NO173703B - POLYURETHANE BASIC ADHESIVE AND PROCEDURES FOR PREPARING THEREOF - Google Patents
POLYURETHANE BASIC ADHESIVE AND PROCEDURES FOR PREPARING THEREOF Download PDFInfo
- Publication number
- NO173703B NO173703B NO91910460A NO910460A NO173703B NO 173703 B NO173703 B NO 173703B NO 91910460 A NO91910460 A NO 91910460A NO 910460 A NO910460 A NO 910460A NO 173703 B NO173703 B NO 173703B
- Authority
- NO
- Norway
- Prior art keywords
- polyol
- polyurethane
- groups
- basis
- adhesive according
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 17
- 239000004814 polyurethane Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920005903 polyol mixture Polymers 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229930182556 Polyacetal Natural products 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 229920005906 polyester polyol Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- -1 photos Substances 0.000 description 15
- 239000004970 Chain extender Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940043276 diisopropanolamine Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229920006295 polythiol Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002091 cationic group Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- 229950006389 thiodiglycol Drugs 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- XIUYWALZDCQJCF-UHFFFAOYSA-N 1,2-diisocyanatododecane Chemical compound CCCCCCCCCCC(N=C=O)CN=C=O XIUYWALZDCQJCF-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KHUREWBUPLDQOU-UHFFFAOYSA-N 1-(6-chlorohexyl)-3-(2-hydroxyethyl)urea Chemical compound OCCNC(=O)NCCCCCCCl KHUREWBUPLDQOU-UHFFFAOYSA-N 0.000 description 1
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 description 1
- WJVAPEMLIPHCJB-UHFFFAOYSA-N 1-n-methylpropane-1,2-diamine Chemical compound CNCC(C)N WJVAPEMLIPHCJB-UHFFFAOYSA-N 0.000 description 1
- NKNIZOPLGAJLRV-UHFFFAOYSA-N 2,2-diphenylpropane-1,1-diamine Chemical compound C=1C=CC=CC=1C(C(N)N)(C)C1=CC=CC=C1 NKNIZOPLGAJLRV-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical class NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- FRSFUBGQKHJCKM-UHFFFAOYSA-N 2,3-diaminonaphthalene-1-carboxylic acid Chemical class C1=CC=C2C(C(O)=O)=C(N)C(N)=CC2=C1 FRSFUBGQKHJCKM-UHFFFAOYSA-N 0.000 description 1
- DFQNMODTAFTGHS-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(O)CO)C=C1 DFQNMODTAFTGHS-UHFFFAOYSA-N 0.000 description 1
- KHKXPBTUCRNATA-UHFFFAOYSA-N 2,3-dihydroxypropyl methanesulfonate Chemical compound CS(=O)(=O)OCC(O)CO KHKXPBTUCRNATA-UHFFFAOYSA-N 0.000 description 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical group NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 1
- MVVQNBYRSDXHRF-UHFFFAOYSA-N 2-[2-hydroxyethyl(2-methylpropyl)amino]ethanol Chemical compound CC(C)CN(CCO)CCO MVVQNBYRSDXHRF-UHFFFAOYSA-N 0.000 description 1
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 1
- ZAYJKJNSENNBGW-UHFFFAOYSA-N 2-[2-hydroxyethyl(prop-2-enyl)amino]ethanol Chemical compound OCCN(CCO)CC=C ZAYJKJNSENNBGW-UHFFFAOYSA-N 0.000 description 1
- HHRGNKUNRVABBN-UHFFFAOYSA-N 2-[2-hydroxyethyl(propan-2-yl)amino]ethanol Chemical compound OCCN(C(C)C)CCO HHRGNKUNRVABBN-UHFFFAOYSA-N 0.000 description 1
- OZICRFXCUVKDRG-UHFFFAOYSA-N 2-[2-hydroxyethyl(propyl)amino]ethanol Chemical compound CCCN(CCO)CCO OZICRFXCUVKDRG-UHFFFAOYSA-N 0.000 description 1
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 description 1
- UOQYWMZLTNEIFI-UHFFFAOYSA-N 2-[3-aminopropyl(methyl)amino]ethanol Chemical compound OCCN(C)CCCN UOQYWMZLTNEIFI-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- XRXRUQDIOMYAQQ-UHFFFAOYSA-N 2-[ethyl-[4-[ethyl(2-hydroxyethyl)amino]cyclohexyl]amino]ethanol Chemical compound OCCN(CC)C1CCC(N(CC)CCO)CC1 XRXRUQDIOMYAQQ-UHFFFAOYSA-N 0.000 description 1
- WWVTXMSUNCZZBM-UHFFFAOYSA-N 2-methyl-n,n-dioctylaniline Chemical compound CCCCCCCCN(CCCCCCCC)C1=CC=CC=C1C WWVTXMSUNCZZBM-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- OPGTXRAKKZSBOS-UHFFFAOYSA-N 6-phenyl-1h-triazine-2,4-diamine Chemical compound NC1=NN(N)NC(C=2C=CC=CC=2)=C1 OPGTXRAKKZSBOS-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- QQBPWEUZTBTTFD-UHFFFAOYSA-N [2-(benzenesulfonyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OCC(CO)(CO)COS(=O)(=O)C1=CC=CC=C1 QQBPWEUZTBTTFD-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IVHKZGYFKJRXBD-UHFFFAOYSA-N amino carbamate Chemical class NOC(N)=O IVHKZGYFKJRXBD-UHFFFAOYSA-N 0.000 description 1
- BTXCHYCUHBGRMK-UHFFFAOYSA-N amino sulfamate Chemical compound NOS(N)(=O)=O BTXCHYCUHBGRMK-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RVZMMIYOJPKHQH-UHFFFAOYSA-N ethyl n-(2-chloroethyl)carbamate;propane-1,2,3-triol Chemical compound OCC(O)CO.CCOC(=O)NCCCl RVZMMIYOJPKHQH-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- COJUXMTZOSXAOW-UHFFFAOYSA-N n'-[2-[3-aminopropyl(methyl)amino]ethyl]-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCN(C)CCCN COJUXMTZOSXAOW-UHFFFAOYSA-N 0.000 description 1
- VLYJTJAYGSDXDI-UHFFFAOYSA-N n'-methyl-n'-[2-(methylamino)ethyl]propane-1,3-diamine Chemical compound CNCCN(C)CCCN VLYJTJAYGSDXDI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical class OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Materials For Medical Uses (AREA)
- Adhesive Tapes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- General Preparation And Processing Of Foods (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Description
Foreliggende oppfinnelse vedrører et husholdningsklebemiddel på basis av en i det vesentlige klar, og i det minste hovedsakelig oppløsningsmiddelfri, vandig enkomponent polyuretandispersjon og fremgangsmåte for fremstilling derav. The present invention relates to a household adhesive based on an essentially clear, and at least mainly solvent-free, aqueous one-component polyurethane dispersion and a method for its production.
Husholdningsklebemidler - også kalt universalklebemidler-har det formål å klebe et stort antall i husholdning forekommende substrater (papir, papp, fotos, tekstiler, lær, filt, bast, kork, folier, metaller, som aluminium og jern, porselen, keramiske materialer, glass, tre, forskjellige plaster, som også for eksempel polystyrenskum). Derved ventes det at det på dette store antallet substrater, som adskiller seg fra hverandre kjemisk og fysikalsk når det gjelder overflatestruktur, og som vanligvis ikke er underkastet noen spesiell overflatebehandling før klebing, oppnås tilstrekkelig vedhengsvirkning. Household adhesives - also called universal adhesives - have the purpose of gluing a large number of substrates found in households (paper, cardboard, photos, textiles, leather, felt, bast, cork, foils, metals, such as aluminum and iron, porcelain, ceramic materials, glass , wood, various plastics, such as polystyrene foam). Thereby, it is expected that on this large number of substrates, which differ from each other chemically and physically in terms of surface structure, and which are not usually subjected to any special surface treatment before gluing, a sufficient adhesion effect is achieved.
Sammenlignet med det store antallet klebestoffklasser og - typer, som anvendes innen industri og håndverk, finnes det bare få stoffer som tilfredsstiller de høye kravene som stilles til universell anvendelighet av et husholdningsklebemiddel. Bred anvendelse har derved polyvinylacetat og dens kopolymerer funnet, disse tilføres vanligvis i oppløs-ning eller, for treklebing, som dispersjon. Compared to the large number of adhesive classes and types used in industry and crafts, there are only a few substances that satisfy the high demands placed on the universal applicability of a household adhesive. Polyvinyl acetate and its copolymers have thus found wide application, these are usually added in solution or, for wood bonding, as a dispersion.
