JP2004189877A - Aqueous polyurethane resin composition - Google Patents
Aqueous polyurethane resin composition Download PDFInfo
- Publication number
- JP2004189877A JP2004189877A JP2002359336A JP2002359336A JP2004189877A JP 2004189877 A JP2004189877 A JP 2004189877A JP 2002359336 A JP2002359336 A JP 2002359336A JP 2002359336 A JP2002359336 A JP 2002359336A JP 2004189877 A JP2004189877 A JP 2004189877A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- insulating
- resin composition
- polyol
- aqueous polyurethane
- 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.)
- Withdrawn
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 229920005862 polyol Polymers 0.000 claims abstract description 50
- 150000003077 polyols Chemical class 0.000 claims abstract description 48
- -1 benzimidazole compound Chemical class 0.000 claims abstract description 30
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 29
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 239000011630 iodine Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims 1
- 241000233866 Fungi Species 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 18
- 230000000855 fungicidal effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000417 fungicide Substances 0.000 description 12
- 239000011810 insulating material Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000000843 anti-fungal effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 5
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229960003656 ricinoleic acid Drugs 0.000 description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004308 thiabendazole Substances 0.000 description 3
- 229960004546 thiabendazole Drugs 0.000 description 3
- 235000010296 thiabendazole Nutrition 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 235000011187 glycerol Nutrition 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 2
- 229950005308 oxymethurea Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- IDUWIXCWGYJVKL-UHFFFAOYSA-N 2-(aminomethyl)propane-1,3-diol Chemical compound NCC(CO)CO IDUWIXCWGYJVKL-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- QLKDMIUEWFNEPV-UHFFFAOYSA-N 4,5,6,7-Tetrachloro-2-trifluoromethylbenzimidazole Chemical compound ClC1=C(Cl)C(Cl)=C2NC(C(F)(F)F)=NC2=C1Cl QLKDMIUEWFNEPV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010052143 Ocular discomfort Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UFAPLAOEQMMKJA-UHFFFAOYSA-N hexane-1,2,5-triol Chemical compound CC(O)CCC(O)CO UFAPLAOEQMMKJA-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- VLHZUYUOEGBBJB-UHFFFAOYSA-N hydroxy stearic acid Natural products OCCCCCCCCCCCCCCCCCC(O)=O VLHZUYUOEGBBJB-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物に関する。
【０００２】
【従来の技術】
一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物は、ポリウレタン樹脂の原料であるポリオールとポリイソシアネートとを適宜選択することにより、低硬度のゴム状弾性体から架橋密度の高い硬質樹脂まで、幅広い硬度を有する絶縁性硬化物を提供できる。また、人体に有害で、飛散し易いために作業環境を汚染しやすく、しかも火災や爆発の危険性もある有機溶剤を殆ど含有していないので取扱い易い。そのため、種々の電気・電子部品の絶縁材料として幅広く用いられている。例えば、プリントサーキットボードは、プラスチック板等の基板の上に銅等の導体により電気回路が形成されているものであるが、衝撃及び周辺に存在する水分やごみ等から電気回路を保護するために、一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物によって封止されている。（例えば、特許文献１参照）
【０００３】
【特許文献１】
特開昭６２−２３０８６５号公報（請求項１、第５頁、左下段、第５〜１２行）
【０００４】
【発明が解決しようとする課題】
ところが、このような構造をもつプリントサーキットボードは、電気回路が絶縁性硬化物中に閉じ込められているため電気回路から発生する熱が外に逃げられず、その熱によって電気回路を保護している絶縁性硬化物の硬度等の物性が変化する問題がある。また、高温多湿下で使用される場合にも、前記絶縁性硬化物が熱と水分とで加水分解されることによって絶縁性硬化物の硬度等の物性がより変化することになるという問題もある。絶縁性硬化物の硬度は、電気回路を衝撃から有効に保護するように調整されているので、該硬度が変化すると電気回路を衝撃から有効に保護できなくなる。更に、高温多湿下の使用においては、絶縁性硬化物の表面に付着した黴が成長し、見た目の不快感ばかりでなく衛生上も問題となり、さらに絶縁性硬化物の物性変化の原因にもなる。従って絶縁性硬化物は優れた耐熱性（高温下に曝されても硬度等の物性が変化し難いこと）、耐湿熱性（高温多湿下に曝されても硬度等の物性が変化し難いこと）及び防黴性（黴が成長し難いこと）をもつことが要求される。硬化物がこのような物性をもつことはプリントサーキットボードの分野に限らず、絶縁性ポリウレタン樹脂が使用される種々の分野においても要望されるところである。
【０００５】
本発明は、上記要望に鑑み、取扱いが容易で、かつ耐熱性、耐湿熱性及び防黴性に優れた絶縁性硬化物を与える水系ポリウレタン樹脂組成物を提供することを課題とする。
