JPS6121167A - Resin composition for cationic electroplating - Google Patents
Resin composition for cationic electroplatingInfo
- Publication number
- JPS6121167A JPS6121167A JP14316184A JP14316184A JPS6121167A JP S6121167 A JPS6121167 A JP S6121167A JP 14316184 A JP14316184 A JP 14316184A JP 14316184 A JP14316184 A JP 14316184A JP S6121167 A JPS6121167 A JP S6121167A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- epoxy resin
- reaction
- acid
- resin composition
- 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.)
- Granted
Links
- 125000002091 cationic group Chemical group 0.000 title claims description 11
- 239000011342 resin composition Substances 0.000 title claims description 8
- 238000009713 electroplating Methods 0.000 title 1
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- -1 amino compound Chemical class 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims description 28
- 239000004814 polyurethane Substances 0.000 claims description 27
- 229920002635 polyurethane Polymers 0.000 claims description 27
- 238000004070 electrodeposition Methods 0.000 claims description 20
- 239000003973 paint Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000005056 polyisocyanate Substances 0.000 abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 description 20
- 150000003077 polyols Chemical class 0.000 description 20
- 239000005062 Polybutadiene Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 150000001412 amines Chemical class 0.000 description 9
- 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 9
- 239000007787 solid Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- 230000005856 abnormality Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 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 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 150000003335 secondary amines Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 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
- 125000003700 epoxy group Chemical group 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 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
- 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
- 150000003839 salts Chemical class 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- HHBXONIFOUTHAX-UHFFFAOYSA-N n,n-dichloro-6-methylidenecyclohexa-2,4-dien-1-amine Chemical compound ClN(Cl)C1C=CC=CC1=C HHBXONIFOUTHAX-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、カチオン電着塗料用樹脂組成物に関する。更
に詳しくは、特定の塩基性アミン化合物を用いた変性エ
ポキシ樹脂を基体とする耐食性、並びに塗膜特性の優れ
たカチオン電着塗料用樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for cationic electrodeposition paint. More specifically, the present invention relates to a resin composition for cationic electrodeposition coatings which is based on a modified epoxy resin using a specific basic amine compound and has excellent corrosion resistance and coating properties.
従来、主流であったアニオン型電着塗料は、近年の自動
車車体を中心とした高度の耐食性要求に対応できず、現
在では殆んど、エポキシ樹脂をベースとしたカチオン電
着塗料に転換されるに至っている。Anionic electrodeposition paints, which have been the mainstream in the past, cannot meet the high corrosion resistance requirements of recent automobile bodies, and are now mostly converted to cationic electrodeposition paints based on epoxy resins. It has reached this point.
カチオン電着塗料用樹脂については、既に多数の提案が
なされており、例えば、ビスフェノールＡ・エピクロル
ヒドリン型エポキシ樹脂のようなエポキシ樹脂が耐食性
に優れたベース樹脂として有用であること、分子中又は
、末端に第−級又は第二級アミン基、水酸基、カルボキ
シル基等を含有するポリエーテル、ポリエステルポリア
ミド、アクリルポリマー等が硬化塗膜の諸物性改良のた
め前記エポキシ樹脂の変性剤として有効であること、水
溶性化の手段として、第−級又は第二級アミン基を含有
する塩基性アミン化合物を前記エポキシ樹脂に付加反応
後、有機酸中和すること、架橋成分として、プロックポ
リインシアネート化合物を骨格中に導入又は混合するこ
と等が広く知られている。Many proposals have already been made regarding resins for cationic electrodeposition paints. that polyethers, polyester polyamides, acrylic polymers, etc. containing primary or secondary amine groups, hydroxyl groups, carboxyl groups, etc. are effective as modifiers for the epoxy resin in order to improve the physical properties of the cured coating film; As a means of water solubility, a basic amine compound containing a primary or secondary amine group is added to the epoxy resin, and then neutralized with an organic acid, and a block polyincyanate compound is added to the skeleton as a crosslinking component. It is widely known to introduce or mix with.
しかしながら、硬化塗膜の可撓性、耐衝撃性、密着性等
の改良に有効な上記変性剤を用いる先行技術は、反面、
耐蝕性を劣化せしめること、更には塗膜面平滑性、つき
まわり性、浴安定性等電着塗装の実用面において充分で
ない等の欠点を有していた。However, the prior art using the above-mentioned modifier, which is effective in improving the flexibility, impact resistance, adhesion, etc. of the cured coating film, on the other hand,
This method has disadvantages such as deterioration of corrosion resistance and unsatisfactory coating surface smoothness, throwing power, bath stability, and other practical aspects of electrodeposition coating.
一方、これらの問題を解決する手段として、分子末端又
は、中途にカルボキシル基を含有する共役ジエン重合体
又は、共役ジエンと、ビニルモノマーの共重合体を、エ
ポキシ樹脂の変性剤に用いる方法が提案されているが、
これらは、エポキシ樹脂との相溶性及び反応性が不良で
あり、その分子量及び反応条件によっては、エポキシ樹
脂との結合不良や、粘度の異常」二昇及びゲル化の懸念
がある等の変性過程における問題があり、充分に目的が
達成されていないのが実情であった。On the other hand, as a means to solve these problems, a method has been proposed in which a conjugated diene polymer containing a carboxyl group at the end of the molecule or in the middle, or a copolymer of a conjugated diene and a vinyl monomer is used as a modifier for epoxy resin. Although it has been
These have poor compatibility and reactivity with epoxy resins, and depending on their molecular weight and reaction conditions, there may be concerns about poor bonding with epoxy resins, abnormal viscosity, gelation, etc. during the modification process. The reality is that there are problems with this, and the objective has not been fully achieved.
本発明者等は、上記の問題点を解消するため鋭意研究を
重ねた結果、エポキシ樹脂の変性剤として、分子末端に
第一級アミノ基を含有するポリウレタンポリアミンが有
効であることを見い出し、硬化塗膜物性に優れ、且つ、
塗装実用性に優れたカチオン電着塗料用樹脂組成物を得
るに至ったものである。As a result of extensive research to solve the above problems, the present inventors discovered that polyurethane polyamine containing a primary amino group at the molecular end is effective as a modifier for epoxy resins, and Excellent coating film properties, and
A resin composition for cationic electrodeposition paint which has excellent coating practicality has been obtained.
