JPS6360774B2 - - Google Patents
Info
- Publication number
- JPS6360774B2 JPS6360774B2 JP56057354A JP5735481A JPS6360774B2 JP S6360774 B2 JPS6360774 B2 JP S6360774B2 JP 56057354 A JP56057354 A JP 56057354A JP 5735481 A JP5735481 A JP 5735481A JP S6360774 B2 JPS6360774 B2 JP S6360774B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- epoxy
- parts
- resin
- 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.)
- Expired
Links
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000003822 epoxy resin Substances 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- 239000003973 paint Substances 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 21
- -1 hydrogenated 2 Chemical compound 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 125000002723 alicyclic group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 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 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 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 3
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 2
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002636 imidazolinyl group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SQFQIHCPTTUZCP-UHFFFAOYSA-N 1,2-bis(chloromethyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(CCl)C(CCl)=C1C SQFQIHCPTTUZCP-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-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
- 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
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- FJJYYMJJQCQPAT-UHFFFAOYSA-N 2,3,5,6-tetrachloro-4-(2,3,5,6-tetrachloro-4-hydroxyphenyl)phenol Chemical group ClC1=C(Cl)C(O)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(O)C(Cl)=C1Cl FJJYYMJJQCQPAT-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical class OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- JOBYTHHZLJPOLW-UHFFFAOYSA-N 2-(chloromethyl)-2-ethyloxirane Chemical compound CCC1(CCl)CO1 JOBYTHHZLJPOLW-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- MRTGZAHZKQIISW-UHFFFAOYSA-N 3,6-dioxatetracyclo[6.3.0.02,4.05,7]undecane Chemical compound C12OC2C2CCCC2C2C1O2 MRTGZAHZKQIISW-UHFFFAOYSA-N 0.000 description 1
- WDBZEBXYXWWDPJ-UHFFFAOYSA-N 3-(2-methylphenoxy)propanoic acid Chemical compound CC1=CC=CC=C1OCCC(O)=O WDBZEBXYXWWDPJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- YXVSYZRICGNXIH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-2-phenylethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)CC1=CC=CC=C1 YXVSYZRICGNXIH-UHFFFAOYSA-N 0.000 description 1
- KHXIJDYIFQMBNQ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol prop-1-ene Chemical group CC=C.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KHXIJDYIFQMBNQ-UHFFFAOYSA-N 0.000 description 1
- KWQRQJQLSQOJFN-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C)(C)C1=CC=C(O)C=C1 KWQRQJQLSQOJFN-UHFFFAOYSA-N 0.000 description 1
- IQIQZPUFQOLLKG-UHFFFAOYSA-N 4-[[4-[(4-hydroxyphenyl)methyl]-2,3,5,6-tetramethylphenyl]methyl]phenol Chemical compound CC=1C(C)=C(CC=2C=CC(O)=CC=2)C(C)=C(C)C=1CC1=CC=C(O)C=C1 IQIQZPUFQOLLKG-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 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
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 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
- 238000005336 cracking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- FTAORUVBXKFVDA-UHFFFAOYSA-N cyclohexylsulfanylcyclohexane Chemical compound C1CCCCC1SC1CCCCC1 FTAORUVBXKFVDA-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
本発明はカチオン化可能な塗料用樹脂の製造方
法に関するものである。特に本発明はポリウレタ
ンプレポリマーをエポキシ樹脂中に含有される水
酸基と反応させたエポキシ樹脂を基体にカチオン
化可能な化合物と反応せしめて得られる樹脂であ
つて、種々の硬化剤と併用することにより優れた
密着性、可撓性及び耐蝕性等を持つた塗膜を得る
ことができるカチオン化可能な塗料用樹脂の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a cationizable coating resin. In particular, the present invention is a resin obtained by reacting a polyurethane prepolymer with a hydroxyl group contained in an epoxy resin, and reacting the epoxy resin with a compound capable of cationizing the base material. The present invention relates to a method for producing a cationizable paint resin that can provide a coating film with excellent adhesion, flexibility, corrosion resistance, etc.
近年、エポキシ樹脂から製造されたカチオン電
着塗料が自動車等のプライマーとして広く使用さ
れるようになつた。かかるカチオン電着塗料はエ
ポキシ樹脂中のエポキシ基をそれと反応性を有す
る基およびカチオン化可能な基を有する化合物と
反応させて得られる反応生成物を酸等によつて中
和して、硬化剤と共に電着浴を形成して使用され
るものであるが、従来エポキシ樹脂から製造され
るカチオン電着塗料は、通常アニオン電着塗料よ
り、すぐれた塗膜物性を与えるものの、密着性、
可撓性、耐蝕性、耐衝撃性、平面平滑性等の面
で、必ずしも充分に満足しうる塗膜を形成しうる
ものとはいえない。 In recent years, cationic electrodeposition paints made from epoxy resins have come to be widely used as primers for automobiles and the like. Such cationic electrodeposition paints are produced by reacting the epoxy group in the epoxy resin with a compound having a reactive group and a cationizable group, and neutralizing the reaction product with an acid or the like to form a curing agent. Conventionally, cationic electrodeposition paints made from epoxy resins provide superior coating properties than anionic electrodeposition paints, but they have poor adhesion and poor adhesion.
It cannot be said that it is possible to form a coating film that is completely satisfactory in terms of flexibility, corrosion resistance, impact resistance, surface smoothness, etc.
本発明者らはかかる点に着目し、更に密着性、
可撓性、耐蝕性、耐衝撃性、表面平滑性等につい
て改良されたカチオン電着塗料等に適した塗料用
樹脂をエポキシ樹脂から製造すべく、鋭意研究を
進めた結果本発明に到達した。 The present inventors focused on this point, and further improved the adhesion and
The present invention was achieved as a result of intensive research in order to produce a coating resin suitable for cationic electrodeposition coatings and the like with improved flexibility, corrosion resistance, impact resistance, surface smoothness, etc. from epoxy resin.
すなわち、本発明は例えばカチオン電着塗料等
に適したカチオン化可能な塗料用樹脂の製造方法
に関し、本発明のカチオン化可能な塗料用樹脂の
製造方法はポリイソシアネートと分子量300〜
3000、水酸基当量200〜1500の2官能以上のポリ
ヒドロキシ化合物とを反応せしめて得られる末端
イソシアネート基を有するポリウレタンプレポリ
マーを水酸基当量150〜1500、エポキシ当量150〜
1500を有するエポキシ樹脂とイソシアネート基/
水酸基の比率(以下、NCO/OH比という)が
0.05〜1.0となるように反応させ、さらにエポキ
シ基と反応性を有し、しかもカチオン化可能な基
を有する化合物を反応せしめることを特徴とする
ものである。 That is, the present invention relates to a method for producing a cationizable coating resin suitable for, for example, cationic electrodeposition coatings, and the method for producing a cationizable coating resin of the present invention includes a polyisocyanate and a molecular weight of 300 to 300.
3000, a polyurethane prepolymer having a terminal isocyanate group obtained by reacting with a bifunctional or higher-functional polyhydroxy compound having a hydroxyl equivalent of 200 to 1500 and a hydroxyl equivalent of 150 to 1500 and an epoxy equivalent of 150 to
Epoxy resin and isocyanate group with 1500/
The ratio of hydroxyl groups (hereinafter referred to as NCO/OH ratio) is
This method is characterized by reacting the epoxy group so that the epoxy group is 0.05 to 1.0, and further reacting with a compound that is reactive with an epoxy group and has a cationizable group.