Kravet til universell anvendelighet utgjør et meget strengt utvalgskriterium for et klebestoff. Det betyr til syvende og sist at klebestoffmolekylene på samme måte må oppvise høy affinitet til polare og upolare grenseflater. En uttalelse om at et bestemt stoff er egnet som klebestoff, gir dermed fagmannen ingen antydning om det kan anvendes som husholdningsklebemiddel . The demand for universal applicability constitutes a very strict selection criterion for an adhesive. Ultimately, this means that the adhesive molecules must similarly exhibit a high affinity to polar and non-polar interfaces. A statement that a certain substance is suitable as an adhesive therefore gives the expert no indication as to whether it can be used as a household adhesive.
Ved siden av kravet til universell anvendelighet, består for husholdningsklebemidler videre også ønsket om å oppnå lukt-nøytrale, oppløsningsmiddelfrie, fysiologisk godtagbare, klare, vandige formuleringer. Disse formuleringene skal imidlertid samtidig føre til klebestoffer hvis tørkede filmer igjen har en viss vannfasthet. Videre skal disse vannbaserte klebestoffene også være i stand til å binde vanskelig klebbare substrater, som plaster. Alongside the requirement for universal applicability, for household adhesives there is also the desire to achieve odor-neutral, solvent-free, physiologically acceptable, clear, aqueous formulations. However, these formulations should also lead to adhesives whose dried films again have a certain water resistance. Furthermore, these water-based adhesives must also be able to bind difficult-to-glue substrates, such as plaster.
Denne kravprofilen har hittil ikke kunnet oppfylles på alle punkter, hverken på basis av de hittil for universalklebemidler foretrukne bindemidlene polyvinylacetat og vinyl-acetatkopolymerer eller ved alternativer som nitrocellulose. Riktignok kan polyvinylacetat fremstilles oppløsnings-middelfritt i form av vandige dispersjoner, disse dispersjonene er imidlertid ikke transparente, men derimot melkehvite. De viser for eksempel gode bruksegenskaper ved anvendelse som trelim. Heller ikke de som dispersjonskle-bemidler meget anvendte akrylatene og styren-akrylatene er kjent på markedet i form av transparente husholdningsklebemidler med de nevnte egenskapene. This requirement profile has so far not been able to be met at all points, either on the basis of the binders polyvinyl acetate and vinyl acetate copolymers, which have been preferred for universal adhesives up to now, or with alternatives such as nitrocellulose. Admittedly, polyvinyl acetate can be prepared solvent-free in the form of aqueous dispersions, however, these dispersions are not transparent, but rather milky white. They show, for example, good application properties when used as wood glue. Nor are the acrylates and styrene acrylates widely used as dispersion adhesives known on the market in the form of transparent household adhesives with the aforementioned properties.
Det er nå overraskende funnet at spesielt utvalgte ut-førelsesformer av de i flere tiår kjente vandige polyuretan-dispersjonene egner seg som universalklebemidler. Polyuretan-dispersjoner består av addukter av flerfunksjonene isocyanater til flerfunksjonene OH-forbindelser, som inneholder innkondenserte byggestener som i vandig opp-løsning er i stand til saltdannelse. It has now surprisingly been found that specially selected embodiments of the aqueous polyurethane dispersions known for several decades are suitable as universal adhesives. Polyurethane dispersions consist of adducts of multifunctional isocyanates to multifunctional OH compounds, which contain condensed building blocks which in aqueous solution are capable of salt formation.
I det tyske utlegningsskrift nr. 15 95 602 som går tilbake til året 1966, beskrives på omfattende måte en fremgangsmåte for fremstilling av kationisk modifiserte polyuretandispersjoner, som, som dispergerende komponenter, inneholder kvartære ammoniumgrupper i en mengde på minst 0,21 %. Utlegningsskriftet nevner tallrike polyoler, tallrike isocyanatforbindelser og tallrike kationiske saltdannendekomponenter som modifiseringsmidler. Nevnt er videre også de her vanlige kjedeforlengelsesmidlene. Ved den fremgangsmåten som der er beskrevet, er det mulig å fremstille optisk tilnærmet klare kolloidale oppløsninger av assosiater, som gir klebefrie eller klebende filmer. Nevnt er generelt, og uten nærmere angivelser, også anvendelsen av produktene som klebestoffer. In the German specification no. 15 95 602 which goes back to the year 1966, a method for the production of cationically modified polyurethane dispersions, which, as dispersing components, contain quaternary ammonium groups in an amount of at least 0.21% is described in a comprehensive way. The specification mentions numerous polyols, numerous isocyanate compounds and numerous cationic salt-forming components as modifiers. Also mentioned are the common chain extenders here. With the method described there, it is possible to produce optically approximately clear colloidal solutions of associates, which give adhesive-free or adhesive films. The use of the products as adhesives is also mentioned in general, and without further details.
Den omfattende beskrivelsen i DE 15 95 602 omfatter såvel polyuretan-dispersjoner, hvorved det som OH-funksjonelle komponenter anvendes polyestere, og også slike hvor det anvendes polyetere eller polyacetaler. Polyuretan-dispersjoner på basis av polyuretaner, som er oppbygget av OH-funksjonelle polyestere, er imidlertid mindre egnede som husholdningsklebemidler, idet de ved lagring undergår hydrolyse og dermed ikke oppviser den krevede lagrings-stabiliteten. Polyuretan-dispersjoner hvis grunnleggende OH-funksjonelle komponenter er polyetylenoksyd og/eller polypropylenoksyd, er heller ikke egnet som universalklebemidler, idet de viser dårlig vedheng til plastoverflater og dermed ikke oppfyller kravene til universell anvendelighet. The comprehensive description in DE 15 95 602 includes both polyurethane dispersions, whereby polyesters are used as OH-functional components, and also those where polyethers or polyacetals are used. However, polyurethane dispersions based on polyurethanes, which are made up of OH-functional polyesters, are less suitable as household adhesives, as they undergo hydrolysis upon storage and thus do not exhibit the required storage stability. Polyurethane dispersions whose basic OH-functional components are polyethylene oxide and/or polypropylene oxide are also not suitable as universal adhesives, as they show poor adhesion to plastic surfaces and thus do not meet the requirements for universal applicability.
DE 15 95 602 nevner riktignok polytetrahydrofuran som mulig polyol. Det finnes imidlertid ingen antydning om at nettopp denne polyolen utgjør en egnet basis for polyuretan-dispersjoner for husholdningsklebemidler. DE 15 95 602 does indeed mention polytetrahydrofuran as a possible polyol. However, there is no indication that this particular polyol constitutes a suitable basis for polyurethane dispersions for household adhesives.
Fra den ålment tilgjengelige japanske patentpublikasjonen nr. 62(1987 )-112676, offentliggjort 23.05.1987, er et vandig polyuretanklebestoff kjent som omfatter en vandig polyuretan dispersjon, oppnådd ved omsetning av en polytetrahydrofuran-diol med et flerfunksjonelt isocyanat. Nærmere bestemt lærer det japanske utlegningsskriftet å omsette polytetrahydro-furandiol (molekylvekt 400 til 2000) med organiske diisocyanater og en dimetylolalkansyre, og underkaste dette et kjedeforlengelsestrinn med hydrazin og etter nøytralisasjon med et tertiært amin og omsette med et vannoppløselig epoksyd eller et vannoppløslig aziridin. Klebingen oppnås ved at polyuretanet med sine karboksylen-degrupper tverr-bindes ved polypeptidet eller polyaziridinet. Den japanske publikasjonen gir imidlertid ingen antydning om at slike polyuretan dispersjoner i seg selv med fordel kan anvendes som husholdningsklebemidler. From the widely available Japanese patent publication No. 62(1987)-112676, published on 23/05/1987, an aqueous polyurethane adhesive is known which comprises an aqueous polyurethane dispersion, obtained by reacting a polytetrahydrofuran diol with a multifunctional isocyanate. Specifically, the Japanese specification teaches to react polytetrahydrofurandiol (molecular weight 400 to 2000) with organic diisocyanates and a dimethylolalkanoic acid, subjecting this to a chain extension step with hydrazine and after neutralization with a tertiary amine and reacting with a water-soluble epoxide or a water-soluble aziridine. The bonding is achieved by cross-linking the polyurethane with its carboxyl groups at the polypeptide or polyaziridine. However, the Japanese publication gives no indication that such polyurethane dispersions in themselves can be advantageously used as household adhesives.
Oppgaven ved foreliggende oppfinnelse er følgelig å påpeke at spesielle, vandige, transparente polyuretandispersjoner oppfyller de komplekse og til dels motstridende tidligere nevnte kravene til husholdningsklebemidler. The task of the present invention is therefore to point out that special, aqueous, transparent polyurethane dispersions meet the complex and partly contradictory previously mentioned requirements for household adhesives.