即ち、本発明は、エポキシ樹脂と塩基性アミン化合物を
必須成分として反応せしめて得られる変性エポキシ樹脂
を基体とするカチオン電着塗料用樹脂組成物において、
塩基性アミノ化合物の少なくとも、一部に分子末端に第
一級アミノ基を含有するポリウレタンポリアミンを配合
してなることを特徴とするカチオン電着塗料用樹脂組成
物を提供するものである。That is, the present invention provides a resin composition for cationic electrodeposition coatings that is based on a modified epoxy resin obtained by reacting an epoxy resin and a basic amine compound as essential components.
The present invention provides a resin composition for a cationic electrodeposition coating, characterized in that a polyurethane polyamine containing a primary amino group at the molecular end is blended with at least a portion of a basic amino compound.
本発明の特徴であり、主要構成要素で、且つエポキシ樹
脂変性剤である分子末端に第一級アミノ基を含有するポ
リウレタンポリアミンは、分子中に少なくとも２個の活
性水素原子を含有する化合物と、有機ポリイソシアネー
トとを、インシアネート基／活性水素原子モル比１以上
で、従来公知のイソシアネート重付加反応法により得ら
れる分子末端に少なくとも１個以上の遊離インシアネー
ト基を含有するウレタンプレポリマーを加水分解するこ
とにより得られる。The polyurethane polyamine containing a primary amino group at the molecular end, which is a feature of the present invention, is a main component, and is an epoxy resin modifier, is a compound containing at least two active hydrogen atoms in the molecule; An organic polyisocyanate is hydrated with a urethane prepolymer containing at least one free incyanate group at the molecular end obtained by a conventionally known isocyanate polyaddition reaction method at an incyanate group/active hydrogen atom molar ratio of 1 or more. Obtained by decomposition.
分子中に少なくとも２個の活性水素原子を含有する化合
物は、通常ポリウレタン製造に使用される末端に、ヒド
ロキシル−、カルボキシル−、アミノ−又は、メルカプ
ト−基を含有するポリエーテル、ポリエステル、ポリア
セタール、ポリチオエーテル、ポリアシド。Compounds containing at least two active hydrogen atoms in the molecule include polyethers, polyesters, polyacetals, polyesters containing terminal hydroxyl, carboxyl, amino or mercapto groups, which are usually used in the production of polyurethanes. Thioether, polyacid.
ポリエステルアミド化合物及びポリブタジエンボリオー
ル、ポリブタジェン−アクリロニトリル共重合体ポリオ
ールポリブタジェン−スチレン共重合体ポリオール、ポ
リクロロプレンポリオール、ポリアクリルポリオール等
のポリマーポリオール並びに鎖伸長剤として通常使用さ
れるエチレングリコール、ブチレングリコール、トリメ
チロールプロパン、ジエチレングリコール等の低級ポリ
オール類モノエタノールアミン、ジェタノールアミン等
のアミノアルコール類、ジアミノジフェニルメタン、メ
チレンビスクロロアニリン等のポリアミン類等が挙げら
れるが、ポリブタジエンボリオール、ポリブタジェン−
７クリロニトリル共重合ポリオール、ポリブタジェン−
スチレン共重合ポリオール等が特に好ましい。ポリブタ
ジェンポリオールは、次式に示した如く、その微細構造
として、トランス−１，４，シス−１，４及びビニル−
１，２のいずれか単独又は、それらの任意の混合割合の
全ての化合物が含まれる。これらの例としては、Ｐｏ１
ｙｂｄＲ−４５ＨＴ （Ａ ＲＣＯＣｈｅｍｉｃａｌ
Ｃｏｍｐａｎｙ）、Ｎ Ｉ Ｓ Ｓ Ｏ−Ｐ Ｂ Ｇ
（日本曹達−）等が挙げられる。Polyesteramide compounds and polymer polyols such as polybutadiene boriol, polybutadiene-acrylonitrile copolymer polyol, polybutadiene-styrene copolymer polyol, polychloroprene polyol, polyacrylic polyol, and ethylene glycol and butylene glycol commonly used as chain extenders. , lower polyols such as trimethylolpropane and diethylene glycol; amino alcohols such as monoethanolamine and jetanolamine; polyamines such as diaminodiphenylmethane and methylenebischloroaniline;
7 Acrylonitrile copolymerized polyol, polybutadiene
Styrene copolymer polyols and the like are particularly preferred. As shown in the following formula, polybutadiene polyol has a fine structure of trans-1,4, cis-1,4 and vinyl-
It includes all the compounds of either 1 or 2 alone or any mixture thereof. Examples of these are Po1
ybdR-45HT (A RCO Chemical
Company), NISSO-PBG
(Nippon Soda-) and the like.
（１）ポリブタジェンポリオール
ＨＯ−［（ＣＨ２ＣＨ＝ ＣＨＣＨ２） ａ−（ＣＨ２
ＣＨ） （ＣＨ２ＣＨ＝ＣＨＣＨ＝ ＣＨ２
−ＣＨ２）Ｃ］ ｎ０Ｈ
（但し、ａ＋ｂ＋ｃ＝ｌ、ｌ≧ａ、ｂ、ｃ≧０、ｎ−５
〜２００）
又、ポリブタジェン共重合体ポリオールは、次式に示し
た、ポリブタジェン−アクリロニトリル共重合体ポリオ
ール及びポリブタジェン−スチレン共重合体ポリオール
が挙げられ、これらの例としては、ＣＮ−１５及びＣ５
−１５（いずれもＡ ＲＣＯＣｈｅｍｉｃａｌ Ｃｏｗ
ｐａｎｙ）がある。(1) Polybutadiene polyol HO-[(CH2CH= CHCH2) a-(CH2
CH) (CH2CH=CHCH= CH2 -CH2)C] n0H (However, a+b+c=l, l≧a, b, c≧0, n-5
~200) Examples of polybutadiene copolymer polyols include polybutadiene-acrylonitrile copolymer polyols and polybutadiene-styrene copolymer polyols shown in the following formulas, examples of which include CN-15 and C5.