【０００６】
【課題を解決するための手段】
本発明者らは、前記課題に鑑み、鋭意研究した結果、一液型絶縁性ポリウレタン樹脂を造るポリオールの酸素含有率を２０重量％以下に、かつヨウ素価を１５５ｍｇＫＯＨ／ｇ以下に調整すると、耐熱性及び耐湿熱性に優れた絶縁性硬化物を提供することができ、かつ該一液型絶縁性ポリウレタン樹脂の防黴剤としてベンゾイミダゾール化合物を用いると、優れた耐熱性及び耐湿熱性を損なうことなく、防黴性にも優れた絶縁性硬化物を提供することができることを見出し、本発明を完成した。
【０００７】
即ち本発明の水系ポリウレタン樹脂組成物は、酸素含有率が２０重量％以下及びヨウ素価が１５５ｍｇＫＯＨ／ｇ以下のポリオールとポリイソシアネートとを反応させて得られる一液型絶縁性ポリウレタン樹脂と、ベンゾイミダゾール化合物とを含有することを特徴とする。
【０００８】
本発明の水系ポリウレタン樹脂組成物に含有されている一液型絶縁性ポリウレタン樹脂は、酸素含有率が２０重量％以下及びヨウ素価が１５５ｍｇＫＯＨ／ｇ以下のポリオールとポリイソシアネートとの反応物であるので、耐熱性及び耐湿熱性に優れた絶縁性硬化物を提供できる。又、本発明の水系ポリウレタン樹脂組成物は、ベンゾイミダゾール化合物を含有するので、優れた耐熱性及び耐湿熱性を損なうことなく、防黴性にも優れた絶縁性硬化物を提供することができる。更に、本発明の水系ポリウレタン樹脂組成物は、水系であるので、人体に有害で、飛散し易いために作業環境を汚染しやすく、しかも火災や爆発の危険性もある有機溶剤を殆ど含有していないため、取扱い易い。
【０００９】
本発明によれば、ベンゾイミダゾール化合物が、一液型絶縁性ポリウレタン樹脂に対して０．０１〜２重量％含有されているのが好ましい。
ベンゾイミダゾール化合物の含有率がこの範囲であると、特に優れた耐熱性、耐湿熱性及び防黴性を有する絶縁性硬化物を提供できる。
【００１０】
又、本発明によれば、電気又は電子部品、とりわけプリントサーキットボード、温度センサーの絶縁用、及びフィルムコンデンサの下塗り塗料として用いられる前記水系ポリウレタン樹脂組成物が提供される。
【００１１】
【発明の実施の形態】
本発明の水系ポリウレタン樹脂組成物は、水分散体であってもよく、又ポリウレタン樹脂が水に可溶化していてもよい。
本発明で使用される一液型絶縁性ポリウレタン樹脂を造るポリオールの酸素含有率は２０重量％以下で、ヨウ素価は１５５ｍｇＫＯＨ／ｇ以下である。ポリオールの酸素含有率が２０重量％を超えると、得られる絶縁性硬化物の耐湿熱性が劣り、高温多湿状態で硬度が大きく減少してしまう。又、ヨウ素価が１５５ｍｇＫＯＨ／ｇを超えると、絶縁性硬化物の耐熱性が劣り、高温下で硬くもろくなる。
ポリオールの酸素含有率は、好ましくは１〜１５重量％である。酸素含有率がこの範囲であると絶縁性硬化物の耐湿熱性が特によくなる。
又、ヨウ素価は、好ましくは１〜１２０ｍｇＫＯＨ／ｇである。ヨウ素価がこの範囲であると絶縁性硬化物の耐熱性が特によくなる。
ここで酸素含有率（重量％）は
【００１２】
【式１】
で計算される。
又、ヨウ素価（ｍｇＫＯＨ／ｇ）は、ＪＩＳ Ｋ ３３３１−１９９５に従って測定される。
【００１４】
本発明で使用される一液型絶縁性ポリウレタン樹脂はポリオールとポリイソシアネートとから製造される。本発明において絶縁性ポリウレタン樹脂とは、２５±５℃、６５±５％ＲＨで測定した体積固有抵抗値（Ω・ｃｍ）が、１０１０Ω・ｃｍ以上の硬化物を得ることができるものを言う。
さらに誘電率が６以下（１ＭＨｚ）、絶縁破壊電圧が１５ＫＶ／ｍｍ以上が好ましい。
絶縁性ポリウレタン樹脂は、ポリオールの酸素含有率、溶出イオン濃度あるいは溶出イオンの種類の数等を調整することによって、得られる絶縁性硬化物の体積固有抵抗値を、１０１０Ω・ｃｍ以上、好ましくは１０１１Ω・ｃｍ以上に調整して得ることができる。特に体積固有抵抗値が１０１１Ω・ｃｍ以上であると、硬化物の絶縁性が良好に保持され、例えばフィルムコンデンサの絶縁材料、電子部品の封止剤等として好適に使用できる。
体積固有抵抗値の測定は、ＪＩＳ Ｃ ２１０５に従って行う。具体的には、東亜電波工業社製ＳＥ−１０Ｅを用い、２５±５℃、６５±５％ＲＨで、サンプル（厚さ：３ｍｍ）に５００Ｖの測定電圧を印加し、６０秒後の数値を測定する。
【００１５】
本発明において、一液型絶縁性ポリウレタン樹脂としては、得られる硬化物が絶縁性を示す限り、ポリオールとして、ポリエステルポリオールを用いたポリエステル系樹脂、ポリエーテルポリオールを用いたポリエーテル系樹脂、その他のポリオールを用いた樹脂、これらの混合物を用いた樹脂のいずれも使用できる。
【００１６】
ポリエステルポリオールは、脂肪酸とポリオールとの反応物であり、該脂肪酸としては、例えば、リシノール酸、オキシカプロン酸、オキシカプリン酸、オキシウンデカン酸、オキシリノール酸、オキシステアリン酸、オキシヘキサンデセン酸のヒドロキシ含有長鎖脂肪酸等が挙げられる。
脂肪酸と反応するポリオールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール及びジエチレングリコール等のグリコール、グリセリン、トリメチロールプロパン及びトリエタノールアミン等の３官能ポリオール、ジグリセリン及びペンタエリスリトール等の４官能ポリオール、ソルビトール等の６官能ポリオール、シュガー等の８官能ポリオール、これらのポリオールに相当するアルキレンオキサイドと脂肪族、脂環族、芳香族アミンとの付加重合物や、該アルキレンオキサイドとポリアミドポリアミンとの付加重合物等が挙げられる。
【００１７】
なかでも、リシノール酸グリセライド、リシノール酸と１，１，１−トリメチロールプロパンとのポリエステルポリオール等が好ましい。
【００１８】
ポリエーテルポリオールとしては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、４，４’−ジヒドロキシフェニルプロパン、４，４’−ジヒドロキシフェニルメタン等の２価アルコールあるいはグリセリン、１，１，１−トリメチロールプロパン、１，２，５−ヘキサントリオール、ペンタエリスリトール等の３価以上の多価アルコールと、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、α−オレフィンオキサイド等のアルキレンオキサイドとの付加重合物等が挙げられる。
【００１９】
その他のポリオールとして、主鎖が炭素−炭素よりなるポリオール、例えば、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール、水素添加ポリブタジエンポリオール、ＡＮ（アクリロニトリル）やＳＭ（スチレンモノマー）を前記した炭素−炭素ポリオールにグラフト重合したポリオール、ポリカーボネートポリオール、ＰＴＭＧ（ポリテトラメチレングリコール）等が挙げられる。
【００２０】
ポリイソシアネートとしては、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等が使用できる。
芳香族ポリイソシアネートとしては、例えば、ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリメチレンポリフェニレンポリイソシアネート（粗ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、ポリトリレンポリイソシアネート（粗ＴＤＩ）、キシレンジイソシアネート（ＸＤＩ）、ナフタレンジイソシアネート（ＮＤＩ）等が挙げられる。脂肪族ポリイソシアネートとしては、ヘキサメチレンジイソシアネート（ＨＤＩ）等が挙げられる。脂環式ポリイソシアネートとしては、イソホロンジイソシアネート（ＩＰＤＩ）等が挙げられる。この他に、上記ポリイソシアネートをカルボジイミドで変性したポリイソシアネート（カルボジイミド変性ポリイソシアネート）、イソシアヌレート変性ポリイソシアネート、ウレタンプレポリマー（例えばポリオールと過剰のポリイソシアネートとの反応生成物であってイソシアネート基を分子末端にもつもの）等も使用できる。これらは単独あるいは混合物として使用してもよい。
これらの中でも、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、カルボジイミド変性ポリイソシアネートが好ましい。
【００２１】