Gjenstand for foreliggende oppfinnelse er et husholdningsklebemiddel, på basis av en i det vesentlige klar og i det minste hovedsaklig oppløsningsmiddelfri, vandig enkomponent polyuretan-dispersjon på basis av reaksjonsproduktene av en polyolblanding, en to— eller flerfunksjonen isocyanatkomponent, en funksjonell komponent som er i stand til saltdannelse i vandig oppløsning og om ønskelig et kjedeforlengelsesmiddel, kjennetegnet ved at The object of the present invention is a household adhesive, based on an essentially clear and at least essentially solvent-free, aqueous one-component polyurethane dispersion based on the reaction products of a polyol mixture, a bi- or multi-functional isocyanate component, a functional component capable of for salt formation in aqueous solution and, if desired, a chain-extending agent, characterized in that
polyolblandingen helt eller delvis består av polytetrahydrofuran, the polyol mixture consists wholly or partly of polytetrahydrofuran,
isocyanatkomponenten blir brukt i en mengde slik at forholdet mellom OE-grupper fra polyolen og isocyanatgrupper blir 1 : 0,5 til 1 : 2,0, fortrinnsvis 1 : 1,0 til The isocyanate component is used in an amount so that the ratio between OE groups from the polyol and isocyanate groups is 1:0.5 to 1:2.0, preferably 1:1.0 to
1 : 1,7 og spesielt 1 : 1,05 til 1 : 1,6, og at 1 : 1.7 and especially 1 : 1.05 to 1 : 1.6, and that
den flerfunksjonene komponenten som er i stand til saltdannelse i vandig oppløsning er valgt fra gruppen bestående av dimetylolpropionsyre samt av dihydroksy— eller diaminoforbindelser med en ioniserbar sulfonsyre— eller ammoniumgruppe. the multifunctional component capable of salt formation in aqueous solution is selected from the group consisting of dimethylolpropionic acid and of dihydroxy or diamino compounds with an ionizable sulfonic acid or ammonium group.
Polyuretanene som ligger til grunn for de ifølge oppfinnelsen anvendte polyuretan-dispersjonene er basert på en polyolblanding bestående helt eller delvis av polytetrahydrofuran, hvorved innholdet av polytetrahydrofuran, relativt til polyolblandingen, ikke skal være mindre enn 30 og fortrinnsvis ikke mindre enn 70 vekt-#. Under polytetrahydrofuran forstås her polyetere som teoretisk eller reelt kan fremstilles ved ringåpnende polymerisasjon av tetrahydrofuran, og som på begge kjedeendene oppviser en hydroksyl- gruppe. Egnede produkter har derved en oligomerisasjonsgrad på 1,5 til 150, fortrinnsvis på 5 til 100. The polyurethanes which form the basis of the polyurethane dispersions used according to the invention are based on a polyol mixture consisting wholly or partly of polytetrahydrofuran, whereby the content of polytetrahydrofuran, relative to the polyol mixture, shall not be less than 30 and preferably not less than 70 wt-#. Here, polytetrahydrofuran is understood to mean polyethers which can theoretically or actually be produced by ring-opening polymerization of tetrahydrofuran, and which have a hydroxyl group at both chain ends. Suitable products thereby have a degree of oligomerization of 1.5 to 150, preferably of 5 to 100.
Ved siden av, eller i steden for, polytetrahydrofurandiolene kan det også anvendes analoge forbindelser, hvor de i oppbygningen av polyolene deltagende tetrahydrofuranenhetene inntil 50 # er erstattet med etylenoksyd eller propylenoksyd. Blandt disse forbindelsene er slike foretrukket som er oppbygget av 25 til 30 mol-# etylenoksyd-enheter og 75 til 70 mol-% tetrahydrofuranoksyd-enheter. Ved siden av diolene på basis av tetrahydrofuran kan det også anvendes analoge diaminer. Alongside, or instead of, the polytetrahydrofurandiols, analogous compounds can also be used, where the tetrahydrofuran units participating in the structure of the polyols up to 50# have been replaced with ethylene oxide or propylene oxide. Among these compounds, those which are made up of 25 to 30 mol-# ethylene oxide units and 75 to 70 mol-% tetrahydrofuranoxide units are preferred. Alongside the diols based on tetrahydrofuran, analogous diamines can also be used.
De polytetrahydrofuranpolyolene som ligger til grunn for de ifølge oppfinnelsen anvendte polyuretandispersjonene kan videre være erstattet av inntil 70 vekt-# andre, i slike preparater vanlige, polyoler. Generelt gjelder her at disse andre polyolene må ha minst to reaktive hydrogenatomer og i det vesentlige være lineære, hvorved molekylvekten kan ligge mellom 300 og 20.000, fortrinnsvis mellom 500 og 6.000. Foretrukket er her polyestere, polyacetaler, polyetere, polytioetere, polyamider og/eller polyesteramider, som i ethvert tilfelle gjennomsnittlig oppviser 2 til 4 hydrok-sylgrupper. The polytetrahydrofuran polyols which form the basis of the polyurethane dispersions used according to the invention can further be replaced by up to 70% by weight of other polyols common in such preparations. In general, these other polyols must have at least two reactive hydrogen atoms and be essentially linear, whereby the molecular weight can lie between 300 and 20,000, preferably between 500 and 6,000. Preferred here are polyesters, polyacetals, polyethers, polythioethers, polyamides and/or polyesteramides, which in any case have an average of 2 to 4 hydroxyl groups.
Som polyetere kan nevnes for eksempel polymerisasjons-produktene av etylenoksyd, propylenoksyd, butylenoksyd samt deres bland-eller podepolymerisasjonsprodukter, samt de ved kondensasjon av flerverdige alkoholer eller blandinger av slike og de ved alkoksylering av flerverdige alkoholer, aminer, polyaminer og aminoalkoholer oppnådde polyetrene. Også isotaktisk polypropylenglykol kan finne anvendelse. As polyethers can be mentioned, for example, the polymerization products of ethylene oxide, propylene oxide, butylene oxide as well as their mixed or graft polymerization products, as well as the polyethers obtained by condensation of polyhydric alcohols or mixtures thereof and those obtained by alkylation of polyhydric alcohols, amines, polyamines and amino alcohols. Isotactic polypropylene glycol can also be used.
Som polyacetaler kommer for eksempel de av glykoler som dietylenglykol, trietylenglykol, heksandiol og formaldehyd-fremstillbare forbindelsene på tale. Også ved polymerisasjon av cykliske acetaler kan egnede polyacetaler fremstilles. Blandt polytioeterne skal spesielt kondensasjonsproduktene av tiodiglykol med seg selv og/eller med andre glykoler, dikarboksylsyrer, formaldehyd, aminokarboksylsyrer eller aminoalkoholer anføres. Avhengig av ko-komponentene dreier det seg ved produktene om polytioetere, polytioblandetere, polytioeterestere, polytioeteresteramider. Slike polyhydroksylforbindelser kan også anvendes i alkylert form, henholdsvis i blanding med alkyleringsmidler. As polyacetals, for example, those of glycols such as diethylene glycol, triethylene glycol, hexanediol and formaldehyde-producible compounds are mentioned. Suitable polyacetals can also be produced by polymerization of cyclic acetals. Among the polythioethers, the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols should be mentioned in particular. Depending on the co-components, the products are polythioethers, polythioblendethers, polythioetheresters, polythioetheresteramides. Such polyhydroxyl compounds can also be used in alkylated form, or in a mixture with alkylating agents.
Til polyesterne, polyesteramidene og polyamidene hører også de av flerverdige mettede og umettede karboksylsyrer, henholdsvis deres anhydrider og flerverdige mettede og umettede alkoholer, aminoalkoholer, diaminer, polyaminer og deres blandinger utvunnede, overveiende lineære kondensatene, samt for eksempel polytereftalat eller polykarbonat. Også polyestere av laktoner, for eksempel kaprolakton eller av hydroksykarboksylsyrer er anvendbare. Polyesterne kan oppvise hydroksyl- eller karboksylendegrupper. Til deres oppbygning kan det som alkoholkomponenter også anvendes høyere molekylære polymerisater eller kondensater, som for eksempel polyetere, polyacetaler, polyoksymetylen. The polyesters, polyesteramides and polyamides also include the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids, respectively their anhydrides and polyvalent saturated and unsaturated alcohols, amino alcohols, diamines, polyamines and their mixtures, as well as for example polyterephthalate or polycarbonate. Polyesters of lactones, for example caprolactone or of hydroxycarboxylic acids are also usable. The polyesters can have hydroxyl or carboxyl end groups. For their structure, higher molecular polymers or condensates, such as polyethers, polyacetals, polyoxymethylene, can also be used as alcohol components.