-15 (both A RCO Chemical Cow
There is a pany).
（２）ポリブタジェン共重合体ポリオールＨＯ−［（Ｃ
Ｈ２−ＣＨ＝ ＣＨ−ＣＨ２） １ｌＬ−（ＣＨ−ＣＨ
２） ｂ −Ｊ ｎ ＯＨ［但し、ａ＝０．８５、ｂ＝
０．１５、ｎ−７８〜８７、Ｘ＝ＣＮ （ポリブタジェ
ン−アクリロニトリル共重合体ポリオール）またはａ＝
０．７５、ｂ＝０．２５、ｎ＝５４、Ｘ＝Ｃ６Ｈｓ
（ポリブタジェン−スチレン共重合体ポリオール）］
有機ポリイソシアネートとしては、官能数２〜６のポリ
イソシアネートを対象とし、例えば、ヘキサメチレンジ
イソシアネート、キシリレンジイソシアネート、トリレ
ンジイソシアネート、ジフェニルメタンジイソシアネー
ト、イソホロンジイソシアネート等のジイソシアネート
類、トリフェニルメタントリイソシアネート、トリス−
（イソシアネートヘキシル）−ビューレット、ポリメチ
レンポリフェニルポリイソシアネート、ヘキサメチレン
ジイソシアネート及びトリレンジイソシアネートの３量
体化物並びに前記ポリイソシアネート類とエチレングリ
コール、ブチレングリコール、トリメチロールプロパン
等の低分子量ポリオールとを予じめ反応させて得たポリ
イソシアネート等が挙げられる。(2) Polybutadiene copolymer polyol HO-[(C
H2-CH= CH-CH2) 1lL-(CH-CH
2) b −J n OH [However, a=0.85, b=
0.15, n-78 to 87, X=CN (polybutadiene-acrylonitrile copolymer polyol) or a=
0.75, b=0.25, n=54, X=C6Hs
(Polybutadiene-styrene copolymer polyol)] The organic polyisocyanate includes polyisocyanates having a functional number of 2 to 6, such as diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. , triphenylmethane triisocyanate, tris-
(Isocyanatehexyl)-buret, trimerized products of polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate and tolylene diisocyanate, and the above polyisocyanates and low molecular weight polyols such as ethylene glycol, butylene glycol and trimethylolpropane. Examples include polyisocyanates obtained by a first reaction.
分子末端に少なくとも１個以上の遊離イソシアネート基
を含有するウレタンプレポリマーを該当するポリウレタ
ンポリアミンに転換するためには、含有する遊離インシ
アネート基を、水により加水分解する。加水分解の方法
は、遊離のインシアネート基と当量以上の無機強酸及び
水を用いる方法、％当量以上の重亜硫酸塩及び展当量以
下の無機強酸で、且つ両者の当量和が１当量以上である
重亜硫酸塩及び無機強酸の混合水溶液を用いる方法、塩
基の水溶液又は塩基の溶液を含む水性溶媒を用いる方法
等が挙げられ、更に、遊離アミンに変換する方法として
前二者は、アルカリによる中和及び過酸化水素処理後の
アルカリによる中和、後者は、酸性イオン交換体による
処理等がある。In order to convert a urethane prepolymer containing at least one free isocyanate group at the molecular end into the corresponding polyurethane polyamine, the free incyanate groups it contains are hydrolyzed with water. The hydrolysis method is a method using a free incyanate group, a strong inorganic acid with an equivalent amount or more, and water, a bisulfite with a % equivalent or more, and an inorganic strong acid with an equivalent amount or less, and the sum of the equivalents of both is 1 equivalent or more. Examples include a method using a mixed aqueous solution of bisulfite and a strong inorganic acid, and a method using an aqueous solution of a base or an aqueous solvent containing a solution of a base.Furthermore, the former two methods include neutralization with an alkali to convert it into a free amine. and neutralization with an alkali after hydrogen peroxide treatment; the latter includes treatment with an acidic ion exchanger, etc.
特に、製造方法に限定されるものでないが。Although it is not particularly limited to the manufacturing method.
工業的に有利、な繕当量以上の重亜硫酸塩及び展当量以
下の無機強酸で且つ、両者の当量和が１当量以上である
重亜硫酸塩及び無機強酸の混合水溶液で、加水分解し、
更に、過酸化水素処理後アルカリ中和する方法が好まし
い。得られるポリウレタンポリアミンの組成構造、分子
量、官能数は、遊離インシアネート基を含有するウレタ
ンプレポリマーにより決定される。本発明の目的に好適
なポリウレタンポリアミンの分子量は、２００〜１５，
０００であり、特に好ましいポリウレタンポリアミンと
しては、前記ポリブタジェンポリオールまたはポリブタ
ジェン共重合体ポリオールをベースとした次式に示すポ
リブタジェン系ボリウレタンポリアミンまたはポリブタ
ジェン共重合体系ポリウレタンポリアミンが挙げられる
が、これに限定されるものではない。Hydrolyzed with an industrially advantageous mixed aqueous solution of a bisulfite having an amount equal to or more than a dressing equivalent and a strong inorganic acid having an equivalent amount less than a rolling equivalent, and in which the sum of the equivalents of both is 1 equivalent or more,
Furthermore, a method of alkali neutralization after hydrogen peroxide treatment is preferred. The compositional structure, molecular weight, and functionality of the resulting polyurethane polyamine are determined by the urethane prepolymer containing free incyanate groups. The molecular weight of the polyurethane polyamine suitable for the purpose of the present invention is from 200 to 15,
000, and particularly preferred polyurethane polyamines include, but are not limited to, polybutadiene polyurethane polyamines or polybutadiene copolymer polyurethane polyamines shown in the following formula based on the polybutadiene polyol or polybutadiene copolymer polyol. It is not something that will be done.