本発明のカチオン化可能な塗料用樹脂の製造方
法に使用される前記のポリイソシアネートとして
は分子中に2個以上のイソシアネート基を有する
脂肪族、脂環族、芳香族、脂肪―芳香族のポリイ
ソシアネートであり、かかるポリイソシアネート
としては例えばヘキサメチレンジイソシアネート
の如き脂肪族ポリイソシアネート、例えばイソホ
ロンジイソシアネート、水素添加した4,4′―ジ
フエニルメタンジイソシアネート、水素添加した
パラキシリレンジイソシアネート、その他、後記
の芳香族ポリイソシアネートに含まれる芳香族環
を水素添加して得られるポリイソシアネート等の
脂環族ポリイソシアネート、例えば2,4―トル
イレンジイソシアネート、2,6―トルイレンジ
イソシアネート、1,4―ナフチレンジイソシア
ネート、1,5―ナフチレンジイソシアネート、
1,3―フエニレンジイソシアネート、1,4―
フエニレンジイソシアネート、1―イソプロピル
ベンゾール―2,4―ジイソシアネート、ω,
ω′―ジイソシアネート―1,2―ジメチルベン
ゾール、4,4′―ジフエニルメタンジイソシアネ
ート、2,2′―ジメチルジフエニルメタン―4,
4′―ジイソシアネート、ジフエニルジメチルメタ
ン―4,4′―ジイソシアネート、3,3′―ジクロ
ロジフエニルジメチルメタン―4,4′―ジイソシ
アネート、ビフエニル―2,4′―ジイソシアネー
ト、3,3′―ジメチルビフエニル―4,4′―ジイ
ソシアネート、ジフエニルスルホン―4,4′―ジ
イソシアネートの如き芳香族ジイソシアネート、
例えばベンゼン―1,2,4―トリイソシアネー
ト、2,4,6―トリイソシアネート・トルエ
ン、4,4′,4″―トリフエニルメタントリイソシ
アネート、2,4,4′―トリイソシアネート・ジ
フエニルエーテル、芳香族アミンとホルムアルデ
ヒドの縮合生成物をホスゲン化することによつて
得られるポリメチレンポリフエニルイソシアネー
ト等の芳香族ポリイソシアネート等があげられ
る。 The polyisocyanates used in the method for producing the cationizable coating resin of the present invention include aliphatic, alicyclic, aromatic, and aliphatic-aromatic polyisocyanates having two or more isocyanate groups in the molecule. Isocyanates, such as aliphatic polyisocyanates such as hexamethylene diisocyanate, for example isophorone diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated paraxylylene diisocyanate, and other aromatic compounds as described below. Alicyclic polyisocyanates such as polyisocyanates obtained by hydrogenating aromatic rings contained in group polyisocyanates, such as 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,4-naphthylene diisocyanate , 1,5-naphthylene diisocyanate,
1,3-phenylene diisocyanate, 1,4-
phenylene diisocyanate, 1-isopropylbenzole-2,4-diisocyanate, ω,
ω'-diisocyanate-1,2-dimethylbenzole, 4,4'-diphenylmethane diisocyanate, 2,2'-dimethyldiphenylmethane-4,
4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate, biphenyl-2,4'-diisocyanate, 3,3'-dimethyl Aromatic diisocyanates such as biphenyl-4,4'-diisocyanate and diphenylsulfone-4,4'-diisocyanate;
For example, benzene-1,2,4-triisocyanate, 2,4,6-triisocyanate toluene, 4,4',4''-triphenylmethane triisocyanate, 2,4,4'-triisocyanate diphenyl ether , aromatic polyisocyanates such as polymethylene polyphenyl isocyanate obtained by phosgenating a condensation product of an aromatic amine and formaldehyde.
かかるポリイソシアネート中で好ましいものは
分子中に2〜3個のイソシアネート基を有する脂
環族又は芳香族のポリイソシアネートである。 Preferred among such polyisocyanates are alicyclic or aromatic polyisocyanates having 2 to 3 isocyanate groups in the molecule.
又、本発明の塗料用樹脂の製造に使用されるポ
リヒドロキシ化合物とは分子量300〜3000、水酸
基当量200〜1500の2官能以上のポリヒドロキシ
化合物であり、かかるポリヒドロキシ化合物とし
ては、例えばエチレングリコール、プロピレング
リコール等の2価アルコール;例えばグリセリ
ン、トリメチロールプロパン等の3価アルコー
ル;例えばペンタエリスリトール、ソルビトール
等のその他の多価アルコール;例えば水素添加さ
れた2,2―ビス(4―ヒドロキシフエニル)プ
ロパン(普通商品名:ビスフエノールA)等の脂
環族多価アルコール;例えば2,2―ビス(4―
ヒドロキシフエニル)プロパン等の多価フエノー
ル、例えばヒマシ油、ヒマシ油脂肪酸エステル等
の水酸基含有エステルの如きポリヒドロキシ化合
物およびこれらのポリヒドロキシ化合物に例えば
エチレンオキサイド、プロピレンオキサイド等の
アルキレンオキサイド又はテトラヒドロフランを
反応させて得られるポリエーテルポリオール、ポ
リテトラメチレングリコール;例えばジエタノー
ルアミン、トリエタノールアミン、トリ―イソプ
ロパノールアミン、エチレンジアミン、ジエチレ
ントリアミン、ヘキサメチレンジアミン、尿素等
の脂肪族アミン;例えばアニリン、ジアミノジフ
エニルメタン等の芳香族アミンの如きアミン化合
物に例えばエチレンオキサイド、プロピレンオキ
サイド等のアルキレンオキサイドを反応させて得
られるポリエーテルポリオール、前記の2価アル
コール、3価アルコール、脂環族多価アルコー
ル、多価フエノール、ポリエーテルポリオール等
と例えばアジピン酸、コハク酸、スベリン酸、セ
バシン酸、シユウ酸、メチルアジピン酸、グルタ
ル酸、ピメリン酸、アゼライン酸、マレイン酸、
フマル酸、シトラコン酸、イタコン酸、チオジプ
ロピオン酸、フタル酸、テレフタル酸、イソフタ
ル酸、ベンゼントリカルボン酸等のポリカルボン
酸とを反応させて得られるポリエステルポリオー
ル又はポリエステル―エーテルポリオールおよび
ラクトン類の重合によつて得られるポリラクトン
グリコール等があげられる。 Further, the polyhydroxy compound used in the production of the coating resin of the present invention is a bifunctional or higher functional polyhydroxy compound having a molecular weight of 300 to 3000 and a hydroxyl equivalent of 200 to 1500. Examples of such polyhydroxy compound include ethylene glycol, , dihydric alcohols such as propylene glycol; trihydric alcohols such as glycerin, trimethylolpropane; other polyhydric alcohols such as pentaerythritol, sorbitol; e.g. hydrogenated 2,2-bis(4-hydroxyphenyl); ) Alicyclic polyhydric alcohols such as propane (common trade name: bisphenol A); for example, 2,2-bis(4-
Polyhydric phenols such as (hydroxyphenyl)propane, polyhydroxy compounds such as hydroxyl group-containing esters such as castor oil and castor oil fatty acid esters, and these polyhydroxy compounds are reacted with alkylene oxides such as ethylene oxide and propylene oxide, or tetrahydrofuran. polyether polyols and polytetramethylene glycols obtained by Polyether polyols obtained by reacting alkylene oxides such as ethylene oxide and propylene oxide with amine compounds such as group amines, the aforementioned dihydric alcohols, trihydric alcohols, alicyclic polyhydric alcohols, polyhydric phenols, and polyethers. Polyols such as adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, maleic acid,
Polymerization of polyester polyols or polyester-ether polyols and lactones obtained by reacting with polycarboxylic acids such as fumaric acid, citraconic acid, itaconic acid, thiodipropionic acid, phthalic acid, terephthalic acid, isophthalic acid, and benzenetricarboxylic acid. Examples include polylactone glycols obtained by.