Også polyhydroksylforbindelser som allerede inneholder uretan-eller ureagrupper samt eventuelt modifiserte naturlige polyoler som ricinusolje er anvendbare. Prinsipielt kommer også polyhydroksylforbindelser, som oppviser basiske nitrogenatomer på tale, for eksempel polyalkoksylerte primære aminer eller polyestere henholdsvis polytioetere, som inneholder innkondensert alkyl-dietanolamin. Videre kan polyoler anvendes som er oppnådd ved fullstendig eller delvis ringåpning av epoksiderte triglycerider med primære eller sekundære hydroksylforbindelser, eksempelvis omsetnings-produktet av epoksydert soyaolje med metanol. Polyhydroxyl compounds which already contain urethane or urea groups as well as possibly modified natural polyols such as castor oil can also be used. In principle, polyhydroxyl compounds, which exhibit basic nitrogen atoms, are also mentioned, for example polyalkylated primary amines or polyesters or polythioethers, which contain condensed alkyl-diethanolamine. Furthermore, polyols can be used which have been obtained by complete or partial ring opening of epoxidized triglycerides with primary or secondary hydroxyl compounds, for example the reaction product of epoxidized soybean oil with methanol.
Som polyisocyanater er i polyuretan-dispersjonen ved foreliggende oppfinnelse alle aromatiske og alifatiske diisocyanater egnet, som for eksempel 1,5-naftylendi-isocyanat, 4,4'-difenylmetandllsocyanat, 4,4'-difenyldimetyl-metandiisocyanat, di- og tetraalkyldifenylmetandiisocyanat, 4,4'-dibenzyldiisocyanat, 1,3-fenylendiisocyanat, 1,4-fenylendiisocyanat, isomerene av tolulendiisocyanat, eventuelt i blanding, l-metyl-2,4-diisocyanat-cykloheksan, 1,6-diisocyanat-2,2,4-trimetylheksan, 1,6-diisocyanat-2,4,4-trimetylheksan, l-isocyanat-metyl-3-isocyanat-l,5,5-trimetyl-cykloheksan, klorerte og bromerte diisocyanater, fosforholdige diisocyanater, 4,4 '-diisocyanatfenylperfluor-etan, tetrametoksy-butan-1,4-diisocyanat, butan-1,4-diisocyanat, heksan-1,6-diisocyanat, dicykloheksylmetandiiso-cyanat, cykloheksan-1,4-diisocyanat, etylen-diisocyanat, ftalsyre-bis-isocyanatetylester, videre polyisocyanater med reaktive halogenatomer, som l-klormetylfenyl-2,4-diisocyanat, l-brommetylfenyl-2,6-diisocyanat, 3,3-bis-klormetyleter-4,4'-difenyldiisocyanat. Svovelholdige polyisocyanater oppnår man eksempelvis ved omsetning av 2 mol heksametylen-diisocyanat med 1 mol tiodiglykol eller dihydroksydiheksyl-sulfid. Et foretrukket diisocyanat er isoforondiisocyanat. Ytterligere viktige diisocyanater er trimetylheksametyldiiso-cyanat, meta- og/eller para-tetrametylxylendiisocyanat, 1,4-diisocyanatobutan, 1,2-diisocyanatododekan og dimerfettsyre-diisocyanat. De tidligere nevnte isocyanatene kan anvendes alene eller også i blanding. Foretrukket er cykliske eller forgrenede alifatiske diisocyanater som isoforondiisocyanat. As polyisocyanates in the polyurethane dispersion of the present invention, all aromatic and aliphatic diisocyanates are suitable, such as, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4 ,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of toluene diisocyanate, possibly in a mixture, 1-methyl-2,4-diisocyanate-cyclohexane, 1,6-diisocyanate-2,2,4- trimethylhexane, 1,6-diisocyanate-2,4,4-trimethylhexane, 1-isocyanate-methyl-3-isocyanate-1,5,5-trimethyl-cyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatephenylperfluoro -ethane, tetramethoxy-butane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, phthalic acid bis-isocyanate ethyl ester , further polyisocyanates with reactive halogen atoms, such as l-chloromethylphenyl-2,4-diisocyanate, l-bromomethylphenyl-2,6-diisocyanate at, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate. Sulphur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulphide. A preferred diisocyanate is isophorone diisocyanate. Further important diisocyanates are trimethylhexamethyl diisocyanate, meta- and/or para-tetramethylxylene diisocyanate, 1,4-diisocyanatobutane, 1,2-diisocyanatododecane and dimer fatty acid diisocyanate. The previously mentioned isocyanates can be used alone or in a mixture. Cyclic or branched aliphatic diisocyanates such as isophorone diisocyanate are preferred.
Delvis endesluttede polyisocyanater som fortjener interesse, som muliggjør dannelsen av selv-tverrbindende polyuretaner, er for eksempel dimert toluylendiisocyanat, eller med eksempelvis fenoler, tertiært butanol, ftalimid, kaprolaktam partielt omsatte polyisocyanater. Partially end-capped polyisocyanates that deserve interest, which enable the formation of self-crosslinking polyurethanes, are, for example, dimerized toluene diisocyanate, or polyisocyanates partially reacted with, for example, phenols, tertiary butanol, phthalimide, caprolactam.
Til kjedeforlengelsesmidlene med reaktive hydrogenatomer hører: - de vanlige mettede og umettede glykolene, som etylenglykol eller kondensater av etylenglykol, butandiol-1,3, butandiol-1,4, butendiol, propandiol-1,2, propandiol-1,3, neopentylglykol, heksandiol, bis-hydroksymetyl-cyklo-heksan, dioksyetoksyhydrokinon, tereftalsyre-bis-glukol-ester, ravsyre-di-2-hydroksyetyl-amid, ravsyre-di-N-metyl-(2-hydroksy-etyl)-amid, 1,4-di(2-hydroksy-metyl-merkapto)-2,3,5,6-tetraklorbenzen, 2-metylenpropandiol-(1,3), 2-metyl-propandiol-(l,3); - alifatiske, cykloalifatiske og aromatiske diaminer som etylendiamin, heksametylendiamin, 1,4-cykloheksylendi-amin, piperazin, N-metyl-propylendiamin, diaminodifenyl-sulfon, di-aminodifenyleter, diaminodifenyldimetylmetan, 2,4-diamino-6-fenyltriazin; The chain extenders with reactive hydrogen atoms include: - the usual saturated and unsaturated glycols, such as ethylene glycol or condensates of ethylene glycol, butanediol-1,3, butanediol-1,4, butenediol, propanediol-1,2, propanediol-1,3, neopentylglycol, hexanediol, bis-hydroxymethyl-cyclo-hexane, dioxyethoxyhydroquinone, terephthalic acid bis-glucol ester, succinic acid-di-2-hydroxyethyl-amide, succinic acid-di-N-methyl-(2-hydroxy-ethyl)-amide, 1, 4-di(2-hydroxy-methyl-mercapto)-2,3,5,6-tetrachlorobenzene, 2-methylenepropanediol-(1,3), 2-methylpropanediol-(1,3); - aliphatic, cycloaliphatic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexylenediamine, piperazine, N-methylpropylenediamine, diaminodiphenylsulfone, diaminodiphenylether, diaminodiphenyldimethylmethane, 2,4-diamino-6-phenyltriazine;
Utelukkes må diaminer med ikke ønskede stoffegenskaper, som kan påvirke helsen, som eksempelvis hydrazin, diamino-difenylmetan eller isomerene av fenylendiamin. Videre også karbohydrazider eller hydrazider av dikarboksylsyrer. - Aminoalkoholer som etanolamin, propanolamin, butanolamin, N-metyl-etanolamin, N-metyl-isopropanolamin; - alifatiske, cykloalifatiske, aromatiske og heterocykliske mono- og diaminokarboksylsyrer som glysin, 1- og 2-alanin, 6-aminokapronsyre, 4-aminosmørsyre, isomerene mono- og diaminobenzosyrer, isomerene mono- og diaminonaftosyrer; Diamines with undesirable material properties that can affect health must be excluded, such as hydrazine, diamino-diphenylmethane or the isomers of phenylenediamine. Furthermore, also carbohydrazides or hydrazides of dicarboxylic acids. - Amino alcohols such as ethanolamine, propanolamine, butanolamine, N-methyl-ethanolamine, N-methyl-isopropanolamine; - aliphatic, cycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids such as glycine, 1- and 2-alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomers mono- and diaminobenzoic acids, the isomers mono- and diaminonaphthoic acids;
- vann. - water.