（１）ポリブタジェン系ポリウレタンポリアミン
（ＮＨ２） ｍ−Ａ−ＮＨＣＯＯ−［−（ＣＨ２ＣＩ
（＝Ｃ）（ＣＨ２） ａ （ＣＨ２−ＣＨ）
ｂ （ＣＨ２−ＣＨ＝ ＣＨＣＨ２ＣＨ＝
ＣＨ２
） ｃ−］ ｎｏｃｏＮＷＡ −（ＮＨ２） ｍ
（但し、Ａは有機ポリイソシアネート残基、ｍは１〜５
の整数、ａ、ｂ、ｃはｌ≧ａ。(1) Polybutadiene-based polyurethane polyamine (NH2) m-A-NHCOO-[-(CH2CI
(=C) (CH2) a (CH2-CH)
b (CH2-CH= CHCH2CH=
CH2) c-] nocoNWA-(NH2) m
(However, A is an organic polyisocyanate residue, m is 1 to 5
integers, a, b, c are l≧a.
ｂ、ｃ≧０であって、ａ＋ｂ＋ｃ＝１ となるような
数、ｎは５〜２００の整数）
（２）ポリブタジェン共重合体系ポリウレタンポリアミ
ン
（ＮＨ２） ｍ−Ａ−ＮＨＣＯＯ−［−（ＣＨ２−ＣＨ
＝ ＣＨ−ＣＨ２） ａ −（ＣＨ−ＣＨコ
２ ） ｂ−］ −０ＣＯＮＷＡ −（ＮＨ２） ｍ
（但し、Ａは有機ポリイソシアネート残基、ｍは１〜５
の整数、ａ、ｂは１＞ａ、ｂｏ。(2) Polybutadiene copolymer-based polyurethane polyamine (NH2) m-A-NHCOO-[-(CH2-CH
= CH-CH2) a -(CH-CHco2) b-] -0CONWA -(NH2) m
(However, A is an organic polyisocyanate residue, m is 1 to 5
integers, a, b are 1>a, bo.
であって、ａ＋ｂ＝１となるような数、ｎはｌＯ〜２０
０の整数、ＸはＣ，、）（＋、−またはＣＮ−である。, a number such that a+b=1, n is lO~20
An integer of 0, X is C, , )(+, - or CN-.
）
次に本発明に用いるエポキシ樹脂は、１分子中に２個以
上のエポキシ基を有するポリエポキシドが好ましく、例
えば、ビスフェノールＡ、エピクロルヒドリンから得ら
れるエポキシ樹脂、水添ヒスフェノールＡとエピクロル
ヒドリン又は、ビスフェノールＡと、β−メチルエピク
ロルヒドリンから得られるエポキシ樹脂等が挙げられ、
更に、これらと併用してノボラック型ポリグリシジルエ
ーテル、ポリアルキレンゲリコールのポリグリシジルエ
ーテル、ポリカルボン酸のポリグリシジルエーテル等も
使用できるが、特に好ましいものは、ビスフェノールＡ
・エピクロルヒドリン型エポキシ樹脂である。) Next, the epoxy resin used in the present invention is preferably a polyepoxide having two or more epoxy groups in one molecule, for example, an epoxy resin obtained from bisphenol A, epichlorohydrin, hydrogenated hisphenol A and epichlorohydrin, or bisphenol A. and epoxy resins obtained from β-methylepichlorohydrin.
Furthermore, in combination with these, novolac-type polyglycidyl ethers, polyglycidyl ethers of polyalkylene gelicols, polyglycidyl ethers of polycarboxylic acids, etc. can also be used, but particularly preferred are bisphenol A.
-Epichlorohydrin type epoxy resin.
エポキシ樹脂と分子末端に第一級アミン基を含有するポ
リウレタンポリアミンとの反応は常温で起り、発熱反応
であるが、通常５０〜１５０℃の範囲で反応を完結させ
る。又、ゲル化を防ぐためエポキシ基１当量に対し、ア
ミノ基１モル以上となるポリウレタンポリアミンの量を
用い、ポリウレタンポリアミン中に、エポキシ樹脂を滴
下する方法が好ましいがこれに限定されるものではない
。この場合、反応混合物の粘度を下げ反応を容易にする
ため希釈溶剤を用いても良い。通常インプロパツール、
ｔ−ブタノール、セロソルブ、ブチルセロソルブ、セロ
ソルブアセテート、シクロヘキサノン、メチルエチルケ
トン、メチルイソブチルケトン等の水溶性溶剤が用いら
れるが疎水性の強いポリウレタンボアミン（例えばポリ
ブタジェン系ポリウレタンポリアミン）の場合には、ト
ルエン、キシレン等の疎水性溶剤を単独又は併用するこ
とも可能である。The reaction between the epoxy resin and the polyurethane polyamine containing a primary amine group at the end of the molecule occurs at room temperature and is an exothermic reaction, but the reaction is usually completed in the range of 50 to 150°C. In addition, in order to prevent gelation, it is preferable to use an amount of polyurethane polyamine that is 1 mole or more of amino groups per equivalent of epoxy group, and drop the epoxy resin into polyurethane polyamine, but the method is not limited thereto. . In this case, a diluting solvent may be used to reduce the viscosity of the reaction mixture and facilitate the reaction. Usually improvisational tools,
Water-soluble solvents such as t-butanol, cellosolve, butyl cellosolve, cellosolve acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone are used, but in the case of highly hydrophobic polyurethane polyamines (e.g. polybutadiene polyurethane polyamines), toluene, xylene, etc. It is also possible to use these hydrophobic solvents alone or in combination.
