリープ試験］
初期接着性試験と同様にして作製した９０°剥離試験片を２３℃、５０％ＲＨにて７日間養生した。その後、６０℃無風オーブンに試験片を入れ、９０°剥離試験片の一方のポリオレフィンシートの端部に２００ｇの錘を載せ、６０℃下にて９０°剥離式の耐熱クリープ試験を行った。１時間後の剥離距離に応じて以下の規準にて評価した。
○；剥離距離が０〜１０ｍｍ未満
△；剥離距離が１０ｍｍ以上、２０ｍｍ未満
×；２０ｍｍ以上剥離
[Heat-resistant creep test]
A 90 ° peel test piece prepared in the same manner as the initial adhesion test was cured at 23 ° C. and 50% RH for 7 days. Thereafter, the test piece was placed in a 60 ° C. airless oven, a 200 g weight was placed on the end of one polyolefin sheet of the 90 ° peel test piece, and a 90 ° peel-type heat resistant creep test was performed at 60 ° C. Evaluation was made according to the following criteria according to the peel distance after 1 hour.
○: Peeling distance of 0 to less than 10 mm Δ: Peeling distance of 10 mm or more and less than 20 mm ×: Peeling of 20 mm or more
［温水浸漬後の接着強度］
常態接着強度試験と同様にして作製した試験片を６０℃温水に２４時間浸漬し、更に２３℃にて冷却した後、１８０°剥離接着強度試験を行った。尚、剥離速度は３００ｍｍ／ｍｉｎで測定し、以下の規準にて評価した。
○；２０Ｎ／２５ｍｍ以上
△；５Ｎ／２５ｍｍ以上、２０Ｎ／２５ｍｍ未満
×；５Ｎ／２５ｍｍ未満
[Adhesive strength after immersion in hot water]
A test piece prepared in the same manner as in the normal state adhesive strength test was immersed in warm water at 60 ° C. for 24 hours, further cooled at 23 ° C., and then subjected to a 180 ° peel strength test. The peeling rate was measured at 300 mm / min and evaluated according to the following criteria.
○: 20 N / 25 mm or more Δ; 5 N / 25 mm or more, less than 20 N / 25 mm ×: less than 5 N / 25 mm
［ホルムアルデヒド放散低減効果］
テドラーバックの片面に切れ込みを入れ、メラミン樹脂にて作製された合板（１００ｍｍ×１００ｍｍ×１５ｍｍ）を挿入し、開口部をヒートシール装置で密閉した。その後２３℃に調整された部屋に７日間静置した後、テドラーバック内のアセトアルデヒド濃度を検知管を用いてガス濃度測定を２回行い、その平均値を初期値とした。
同種のメラミン樹脂合板（１００ｍｍ×１００ｍｍ×１５ｍｍ）の全面に上記で作製した各接着剤を塗布し、９号綿帆布にて全面を覆った。各辺の綿帆布同士の重複部は２ｍｍ以内とした。養生１日後、初期値測定と同様に、切り込みを入れたテドラーバックに綿帆布で覆われた試験片を挿入し、開口部を密閉した後、２３℃下にて７日間静置した。その後、テドラーバッグ内のアセトアルデヒド濃度を２回測定し、初期値からの減少率を算出し、以下の規準にて評価した。
○；初期値からの減少率が６０％以上
×；初期値からの減少率が６０％未満
[Formaldehyde emission reduction effect]
A cut was made on one side of the Tedlar bag, a plywood (100 mm × 100 mm × 15 mm) made of melamine resin was inserted, and the opening was sealed with a heat seal device. Then, after standing in a room adjusted to 23 ° C. for 7 days, the concentration of acetaldehyde in the Tedlar bag was measured twice using a detector tube, and the average value was taken as the initial value.
Each adhesive produced above was applied to the entire surface of the same type of melamine resin plywood (100 mm × 100 mm × 15 mm), and the entire surface was covered with No. 9 cotton canvas. The overlapping part between the cotton canvases on each side was within 2 mm. One day after curing, as in the initial value measurement, a test piece covered with a cotton canvas was inserted into a tedlar bag with cuts, the opening was sealed, and then allowed to stand at 23 ° C. for 7 days. Thereafter, the acetaldehyde concentration in the Tedlar bag was measured twice, the reduction rate from the initial value was calculated, and evaluated according to the following criteria.
○: Reduction rate from initial value is 60% or more ×: Reduction rate from initial value is less than 60%
これらの評価結果を、表２に示す。 These evaluation results are shown in Table 2.
本発明の水分散型接着剤組成物は、環境への負荷の大きい揮発性有機溶剤や可塑剤などを含まず、耐水性、初期接着性、コンタクト接着性、常態接着強度、引張剪断強度及び耐熱クリープ性に優れた、木材から金属、各種プラスチックまで幅広く接着できる、例えば建築用途、工業用途及びコーティング用、特に化粧合板、複合パネルなどの建材用途に有用である。 The water-dispersed adhesive composition of the present invention does not contain volatile organic solvents or plasticizers that have a large environmental load, and is water resistant, initial adhesive, contact adhesive, normal adhesive strength, tensile shear strength, and heat resistance. It has excellent creep properties and can be widely bonded from wood to metal and various plastics. For example, it is useful for building applications, industrial applications and coatings, especially for building materials such as decorative plywood and composite panels.
Claims (7)
で表されるエチレン性不飽和単量体；２〜１５質量％及び、
（Ｂ）ベンゼン環を有するエチレン性不飽和単量体；１０〜４０質量％、
（Ｃ）カルボキシル基を有するエチレン性不飽和単量体；１〜５質量％、
（Ｄ）前記（Ａ）〜（Ｃ）以外の単量体であって、且つエチレン、酢酸ビニル、プロピオン酸ビニル及び酪酸ビニルではない共重合可能なエチレン性不飽和単量体；４０〜８７質量％、
を共重合した重合体を含むことを特徴とする水分散型コンタクト接着剤組成物。 (A) The following general formula (a)
An ethylenically unsaturated monomer represented by: 2 to 15% by mass and
(B) an ethylenically unsaturated monomer having a benzene ring;
(C) an ethylenically unsaturated monomer having a carboxyl group; 1 to 5% by mass,
(D) Copolymerizable ethylenically unsaturated monomer that is a monomer other than the above (A) to (C) and is not ethylene, vinyl acetate, vinyl propionate or vinyl butyrate; 40 to 87 mass %,
A water-dispersed contact adhesive composition comprising a polymer obtained by copolymerizing
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