Det skal fremheves at det innenfor rammen av foreliggende oppfinnelse ikke kan skilles strengt mellom forbindelsene med reaktive hydrogenatomer med molekylvekt på 300 til 20 000 og de såkalte "kjedeforlengelsesmidlene", idet overgangene mellom de to forbindelsesklassene er flytende. Forbindelser som ikke er oppbygget av flere monomerenheter, men oppviser en molekylvekt på over 300, som for eksempel 3,3'-dibrom-4,4'-diaminodifenylmetan, regnes til kjedeforlengelsesmidlene, dette gjør også pentaetylenglykol, selv om sist-nevnte i henhold til sin sammensetning egentlig er en polyeterdiol. It must be emphasized that, within the scope of the present invention, no strict distinction can be made between the compounds with reactive hydrogen atoms with a molecular weight of 300 to 20,000 and the so-called "chain extenders", as the transitions between the two compound classes are fluid. Compounds that are not made up of several monomer units, but have a molecular weight of over 300, such as 3,3'-dibromo-4,4'-diaminodiphenylmethane, are considered chain extenders, as is pentaethylene glycol, although the latter according to to its composition is actually a polyetherdiol.
Spesielle kjedeforlengelsesmidler med minst et basisk nitrogenatom er for eksempel mono-, bis- eller polyoksal-kylerte alifatiske, cykloalifatiske, aromatiske eller heterocykliske primære aminer, som N-metyldietanolamin, N-etyl-dietanolamin, N-propyl-dietanolamin, N-isopropyl-dietanolamin, N-butyl-dietanolamin, N-isobutyl-dietanolamin, N-oleyl-dietanolamin, N-stearyl-dietanolamin, oksetylert kokosfettamin, N-allyl-dietanolamin, N-metyl-diisopropanolamin, N-etyl-diisopropanolamin, N-propyl-diisopropanolamin, N-butyl-diisopropanolamin, C-cykloheksyl-diisopropanolamin, N,N-dioksetylanilin, N,N-dioktyltoluidin, N,N-dioktyl-aminopyridin, N,N'-dioksetyl-piperazin, dimetyl-bis-okse-tylhydrazin, N,N'-bis-(2-hydroksy-etyl)-N,N'-dietyl-heksa-hydro-p-fenylendiamin, N-12-hydroksyetyl-piperazin, polyalkoksylerte aminer som oksypropylert metyl-dietanolamin, videre forbindelser som N-metyl-N,N'-bis-3-aminopropylamin, N-(3-aminopropyl)-N,N'-dimetyletylendiamin, N-(3-amino-propyl)-N-metyl-etanolamin, N,N'-bis-(3-aminopropyl)-N,N'-dimetyletylendiamin, N,N'-bis(3-aminopropyl)-piperazin, N-(2-aminoetyl)-piperazin, N,N'-bisoksyetyl-propylendiamin, 2,6-diaminopyridin, dietanolamino-acetamid, dietanolamido-propionamid, N,N-bis-oksyetyl-fenyl-tiosemikarbazid, N,N-bis-oksetyl-metyl-semikarbazid, p,p'-bis-aminometyl-di-benzylmetylamin, 2,6-diaminopyridin, 2-dimetylaminometyl-2-metyl-propandiol-1,3. Special chain extenders with at least one basic nitrogen atom are, for example, mono-, bis- or polyoxalylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, such as N-methyldiethanolamine, N-ethyl-diethanolamine, N-propyl-diethanolamine, N-isopropyl- diethanolamine, N-butyl-diethanolamine, N-isobutyl-diethanolamine, N-oleyl-diethanolamine, N-stearyl-diethanolamine, oxyethylated coconut fat amine, N-allyl-diethanolamine, N-methyl-diisopropanolamine, N-ethyl-diisopropanolamine, N-propyl -diisopropanolamine, N-butyl-diisopropanolamine, C-cyclohexyl-diisopropanolamine, N,N-dioxytylaniline, N,N-dioctyltoluidine, N,N-dioctyl-aminopyridine, N,N'-dioxyethyl-piperazine, dimethyl-bis-oxo- ethylhydrazine, N,N'-bis-(2-hydroxy-ethyl)-N,N'-diethyl-hexa-hydro-p-phenylenediamine, N-12-hydroxyethyl-piperazine, polyalkylated amines such as oxypropylated methyl-diethanolamine, further compounds as N-methyl-N,N'-bis-3-aminopropylamine, N-(3-aminopropyl)-N,N'-dimethylethylenediamine, N-(3-amino-propyl)-N-methyl-ethanolamine, N ,N'-bis-(3-aminopropyl)-N,N'-dimethylethylenediamine, N,N'-bis(3-aminopropyl)-piperazine, N-(2-aminoethyl)-piperazine, N,N'-bisoxyethyl- propylenediamine, 2,6-diaminopyridine, diethanolamino-acetamide, diethanolamido-propionamide, N,N-bis-oxyethyl-phenyl-thiosemicarbazide, N,N-bis-oxetyl-methyl-semicarbazide, p,p'-bis-aminomethyl-di -benzylmethylamine, 2,6-diaminopyridine, 2-dimethylaminomethyl-2-methyl-propanediol-1,3.
Kjedeforlengelsesmidler med halogenatomer som er i stand til kvaternering, henholdsvis R-SOgO-grupper, er eksempelvis glycerol-l-klorhydrin, glycerolmonotosylat, pentaerytrit-bis-benzensulfonat, glycerol-monometansulfonat, addukter av dietanolamin og klormetylerte aromatiske isocyanater eller alifatiske halogenisocyanater som N,N-bis-hydroksyetyl-N'-m-klormetylfenylurea, N-hydroksyetyl-N'-klorheksylurea, glycerol-mono-kloretyl-uretan, bromacetyl-dipropylentriamin, kloreddiksyredietanolamid. Chain extenders with halogen atoms capable of quaternization, respectively R-SOgO groups, are for example glycerol-l-chlorohydrin, glycerol monotosylate, pentaerythritol bis-benzenesulfonate, glycerol monomethanesulfonate, adducts of diethanolamine and chloromethylated aromatic isocyanates or aliphatic halogen isocyanates such as N, N-bis-hydroxyethyl-N'-m-chloromethylphenylurea, N-hydroxyethyl-N'-chlorohexylurea, glycerol-mono-chloroethyl-urethane, bromoacetyl-dipropylenetriamine, chloroacetic acid diethanolamide.
De polyuretanene som ligger til grunn for de ifølge oppfinnelsen anvendte polyuretan-dispersjonene har videre som viktig bestanddel en funksjonell komponent som i vandig oppløsning er i stand til saltdannelse. Som sådanne kan det anvendes dihydroksy- eller også diamino-forbindelser, som inneholder en ioniserbar karboksylsyre-, sulfonsyre- eller ammoniumgruppe. Disse forbindelsene kan enten anvendes som sådanne eller de kan fremstilles in-situ. For å føre forbindelser som bærer ioniserbare karboksylsyregrupper inn i polyuretanen, kan fagmannen tilsette polyolene dihydroksy-karboksylsyrer. En foretrukket dihydroksykarboksylsyre er eksempelvis dimetylolpropionsyre. The polyurethanes which form the basis of the polyurethane dispersions used according to the invention also have as an important component a functional component which in aqueous solution is capable of salt formation. As such, dihydroxy or also diamino compounds can be used, which contain an ionizable carboxylic acid, sulfonic acid or ammonium group. These compounds can either be used as such or they can be prepared in-situ. In order to introduce compounds carrying ionizable carboxylic acid groups into the polyurethane, the person skilled in the art can add dihydroxy carboxylic acids to the polyols. A preferred dihydroxycarboxylic acid is, for example, dimethylolpropionic acid.
For å innføre sulf onsyregrupper som er i stand til saltdannelse, kan polyolene tilsettes en diaminosulfonsyre. Et eksempl er 2,4-diaminobenzensulfonsyre, men også N-(w-amino-alkan)-w'-aminoalkansulfonsyrer slik de er beskrevet i DE 20 35 732. To introduce sulphonic acid groups which are capable of salt formation, a diaminosulphonic acid can be added to the polyols. An example is 2,4-diaminobenzenesulfonic acid, but also N-(w-amino-alkane)-w'-aminoalkanesulfonic acids as described in DE 20 35 732.