本発明の水系ポリウレタン樹脂組成物の製造方法としては、ポリオールとポリイソシアネートとから得られる絶縁性ウレタンプレポリマーを水中に分散させて、得られた水分散体に鎖延長剤を加えて、水系ポリウレタン樹脂組成物を得る方法（以下（ａ）法という）、絶縁性ウレタンプレポリマーの有機溶剤溶液に鎖延長剤加えて一液型絶縁性ポリウレタン樹脂を含有する有機溶剤溶液を得、該有機溶剤溶液に水を加えて水に分散させ、得られた水系組成物から有機溶剤を分離する方法（以下（ｂ）法という）等がある。
【００２２】
（ａ）法として、具体的には以下の方法が例示される。
（１）ポリオール、ポリイソシアネート、及びＮＣＯ基反応性の活性水素及び下記する塩形成剤と反応して塩を形成する基（塩形成基）を含有する化合物とから塩形成基を含有する絶縁性ウレタンプレポリマーを得、該絶縁性塩形成基含有ウレタンプレポリマーを前記塩形成基と反応して塩を形成する塩形成剤を使用して水中に分散させ、得られた水系組成物に鎖延長剤を加えて前記絶縁性ウレタンプレポリマーと反応させて一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物を得る。
塩形成基を含有する化合物として、（ｉ）グリコール酸、アミノカルボン酸、ヒドロキシ酸、ヒドロキシルスルホン酸等の塩形成性のカルボン酸又はスルホン酸基を有する化合物、（ｉｉ）アミノアルコール類やアミン類等の酸で中和可能な第４級又は第３級基になり得る基を有する化合物、（ｉｉｉ）２−クロロエタノール、２−ブロモメタノール等の第４級化反応を起こすハロゲン原子又は相当する強酸のエステルを含有する化合物等が挙げられる。
該塩形成基と反応して塩を形成する塩形成剤としては、化合物（ｉ）に対応する塩形成剤として、例えば、水酸化ナトリウム、水酸化カルシウム等の金属水酸化物、アンモニア、第３級アミン化合物、化合物（ｉｉ）に対応する塩形成剤として、例えば、塩酸、硝酸、酢酸、メチルクロライド等の無機及び有機酸類、反応性ハロゲン原子を有する化合物等、化合物（ｉｉｉ）に対応する塩形成剤として、例えば、第３級アミン、スルフィド類、フォスフィン類等が挙げられる。
【００２３】
（２）ポリオール、ポリイソシアネート及びメタノールやエタノール等のモノアルコール又は多価アルコールのエチレンオキサイド、該エチレンオキサイドとプロピレンオキサイドとの付加物等とから親水性基を含む絶縁性ウレタンプレポリマーを得、該絶縁性ウレタンプレポリマーを水中に分散させ、得られた水系組成物に鎖延長剤を加えて前記絶縁性ウレタンプレポリマーと反応させて一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物を得る。
【００２４】
（３）ポリオールとポリイソシアネートとから絶縁性ウレタンプレポリマーを得、該絶縁性ウレタンプレポリマーをアニオン性、非イオン性、カチオン性、両性界面活性剤を使用して水中に強制的に分散させ、得られた水分散体に鎖延長剤を加えて前記絶縁性ウレタンプレポリマーと反応させて一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物を得る。
界面活性剤として、例えば、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル等の非イオン界面活性剤、アルキルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテルサルフェートアンモニウム又はナトリウム、高級アルコール硫酸エステルナトリウム塩等のアニオン性界面活性剤等が挙げられる。
【００２５】
（４）工程（１）で得られる塩形成基含有絶縁性ウレタンプレポリマーを工程（１）で使用される塩形成剤と工程（３）で使用される界面活性剤とを使用して水中に分散させ、得られた水系組成物に鎖延長剤を加えて前記絶縁性ウレタンプレポリマーと反応させて一液型絶縁性ポリウレタン樹脂を含有する水系ポリウレタン樹脂組成物を得る。
【００２６】
鎖延長剤として、ジメチロールプロピオン酸、トリメチロールメラミンおよびその誘導体、ジメチロールウレア及びその誘導体、ジメチロールエチルアミン、ジエタノールメチルアミン、ジプロパノールエチルアミン、ジブタノールメチルアミン、エチレンジアミン、プロピレンジアミン、ジエチレントリアミン、ヘキシレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イソホロンジアミン、キシリレンジアミン、ジフェニルメタンジアミン、水素添加ジフェニルメタンジアミン、ヒドラジン等の多価アミン化合物、ポリアミドポリアミン、ポリエチレンポリイミン等が挙げられる。
【００２７】
ポリイソシアネート、ポリオール及び鎖延長剤の配合量は、目的とする絶縁性硬化物の硬度等の物性によって適宜決められるが、通常、ポリオール及び鎖延長剤の活性水素の合計に対して、ポリイソシアネートのイソシアネート基が１．４〜２．２倍当量、好ましくは１．６〜２．０倍当量である。
【００２８】
本発明の水系ポリウレタン樹脂組成物中の一液型絶縁性ポリウレタン樹脂含有率は特に限定されないが、通常５〜６５重量％が好ましく、更に好ましくは２０〜５５重量％である。該絶縁性ポリウレタン樹脂の含有率が５〜６５重量％であれば、一液型絶縁性ポリウレタン樹脂が水中に可溶化あるいは安定に分散している。
【００２９】
本発明の水系ポリウレタン樹脂組成物に含有されるベンゾイミダゾール化合物の具体例としては、４，５，６，７−テトラクロル−２−トリフルオロメチルベンゾイミダゾール、１−（ブチルカルバモイル）−２−ベンゾイミダゾールカルバミン酸メチル、２−メトキシカルボニルアミノベンゾイミダゾール、２−（４−チアゾリル）−ベンゾイミダゾール、２−メトキシカルボニルアミノベンゾイミダゾール等が挙げられる。
水系ポリウレタン樹脂組成物中のベンゾイミダゾール化合物の含有量は、特に限定されないが、一液型絶縁性ポリウレタン樹脂に対して０．０１〜２重量％が好ましく、０．１〜１重量％が更に好ましい。
【００３０】
本発明の水系ポリウレタン樹脂組成物には本発明の効果を阻害しない範囲内で、充填剤、難燃剤、消泡剤、防菌剤、安定剤、可塑剤、増粘剤、防錆剤、他の水系分散樹脂等の添加剤を含むことができる。
【００３１】
本発明の水系ポリウレタン樹脂組成物は、電気洗濯機、便座、湯沸し器、浄水器、風呂、食器洗浄機等のスイッチ部や電動工具等に使用されている電子、電気部品に含まれる電気・電子回路を水分、湿気から保護するために該回路を封止する封止剤、電気、電子機器のシーリング剤やコーティング剤、及びコンデンサー、コンバーター、トランス、電線、コイル、電装品（自動車の電子部品）の絶縁材料等として好適に使用される。
特にプリントサーキットボードや温度センサーの絶縁材料として用いた場合、得られた絶縁性硬化物は優れた耐熱性、耐湿熱性及び防黴性をもっているので、プリントサーキットボードや温度センサーの電気回路が高温になっても、あるいは該ボードや温度センサーを水廻り製品等の高温多湿の条件下で長時間使用しても、該プリントサーキットボードや温度センサーを封止している絶縁性硬化物は適切な硬さ、絶縁性などの電気特性を保つことができ、かつ黴が付着して成長することも殆どない。
【００３２】
【実施例】
以下、本発明を実施例に基づいてさらに詳しく説明する。ただし本発明はこれらの実施例に限定されるものではない。
【００３３】
実施例１
ポリオールとして、１，２−ポリブタジエンポリオール（ポリオールＡ、水酸基価：４５ｍｇＫＯＨ／ｇ）と、リシノール酸とトリメチロールプロパンとを反応させて得たポリエステルポリオール（ポリオールＢ、水酸基価：３７ｍｇＫＯＨ／ｇ）との混合物（ポリオールＡ：ポリオールＢ＝８０：２０（重量比））を、ポリイソシアネートとしてナフチレンジイソシアネートを使用し、これらを１：２（ポリオール：ポリイソシアネートの当量比）で９０℃１時間反応させ、ＮＣＯ基を末端に含む絶縁性ウレタンプレポリマーを得た。これをメチルエチルケトン（ＭＥＫ）とトルエン（１：１重量比）との混合溶媒に溶解し、絶縁性ウレタンプレポリマーを５０重量％含む溶液を得た。得られた絶縁性ウレタンプレポリマー溶液に、鎖延長剤としてジメチロールウレアを得られた末端ＮＣＯ基を含む絶縁性ウレタンプレポリマー２当量に対して１当量添加、混合して６０℃で１時間反応させ、一液型絶縁性ポリウレタン樹脂を含有する溶液を得た。イオン交換水を、得られた絶縁性ポリウレタン樹脂含有溶液に対し１倍量添加し、該溶液を水に分散させた。次いで冷却分離器付真空脱溶剤機で水分散体の脱ＭＥＫ／トルエンを８０℃、３トールで２時間行い、次いで、防黴剤として２−（４−チアゾリル）−ベンゾイミダゾール（チアベンダゾール）を、一液型絶縁性ポリウレタン樹脂に対して０．００５重量％加え、一液型絶縁性ポリウレタン樹脂を５３重量％含む水系ポリウレタン樹脂組成物を得た。
【００３４】
得られた水系ポリウレタン樹脂組成物をテフロン（登録商標）容器に流し、２５℃６５％ＲＨで２４時間放置し、次いで８０℃２４時間乾燥して、サンプルを得た。