本発明の必須構成成分である塩基性アミノ化合物中、分
子末端に第一級アミノ基を含有するポリウレタンポリア
ミン以外の成分として次のようなアミノ基含有化合物を
併用してもよい。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、ジエチルアミン、ジ
プロピルアミンのようなモノ及びジアルキルアミン、
モノエタノールアミン、ジェタノールアミンのようなモ
ノ及びジアルカノールアミン、シクロヘキシルアミン、
モルホリンのような脂環族モノアミン、エチレンジアミ
ン、ヘキサメチレンジアミン、ジエチレントリアミン、
プロピレンジアミン、Ｎ−アミノエタノールアミン、ジ
エチルエチレンジアミン、ジエチルアミノプロピルアミ
ン、ピペラジン、Ｎ−メチルビペラジン、Ｎ−アミノエ
チルピペラジンのようなポリアミン、アニリン、Ｎ−メ
チルアニリン、トルイジン、ｍ−キシリレンジアミン、
ジアミノジフェニルメタンのような芳香族アミン、フタ
ル酸、アジピン酸、セパチン酸のようなジカルボン酸と
エチレンジアミン、ヘキサメチレンジアミン、ジエチレ
ントリアミンのようなポリアミンとを縮合して得られる
ポリアミドアミン等の公知の第−級又は第二級アミノ基
含有化合物が挙げられる。エポキシ樹脂とこれら、第−
級又は第二級アミン基含有化合物の反応は前記ポリウレ
タンポリアミンの反応と同時又は、前後いずれに行って
もよく通常これらの使用量は、少なくとも、酸で中和し
た時、反応生成物が水可溶化するに、十分な量であれば
よい。反応は常温で起るが、最終的に、５０〜１５０℃
に加熱して完結させ、ポリウレタンポリアミンを含む塩
基性アミン化合物で変性されたエポキシ樹脂が得られる
。Among the basic amino compounds which are essential constituents of the present invention, the following amino group-containing compounds may be used in combination as components other than the polyurethane polyamine containing a primary amino group at the end of the molecule. For example, mono- and dialkylamines such as methylamine, ethylamine, propylamine, butylamine, diethylamine, dipropylamine, mono- and dialkanolamines such as monoethanolamine, jetanolamine, cyclohexylamine,
Alicyclic monoamines such as morpholine, ethylenediamine, hexamethylenediamine, diethylenetriamine,
Polyamines such as propylene diamine, N-aminoethanolamine, diethylethylenediamine, diethylaminopropylamine, piperazine, N-methylbiperazine, N-aminoethylpiperazine, aniline, N-methylaniline, toluidine, m-xylylenediamine,
Known secondary amines such as polyamide amines obtained by condensing aromatic amines such as diaminodiphenylmethane, dicarboxylic acids such as phthalic acid, adipic acid, and sepatic acid with polyamines such as ethylenediamine, hexamethylenediamine, and diethylenetriamine. Or a secondary amino group-containing compound can be mentioned. Epoxy resin and these, Part-
The reaction of the compound containing a primary or secondary amine group may be carried out simultaneously with or before or after the reaction of the polyurethane polyamine. Usually, the amount used is at least such that the reaction product is water-soluble when neutralized with an acid. The amount may be sufficient for solubilization. The reaction occurs at room temperature, but ultimately at 50-150°C.
The process is completed by heating to obtain an epoxy resin modified with a basic amine compound containing polyurethane polyamine.
更に又、上記ポリウレタンポリアミンを含む塩基性アミ
ノ化合物で変性されたエポキシ樹脂は、分子中又は末端
にカルボキシル基、ヒドロキシル基等を含有するポリエ
ーテル、ポリエステル、ポリアミド、ポリウレタン、ポ
リブタジェン、アクリルポリマー等で変性されてもよい
。Furthermore, the above-mentioned epoxy resin modified with a basic amino compound containing polyurethane polyamine can be modified with polyether, polyester, polyamide, polyurethane, polybutadiene, acrylic polymer, etc. containing carboxyl groups, hydroxyl groups, etc. in the molecule or at the end. may be done.
次に、本発明の生成物に加えられる架橋成分は、公知の
ものが使用でき、特に限定されるものではないが、ブロ
ックポリイソシアネートが好適である。Next, as the crosslinking component added to the product of the present invention, any known crosslinking component can be used, and block polyisocyanate is preferred, although it is not particularly limited.
原料ポリイソシアネートとしては、例えば、トリレンジ
イソシアネート、ジフェニルメタンジイソシアネート、
ヘキサメチレンジイソシアネート等の芳香族、脂肪族ジ
イソシアネート並びに、これらとエチレングリコ−ル、
プロピレングリコール、 ｌ−リメチロールプロパン
等の低級ポリオールとの予備反応物が使用でき、又、ブ
ロック剤としては、メタノール、エタノール、イソプロ
パツール、セロソルブ等のアルコール類、アセトキシム
、メチルエチルケトキシム等のオキシム類、ジエチルア
ミノエタノール等のヒドロキシ第３級アミン類、フェノ
ール、ｍ−クレゾール等のフェノール類、ε−カプロラ
クタム等が挙げられる。Examples of the raw material polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate,
Aromatic and aliphatic diisocyanates such as hexamethylene diisocyanate, and these and ethylene glycol,
Preliminary reaction products with lower polyols such as propylene glycol and l-rimethylolpropane can be used, and as blocking agents, alcohols such as methanol, ethanol, isopropanol, and cellosolve, and oximes such as acetoxime and methyl ethyl ketoxime can be used. , hydroxy tertiary amines such as diethylaminoethanol, phenol, phenols such as m-cresol, and ε-caprolactam.
ブロックポリイソシアネートは、完全ブロックポリイソ
シアネートとして、上記変性エポキシ樹脂に混合するこ
とも可能だがブロック剤の活性水素／イソシアネート基
モル比坏〜ｌの範囲の部分ブロックポリイソシアネート
が適当である。The blocked polyisocyanate can be mixed into the modified epoxy resin as a completely blocked polyisocyanate, but a partially blocked polyisocyanate having a molar ratio of active hydrogen/isocyanate group of the blocking agent in the range of 1 to 1 is suitable.