For å innføre ammoniumgrupper som er i stand til saltdannelse i polymeren, kan også ifølge den tidligere omtalte DE 15 95 602 polyuretan-prepolymeren modifiseres ved hjelp av et alifatisk eller aromatisk diamin på en slik måte at det på kjedeendene foreligger primære aminogrupper, som deretter overføres med vanlige alkyleringsmidler til kvatærnære ammoniumforbindelser eller til aminsalter. In order to introduce ammonium groups which are capable of salt formation into the polymer, according to the previously mentioned DE 15 95 602 the polyurethane prepolymer can also be modified by means of an aliphatic or aromatic diamine in such a way that primary amino groups are present on the chain ends, which are then transferred with common alkylating agents to quaternary ammonium compounds or to amine salts.
Ifølge oppfinnelsen er det foretrukket å gjøre polyuretan-prepolymerene som anvendes vannoppløselige ved hjelp av karboksylsyre- eller sulfonsyregrupper, idet polyuretan-dispersjoner som inneholder slike anioniske modifiseringsmidler kan oppløses igjen under alkaliske betingelser, det vil si slike klebestoffer er fjernbare igjen under vaske-betingelser fra spesielle substrater, for eksempel fra tekstiler. According to the invention, it is preferred to make the polyurethane prepolymers used water-soluble by means of carboxylic acid or sulfonic acid groups, as polyurethane dispersions containing such anionic modifiers can be dissolved again under alkaline conditions, that is to say such adhesives can be removed again under washing conditions from special substrates, for example from textiles.
I polyuretan-dispersjonene som anvendes ifølge oppfinnelsen, foreligger polymerene i saltform. Ved de foretrukne polymerene som er modifisert med karboksylsyrer eller sulfonsyrer, foreligger som motioner alkalimetallsalter, ammoniakk eller aminer, det vil si primære, sekundære eller tertiære aminer. Ved de kationiske modifiserte produktene foreligger som motioner syreanioner, for eksempel klorid, sulfat eller anionene av organiske karboksylsyrer. Gruppene som er i stand til saltdannelse kan følgelig nøytraliseres delvis eller fullstendig av motionene. Også et overskudd av nøytralisasjonsmiddel er mulig. In the polyurethane dispersions used according to the invention, the polymers are present in salt form. In the case of the preferred polymers which have been modified with carboxylic acids or sulphonic acids, alkali metal salts, ammonia or amines, i.e. primary, secondary or tertiary amines, are present as counterions. In the case of the cationic modified products, counterions are acid anions, for example chloride, sulphate or the anions of organic carboxylic acids. The groups capable of salt formation can therefore be partially or completely neutralized by the counterions. An excess of neutralizing agent is also possible.
Som allerede angitt ved diskusjonen av de ifølge oppfinnelsen anvendbare kjedeforlengelsesmidlene, er forbindelser med sunnhetsskadelige eller - påvirkende egenskaper ikke ønskede. Dette gjelder desto mer fordi det ved foreliggende oppfinnelse dreier seg om et universelt anvendbart klebemiddel, som formodentlig også anvendes av personer som sunnhetsmessig er utsatte, som barn, eldre, syke, gravide o.s.v. Derfor er det ved en spesielt foretrukket utførelsesform, ikke bare viktig å legge vekt på kjedeforlengelsesmidlene når det gjelder å unngå fysiologiske betenkelige stoffer som hydrazin, men også når det gjelder de øvrige komponentene av klebestoffet viktig i størst mulig grad å tilstrebe en fysiologisk godtagbarhet av komponentene i klebestoffet. Hertil hører for eksempel den delvise, om mulig fullstendige, utelukkelsen av organiske oppløsningsmidler. Den i for-bindelse med polyuretanklebestoffer ofte diskuterte helse-faren forårsaket av fri isocyanater, henholdsvis ikke utreagerte NCO-grupper av polymerene eller prepolymerene er ikke tilstede ved foreliggende oppfinnelse, idet polyuretanene er dispergerte i vann og isocyanatgrupper utreagerer, som kjent for fagmannen, straks med vann, slik at det kan anses som sikret at polyuretandispersjonene ved oppfinnelsen ikke oppviser reaktive NCO-grupper. As already stated in the discussion of the chain extenders which can be used according to the invention, compounds with health-damaging or - affecting properties are not desired. This applies all the more because the present invention concerns a universally applicable adhesive, which is presumably also used by people who are at risk from a health point of view, such as children, the elderly, the sick, pregnant women, etc. Therefore, in a particularly preferred embodiment, it is not only important to emphasize the chain extenders when it comes to avoiding physiologically questionable substances such as hydrazine, but also when it comes to the other components of the adhesive it is important to strive for physiological acceptability of the components to the greatest extent possible in the adhesive. This includes, for example, the partial, if possible complete, exclusion of organic solvents. The health hazard often discussed in connection with polyurethane adhesives caused by free isocyanates, respectively unreacted NCO groups of the polymers or prepolymers is not present in the present invention, as the polyurethanes are dispersed in water and isocyanate groups react immediately, as is known to the person skilled in the art with water, so that it can be considered assured that the polyurethane dispersions of the invention do not exhibit reactive NCO groups.
For fremstillingen av de for formålene med oppfinnelsen spesielt egnede polyuretanene, omsettes polyolene og et overskudd av diisocyanat under dannelse av en polymer med endestående isocyanatgrupper, hvorved egnede reaksjons-betingelser og reaksjonstider samt temperaturer kan varieres avhengig av det aktuelle isocyanatet. Fagmannen vet at reaksjonsevnen for bestanddelene som skal omsettes nød-vendiggjør en tilsvarende likevekt mellom reaksjonshastighet og uønskede bireaksjoner, som fører til en misfarging og molekylvektsreduksjon. Typisk gjennomføres reaksjonen under omrøring ved 50 til 120°C i løpet av 1 til 6 timer. For the production of the polyurethanes particularly suitable for the purposes of the invention, the polyols and an excess of diisocyanate are reacted to form a polymer with terminal isocyanate groups, whereby suitable reaction conditions and reaction times as well as temperatures can be varied depending on the relevant isocyanate. The person skilled in the art knows that the reactivity of the components to be reacted necessitates a corresponding equilibrium between reaction rate and unwanted side reactions, which lead to discoloration and molecular weight reduction. Typically, the reaction is carried out with stirring at 50 to 120°C during 1 to 6 hours.
Foretrukket fremstillingsmåte er den såkalte acetonfrem-gangsmåten (D. Dietrich, Angew. Makromol. Chem 98, 133 The preferred preparation method is the so-called acetone method (D. Dietrich, Angew. Makromol. Chem 98, 133
(1981)). Videre kan de ifølge oppfinnelsen anvendte polyuretan-dispersjonene også fremstilles ved fremgangsmåten ifølge DE 15 95 602. En nyere fremgangsmåte for fremstilling av polyuretan-dispersjoner er beskrevet i DE 36 03 996 samt i den der angitte teknikkens stand, nemlig: DE-PS 8 80 485, DE-AS 10 44 404, US-PS 30 36 998, DE-PS 11 78 586, DE-PS 11 84 946, DE-AS 12 37 306, DE-AS 14 95 745, DE-OS 15 95 602, DE-OS 17 70 068, DE-OS 24 46 440, DE-OS 23 45 256, DE-OS 24 27 274, US-PS 34 79 310 og Angewandte Chemie 82,53 (1970) og Angew. Makromol. Chem. 26,85 ff. (1972). (1981)). Furthermore, the polyurethane dispersions used according to the invention can also be produced by the method according to DE 15 95 602. A more recent method for producing polyurethane dispersions is described in DE 36 03 996 as well as in the state of the art indicated there, namely: DE-PS 8 80 485, DE-AS 10 44 404, US-PS 30 36 998, DE-PS 11 78 586, DE-PS 11 84 946, DE-AS 12 37 306, DE-AS 14 95 745, DE-OS 15 95 602 , DE-OS 17 70 068, DE-OS 24 46 440, DE-OS 23 45 256, DE-OS 24 27 274, US-PS 34 79 310 and Angewandte Chemie 82,53 (1970) and Angew. Macromol. Chem. 26.85 ff. (1972).