かかるポリヒドロキシ化合物として好ましいも
のは2〜3官能の水酸基含有エステル、ポリエー
テルポリオール、ポリエステルポリオールやポリ
ラクトンポリオールがあげられる。 Preferred examples of such polyhydroxy compounds include di- to trifunctional hydroxyl group-containing esters, polyether polyols, polyester polyols, and polylactone polyols.
本発明の塗料用樹脂の製造に使用されるエポキ
シ樹脂は水酸基当量150〜1500、エポキシ当量150
〜1500を有するものであり、かかるエポキシ樹脂
の代表的な一群は、置換又は非置換のグリシジル
エーテル基を分子内に平均1個より多く有するエ
ポキシ樹脂である。そのようなエポキシ樹脂は芳
香族多価フエノールあるいはそれに、アルキレン
オキサイドを付加せしめたポリヒドロキシ化合
物、あるいはまた芳香族核を含まない脂肪族、脂
環族あるいはヘテロ環含有のポリヒドロキシル化
合物などの各種のポリヒドロキシル化合物とエピ
ハロヒドリンとを常法によつて水酸化ナトリウム
あるいはトリエチルアミンのような塩基性触媒、
あるいは三弗化硼素などの存在下で反応せしめ同
時にあるいは最終的に水酸化ナトリウムのような
塩基性化合物との反応によつてグリシジルエーテ
ル化したものがあげられる。 The epoxy resin used in the production of the paint resin of the present invention has a hydroxyl equivalent of 150 to 1500 and an epoxy equivalent of 150.
-1500, and a typical group of such epoxy resins are epoxy resins having an average of more than one substituted or unsubstituted glycidyl ether group in the molecule. Such epoxy resins include aromatic polyhydric phenols, polyhydroxy compounds to which alkylene oxide is added, and aliphatic, alicyclic, or heterocyclic polyhydroxyl compounds that do not contain an aromatic nucleus. The polyhydroxyl compound and epihalohydrin are treated with a basic catalyst such as sodium hydroxide or triethylamine in a conventional manner.
Alternatively, it may be reacted in the presence of boron trifluoride or the like and simultaneously or finally converted into glycidyl ether by reaction with a basic compound such as sodium hydroxide.
ここにいう芳香族多価フエノールとしては、レ
ゾルシノール、2,7―ジヒドロキシナフタレン
のような単核多価フエノールとともに、たとえば
普通商品名ビスフエノールAと称する2,2―ビ
ス―(p―ヒドロキシフエニル)プロパン、2,
4′―ジヒドロキシジフエニルメタンのようなビス
(ヒドロキシフエニル)アルカン類、4,4′―ジ
ヒドロキシビフエニル、4,4′―ジヒドロキシオ
クタクロロビフエニルのようなジヒドロキシビフ
エニル類、ビス―(4―ヒドロキシフエニル)ス
ルホンのようなジ(ヒドロキシフエニル)スルホ
ン類、ビス(4―ヒドロキシフエニル)エーテ
ル、4,4′―ジヒドロキシ―2,6―ジメチルジ
フエニルエーテルのようなジ(ヒドロキシフエニ
ル)エーテル類、その他に1,1―ビス(p―ヒ
ドロキシフエニル)―2―フエニルエタン、2,
4―ビス(p―ヒドロキシフエニル)―4―メチ
ルペンタン、1′,4―ビス(p―ヒドロキシベン
ジル)ベンゼン、1,4―ビス(p―ヒドロキシ
ベンジル)テトラメチルベンゼン、1,4―ビス
(p―ヒドロキシクミル)ベンゼン等の多核2価
フエノール、例えば1,1,2,2―テトラキス
(4―ヒドロキシフエニル)エタンフエノール類
とカルボニル化合物との初期縮合物類(例:フエ
ノール樹脂縮合物、フエノールとアクロレインと
の縮合反応生成物、フエノールとグルオキザール
の縮合反応生成物、フエノールとペンタンジアリ
ルの縮合反応生成物、レゾルシノールとアセトン
の縮合反応生成物、キシレン―フエノール―ホル
マリン初期縮合物)、フエノール類とポリクロル
メチル化芳香族化合物の縮合生成物(例:フエノ
ールとビスクロルメチルキシレンとの縮合生成
物)等その他の芳香族多価フエノールがあげられ
る。 The aromatic polyhydric phenols mentioned here include mononuclear polyhydric phenols such as resorcinol and 2,7-dihydroxynaphthalene, as well as 2,2-bis-(p-hydroxyphenyl) commonly referred to as bisphenol A. ) propane, 2,
Bis(hydroxyphenyl)alkanes such as 4'-dihydroxydiphenylmethane, dihydroxybiphenyls such as 4,4'-dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl, bis-(4 -di(hydroxyphenyl) sulfones such as -hydroxyphenyl) sulfone, di(hydroxyphenyl) sulfones such as bis(4-hydroxyphenyl) ether, and di(hydroxyphenyl) ether such as 4,4'-dihydroxy-2,6-dimethyldiphenyl ether. enyl) ethers, 1,1-bis(p-hydroxyphenyl)-2-phenylethane, 2,
4-bis(p-hydroxyphenyl)-4-methylpentane, 1',4-bis(p-hydroxybenzyl)benzene, 1,4-bis(p-hydroxybenzyl)tetramethylbenzene, 1,4-bis Initial condensates of polynuclear divalent phenols such as (p-hydroxycumyl)benzene, such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethanephenols and carbonyl compounds (e.g., phenolic resin condensation condensation reaction product of phenol and acrolein, condensation reaction product of phenol and gluoxal, condensation reaction product of phenol and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-phenol-formalin initial condensate), Other aromatic polyhydric phenols include condensation products of phenols and polychloromethylated aromatic compounds (eg, condensation products of phenol and bischloromethylxylene).
又、ここに芳香族核を含まない脂肪族、脂環族
あるいはヘテロ環含有のポリヒドロキシル化合物
としては、例えば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、ジエチレン
グリコール、ジプロピレングリコール、ジブチレ
ングリコール、グリセリン、ペンタエリスリトー
ル等の多価アルコール及びこれらの多価アルコー
ル又はその他の活性水素含有化合物(例えばアミ
ノ基、カルボキシル基、チオヒドロキシル基等の
基を持つ化合物)にアルキレンオキサイドを付加
せしめた多価ポリヒドロキシル化合物、ポリエー
テルポリオール等の脂肪族ポリヒドロキシル化合
物、前記の芳香族多価フエノールおよびそれにア
ルキレンオキサイドを付加せしめて得られるポリ
ヒドロキシル化合物の芳香族核を水素添加して得
られる脂環族ポリヒドロキシ化合物、オキサゾリ
ジノン環、フラン環、ジオキサン環、イミダゾリ
ン環、イミダゾール環、ヒダントイン環、トリア
ジン環などを1つ以上含有するポリヒドロキシル
化合物、たとえば、ヒダントインの二級アミノ基
にアルキレンオキサイドやホルムアルデヒドを付
加して得られるポリヒドロキシ化合物等のヘテロ
環含有ポリヒドロキシ化合物があげられる。 Examples of aliphatic, alicyclic, or heterocyclic polyhydroxyl compounds that do not contain an aromatic nucleus include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and pentyl glycol. polyhydric alcohols such as erythritol, and polyhydroxyl compounds in which alkylene oxide is added to these polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amino groups, carboxyl groups, and thiohydroxyl groups); Aliphatic polyhydroxyl compounds such as polyether polyols, alicyclic polyhydroxy compounds obtained by hydrogenating the aromatic nucleus of the above-mentioned aromatic polyhydric phenols and polyhydroxyl compounds obtained by adding alkylene oxide thereto, and oxazolidinones. Polyhydroxyl compounds containing one or more rings, furan rings, dioxane rings, imidazoline rings, imidazole rings, hydantoin rings, triazine rings, etc., such as polyhydroxyl compounds obtained by adding alkylene oxide or formaldehyde to the secondary amino group of hydantoin. Examples include heterocycle-containing polyhydroxy compounds such as hydroxy compounds.