得られたサンプルについて、下記する熱処理及び湿熱処理を行い、これらの処理前後の体積固有抵抗値、硬度及び重量を測定した。また、防黴試験を行った。
【００３５】
熱処理
ヤマト科学（株）製のＤＮ−６２恒温槽中に得られたサンプルを１５０℃で２４時間放置する。
湿熱処理
株式会社平山製作所製プレッシャークッカー ＰＣ−２４２ＨＳ−Ａ中で得られたサンプルを１２１℃、１００％ＲＨ、２気圧の条件下で２４時間放置する。
【００３６】
体積固有抵抗値（Ω・ｃｍ）の測定
東亜電波工業社製ＳＥ−１０Ｅを用い、２５±５℃、６５±５％ＲＨで、サンプル（５０ｍｍ×５０ｍｍ、厚さ：３ｍｍ）に５００Ｖの測定電圧を印加し、６０秒後の数値を測定する。
【００３７】
硬度の測定
サンプル（５０ｍｍ×５０ｍｍ、厚さ：３ｍｍ）を２枚重ねて（厚さ：６ｍｍ）、硬度をＪＩＳ Ｋ ６２５３に従って測定する。硬度計は高分子計器株式会社アスカーＡ型を用いる。
【００３８】
防黴試験
サンプル（５０ｍｍ×５０ｍｍ、厚さ：１ｍｍ）を、ＪＩＳ Ｚ ２９１１に準じて、２８℃、８５％ＲＨの雰囲気下に２８日間放置した後、サンプルの表面積（２５０ｍｍ２）に対する黴付着面積の割合を計算する。
（評価）
◎：３％未満
○：３％以上１５％未満
△：１５％以上３０％未満
×：３０％以上
【００３９】
結果を表１に示す。硬度および重量については処理前の値（初期値）に対する低下率として示す。表１中、ＶＲは体積固有抵抗値を、ＷＴは初期値に対する重量の減少率を、ＨＡは初期値に対する硬さの減少率を示す。
【００４０】
実施例２〜５
チアベンダゾールの量を表１に示す量に代えた以外は、実施例１と同様にして、水系ポリウレタン樹脂組成物を得た。
得られた水系ポリウレタン樹脂組成物から、実施例１に準じて、サンプルを得た。実施例１と同様にして、得られたサンプルの熱処理及び湿熱処理前後の体積固有抵抗値、硬度及び重量を測定し、又、防黴試験を行った。結果を表１に示す。
【００４１】
比較例１
実施例１と同様にして一液型絶縁性ポリウレタン樹脂を水分散体として得た後、防黴剤を添加しなかった。
得られた水分散体から、実施例１に準じてサンプルを得た。実施例１と同様にして、得られたサンプルの熱処理及び湿熱処理前後の体積固有抵抗値、硬度及び重量を測定し、又、防黴試験を行った。結果を表１に示す。
【００４２】
比較例２
防黴剤として、チアベンダゾールの代わりに、１，２−ベンゾイソチアゾロン−３−オンアルカリ塩を使用した以外は実施例４と同様にして、水系ポリウレタン樹脂組成物を得た。
得られた水系ポリウレタン樹脂組成物から、実施例１に準じて、サンプルを得た。実施例１と同様にして、得られたサンプルの熱処理及び湿熱処理前後の体積固有抵抗値、硬度及び重量を測定し、又、防黴試験を行った。結果を表１に示す。
【００４３】
比較例３
ヨウ素価が１９０ｍｇＫＯＨ／ｇ、酸素含有率が１．５であるポリオールを使用した以外は実施例３と同様にして、水系ポリウレタン樹脂組成物を得た。
得られた水系ポリウレタン樹脂組成物から、実施例１に準じて、サンプルを得た。実施例１と同様にして、得られたサンプルの熱処理及び湿熱処理前後の体積固有抵抗値、硬度及び重量を測定し、又防黴試験を行った。結果を表１に示す。
【００４４】
比較例４
酸素含有率が２７％、ヨウ素価が１ｍｇＫＯＨ／ｇであるポリオールを使用した以外は実施例３と同様にして、水系ポリウレタン樹脂組成物を得た。
得られた水系ポリウレタン樹脂組成物から、実施例１に準じて、サンプルを得た。実施例１と同様にして、得られたサンプルの熱処理及び湿熱処理前後の体積固有抵抗値、硬度及び重量を測定し、又、防黴試験を行った。結果を表１に示す。
【００４５】
【表１】
表１から明らかなように、防黴剤を含まない比較例１の一液型絶縁性ポリウレタン樹脂の水分散体から得たサンプルは、防黴性に劣り、ベンゾイミダゾール化合物以外の防黴剤を含む比較例２の水系ポリウレタン樹脂組成物から得たサンプルは、耐熱性に劣るばかりでなく防黴性にも劣り、ヨウ素価が１９０ｍｇＫＯＨ／ｇのポリオールを使用した比較例３の水系ポリウレタン樹脂組成物から得たサンプルは、耐熱性に劣り、酸素含有率が２７重量％のポリオールを使用した比較例４の水系ポリウレタン樹脂組成物から得たサンプルは、耐湿熱性に劣っていた。一方、酸素含有率が２０重量％以下及びヨウ素価が１５５ｍｇＫＯＨ／ｇ以下のポリオールを使用して得た一液型絶縁性ポリウレタン樹脂と、ベンゾイミダゾールを含有する実施例１〜５の水系ポリウレタン樹脂組成物から得たサンプルは、いづれも、耐熱性、耐湿熱性及び防黴性の全てに優れていた。
【００４７】
【発明の効果】
本発明の水系ポリウレタン樹脂組成物は、耐熱性、耐湿熱性及び防黴性に優れた絶縁性硬化物を提供し、かつ取扱い易いという効果を奏する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aqueous polyurethane resin composition containing a one-pack type insulating polyurethane resin.
[0002]
[Prior art]
The aqueous polyurethane resin composition containing the one-pack type insulating polyurethane resin can be selected from a polyol and a polyisocyanate, which are raw materials of the polyurethane resin, from a rubber-like elastic material having a low hardness to a hard resin having a high crosslinking density. And an insulating cured material having a wide range of hardness can be provided. Further, it is harmful to the human body, easily scattered, easily pollutes the working environment, and is easy to handle because it contains almost no organic solvent that may cause fire or explosion. Therefore, it is widely used as an insulating material for various electric and electronic parts. For example, in a printed circuit board, an electric circuit is formed by a conductor such as copper on a substrate such as a plastic plate, but in order to protect the electric circuit from shock and moisture or dust existing in the vicinity. And sealed with an aqueous polyurethane resin composition containing a one-component insulating polyurethane resin. (For example, see Patent Document 1)
[0003]
[Patent Document 1]
JP-A-62-230865 (Claim 1, page 5, lower left column, lines 5 to 12)
[0004]
[Problems to be solved by the invention]