Av de nevnte fremgangsmåtene er spesielt "acetonfrem-gangsmåten" analogt læren i DE-OS 14 95 745 (=US-PS 34 79 310) henholdsvis DE-OS 14 95 847 (GB-PS 10 67 788) av betydning. Herved fremstilles generelt først en prepolymer med -NCO endegrupper, som deretter oppløses i et inert oppløsningsmiddel, deretter følger kjedeforlengelse i oppløsning til høyeremolekylær polyuretan. Innbyggingen av de for dispergeringen påkrevde hydrofile gruppene foregår fortrinnsvis enten ved innbygning av dioler som bærer ioniske og/eller potensielt ioniske og ikke-ioniske hydrofile grupper i prepolymeren eller ved anvendelse av tilsvarende aminer som kjedeforlengelsesmiddel. Dispergeringen foregår diskontinuerlig i rørebeholdere med rørere og eventuelt strømbrytere. Det anvendte oppløsningsmidlet avdestilleres som regel umiddelbart etter dispergeringen i vann fra rørebeholderen. Of the methods mentioned, the "acetone method" is particularly important, analogously to the teaching in DE-OS 14 95 745 (=US-PS 34 79 310) and DE-OS 14 95 847 (GB-PS 10 67 788). In this way, a prepolymer with -NCO end groups is generally produced first, which is then dissolved in an inert solvent, followed by chain extension in solution to higher molecular weight polyurethane. The incorporation of the hydrophilic groups required for the dispersion preferably takes place either by incorporation of diols carrying ionic and/or potentially ionic and non-ionic hydrophilic groups in the prepolymer or by using corresponding amines as chain extenders. Dispersion takes place discontinuously in stirring containers with stirrers and possibly circuit breakers. The solvent used is usually distilled off immediately after dispersion in water from the mixing container.
Ytterligere fremgangsmåter for fremstilling av polyuretan-prepolymerer, spesielt for kontinuerlig fremstilling av polyuretan-prepolymerer, er beskrevet i de tyske utleg-ningsskriftene 22 60 870, 23 11 635 og 23 44 135. Further methods for the production of polyurethane prepolymers, in particular for the continuous production of polyurethane prepolymers, are described in German specification documents 22 60 870, 23 11 635 and 23 44 135.
For å oppnå i det vesentlige klare, det vil si opake til vannklare polyuretan-dispersjoner, må fagmannen legge vekt på et bestemt forhold mellom komponentene som er i stand til saltdannelse og de øvrige stoffene som bygger polyuretanen opp. Følgelig er det hensiktsmessig å anvende komponentene som er i stand til saltdannelse, beregnet som dimetylolpropionsyre, i mengder på 1 til 30, fortrinnsvis på 2 til 20, og spesielt på 10 til 18 vekt-#, beregnet på basis av polyol. Videre avhenger transparensen av nøytral isasjonsgraden. Herved kan fagmannen gjennom små forforsøk fastslå fra hvilken mengde av modifiseringsmidler som er i stand til ionedannelse, henholdsvis fra hvilken mengde nøytralisa-sjonsmiddel det oppnås en tilstrekkelig grad av transparens. Generelt anvendes så lite som mulig av disse stoffene, idet vannfastheten av klebemiddel kan forstyrres ved for stor anvendelse. In order to achieve essentially clear, i.e. opaque to water-clear polyurethane dispersions, the person skilled in the art must emphasize a certain ratio between the components that are capable of salt formation and the other substances that make up the polyurethane. Accordingly, it is appropriate to use the components which are capable of salt formation, calculated as dimethylol propionic acid, in amounts of 1 to 30, preferably of 2 to 20, and especially of 10 to 18 weight-#, calculated on the basis of polyol. Furthermore, the transparency depends on the degree of neutralisation. In this way, the person skilled in the art can, through small preliminary experiments, determine from which quantity of modifiers are capable of ion formation, respectively from which quantity of neutralizing agent a sufficient degree of transparency is achieved. In general, as little of these substances as possible is used, as the water resistance of the adhesive can be disturbed if too much is used.
Foreliggende oppfinnelse tilveiebringer videre en fremgangsmåte for fremstilling av et husholdningsklebemiddel som beskrevet ovenfor som er kjennetegnet ved at The present invention further provides a method for producing a household adhesive as described above, which is characterized in that
det først fremstilles en prepolymer med NCO-endegrupper av en helt eller delvis av polytetrahydrofuran bestående polyolblanding, a prepolymer with NCO end groups is first prepared from a polyol mixture consisting wholly or partly of polytetrahydrofuran,
en dertil i forhold OH : NCO som 1 : 0,5 til 1 : 2,0, fortrinnsvis 1 : 1,0 til 1 : 1,7 og spesielt 1 : 1,05 a ratio OH : NCO such as 1 : 0.5 to 1 : 2.0, preferably 1 : 1.0 to 1 : 1.7 and especially 1 : 1.05
til 1 : 1,6 anvendt to- eller flerfunksjonen isocyanatkomponent og to 1:1.6 used bi- or multi-functional isocyanate component and
en dimetylolpropionsyre som en funksjonell komponent som a dimethylolpropionic acid as a functional component which
er i stand til saltdannelse i vandig oppløsning, prepolymeren deretter oppløses i et inert oppløsnings-middel, is capable of salt formation in aqueous solution, the prepolymer is then dissolved in an inert solvent,
det deretter foretas dispergering diskontinuerlig i røre-beholdere med rører og om ønsket strømbrytere og dispersing is then carried out discontinuously in stirring containers with stirrers and, if desired, circuit breakers and
til slutt avdestillering av anvendt oppløsningsmiddel, om ønsket umiddelbart etter dispergeringen i vann fra rørebeholderen. finally distilling off the used solvent, if desired immediately after the dispersion in water from the mixing container.
Under polyuretan-dispersjonen ifølge oppfinnelsen forstås to-fasede vann/polyuretan-systemer, som fortrinnsvis omfatter kolloidale systemer og soler med partikkeldiameter på 10 til 100 nm. Disse systemene er fortrinnsvis optisk opake til transparente. Herfra må avgrenses optisk klare "ekte" oppløsninger. The polyurethane dispersion according to the invention means two-phase water/polyurethane systems, which preferably comprise colloidal systems and sols with a particle diameter of 10 to 100 nm. These systems are preferably optically opaque to transparent. From here, optically clear "real" resolutions must be delineated.
Faststoffinnholdet for klebestoffoppløsningen kan varieres innenfor vide grenser. I praksis har faststoffinnholdet mellom 20 og 70 vekt-#, spesielt mellom 30 og 50 vekt-5é vist seg hensiktsmessig. The solids content of the adhesive solution can be varied within wide limits. In practice, the solids content between 20 and 70 wt-#, especially between 30 and 50 wt-5é has proven appropriate.
Eksempler Examples
Generelle fremstillingsprosedyrer General manufacturing procedures
Polyolene fortynnes med aceton eller oppløses henholdsvis dispergeres deri. Under omrøring foregår tilsatsen av komponentene som er i stand til ionedannelse. Ved temperaturer mellom 50 og 70°C tilsettes det deretter diisocyanat inntil NCO-innholdet ikke lenger synker. Det nøytraliseres så ved 60°C, for eksempel med N-metyl-morfolin. Etter en varighet på ca. 30 minutter foregår så tilsatsen av vann. Etter 30 minutters dispergering avdestilleres så aceton, senere under forhøyet vakuum ved temperaturer på 55 til 60°C. Klebekraft (strekkskjaerfastheter) i henhold til "DIN 53254" The polyols are diluted with acetone or dissolved or dispersed therein. During stirring, the components that are capable of ion formation are added. At temperatures between 50 and 70°C, diisocyanate is then added until the NCO content no longer decreases. It is then neutralized at 60°C, for example with N-methyl-morpholine. After a duration of approx. After 30 minutes, the addition of water takes place. After 30 minutes of dispersion, acetone is then distilled off, later under elevated vacuum at temperatures of 55 to 60°C. Adhesive force (tensile shear strengths) according to "DIN 53254"
60 um - Verdi på krompapir 60 um - Value on chrome paper
Påføring av en 60 >jm klebestof f film med en spiralsjaber på krompapir. Øyeblikkelig sammenklebing med likeartet papir. Application of a 60 >jm adhesive f film with a spiral squeegee on chrome paper. Instant bonding with similar paper.