又、前記エピハロヒドリンとは、一般式
(ここにZは水素原子、メチル基、エチル基、
Xはハロゲン原子である)で表わされるものであ
り、かかるエピハロヒドリンの例としては、例え
ばエピクロルヒドリン、エピブロムヒドリン、
1,2―エポキシ―2―メチル―3―クロルプロ
パン、1,2―エポキシ―2―エチル―3―クロ
ルプロパンなどが挙げられる。 In addition, the epihalohydrin has the general formula (Here, Z is a hydrogen atom, a methyl group, an ethyl group,
X is a halogen atom), and examples of such epihalohydrin include epichlorohydrin, epibromohydrin,
Examples include 1,2-epoxy-2-methyl-3-chloropropane and 1,2-epoxy-2-ethyl-3-chloropropane.
又、エポキシ樹脂の他の代表的一群としては、
置換又は非置換のグリシジルエステル基を分子内
に平均1個以上有するエポキシ樹脂がある。かか
るエポキシ樹脂としては脂肪族ポリカルボン酸或
いは芳香族ポリカルボン酸(例えばフタル酸、イ
ソフタル酸、テレフタル酸、テトラヒドロフタル
酸、メチルテトラヒドロフタル酸、ヘキサヒドロ
フタル酸、メチルヘキサヒドロフタル酸、エンド
メチレンテトラヒドロフタル酸、メチルエンドメ
チレンテトラヒドロフタル酸、マレイン酸、フタ
ル酸、イタコン酸、コハク酸、グルタル酸、アジ
ピン酸、ピメリン酸、スベリン酸、アゼライン
酸、セバシン酸、二量体脂肪酸、トリメリツト
酸、トリメシン酸、ピロメリツト酸、シクロペン
タンテトラカルボン酸、これらのハロゲン置換化
合物のほか、これら多価カルボン酸と多価アルコ
ールとから得られる末端カルボキシルポリエステ
ルオリゴマーなども含まれ得る)のポリグリシジ
ルエステル、例えばエピハロヒドリンとメタクリ
ル酸とから合成されるグリシジルメタアクリレー
トを重合せしめて得られる如きエポキシ樹脂、ヘ
テロ環含有ポリカルボン酸たとえばヒダントイン
環を有するジカルボン酸、有橋炭化水素環を含有
するポリカルボン酸たとえば式
なる構造を有するポリカルボン酸のポリグリシジ
ルエステル等があげられる。 In addition, as another representative group of epoxy resins,
There are epoxy resins that have on average one or more substituted or unsubstituted glycidyl ester groups in their molecules. Such epoxy resins include aliphatic polycarboxylic acids or aromatic polycarboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid). Phthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, phthalic acid, itaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer fatty acid, trimellitic acid, trimesic acid , pyromellitic acid, cyclopentanetetracarboxylic acid, and halogen-substituted compounds thereof, as well as terminal carboxyl polyester oligomers obtained from these polyhydric carboxylic acids and polyhydric alcohols), such as epihalohydrin and methacrylate. Epoxy resins such as those obtained by polymerizing glycidyl methacrylate synthesized from acids, heterocyclic-containing polycarboxylic acids such as dicarboxylic acids having a hydantoin ring, polycarboxylic acids containing a bridged hydrocarbon ring, such as those of the formula Examples include polyglycidyl esters of polycarboxylic acids having the following structure.
又、エポキシ樹脂のその他の一群としては、式
(式中、Zは水素、メチル基、エチル基であ
る)で表わされるN置換の置換又は非置換1,2
―エポキシプロピル基を分子内に平均1個より多
く有するエポキシ樹脂がある。 In addition, as another group of epoxy resins, the formula (In the formula, Z is hydrogen, methyl group, ethyl group) N-substituted or unsubstituted 1,2
-There are epoxy resins that have an average of more than one epoxypropyl group in the molecule.
このようなエポキシ樹脂の例としては、芳香族
アミン(例えばアニリン又は核にアルキル置換基
を有するアニリン)と前記のエピハロヒドリンと
から得られるエポキシ樹脂、芳香族アミンとアル
デヒドとの初期縮合物(例えばアニリン―ホルム
アルデヒド初期縮合体、アニリン―フエノール―
ホルムアルデヒド初期縮合体)とエピハロヒドリ
ンとから得られるエポキシ樹脂、さらにはトリグ
リシジルイソシアヌレート、ジグリシジルヒダン
トイン化合物などがあげられる。さらにその他の
エポキシ樹脂としてエポキシ化油(例えばエポキ
シ化あまに油、エポキシ化大豆油、エポキシ化サ
フラワー油、エポキシ化桐油、エポキシ化エノ
油、エポキシ化脱水ひまし油、エポキシ化オイチ
シカ油、エポキシ化トール油など)、エポキシ化
脂肪酸、エポキシ化環状オレフイン化合物〔例え
ばビニルシクロヘキセンジオキサイド、1―(1
―メチル―1,2―エポキシエチル)―3,4―
エポキシ―4―メチルシクロヘキサン、3,4―
エポキシシクロヘキシルメチル―3,4―エポキ
シシクロヘキサンカルボキシレート、3,4―エ
ポキシ―6―メチルシクロヘキシルメチル―3,
4―エポキシ―6―メチルシクロヘキサンカルボ
キシレート、ビス(3,4―エポキシ―6―メチ
ルシクロヘキシルメチル)アジペート、ジシクロ
ペンタジエンジオキサイド、ジペンテンジオキサ
イド、テトラヒドロインデンジオキサイド、或い
はこれらの環が二価の基で結合された化合物、そ
の他Aralddite CY―175(チバ社製)など〕、共役
ジエン重合体のエポキシ化物(例えばエポキシ化
ポリブタジエン、エポキシ化ポリペンタジエン、
エポキシ化されたスチレン―ブタジエン共重合
体、エポキシ化されたアクリロニトリル―スチレ
ン共重合体)、不飽和結合を含む重合体のエポキ
シ化物(例えばポリプロピレンのエポキシ化物ポ
リイソブチンのエポキシ化物)、ポリシロキサン
のポリグリシジルエーテル、例えばオキサゾリジ
ノン環に炭素原子を介してエポキシ基が結合した
エポキシ樹脂、2の位置の多不飽和のアルケニル
基が置換したイミダゾリンから得られるポリエポ
キシ化合物等の如き複素環含有エポキシ樹脂その
他「エポキシ樹脂の製造と応用」(垣内弘編)に
記載されている如き種々のエポキシ樹脂等の従来
公知のエポキシ樹脂があげられる。 Examples of such epoxy resins include epoxy resins obtained from aromatic amines (e.g. aniline or aniline having an alkyl substituent in the nucleus) and the above-mentioned epihalohydrins, precondensates of aromatic amines and aldehydes (e.g. aniline -Formaldehyde initial condensate, aniline-phenol-
Examples include epoxy resins obtained from formaldehyde initial condensates) and epihalohydrin, as well as triglycidyl isocyanurate and diglycidyl hydantoin compounds. Furthermore, other epoxy resins include epoxidized oils (e.g., epoxidized linseed oil, epoxidized soybean oil, epoxidized safflower oil, epoxidized tung oil, epoxidized eno oil, epoxidized dehydrated castor oil, epoxidized oiticica oil, epoxidized toll). oil, etc.), epoxidized fatty acids, epoxidized cyclic olefin compounds [e.g. vinyl cyclohexene dioxide, 1-(1
-Methyl-1,2-epoxyethyl)-3,4-
Epoxy-4-methylcyclohexane, 3,4-
Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,
4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentadiene dioxide, dipentene dioxide, tetrahydroindene dioxide, or these rings are divalent [Aralddite CY-175 (manufactured by Ciba), etc.], epoxidized products of conjugated diene polymers (e.g., epoxidized polybutadiene, epoxidized polypentadiene,
epoxidized styrene-butadiene copolymer, epoxidized acrylonitrile-styrene copolymer), epoxidized polymers containing unsaturated bonds (e.g. epoxidized polypropylene, epoxidized polyisobutyne), polyglycidyl polysiloxane Ethers, such as epoxy resins in which an epoxy group is bonded to the oxazolidinone ring via a carbon atom, polyepoxy compounds obtained from imidazolines substituted with a polyunsaturated alkenyl group at the 2-position, and other heterocycle-containing epoxy resins. Conventionally known epoxy resins include various epoxy resins such as those described in "Production and Application of Resins" (edited by Hiroshi Kakiuchi).