However, in a printed circuit board having such a structure, heat generated from the electric circuit cannot escape to the outside because the electric circuit is confined in the insulating cured material, and the heat protects the electric circuit. There is a problem that physical properties such as hardness of the insulating cured product change. Further, even when used under high temperature and high humidity, there is a problem that physical properties such as hardness of the cured insulating material are further changed by hydrolysis of the cured insulating material with heat and moisture. . Since the hardness of the insulating cured product is adjusted so as to effectively protect the electric circuit from impact, if the hardness changes, the electric circuit cannot be effectively protected from impact. Furthermore, when used under high temperature and high humidity, molds adhered to the surface of the cured insulating material grow, causing not only visual discomfort but also hygiene problems, and further causing physical property changes of the cured insulating material. . Therefore, the cured insulating material has excellent heat resistance (the physical properties such as hardness are hardly changed even when exposed to high temperature), and moist heat resistance (the physical properties such as hardness are hard to change even when exposed to high temperature and high humidity). And it is required to have fungicidal properties (the mold is difficult to grow). The fact that the cured product has such physical properties is not limited to the field of printed circuit boards, but is demanded in various fields where insulating polyurethane resins are used.
[0005]
In view of the above demand, an object of the present invention is to provide an aqueous polyurethane resin composition which is easy to handle and provides an insulating cured product excellent in heat resistance, moisture heat resistance and mold resistance.
[0006]
[Means for Solving the Problems]
In view of the above problems, the inventors of the present invention have conducted intensive studies and found that when the oxygen content of the polyol for forming the one-component insulating polyurethane resin was adjusted to 20% by weight or less and the iodine value was adjusted to 155 mgKOH / g or less, the heat resistance was lowered. When a benzimidazole compound is used as a fungicide for the one-pack type insulating polyurethane resin, it is possible to provide an insulating cured product excellent in heat resistance and wet heat resistance without impairing excellent heat resistance and wet heat resistance. The present inventors have found that it is possible to provide an insulative cured product having excellent antifungal properties and have completed the present invention.
[0007]
That is, the aqueous polyurethane resin composition of the present invention comprises a one-pack insulating polyurethane resin obtained by reacting a polyol having an oxygen content of 20% by weight or less and an iodine value of 155 mg KOH / g or less with a polyisocyanate, and benzimidazole And a compound.
[0008]
The one-pack insulating polyurethane resin contained in the aqueous polyurethane resin composition of the present invention is a reaction product of a polyol having an oxygen content of 20% by weight or less and an iodine value of 155 mgKOH / g or less and a polyisocyanate. In addition, it is possible to provide an insulating cured product having excellent heat resistance and heat and humidity resistance. Further, since the water-based polyurethane resin composition of the present invention contains a benzimidazole compound, it is possible to provide an insulating cured product excellent in antifungal properties without impairing excellent heat resistance and wet heat resistance. Furthermore, since the water-based polyurethane resin composition of the present invention is water-based, it is harmful to the human body, easily scatters, easily pollutes the working environment, and almost contains an organic solvent that may cause fire or explosion. Not easy to handle.