部分ブロックポリイソシアネートと変性エポキシ樹脂と
の反応は、５０〜１５０℃、好ましくは５０−１００℃
で加熱することにより容易になされ、変性エポキシ樹脂
中のアミン基、水酸基等の活性水素に遊離のインシアネ
ート基が付加する。The reaction between the partially blocked polyisocyanate and the modified epoxy resin is carried out at 50-150°C, preferably at 50-100°C.
This can be easily done by heating at a temperature of 100.degree. C., and free incyanate groups are added to active hydrogen groups such as amine groups and hydroxyl groups in the modified epoxy resin.
このようにして得た１本発明の反応生成物は、蟻酸、酢
酸、プロピオン酸、酪酸、乳酸等の有機酸、リン酸、塩
酸、硫酸等の無機酸で、電着塗料作成時に中和され、水
溶性化される。The reaction product of the present invention thus obtained is an organic acid such as formic acid, acetic acid, propionic acid, butyric acid, or lactic acid, or an inorganic acid such as phosphoric acid, hydrochloric acid, or sulfuric acid, and is neutralized during the preparation of the electrodeposition coating. , made water-soluble.
中和剤の量は、少なくとも、樹脂を水に可溶化又は分散
させるのに必要な量以上で、且つ樹脂のアミ７基の当量
以下であることが好ましい。The amount of the neutralizing agent is preferably at least the amount necessary to solubilize or disperse the resin in water, and not more than the equivalent of amine 7 groups of the resin.
本発明の反応生成物は界面活性剤を必要とせずに水に可
溶化又は分散し得るが、場合により、ノニオン系又はカ
チオン系界面活性剤を併用してもよい。Although the reaction product of the present invention can be solubilized or dispersed in water without the need for a surfactant, a nonionic or cationic surfactant may optionally be used in combination.
更に又、必要に応じ、ジブチル錫ジラウレート等の硬化
触媒、ベンガラ、チタン白、カーボンブラック、タルク
等の顔料、ジオクチルフタレート等の可塑剤、及びノニ
オン性又はカチオン性の他の水溶性樹脂をブレンドする
ことも可能である。Furthermore, if necessary, a curing catalyst such as dibutyltin dilaurate, pigments such as red iron, titanium white, carbon black, and talc, a plasticizer such as dioctyl phthalate, and other nonionic or cationic water-soluble resins are blended. It is also possible.
次に、本発明を実施例により具体的に説明する。（％、
部は重量基準を示す。）
製造例１（ポリウレタンポリアミンの合成例）ビスフェ
ノールＡのプロピレンオキサイド付加物（平均分子量９
００）１００部 トリレンジイソシアネート（２，４−
、２，８−異性体比８０：２０）３９．１部を７０℃で
２時間反応させ遊離イソシアネート基含有量６．８１％
のウレタンプレポリマー１４０．１部を得た。このウレ
タンプレポリマーを９８％硫酸５．４部、重亜硫酸ソー
ダ１４．１部、水８．５部およびジオキサン１４０．１
部からなる混合水溶液１６８．１部に、５０℃で６０分
を要して徐々に添加したのち、更に６０℃で６０分反応
させた。反応終了後３００Ｃに冷却し、３５％過酸化水
素水１３．１部を添加し、そのまま１２０分反応させた
。４０％水酸化ナトリウム水溶液２４．３部で中和し、
生成した中和塩を分離した。口液を脱溶媒することによ
り黄かっ色の粘稠液体を得た。この生成物のアミン価は
、８６．３（ｍｇ−ＫＯＨ／ｇ）であった。Next, the present invention will be specifically explained using examples. (%,
Parts are based on weight. ) Production Example 1 (Synthesis example of polyurethane polyamine) Propylene oxide adduct of bisphenol A (average molecular weight 9
00) 100 parts Tolylene diisocyanate (2,4-
, 39.1 parts of 2,8-isomer ratio 80:20) were reacted at 70°C for 2 hours, and the free isocyanate group content was 6.81%.
140.1 parts of urethane prepolymer was obtained. This urethane prepolymer was mixed with 5.4 parts of 98% sulfuric acid, 14.1 parts of sodium bisulfite, 8.5 parts of water and 140.1 parts of dioxane.
The mixture was gradually added to 168.1 parts of a mixed aqueous solution consisting of 168.1 parts at 50° C. over 60 minutes, and the mixture was further reacted at 60° C. for 60 minutes. After the reaction was completed, the mixture was cooled to 300C, 13.1 parts of 35% hydrogen peroxide solution was added, and the mixture was allowed to react for 120 minutes. Neutralized with 24.3 parts of 40% aqueous sodium hydroxide solution,
The neutralized salt produced was separated. A yellowish-brown viscous liquid was obtained by removing the solvent from the oral fluid. The amine value of this product was 86.3 (mg-KOH/g).
製造例２（ポリウレタンポリアミンの合成例）ポリブジ
タジェングリコール（ＮＩＳＳＯ−ＰＢＧ−２０００：
日本曹達■製）１００部、ヘキサメチレンジイソシアー
ト１７．２部を８０℃で９０分反応させ遊離イソシアネ
ート基含有量３．７６％のウレタンプレポリマー１１７
．２部を得た。Production Example 2 (Synthesis example of polyurethane polyamine) Polybutytadine glycol (NISSO-PBG-2000:
Urethane Prepolymer 117 with a free isocyanate group content of 3.76% was obtained by reacting 100 parts of Nippon Soda ■ and 17.2 parts of hexamethylene diisocyanate at 80°C for 90 minutes.
．． Got 2 copies.
このウレタンプレポリマーを８８％硫酸２．４部、重亜
硫酸ソーダ６．０部、水９．４部およびメチルエチルケ
トン１７５．８部からなる混合水溶液１９３．６部に５
０℃で６０分を要して徐々に添加した後、更に６０℃で
６０分反応させた。反応終了後４０℃に冷却し、３５％
過酸化水素水５．６部を添加し、そのまま６０分反応さ
せた。水酸化カルシラム４．１部、水２０部を加え、６
０℃で６０分中和し、生成した中和塩を分離した。口液
を脱溶媒することにより、淡黄色の粘稠液体を得た。こ
の生成物のアミン価は、４７．２（ｍｇＫＯＨ／ｇ）で
あった。This urethane prepolymer was added to 193.6 parts of a mixed aqueous solution consisting of 2.4 parts of 88% sulfuric acid, 6.0 parts of sodium bisulfite, 9.4 parts of water, and 175.8 parts of methyl ethyl ketone.