かかるエポキシ樹脂の中で好ましい一群のもの
は多核2価フエノールおよびそれにアルキレンオ
キサイドを付加せしめて得られるポリヒドロキシ
化合物のポリグリシジルエーテル、又はそれらに
含有されている芳香族核が水素添加されていると
ころの脂環族のポリグリシジルエーテルである。 Among such epoxy resins, a preferred group of epoxy resins are polyglycidyl ethers of polynuclear dihydric phenols and polyhydroxy compounds obtained by adding alkylene oxide to them, or those in which the aromatic nucleus contained therein is hydrogenated. is an alicyclic polyglycidyl ether.
本発明の塗料用樹脂の製造に使用されるエポキ
シ基と反応性を有し、しかもカチオン化可能な基
を有する化合物としてはエポキシ基と反応性を有
する基とカチオン化可能な基を有するものであれ
ば何でも使用しうるが、例えばメチルアミン、エ
チルアミン、プロピルアミン、ブチルアミン、ジ
メチルアミン、ジエチルアミン、ジプロピルアミ
ン、ジブチルアミン、メチルブチルアミンの如き
第1級アミン又は第2級アミン、例えばエタノー
ルアミン、プロパノールアミン、ジエタノールア
ミン、ジイソプロパノールアミンの如きヒドロキ
シルアミン、例えばピペラジン、N―メチルピペ
ラジン等のその他のアミン化合物、例えば硫化ジ
エチル、硫化ジプロピル、硫化ジブチル、硫化ジ
フエニル、硫化ジシクロヘキシル、硫化テトラメ
チレン、チオジエタノール、チオジプロパノール
の如き硫化物、例えば無水コハク酸、無水フタル
酸、無水マレイン酸のような酸無水物とジメチル
エタノールアミン、メチルジエタノールアミンの
ようなアルカノールアミンと反応させて得られる
ようなカルボキシル基を含むアミン、例えば有機
基の少くとも1個がアミノ基で置換されているホ
ウ酸トリエステル、例えばトリメチルホスフイ
ン、トリエチルホスフイン、ジフエニルメチルホ
スフインの如きホスフイン化合物等があげられ、
これらの中で好ましいものは水溶性アミン化合物
であり、特に好ましいものは水酸基を含有するヒ
ドロキシルアミンである。 Compounds that are reactive with an epoxy group and have a cationizable group used in the production of the paint resin of the present invention include a group that is reactive with an epoxy group and a cationizable group. Any primary amines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine or secondary amines such as ethanolamine, propanol can be used. Hydroxylamines such as amines, diethanolamine, diisopropanolamine, other amine compounds such as piperazine, N-methylpiperazine, etc., such as diethyl sulfide, dipropyl sulfide, dibutyl sulfide, diphenyl sulfide, dicyclohexyl sulfide, tetramethylene sulfide, thiodiethanol, thio Amines containing a carboxyl group, such as those obtained by reacting a sulfide such as dipropanol, an acid anhydride such as succinic anhydride, phthalic anhydride, or maleic anhydride with an alkanolamine such as dimethylethanolamine or methyldiethanolamine. Examples include boric acid triesters in which at least one of the organic groups is substituted with an amino group, such as phosphine compounds such as trimethylphosphine, triethylphosphine, diphenylmethylphosphine, etc.
Preferred among these are water-soluble amine compounds, and particularly preferred is hydroxylamine containing a hydroxyl group.
本発明の塗料用樹脂の製造方法においては、ま
ず、前記のポリイソシアネートを分子量300〜
3000、水酸基当量200〜1500の2官能以上のポリ
ヒドロキシ化合物と反応せしめ、末端イソシアネ
ート基を有するポリウレタンプレポリマーを製造
する。この反応は、ポリイソシアネートのイソシ
アネート基に対するポリヒドロキシ化合物の水酸
基の比率が1未満、好ましくは0.7〜0.2となるよ
うな量の前記の反応成分を例えば60〜120℃で1
〜6時間程度撹拌しつつ行えばよい。 In the method for producing a coating resin of the present invention, first, the above-mentioned polyisocyanate has a molecular weight of 300 to 300.
3,000 and a difunctional or more functional polyhydroxy compound having a hydroxyl equivalent of 200 to 1,500 to produce a polyurethane prepolymer having terminal isocyanate groups. This reaction is carried out by using an amount of the above-mentioned reaction components such that the ratio of the hydroxyl groups of the polyhydroxy compound to the isocyanate groups of the polyisocyanate is less than 1, preferably 0.7 to 0.2.
This may be carried out with stirring for about 6 hours.
このようにして得られた末端イソシアネート基
を有するポリウレタンプレポリマーは次いで水酸
基当量150〜1500、エポキシ当量150〜1500を有す
るエポキシ樹脂と反応せしめる。 The polyurethane prepolymer having terminal isocyanate groups thus obtained is then reacted with an epoxy resin having a hydroxyl equivalent weight of 150 to 1500 and an epoxy equivalent weight of 150 to 1500.
エポキシ樹脂と末端イソシアネート基を有する
ポリウレタンプレポリマーとの反応はNCO/OH
比が0.05〜1.0、好ましくは0.3〜0.9となるように
前記の化合物を混合し、例えば60〜120℃で1〜
10時間、撹拌しつつ行えばよい。 The reaction between epoxy resin and polyurethane prepolymer having terminal isocyanate groups is NCO/OH
The above compounds are mixed so that the ratio is 0.05 to 1.0, preferably 0.3 to 0.9, and the
This can be done for 10 hours with stirring.
このようにして得られた反応生成物は必要な
ら、未反応物等を除去し、次いでエポキシ基と反
応性を有し、しかもカチオン化可能な基を有する
化合物と反応せしめる。この反応は常温で混合し
ただけでも起るが、反応を完全に行わせるために
も50℃〜130℃、好ましくは70〜100℃に加熱して
行うのが好ましい。 If necessary, unreacted substances and the like are removed from the reaction product thus obtained, and then the reaction product is reacted with a compound having reactivity with an epoxy group and a cationizable group. Although this reaction can occur simply by mixing at room temperature, it is preferable to conduct the reaction by heating to 50°C to 130°C, preferably 70°C to 100°C, in order to complete the reaction.