[0009]
According to the present invention, it is preferable that the benzimidazole compound is contained in an amount of 0.01 to 2% by weight based on the one-pack type insulating polyurethane resin.
When the content of the benzimidazole compound is in this range, it is possible to provide an insulating cured product having particularly excellent heat resistance, moist heat resistance, and mold resistance.
[0010]
Further, according to the present invention, there is provided the water-based polyurethane resin composition for use in insulating electric or electronic components, especially printed circuit boards and temperature sensors, and used as an undercoat for film capacitors.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The aqueous polyurethane resin composition of the present invention may be an aqueous dispersion, or the polyurethane resin may be solubilized in water.
The oxygen content of the polyol for forming the one-component insulating polyurethane resin used in the present invention is 20% by weight or less, and the iodine value is 155 mgKOH / g or less. If the oxygen content of the polyol exceeds 20% by weight, the resulting insulating cured product will have poor moisture and heat resistance, and its hardness will be greatly reduced in a high temperature and high humidity state. On the other hand, when the iodine value exceeds 155 mgKOH / g, the heat resistance of the cured insulating material is poor, and the insulating cured product becomes hard and brittle at high temperatures.
The oxygen content of the polyol is preferably 1 to 15% by weight. When the oxygen content is within this range, the heat and moisture resistance of the cured insulating material is particularly improved.
Further, the iodine value is preferably 1 to 120 mgKOH / g. When the iodine value is in this range, the heat resistance of the insulating cured product is particularly improved.
Here, the oxygen content (% by weight) is
(Equation 1)
Is calculated.
Further, the iodine value (mgKOH / g) is measured according to JIS K3331-1995 .
[0014]
The one-component insulating polyurethane resin used in the present invention is produced from a polyol and a polyisocyanate. In the present invention, the term "insulating polyurethane resin" refers to a resin capable of obtaining a cured product having a volume resistivity (Ω · cm) of 10 10 Ω · cm or more measured at 25 ± 5 ° C. and 65 ± 5% RH. To tell.
Further, the dielectric constant is preferably 6 or less (1 MHz), and the dielectric breakdown voltage is preferably 15 KV / mm or more.
The insulating polyurethane resin has a volume specific resistance of 10 10 Ω · cm or more, preferably at least 10 10 Ω · cm, by adjusting the oxygen content of the polyol, the number of types of eluted ions or the number of eluted ions, and the like. Can be obtained by adjusting to 10 11 Ω · cm or more. In particular, when the volume specific resistance value is 10 11 Ω · cm or more, the insulating property of the cured product is well maintained, and it can be suitably used as, for example, an insulating material for a film capacitor, a sealant for an electronic component, and the like.
The measurement of the volume specific resistance is performed according to JIS C 2105. Specifically, a measurement voltage of 500 V was applied to the sample (thickness: 3 mm) at 25 ± 5 ° C. and 65 ± 5% RH using SE-10E manufactured by Toa Denpa Kogyo Co., Ltd. Measure.
[0015]
In the present invention, as the one-pack type insulating polyurethane resin, as long as the obtained cured product shows insulating properties, as the polyol, a polyester-based resin using a polyester polyol, a polyether-based resin using a polyether polyol, and other Either a resin using a polyol or a resin using a mixture thereof can be used.
[0016]
Polyester polyol is a reaction product of a fatty acid and a polyol. Examples of the fatty acid include ricinoleic acid, oxycaproic acid, oxycapric acid, oxyundecanoic acid, oxylinoleic acid, oxystearic acid, and hydroxy of oxyhexanedecenoic acid. Containing long-chain fatty acids and the like.
Examples of polyols that react with fatty acids include glycols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and diethylene glycol, trifunctional polyols such as glycerin, trimethylolpropane and triethanolamine, and tetrafunctional polyols such as diglycerin and pentaerythritol. Hexafunctional polyols such as polyols and sorbitol, octafunctional polyols such as sugar, addition polymers of alkylene oxides corresponding to these polyols with aliphatic, alicyclic, and aromatic amines, and of the alkylene oxides and polyamide polyamines Addition polymers and the like can be mentioned.
[0017]
Of these, ricinoleic acid glyceride, polyester polyol of ricinoleic acid and 1,1,1-trimethylolpropane, and the like are preferable.
[0018]
Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane, and 4,4′-dihydroxyphenylmethane. Or a trihydric or higher alcohol such as glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, pentaerythritol and ethylene oxide, propylene oxide, butylene oxide, α- An addition polymer with an alkylene oxide such as an olefin oxide is exemplified.
[0019]
As other polyols, polyols having a main chain of carbon-carbon, such as acrylic polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, AN (acrylonitrile) and SM (styrene monomer) may be used as the above-mentioned carbon-carbon polyol. Examples include graft-polymerized polyol, polycarbonate polyol, PTMG (polytetramethylene glycol), and the like.
[0020]
As the polyisocyanate, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be used.
Examples of the aromatic polyisocyanate include diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), tolylene diisocyanate (TDI), polytolylene polyisocyanate (crude TDI), xylene diisocyanate (XDI), and naphthalene diisocyanate (NDI) and the like. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI). Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI). In addition, polyisocyanates obtained by modifying the above polyisocyanates with carbodiimides (carbodiimide-modified polyisocyanates), isocyanurate-modified polyisocyanates, and urethane prepolymers (for example, a reaction product of a polyol and an excess of polyisocyanate, wherein an isocyanate group is Can be used. These may be used alone or as a mixture.
Among these, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and carbodiimide-modified polyisocyanate are preferred.
[0021]
As a method for producing the water-based polyurethane resin composition of the present invention, an insulating urethane prepolymer obtained from a polyol and a polyisocyanate is dispersed in water, and a chain extender is added to the obtained water dispersion. A method for obtaining a resin composition (hereinafter referred to as a method (a)), a method of adding a chain extender to an organic solvent solution of an insulating urethane prepolymer to obtain an organic solvent solution containing a one-pack insulating polyurethane resin, (Hereinafter referred to as a method (b)) in which an organic solvent is separated from the resulting aqueous composition by adding water to the resulting mixture.
[0022]
The following method is specifically exemplified as the method (a).
(1) Insulating properties containing a salt-forming group from a compound containing a polyol, a polyisocyanate, and an NCO group-reactive active hydrogen and a group that forms a salt by reacting with a salt-forming agent described below (salt-forming group) A urethane prepolymer is obtained, the insulating salt-forming group-containing urethane prepolymer is dispersed in water using a salt-forming agent that reacts with the salt-forming group to form a salt, and the obtained aqueous composition is chain-extended. An aqueous polyurethane resin composition containing a one-pack insulating polyurethane resin is obtained by adding an agent and reacting with the insulating urethane prepolymer.