After gradually adding the mixture at 0°C over 60 minutes, the reaction was further carried out at 60°C for 60 minutes. After the reaction is completed, cool to 40°C and reduce to 35%
5.6 parts of hydrogen peroxide solution was added, and the mixture was allowed to react for 60 minutes. Add 4.1 parts of calcium hydroxide and 20 parts of water,
Neutralization was carried out at 0°C for 60 minutes, and the generated neutralized salt was separated. By removing the solvent from the oral fluid, a pale yellow viscous liquid was obtained. The amine value of this product was 47.2 (mgKOH/g).
実施例１
エポキシ当量１９０のビスフェノールＡ型エポキシ樹脂
（エピコー）８２８ ニジエル化学■製）２００部をメ
チルイソブチルケトン５０部に溶解し、製造例１．のポ
リウレタンポリアミン２００部、ジエチルアミン５０部
、メチルイソブチルケトン１００部よりなる混合液に、
常温下、徐々に添加し、発熱がおさまってから、 １０
０℃で１時間加熱し６００部の変性エポキシ樹脂組成物
を得た。これに、予じめトリレンジイソシアネー） （
２，４−。Example 1 200 parts of a bisphenol A type epoxy resin (Epicor 828 manufactured by Nisiel Chemical Co., Ltd.) having an epoxy equivalent of 190 was dissolved in 50 parts of methyl isobutyl ketone. In a mixed solution consisting of 200 parts of polyurethane polyamine, 50 parts of diethylamine, and 100 parts of methyl isobutyl ketone,
Add it gradually at room temperature, and after the heat generation subsides, 10
It was heated at 0° C. for 1 hour to obtain 600 parts of a modified epoxy resin composition. To this, add tolylene diisocyanate (tolylene diisocyanate) (
2,4-.
２．６＝ 異性体比８０／２０）１０５部に、ｎ−ブタ
ノール４５部を６０℃で１時間反応して、得た部分ブロ
ックジイソシアネート１５０部を加え、８０°Ｃで１時
間反応して、固型分８０．５％、アミン価８５ （ｍｇ
−ＫＯＨ／ｇ）の本発明の組成物を得た。2.6 = isomer ratio 80/20) 150 parts of partially blocked diisocyanate obtained by reacting 45 parts of n-butanol at 60°C for 1 hour were added, and the mixture was reacted at 80°C for 1 hour. Solid content 80.5%, amine value 85 (mg
-KOH/g) of the composition of the present invention was obtained.
この組成物１５０部に酢酸６．８部および脱イオン水１
．０５０部を加え固型分ｌＯ％。150 parts of this composition plus 6.8 parts of acetic acid and 1 part of deionized water.
．． Add 050 parts to make solid content 10%.
ＰＨ５，０の均一水性分散液を得た。これを電着浴とし
て、リン酸亜鉛処理鋼板をカソードとして、２５℃で３
分間２００ｖで電着して、１８０℃で３０分焼付、厚さ
２０ｇの硬化塗膜を得た。得られた塗膜の性能は、以下
の通りであった。この時のつきまわり性（パイプ法）は
、２２ａｌであった。A homogeneous aqueous dispersion with pH 5.0 was obtained. Using this as an electrodeposition bath and a zinc phosphate treated steel plate as a cathode,
Electrodeposition was performed at 200 V per minute and baked at 180° C. for 30 minutes to obtain a cured coating film with a thickness of 20 g. The performance of the obtained coating film was as follows. The throwing power (pipe method) at this time was 22al.
鉛筆硬度 ２Ｈ酎衝撃性（繕イ
ンチ、 ５００ｇ、５０ｏ）異常なし密着性（ゴバン目
試験） １００／１００エリクセン
６ｍ以上耐蝕性（７２０時間）
異常なし塗面平滑性 良
好実施例２
エポキシ当量５００のビスフェノールＡ型エポキシ樹脂
（エピコー）１００１ニジエル化学■製）２００部をメ
チルイソブチルケトン１００部に溶解し、ジイソプロピ
ルアミン５０部と、ジェタノール７３７１０部を６００
０で滴下し、８０℃で２時間反応した。Pencil hardness: 2H impact resistance (tempering inch, 500g, 50o) No abnormality Adhesion (goban test) 100/100 Erichsen
Corrosion resistance over 6m (720 hours)
No abnormality. Painted surface smoothness. Good Example 2 200 parts of bisphenol A epoxy resin (Epicor 1001 manufactured by Nisiel Chemical Co., Ltd.) with an epoxy equivalent of 500 was dissolved in 100 parts of methyl isobutyl ketone, and 50 parts of diisopropylamine and 73,710 parts of jetanol were dissolved. 600
It was added dropwise at 0 and reacted at 80°C for 2 hours.
次に、これを製造例２．のポリウレタンポリアミン２０
０部メチルイソブチルケトン１００部よりなる混合液に
加えて、１００℃に加熱し１時間反応し６６０部の変性
エポキシ樹脂組成物を得た。Next, this was prepared in Production Example 2. polyurethane polyamine 20
The mixture was added to a mixed solution consisting of 100 parts of methyl isobutyl ketone, heated to 100° C., and reacted for 1 hour to obtain 660 parts of a modified epoxy resin composition.
実施例１．と同様、予じめ調整しておいた、トリレンジ
イソシアネート１２０部とエチルセロソルブ６２部から
なる部分ブロックジイソシアネート１８２部を加え、１
００℃で１時間反応して、固型分７６％の本発明の組成
物を得た。Example 1. Similarly, 182 parts of partially blocked diisocyanate consisting of 120 parts of tolylene diisocyanate and 62 parts of ethyl cellosolve, which had been prepared in advance, were added, and 1
After reacting at 00° C. for 1 hour, a composition of the present invention with a solids content of 76% was obtained.