エポキシ基と反応性を有し、しかもカチオン化
可能な基を有する化合物は前記の反応生成物が有
しているエポキシ基に対するエポキシ基と反応性
を有する基の比率が0.2〜1.0好ましくは0.5〜1.0
となるような量を使用し、急激な発熱を防ぐため
に前記の反応生成物中に徐々に加えることが好ま
しい。反応を容易に進行させるために、溶剤を使
用してもよく、かかる溶剤としては例えばイソプ
ロパノール、イソブタノール、エチルセロソルブ
等のアルコール系、例えばメチルエチルケトン、
メチルイソブチルケトン、シクロヘキサノン等の
ケトン系の他、種種の溶剤が使用しうる。 In a compound having a group that is reactive with an epoxy group and can be cationized, the ratio of the group that is reactive with an epoxy group to the epoxy group contained in the reaction product is 0.2 to 1.0, preferably 0.5 to 1.0. 1.0
It is preferable to use such an amount that the compound is added gradually to the reaction product in order to prevent rapid heat generation. In order to facilitate the reaction, a solvent may be used, such as alcohols such as isopropanol, isobutanol, and ethyl cellosolve, such as methyl ethyl ketone,
In addition to ketones such as methyl isobutyl ketone and cyclohexanone, various other solvents can be used.
このようにして本発明によつて得られたカチオ
ン化可能な塗料用樹脂は例えば、ギ酸、酢酸、プ
ロピオン酸、乳酸の如き有機酸又は例えばリン
酸、塩酸、ホウ酸、硫酸等の無機酸を含む水性
液、場合によつては単に水と混合して塗料用樹脂
の水性エマルジヨン又は水溶液とすることができ
る。 The cationizable coating resin thus obtained according to the invention can be used, for example, with organic acids such as formic acid, acetic acid, propionic acid, lactic acid, or with inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, etc. The aqueous liquid containing the coating resin may optionally be simply mixed with water to form an aqueous emulsion or solution of the coating resin.
なお、前記のエポキシ基と反応性を有し、しか
もカチオン化可能の基を有する化合物を反応させ
る際に、前記のような酸を同時に添加し、その反
応終了後、水を加えることにより同様に、塗料用
樹脂の水性エマルジヨン又は水溶液とすることも
できる。酸の量は少くとも樹脂を水に可溶化又は
分散させるのに必要な量以上でかつ樹脂中に含ま
れるカチオン化可能な基の当量以下であることが
好ましい。 In addition, when reacting a compound that is reactive with the above-mentioned epoxy group and has a group that can be cationized, the above-mentioned acid is added at the same time, and after the reaction is completed, water is added to react in the same manner. , an aqueous emulsion or an aqueous solution of a coating resin. The amount of acid is preferably at least the amount necessary to solubilize or disperse the resin in water and not more than the equivalent of the cationizable groups contained in the resin.
本発明によつて得られた塗料用樹脂は、種々の
硬化剤と併用して被塗装物を塗布、浸漬、電着等
により被覆後、硬化することによりすぐれた密着
性、可撓性及び耐蝕性を持つた塗膜を与える。 The coating resin obtained by the present invention can be used in combination with various curing agents to coat the object to be coated by coating, dipping, electrodeposition, etc., and then cured to provide excellent adhesion, flexibility, and corrosion resistance. Provides a coating film with properties.
硬化剤としては例えばブロツクイソシアネー
ト、部分的にキヤツプした有機ポリイソシアネー
トやメラミン樹脂、グアナミン樹脂、尿素樹脂等
が使用でき、特にブロツクイソシアネート、部分
的にキヤツプした有機ポリイソシアネートが好ま
しい。 As the curing agent, for example, blocked isocyanates, partially capped organic polyisocyanates, melamine resins, guanamine resins, urea resins, etc. can be used, and blocked isocyanates and partially capped organic polyisocyanates are particularly preferred.
本発明で得られた塗料用樹脂は界面活性剤を必
要とせずに水に可溶化又は分散しうるが、場合に
よつては界面活性剤を使用しても良く、また溶剤
は水と親和性のあるものならば使用してもよい。
本発明で得られた塗料用樹脂を種々の硬化剤と使
用する場合、硬化をより迅速にかつ完全に行わせ
しめるため硬化促進剤として例えば第3級アミ
ン、アルキル金属塩等を使用することができる。
また本発明によつて得られた塗料用樹脂はこれに
顔料を加えて使用しても良く顔料としては酸と反
応性を有しないものが好ましい。 The coating resin obtained in the present invention can be solubilized or dispersed in water without the need for a surfactant, but a surfactant may be used in some cases, and the solvent has an affinity for water. You may use it if it is available.
When the coating resin obtained in the present invention is used with various curing agents, for example, tertiary amines, alkyl metal salts, etc. can be used as curing accelerators in order to make curing occur more quickly and completely. .
Further, the coating resin obtained according to the present invention may be used with a pigment added thereto, and the pigment preferably does not have reactivity with acids.
尚、本発明で得られた塗料用樹脂に相溶しうる
範囲内で他の中性またはカチオン性の樹脂を混合
することもできる。 It is also possible to mix other neutral or cationic resins within a range that is compatible with the coating resin obtained in the present invention.
本発明で得られる塗料用樹脂は従来の例えばカ
チオン電着塗料に使用されているカチオン化可能
な塗料用樹脂に比較して密着性、可撓性、耐蝕
性、表面平滑性、および耐衝撃性において非常に
優れた塗膜を与え、特に電着用塗料に適してい
る。 The coating resin obtained in the present invention has better adhesion, flexibility, corrosion resistance, surface smoothness, and impact resistance than conventional cationizable coating resins used in cationic electrodeposition coatings. It provides an excellent coating film and is particularly suitable for electrodeposition coatings.
以下に実施例を示し本発明を詳述する。尚、例
中の部は重量基準である。 The present invention will be explained in detail with reference to Examples below. Note that parts in the examples are based on weight.
〔実施例 1〕
ポリエチレングリコール(平均分子量=1500)
50部と2,4―トルイレンジイソシアネート12部
を85℃で3時間撹拌し、イソシアネート基末端の
ポリウレタンプレポリマーを得た。[Example 1] Polyethylene glycol (average molecular weight = 1500)
50 parts and 12 parts of 2,4-toluylene diisocyanate were stirred at 85°C for 3 hours to obtain a polyurethane prepolymer terminated with isocyanate groups.
このポリウレタンプレポリマー62部に2,2―
ビス(4―ヒドロキシフエニル)プロパンプロピ
レン付加物のポリグリシジルエーテル(エポキシ
当量=450、水酸基当量=1050)100部を加え、95
℃で6時間撹拌しエポキシ当量730の反応生成物
を得た。この反応生成物にメチルイソブチルケト
ン40部を加え溶剤溶液(A)とした後、ジエチルアミ
ン14部を60℃にて徐々に添加し、再び90℃に加熱
し更に3時間保持した。このようにして得られた
本発明の塗料用樹脂のブロツクイソシアネート
(B―1065、フエバ社製、イソホロンジイソシア
ネートラクタムマスク品、NCO含量=11%)45
部を添加し、充分混合溶解させた後、50℃に温度
を下げ10%酢酸115部を徐々に添加し、その後1
時間撹拌し均一になつたところで、1170部の脱イ
オン水を加える。このようにして得られた15%の
不揮発物を含有する塗料用樹脂溶液は、PH6.3で
あつた。このものを電着浴として脱脂鋼板に
250Vで2分間電着し、得られた塗膜を200℃で20
分間焼付けて、厚さ17μ、鉛筆硬度3Hの塗膜を得
た。この塗膜の性能は以下のようであつた。 62 parts of this polyurethane prepolymer contains 2,2-
Add 100 parts of polyglycidyl ether (epoxy equivalent = 450, hydroxyl equivalent = 1050) of bis(4-hydroxyphenyl)propane propylene adduct, and add 95
The mixture was stirred at ℃ for 6 hours to obtain a reaction product having an epoxy equivalent weight of 730. After adding 40 parts of methyl isobutyl ketone to this reaction product to obtain a solvent solution (A), 14 parts of diethylamine were gradually added at 60°C, and the mixture was heated again to 90°C and held for an additional 3 hours. Blocked isocyanate of the coating resin of the present invention thus obtained (B-1065, manufactured by Fueva, isophorone diisocyanate lactam mask product, NCO content = 11%) 45
After thoroughly mixing and dissolving, 115 parts of 10% acetic acid was gradually added, and then 115 parts of 10% acetic acid was added.