Examples of the compound containing a salt-forming group include (i) compounds having a salt-forming carboxylic acid or sulfonic acid group such as glycolic acid, aminocarboxylic acid, hydroxy acid, and hydroxylsulfonic acid; and (ii) amino alcohols and amines. A compound having a quaternary or tertiary group which can be neutralized with an acid such as (iii) a halogen atom which causes a quaternization reaction such as 2-chloroethanol, 2-bromomethanol or the like; Examples include compounds containing esters of strong acids.
Examples of the salt-forming agent that reacts with the salt-forming group to form a salt include a salt-forming agent corresponding to compound (i), for example, a metal hydroxide such as sodium hydroxide and calcium hydroxide, ammonia, Examples of the salt-forming agent corresponding to the secondary amine compound and the compound (ii) include salts corresponding to the compound (iii) such as inorganic and organic acids such as hydrochloric acid, nitric acid, acetic acid, and methyl chloride, and compounds having a reactive halogen atom. Examples of the forming agent include tertiary amines, sulfides, and phosphines.
[0023]
(2) An insulating urethane prepolymer containing a hydrophilic group is obtained from a polyol, a polyisocyanate, ethylene oxide of a monoalcohol or a polyhydric alcohol such as methanol or ethanol, and an adduct of the ethylene oxide and propylene oxide. Dispersing the insulating urethane prepolymer in water, adding a chain extender to the obtained aqueous composition and reacting with the insulating urethane prepolymer to form an aqueous polyurethane resin composition containing a one-pack insulating polyurethane resin. obtain.
[0024]
(3) an insulating urethane prepolymer is obtained from a polyol and a polyisocyanate, and the insulating urethane prepolymer is forcibly dispersed in water using an anionic, nonionic, cationic, or amphoteric surfactant; A chain extender is added to the obtained aqueous dispersion and reacted with the insulating urethane prepolymer to obtain an aqueous polyurethane resin composition containing a one-pack insulating polyurethane resin.
As surfactants, for example, nonionic surfactants such as polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate Examples include anionic surfactants such as ammonium or sodium, and higher alcohol sulfate sodium salt.
[0025]
(4) Using the salt-forming group-containing insulating urethane prepolymer obtained in step (1) in water using the salt-forming agent used in step (1) and the surfactant used in step (3). The dispersion is added, and a chain extender is added to the obtained aqueous composition to react with the insulating urethane prepolymer to obtain an aqueous polyurethane resin composition containing a one-pack insulating polyurethane resin.
[0026]
As chain extenders, dimethylolpropionic acid, trimethylolmelamine and its derivatives, dimethylolurea and its derivatives, dimethylolethylamine, diethanolmethylamine, dipropanolethylamine, dibutanolmethylamine, ethylenediamine, propylenediamine, diethylenetriamine, hexylene Examples thereof include polyamine compounds such as diamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, xylylenediamine, diphenylmethanediamine, hydrogenated diphenylmethanediamine, and hydrazine; polyamidepolyamine; and polyethylenepolyimine.
[0027]
The amount of the polyisocyanate, the polyol and the chain extender is appropriately determined depending on the physical properties such as the hardness of the intended insulating cured product. The isocyanate group is 1.4 to 2.2 times equivalent, preferably 1.6 to 2.0 times equivalent.
[0028]
The content of the one-component insulating polyurethane resin in the aqueous polyurethane resin composition of the present invention is not particularly limited, but is usually preferably 5 to 65% by weight, more preferably 20 to 55% by weight. When the content of the insulating polyurethane resin is 5 to 65% by weight, the one-pack type insulating polyurethane resin is solubilized or stably dispersed in water.
[0029]
Specific examples of the benzimidazole compound contained in the aqueous polyurethane resin composition of the present invention include 4,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole, 1- (butylcarbamoyl) -2-benzimidazole Examples include methyl carbamate, 2-methoxycarbonylaminobenzimidazole, 2- (4-thiazolyl) -benzimidazole, and 2-methoxycarbonylaminobenzimidazole.
The content of the benzimidazole compound in the aqueous polyurethane resin composition is not particularly limited, but is preferably 0.01 to 2% by weight, more preferably 0.1 to 1% by weight based on the one-pack type insulating polyurethane resin. .
[0030]
In the aqueous polyurethane resin composition of the present invention, a filler, a flame retardant, an antifoaming agent, a bactericide, a stabilizer, a plasticizer, a thickener, a rust inhibitor, and the like, as long as the effects of the present invention are not impaired. And an additive such as an aqueous dispersion resin.
[0031]
The water-based polyurethane resin composition of the present invention is used for an electric washing machine, a toilet seat, a water heater, a water purifier, a bath, a switch portion of a dishwasher, an electric tool, etc. Sealing agents for sealing circuits to protect the circuits from moisture and moisture, sealing agents and coating agents for electric and electronic equipment, and capacitors, converters, transformers, electric wires, coils, and electrical components (automobile electronic components) It is suitably used as an insulating material or the like.
In particular, when used as an insulating material for a printed circuit board or temperature sensor, the resulting cured insulating material has excellent heat resistance, moisture heat resistance, and mold resistance. Even if the board or temperature sensor is used for a long time under hot and humid conditions, such as when the product is used in water, the insulated cured product that seals the printed circuit board or temperature sensor has an appropriate hardness. In addition, electrical characteristics such as insulating properties can be maintained, and there is almost no growth due to adhesion of mold.
[0032]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples.
[0033]
Example 1
As a polyol, a 1,2-polybutadiene polyol (polyol A, hydroxyl value: 45 mgKOH / g) and a polyester polyol (polyol B, hydroxyl value: 37 mgKOH / g) obtained by reacting ricinoleic acid with trimethylolpropane are used. Using a mixture (polyol A: polyol B = 80: 20 (weight ratio)) with naphthylene diisocyanate as a polyisocyanate, reacting them at 1: 2 (equivalent ratio of polyol: polyisocyanate) at 90 ° C. for 1 hour, An insulating urethane prepolymer having an NCO group at the end was obtained. This was dissolved in a mixed solvent of methyl ethyl ketone (MEK) and toluene (1: 1 weight ratio) to obtain a solution containing 50% by weight of an insulating urethane prepolymer. To the obtained insulating urethane prepolymer solution, dimethylol urea was added as a chain extender in an amount of 1 equivalent to 2 equivalents of the obtained insulating urethane prepolymer containing a terminal NCO group, mixed and reacted at 60 ° C. for 1 hour. Thus, a solution containing a one-pack type insulating polyurethane resin was obtained. Ion-exchanged water was added in an amount of 1 time to the obtained insulating polyurethane resin-containing solution, and the solution was dispersed in water. Next, MEK / toluene removal of the aqueous dispersion was carried out at 80 ° C. and 3 torr for 2 hours using a vacuum desolvator equipped with a cooling separator, and then 2- (4-thiazolyl) -benzimidazole (thiabendazole) was used as a fungicide. An aqueous polyurethane resin composition containing 0.005% by weight of the one-component insulating polyurethane resin and 53% by weight of the one-component insulating polyurethane resin was obtained.