- Langsomt sjabring mot hverandre inntil materialbrudd i tidsenhet: - Slow scraping against each other until material failure in time unit:
Lagringstest Storage test
Polyuretan-dispersjoner som anvendes ifølge oppfinnelsen ifølge eksemplene og ifølge sammenligningseksemplene 1 til 4 ble underkastet en lagringstest ved temperaturer på 50°C. Det ble observert følgende utvikling av viskositeten: Polyurethane dispersions used according to the invention according to the examples and according to comparative examples 1 to 4 were subjected to a storage test at temperatures of 50°C. The following development of the viscosity was observed:
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE3827378A DE3827378A1 (en) | 1988-08-12 | 1988-08-12 | HOUSEHOLD ALL-PURPOSE GLUE BASED ON POLYURETHANE |
PCT/EP1989/000915 WO1990001508A1 (en) | 1988-08-12 | 1989-08-03 | General purpose household adhesive based on polyurethane |
Publications (4)
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NO910460L NO910460L (en) | 1991-02-06 |
NO910460D0 NO910460D0 (en) | 1991-02-06 |
NO173703B true NO173703B (en) | 1993-10-11 |
NO173703C NO173703C (en) | 1994-01-19 |
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NO910460A NO173703C (en) | 1988-08-12 | 1991-02-06 | Polyurethane-based household adhesive and its manufacturing process |
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EP (2) | EP0354471B1 (en) |
JP (1) | JP2892409B2 (en) |
KR (1) | KR900701883A (en) |
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CA (1) | CA1339656C (en) |
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TR (1) | TR25089A (en) |
WO (1) | WO1990001508A1 (en) |
ZA (1) | ZA896159B (en) |
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DE3942681A1 (en) * | 1989-12-22 | 1991-06-27 | Henkel Kgaa | HOUSEHOLD GLUE BASED ON POLYURETHANE |
DE4011455A1 (en) * | 1990-04-09 | 1991-10-10 | Henkel Kgaa | HOUSEHOLD ALL-PURPOSE GLUE BASED ON POLYURETHANE |
DE4023005A1 (en) * | 1990-07-19 | 1992-01-23 | Henkel Kgaa | THIXOTROPE POLYURETHANE SYSTEMS |
DE4109477A1 (en) * | 1991-03-22 | 1992-09-24 | Henkel Kgaa | POLYMER DISPERSIONS SUITABLE FOR REACTIVE SYSTEMS |
DE4120432A1 (en) * | 1991-06-20 | 1992-12-24 | Henkel Kgaa | DIHYDROXY FATTY ACIDS AS POLYURETHANE BUILDING BLOCKS |
JP3584480B2 (en) * | 1993-09-28 | 2004-11-04 | 大日本インキ化学工業株式会社 | Solvent-free composite laminate adhesive composition and bonding method using the same |
DE4408487A1 (en) * | 1994-03-14 | 1995-09-21 | Henkel Kgaa | Aqueous polyurethane primer |
GB0207205D0 (en) * | 2002-03-27 | 2002-05-08 | Avecia Ltd | Polyurethane dispersion, manufacture and uses |
CN101585927B (en) * | 2008-05-20 | 2011-05-25 | 聚和国际股份有限公司 | Floating additive of aqueous-based PU |
US20130199699A1 (en) | 2010-04-08 | 2013-08-08 | Construction Research & Technology Gmbh | Conductive Adhesive For A Floorcovering |
EP3172254B1 (en) * | 2014-07-25 | 2019-08-21 | Dow Global Technologies LLC | One-component structural adhesive containing isocyanate-terminated prepolymer |
CN110330627A (en) * | 2019-07-10 | 2019-10-15 | 福建元发树脂有限公司 | Non-solvent single-component polyurethane casting resin |
CN111704883B (en) * | 2020-07-09 | 2021-09-17 | 旭川化学(苏州)有限公司 | Solvent-free single-component moisture curing polyurethane adhesive suitable for wood and preparation method thereof |
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DE1495745C3 (en) | 1963-09-19 | 1978-06-01 | Bayer Ag, 5090 Leverkusen | Process for the production of aqueous, emulsifier-free polyurethane latices |
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DE1237306B (en) | 1964-09-26 | 1967-03-23 | Bayer Ag | Process for the production of polyurethane plastics |
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DE1595602A1 (en) | 1966-03-12 | 1969-09-18 | Bayer Ag | Process for the production of polyurethane plastics |
DE1770068C3 (en) | 1968-03-27 | 1981-01-15 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethanes Bayer AG, 5090 Leverkusen |
DE1769387A1 (en) * | 1968-05-17 | 1971-10-28 | Bayer Ag | Use of aqueous polyurethane dispersions for bonding plasticized polyvinyl chloride plastics |
DE2019324C3 (en) | 1970-04-22 | 1979-02-22 | Bayer Ag, 5090 Leverkusen | Process for the production of lightfast polyurethane ionomers |
DE2035732A1 (en) | 1970-07-18 | 1972-01-27 | Farbenfabriken Bayer AG, 5090 Le verkusen | N (omega ammo a / kan) omega ammo a / kan sulfonic acid salts and their use as anionic structural components in the production of emulsifier-free polyurethane dispersions |
DE2260870A1 (en) | 1972-12-13 | 1974-06-27 | Bayer Ag | PROCESS FOR THE CONTINUOUS PREPARATION OF Aqueous SOLID DISPERSIONS |
DE2344135C2 (en) | 1973-09-01 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | Process for the continuous production of aqueous polyurethane dispersions |
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DE2446440C3 (en) | 1974-09-28 | 1981-04-30 | Bayer Ag, 5090 Leverkusen | Process for the preparation of aqueous dispersions of polyurethanes containing sulfonate groups |
GB1575637A (en) * | 1976-10-04 | 1980-09-24 | Textron Inc | Aqueous colloidal polyurea-urethane ionomer dispersions |
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DE3603996A1 (en) | 1986-02-08 | 1987-08-13 | Bayer Ag | METHOD FOR THE CONTINUOUS PRODUCTION OF AQUEOUS POLYURETHANE DISPERSIONS AND THEIR USE AS A COATING AGENT OR AS AN ADHESIVE |
-
1988
- 1988-08-12 DE DE3827378A patent/DE3827378A1/en not_active Withdrawn
-
1989
- 1989-07-05 TR TR89/0626A patent/TR25089A/en unknown
- 1989-08-03 DE DE8989114337T patent/DE58901469D1/en not_active Expired - Lifetime
- 1989-08-03 AT AT89114337T patent/ATE76415T1/en not_active IP Right Cessation
- 1989-08-03 EP EP89114337A patent/EP0354471B1/en not_active Expired - Lifetime
- 1989-08-03 BR BR898907594A patent/BR8907594A/en not_active Application Discontinuation
- 1989-08-03 AU AU40455/89A patent/AU4045589A/en not_active Abandoned
- 1989-08-03 JP JP1508460A patent/JP2892409B2/en not_active Expired - Fee Related
- 1989-08-03 EP EP89908989A patent/EP0428578A1/en active Pending
- 1989-08-03 WO PCT/EP1989/000915 patent/WO1990001508A1/en not_active Application Discontinuation
- 1989-08-03 KR KR1019900700738A patent/KR900701883A/en not_active Application Discontinuation
- 1989-08-03 ES ES198989114337T patent/ES2037352T3/en not_active Expired - Lifetime
- 1989-08-08 PT PT91404A patent/PT91404B/en not_active IP Right Cessation
- 1989-08-10 CA CA000607989A patent/CA1339656C/en not_active Expired - Fee Related
- 1989-08-10 CN CN89105528A patent/CN1040386A/en active Pending
- 1989-08-11 ZA ZA896159A patent/ZA896159B/en unknown
- 1989-08-11 IE IE258889A patent/IE63014B1/en not_active IP Right Cessation
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1990
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1991
- 1991-02-06 NO NO910460A patent/NO173703C/en unknown
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1992
- 1992-07-24 GR GR920401594T patent/GR3005265T3/el unknown
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- 1994-01-06 HK HK17/94A patent/HK1794A/en not_active IP Right Cessation
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CN1040386A (en) | 1990-03-14 |
JP2892409B2 (en) | 1999-05-17 |
NO910460L (en) | 1991-02-06 |
HK1794A (en) | 1994-01-14 |
ATE76415T1 (en) | 1992-06-15 |
EP0354471B1 (en) | 1992-05-20 |
DE58901469D1 (en) | 1992-06-25 |
ZA896159B (en) | 1990-07-25 |
NO910460D0 (en) | 1991-02-06 |
BR8907594A (en) | 1991-07-30 |
DK305190A (en) | 1990-12-21 |
ES2037352T3 (en) | 1993-06-16 |
DK305190D0 (en) | 1990-12-21 |
EP0428578A1 (en) | 1991-05-29 |
WO1990001508A1 (en) | 1990-02-22 |
AU4045589A (en) | 1990-03-05 |
JPH04500083A (en) | 1992-01-09 |
PT91404A (en) | 1990-03-08 |
CA1339656C (en) | 1998-02-03 |
PT91404B (en) | 1995-05-04 |
EP0354471A1 (en) | 1990-02-14 |
GR3005265T3 (en) | 1993-05-24 |
NO173703C (en) | 1994-01-19 |
IE892588L (en) | 1990-02-12 |
KR900701883A (en) | 1990-12-04 |
IE63014B1 (en) | 1995-03-22 |
TR25089A (en) | 1992-09-23 |
DE3827378A1 (en) | 1990-02-22 |
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