After stirring for a period of time until the mixture becomes homogeneous, add 1170 parts of deionized water. The paint resin solution thus obtained containing 15% non-volatile matter had a pH of 6.3. Apply this to a degreased steel plate as an electrodeposition bath.
Electrodeposition was performed at 250V for 2 minutes, and the resulting coating was heated at 200℃ for 20 minutes.
After baking for minutes, a coating film with a thickness of 17 μm and a pencil hardness of 3H was obtained. The performance of this coating film was as follows.
耐衝撃性(1Kgr×50cm) 異常なし
耐蝕性 (250時間) 〃
表面平滑性 優
耐エリクセン値 8mm以上
〔実施例 2〕
水素添加されたビスフエノールAとアジピン酸
との脱水反応によつて得られたポリエステルポリ
オール(平均分子量=2200)50部とメチレンビス
フエニルジイソシアネート10部を85℃で3時間撹
拌し、イソシアネート末端のウレタンプレポリマ
ーを得た。Impact resistance (1Kgr x 50cm) Corrosion resistance (250 hours) with no abnormality Surface smoothness Excellent Erichsen resistance 8mm or more [Example 2] Obtained by the dehydration reaction of hydrogenated bisphenol A and adipic acid. 50 parts of polyester polyol (average molecular weight = 2200) and 10 parts of methylene bisphenyl diisocyanate were stirred at 85°C for 3 hours to obtain an isocyanate-terminated urethane prepolymer.
このウレタンプレポリマー60部に2,2―ビス
(4―ヒドロキシシクロフエニル)プロパンのポ
リグリシジルエーテル(エポキシ当量=320、水
酸基当量=1250)50部を加え85℃で7時間撹拌し
エポキシ当量720の反応生成物を得た。この反応
生成物にメチルエチルケトン25部を加え溶剤溶液
とした後ジイソプロパノールアミン8部を50℃に
て徐々に添加した。再び90℃に加熱し更に4時間
保持した。このようにして得られた本発明の塗料
用樹脂に部分キヤツプされたイソシアネート(ト
リレンジイソシアネート・トリメチロールプロパ
ン付加体のメチルエチルケトオキシム部分マスク
物、NCO含量15%)30部を添加し、充分混合溶
解させた後、50℃まで温度を下げ、10%酢酸105
部を徐々に添加し、その後2時間撹拌し均一にな
つたところで580部の脱イオン水を加えた。この
ようにして得られた18%の不揮発物を含有する塗
料溶液は、PH5.9であつた。このものを電着浴と
して脱脂鋼板に220Vで3分間電着した。得られ
た塗膜を170℃で30分間焼付けて、厚さ15μ、鉛
筆硬度2Hの塗膜を得た。この塗膜の性能は以下
のようであつた。 To 60 parts of this urethane prepolymer, 50 parts of polyglycidyl ether of 2,2-bis(4-hydroxycyclophenyl)propane (epoxy equivalent = 320, hydroxyl equivalent = 1250) was added and stirred at 85°C for 7 hours, resulting in an epoxy equivalent of 720. A reaction product was obtained. To this reaction product, 25 parts of methyl ethyl ketone was added to form a solvent solution, and then 8 parts of diisopropanolamine was gradually added at 50°C. It was heated again to 90°C and held for an additional 4 hours. Add 30 parts of partially capped isocyanate (methyl ethyl ketoxime partially masked product of tolylene diisocyanate/trimethylolpropane adduct, NCO content 15%) to the coating resin of the present invention thus obtained, and thoroughly mix and dissolve. After that, lower the temperature to 50℃ and add 10% acetic acid 105
After stirring for 2 hours, 580 parts of deionized water was added to the mixture until the mixture became homogeneous. The paint solution thus obtained containing 18% non-volatile matter had a pH of 5.9. This product was used as an electrodeposition bath to electrodeposit on a degreased steel plate at 220V for 3 minutes. The resulting coating film was baked at 170° C. for 30 minutes to obtain a coating film with a thickness of 15 μm and a pencil hardness of 2H. The performance of this coating film was as follows.
耐衝撃性(1Kg/50cm) 異常なし
耐蝕性 (250時間) 〃
表面平滑性 優
耐エリクセン値 7mm
〔実施例 3〕
ポリラクトンポリオール(平均分子量=1200)
50部とトリレンジイソシアネート17部を90℃で4
時間撹拌し、イソシアネート基末端のポリウレタ
ンプレポリマーを得た。Impact resistance (1Kg/50cm) No abnormality Corrosion resistance (250 hours) Surface smoothness Excellent Erichsen resistance 7mm [Example 3] Polylactone polyol (average molecular weight = 1200)
50 parts and 17 parts of tolylene diisocyanate at 90℃
The mixture was stirred for hours to obtain a polyurethane prepolymer with isocyanate group terminals.
このポリウレタンプレポリマー67部に2,2―
ビス―(4―ヒドロキシフエニル)プロパンジグ
リシジルエーテル(エポキシ当量=625、水酸基
当量=525)70部とメチルイソブチルケトン35部
を加え85℃で8時間撹拌し、エポキシ当量1250の
反応生成物の溶剤溶液を得た。この溶液にジエチ
ルアミン7部を60℃にて徐々に添加し、再び95℃
まで加熱し更に3時間保持した。 67 parts of this polyurethane prepolymer contains 2,2-
70 parts of bis-(4-hydroxyphenyl)propane diglycidyl ether (epoxy equivalent = 625, hydroxyl equivalent = 525) and 35 parts of methyl isobutyl ketone were added and stirred at 85°C for 8 hours to form a reaction product with an epoxy equivalent of 1250. A solvent solution was obtained. To this solution, 7 parts of diethylamine was gradually added at 60°C, and then again at 95°C.
The mixture was heated to a temperature of 100.degree. C. and held for an additional 3 hours.
このようにして得られた本発明の塗料用樹脂に
部分キヤツプされたイソシアネート(トリレンジ
イソシアネートのエチルセロソルブ部分マスク、
NCO含量24%)20部を添加し、充分混合溶解さ
せた後50℃まで温度を下げ、10%プロピオン酸水
溶液70部を徐々に添加し、その後2時間撹拌し均
一になつたところで、脱イオン水590部を加えた。
このようにして得られた20%の不揮発物を含有す
る塗料溶液はPH6.1であつた。このものを電着浴
として脱脂鋼板に200Vで2分間電着し、得られ
た塗膜を210℃で30分間焼付けて厚さ20μ、鉛筆
硬度3Hの塗膜を得た。この塗膜の性能は以下の
ようであつた。 The isocyanate partially capped in the coating resin of the present invention thus obtained (ethyl cellosolve partial mask of tolylene diisocyanate,
Add 20 parts of NCO content (24%), mix and dissolve thoroughly, lower the temperature to 50℃, gradually add 70 parts of a 10% propionic acid aqueous solution, stir for 2 hours, and when the mixture becomes homogeneous, deionize. Added 590 parts of water.