[0034]
The obtained aqueous polyurethane resin composition was poured into a Teflon (registered trademark) container, left at 25 ° C. and 65% RH for 24 hours, and then dried at 80 ° C. for 24 hours to obtain a sample.
The obtained sample was subjected to the following heat treatment and wet heat treatment, and the volume resistivity, hardness and weight before and after these treatments were measured. Further, an antifungal test was conducted.
[0035]
Heat treatment A sample obtained in a DN-62 thermostat manufactured by Yamato Scientific Co., Ltd. is left at 150 ° C. for 24 hours.
The sample obtained in the pressure cooker PC-242HS-A manufactured by Hirayama Seisakusho Co., Ltd. is left for 24 hours at 121 ° C., 100% RH and 2 atm.
[0036]
Measurement of volume specific resistance value (Ω · cm) Using SE-10E manufactured by Toa Denpa Kogyo Co., Ltd., a measurement voltage of 500 V was applied to a sample (50 mm × 50 mm, thickness: 3 mm) at 25 ± 5 ° C. and 65 ± 5% RH. Is applied, and the value after 60 seconds is measured.
[0037]
Two hardness measurement samples (50 mm × 50 mm, thickness: 3 mm) are stacked (thickness: 6 mm), and the hardness is measured according to JIS K6253. Asker A type A is used as the hardness meter.
[0038]
A mold-proof test sample (50 mm × 50 mm, thickness: 1 mm) was allowed to stand in an atmosphere of 28 ° C. and 85% RH for 28 days in accordance with JIS Z 2911, and then a mold adhesion area with respect to the surface area (250 mm 2 ) of the sample Calculate the percentage of
(Evaluation)
◎: less than 3% ：: 3% or more and less than 15% △: 15% or more and less than 30% X: 30% or more
Table 1 shows the results. The hardness and the weight are shown as a decrease rate with respect to the value (initial value) before the treatment. In Table 1, VR indicates the volume resistivity, WT indicates the weight reduction rate relative to the initial value, and HA indicates the hardness reduction rate relative to the initial value.
[0040]
Examples 2 to 5
An aqueous polyurethane resin composition was obtained in the same manner as in Example 1, except that the amount of thiabendazole was changed to the amount shown in Table 1.
A sample was obtained from the obtained water-based polyurethane resin composition according to Example 1. In the same manner as in Example 1, the obtained sample was measured for volume specific resistance, hardness and weight before and after heat treatment and wet heat treatment, and was subjected to a fungicide test. Table 1 shows the results.
[0041]
Comparative Example 1
After obtaining a one-pack type insulating polyurethane resin as an aqueous dispersion in the same manner as in Example 1, no fungicide was added.
A sample was obtained from the obtained aqueous dispersion according to Example 1. In the same manner as in Example 1, the obtained sample was measured for volume specific resistance, hardness and weight before and after heat treatment and wet heat treatment, and was subjected to a fungicide test. Table 1 shows the results.
[0042]
Comparative Example 2
An aqueous polyurethane resin composition was obtained in the same manner as in Example 4, except that 1,2-benzisothiazolone-3-one alkali salt was used instead of thiabendazole as a fungicide.
A sample was obtained from the obtained water-based polyurethane resin composition according to Example 1. In the same manner as in Example 1, the obtained sample was measured for volume specific resistance, hardness and weight before and after heat treatment and wet heat treatment, and was subjected to a fungicide test. Table 1 shows the results.
[0043]
Comparative Example 3
An aqueous polyurethane resin composition was obtained in the same manner as in Example 3, except that a polyol having an iodine value of 190 mgKOH / g and an oxygen content of 1.5 was used.
A sample was obtained from the obtained water-based polyurethane resin composition according to Example 1. In the same manner as in Example 1, the obtained sample was measured for the volume resistivity, the hardness and the weight before and after the heat treatment and the wet heat treatment, and a fungicide test was performed. Table 1 shows the results.
[0044]
Comparative Example 4
An aqueous polyurethane resin composition was obtained in the same manner as in Example 3, except that a polyol having an oxygen content of 27% and an iodine value of 1 mgKOH / g was used.
A sample was obtained from the obtained water-based polyurethane resin composition according to Example 1. In the same manner as in Example 1, the obtained sample was measured for volume specific resistance, hardness and weight before and after heat treatment and wet heat treatment, and was subjected to a fungicide test. Table 1 shows the results.
[0045]
[Table 1]
As is clear from Table 1, the sample obtained from the aqueous dispersion of the one-pack insulating polyurethane resin of Comparative Example 1 containing no antifungal agent was inferior in antifungal activity, and used a fungicide other than the benzimidazole compound. The sample obtained from the aqueous polyurethane resin composition of Comparative Example 2 contained not only poor heat resistance but also poor antifungal properties, and the aqueous polyurethane resin composition of Comparative Example 3 using a polyol having an iodine value of 190 mgKOH / g. Were inferior in heat resistance, and the sample obtained from the aqueous polyurethane resin composition of Comparative Example 4 using a polyol having an oxygen content of 27% by weight was inferior in wet heat resistance. On the other hand, a one-pack insulating polyurethane resin obtained using a polyol having an oxygen content of 20% by weight or less and an iodine value of 155 mgKOH / g or less, and the aqueous polyurethane resin compositions of Examples 1 to 5 containing benzimidazole All of the samples obtained from the products were excellent in heat resistance, moist heat resistance and fungicide resistance.
[0047]
【The invention's effect】
The water-based polyurethane resin composition of the present invention has an effect of providing an insulating cured product having excellent heat resistance, wet heat resistance and fungicide resistance, and being easy to handle.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002359336A JP2004189877A (en) | 2002-12-11 | 2002-12-11 | Aqueous polyurethane resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002359336A JP2004189877A (en) | 2002-12-11 | 2002-12-11 | Aqueous polyurethane resin composition |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2006306833A Division JP3973227B2 (en) | 2006-11-13 | 2006-11-13 | Water-based polyurethane resin composition |
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| JP2004189877A true JP2004189877A (en) | 2004-07-08 |
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