The paint solution thus obtained containing 20% non-volatile matter had a pH of 6.1. This product was used as an electrodeposition bath to electrodeposit on a degreased steel plate at 200V for 2 minutes, and the resulting coating film was baked at 210°C for 30 minutes to obtain a coating film with a thickness of 20μ and a pencil hardness of 3H. The performance of this coating film was as follows.
耐衝撃性(1Kg×50cm) 異常なし
耐蝕性 (250時間) 〃
表面平滑性 優
耐エリクセン値 8mm以上
〔実施例 4〕
実施例1により得られたエポキシ当量730の反
応生成物の溶剤溶液(A)200部にジエチルアミン14
部を60℃にて徐々に添加し、再び90℃に加熱し更
に3時間保持して、本発明の塗料用樹脂を得た。
その後、メチル化メラミン樹脂(サイメル370、
三井東圧製、当量=225〜325)30部を添加し充分
混合溶解させ10%酢酸115部を徐々に添加して、
60%の不揮発物を含有する塗料溶液を得た。この
溶液を脱脂鋼板に塗布し180℃で30分間焼付け、
厚さ25μ、鉛筆硬度4Hの塗膜を得た。この塗膜の
性能は以下のようであつた。Impact resistance (1Kg x 50cm) No abnormality Corrosion resistance (250 hours) Surface smoothness Excellent Erichsen resistance 8mm or more [Example 4] Solvent solution of the reaction product with an epoxy equivalent of 730 obtained in Example 1 (A ) 200 parts diethylamine 14
The mixture was gradually added at 60° C., heated again to 90° C., and held for an additional 3 hours to obtain a coating resin of the present invention.
Then, methylated melamine resin (Cymel 370,
Add 30 parts (manufactured by Mitsui Toatsu, equivalent weight = 225-325), mix and dissolve thoroughly, and gradually add 115 parts of 10% acetic acid.
A coating solution containing 60% non-volatile matter was obtained. Apply this solution to a degreased steel plate and bake it at 180℃ for 30 minutes.
A coating film with a thickness of 25μ and a pencil hardness of 4H was obtained. The performance of this coating film was as follows.
耐衝撃性(1Kg×50cm) 異常なし
耐蝕性 (250時間) 〃
表面平滑性 優
耐エリクセン値 8mm以上
〔比較例 1〕
2,2―ビス―(4―ヒドロキシフエニル)プ
ロパンジグリシジルエーテル(エポキシ当量=
625)100部を、メチルエチルケトン30部に混合溶
解せしめ、ジエチルアミン10部を60℃にて徐々に
添加し、再び110℃に加熱し更に2時間保持して
塗料用樹脂を製造した。この塗料用樹脂に部分キ
ヤツプされたイソシアネート(トリレンジイソシ
アネートのエチルセロソルブ部分マスク品、
NCO含量24%)45部を添加し、充分混合溶解さ
せた後50℃まで温度を下げ、10%プロピオン酸水
溶液100部を徐々に添加した。その後2時間撹拌
し均一になつたところで脱イオン水810部を加え
た。15%の不揮発物を含有する塗料用樹脂溶液は
PH5.8であつた。このものを電着浴として脱脂鋼
板に220Vで2分間電着した。得られた塗膜を210
℃で30分間焼付けて厚さ15μ、鉛筆硬度4Hの塗膜
を得た。この塗膜の性能は、以下のようである。Impact resistance (1Kg x 50cm) No abnormality Corrosion resistance (250 hours) Surface smoothness Excellent Erichsen resistance 8mm or more [Comparative example 1] 2,2-bis-(4-hydroxyphenyl) propane diglycidyl ether (epoxy Equivalent =
625) was mixed and dissolved in 30 parts of methyl ethyl ketone, 10 parts of diethylamine was gradually added at 60°C, and the mixture was heated again to 110°C and held for another 2 hours to produce a coating resin. Isocyanate partially capped in this paint resin (ethyl cellosolve partial mask product of tolylene diisocyanate,
After thoroughly mixing and dissolving 45 parts (NCO content 24%), the temperature was lowered to 50°C, and 100 parts of a 10% aqueous propionic acid solution was gradually added. Thereafter, the mixture was stirred for 2 hours, and when the mixture became uniform, 810 parts of deionized water was added. Paint resin solution containing 15% non-volatile matter is
The pH was 5.8. This product was used as an electrodeposition bath to electrodeposit on a degreased steel plate at 220V for 2 minutes. The obtained coating film is 210
A coating film with a thickness of 15μ and a pencil hardness of 4H was obtained by baking at ℃ for 30 minutes. The performance of this coating film is as follows.
耐衝撃性(1Kg/20cm) 割れを生ず
耐蝕性 (250時間) 異常なし
表面平滑性 ハジキ、ピンホールあり平滑性劣
る。 Impact resistance (1Kg/20cm) No cracking Corrosion resistance (250 hours) No abnormality Surface smoothness Poor smoothness with cracks and pinholes.
耐エリクセン値 2mm Erichsen resistance value 2mm
Claims (1)
酸基当量200〜1500の2官能性以上のポリヒドロ
キシ化合物とを反応せしめて得られる末端イソシ
アネート基を有するポリウレタンプレポリマーを
水酸基当量150〜1500、エポキシ当量150〜1500を
有するエポキシ樹脂とイソシアネート基/水酸基
の比率が0.05〜1.0となるように反応せしめ、さ
らにエポキシ基と反応性を有し、しかもカチオン
化可能な基を有する化合物を反応せしめることを
特徴とするカチオン化可能な塗料用樹脂の製造方
法。1. A polyurethane prepolymer having a terminal isocyanate group obtained by reacting a polyisocyanate with a bifunctional or higher polyhydroxy compound having a molecular weight of 300 to 3000 and a hydroxyl equivalent of 200 to 1500 and a hydroxyl equivalent of 150 to 1500 and an epoxy equivalent of 150 to 1500. A cation characterized by reacting an epoxy resin having an isocyanate group/hydroxyl group such that the ratio of isocyanate groups to hydroxyl groups is 0.05 to 1.0, and further reacting a compound having a group that is reactive with an epoxy group and can be cationized. A method for producing paint resin that can be used as a coating material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56057354A JPS57170919A (en) | 1981-04-16 | 1981-04-16 | Preparation of coating resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56057354A JPS57170919A (en) | 1981-04-16 | 1981-04-16 | Preparation of coating resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57170919A JPS57170919A (en) | 1982-10-21 |
JPS6360774B2 true JPS6360774B2 (en) | 1988-11-25 |
Family
ID=13053234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56057354A Granted JPS57170919A (en) | 1981-04-16 | 1981-04-16 | Preparation of coating resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57170919A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162863A (en) * | 1997-12-04 | 2000-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
KR100579795B1 (en) * | 1997-12-31 | 2007-01-18 | 주식회사 케이씨씨 | A paint composition of combination under-coating for anticorrosive pre-coated metal |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5665052A (en) * | 1979-10-31 | 1981-06-02 | Dainippon Ink & Chem Inc | Water-soluble film-forming resin composition |
JPS5693727A (en) * | 1979-12-28 | 1981-07-29 | Asahi Chem Ind Co Ltd | Novel epoxy resin composition, paint therefrom, crosslinked product therefrom and film formation therefrom |
-
1981
- 1981-04-16 JP JP56057354A patent/JPS57170919A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5665052A (en) * | 1979-10-31 | 1981-06-02 | Dainippon Ink & Chem Inc | Water-soluble film-forming resin composition |
JPS5693727A (en) * | 1979-12-28 | 1981-07-29 | Asahi Chem Ind Co Ltd | Novel epoxy resin composition, paint therefrom, crosslinked product therefrom and film formation therefrom |
Also Published As
Publication number | Publication date |
---|---|
JPS57170919A (en) | 1982-10-21 |
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