この樹脂１５０部にプロピオン酸８部及び脱イオン水７
９２部を加え、固型分１２％、ＰＨ６，８の電着浴をつ
くった。リン酸亜鉛処理鋼板をカソードとして３０℃、
２００Ｖで３分間型着し、更に、１８０℃で４０分焼付
け、厚さ２５ＩＬの塗膜を得た。得られた塗膜の性能は
、以下の通りであった。150 parts of this resin, 8 parts of propionic acid and 7 parts of deionized water.
92 parts were added to prepare an electrodeposition bath with a solid content of 12% and a pH of 6.8. 30℃ using a zinc phosphate treated steel plate as a cathode.
The mold was molded at 200 V for 3 minutes and then baked at 180° C. for 40 minutes to obtain a coating film with a thickness of 25 IL. The performance of the obtained coating film was as follows.
鉛筆硬度 ３Ｈ酎衝撃性（３４
インチ、 ５００ｇ、５０ｃ、）異常なし耐蝕性（１，
２００時間） 異常なしエリクセン
６ＩＩＩｍ以上塗面平滑性
良好比較例１゜
エポキシ当量１９０のビスフェノールＡ型エポキシ樹脂
（エビコー）８２８ ニジエル化学■製）２００部をメ
チルイソブチルケトン５０部に溶解し、アミン価１００
のダイマー酸型ポリアミド樹脂（トーマイド２１０：富
士化成■製）２００部、ジエチルアミン５０部、メチル
イソブチルケトン１００部よりなる混合液に常温下、徐
々に添加し、発熱がおさまってから１００℃で１時間加
熱し、６００部の変性エポキシ樹脂組成物を得た。これ
に予じめトリレンジイソシアネート（２，４−。Pencil hardness 3H impact resistance (34
inch, 500g, 50c,) No abnormality Corrosion resistance (1,
200 hours) No abnormality Eriksen
Painted surface smoothness of 6IIIm or more
Good Comparative Example 1 200 parts of bisphenol A type epoxy resin (Ebicor 828 manufactured by Nigel Chemical Co., Ltd.) with an epoxy equivalent of 190 was dissolved in 50 parts of methyl isobutyl ketone, and the amine value was 100.
It was gradually added at room temperature to a mixed solution consisting of 200 parts of dimer acid type polyamide resin (Tomide 210: manufactured by Fuji Kasei ■), 50 parts of diethylamine, and 100 parts of methyl isobutyl ketone, and after the heat generation subsided, it was heated at 100°C for 1 hour. It was heated to obtain 600 parts of a modified epoxy resin composition. Add tolylene diisocyanate (2,4-) to this in advance.
２．６−異性体比８０／２０） Ｉ Ｏ５部に、ｎ−ブ
タノール４５部を６０℃で１時間反応して得た部分ブロ
ックジイソシアネー）１５０部を加え８０℃で１時間反
応して、固型分８０％、アミン価９２ （ｍｇ−ＫＯＨ
／ｇ）１７）組成物を得た。この１５０部に酢酸７．９
部および脱イオン水１，０４２部を加え固型分ｌＯ％Ｐ
Ｈ５，２の均一水性分散液を得た。これを電着浴として
、リン酸亜鉛処理鋼板をカソードとして、２５℃で３分
間２００ｖで電着して、１８０℃で３０分焼付、厚さ２
０ＩＬの硬化塗膜を得た。2.6 - 150 parts of partially blocked diisocyanate obtained by reacting 45 parts of n-butanol at 60°C for 1 hour were added to 5 parts of IO (isomer ratio 80/20) and reacted at 80°C for 1 hour. , solid content 80%, amine value 92 (mg-KOH
/g) 17) A composition was obtained. Acetic acid 7.9 to this 150 parts
and 1,042 parts of deionized water to reduce the solid content to lO%P.
A homogeneous aqueous dispersion of H5,2 was obtained. Using this as an electrodeposition bath and using a zinc phosphate treated steel plate as a cathode, electrodeposition was carried out at 25℃ for 3 minutes at 200V, and baked at 180℃ for 30 minutes to a thickness of 2.
A cured coating film of 0IL was obtained.
この時のつきまわり性（パイプ法）は、１６〔であった
。得られた塗膜の性能は、以下の通りであった。The throwing power (pipe method) at this time was 16. The performance of the obtained coating film was as follows.
鉛筆硬度 ２Ｈ酎衝撃性（３４
インチ、 ５００ｇ、５０印）異常なし密着性
１００／１００エリクセン
６．以上耐蝕性（４８０時間）
異常あり塗面平滑性 良好比
較例２゜
分子末端にカルボキシル基を含有するポリブタジェンカ
ルポン酸（ＮＩＳＳＯ−ＰＢＣ−１０００：日本曹達■
製）３００部およびエポキシ当量１９０のビスフェノー
ルＡ型エポキシ樹脂（エピコート８２８ニジエル化学■
製）２００部を１５０℃で３時間加熱反応した。次にセ
ロソルブアセテート１５０部を加えた後、ジエチルアミ
ン４１．５部及びエチレンジアミン８．５部よりなる混
合液を３０分間で滴下し、更に１００℃で２時間反応し
て変性エポキシ樹脂組成物を得た。この組成物は、均一
性不良で、層分離が認められた。Pencil hardness 2H impact resistance (34
inch, 500g, 50 mark) Adhesion without any abnormality
100/100 Eriksen
6. Corrosion resistance (480 hours)
Abnormality Painted surface smoothness Good Comparative Example 2゜Polybutadienecarboxylic acid containing carboxyl groups at the end of the molecule (NISSO-PBC-1000: Nippon Soda■
) 300 parts and epoxy equivalent weight 190 bisphenol A epoxy resin (Epicote 828 Nigel Chemical)
200 parts of the product (manufactured by M.D.) were heated and reacted at 150° C. for 3 hours. Next, after adding 150 parts of cellosolve acetate, a mixed solution consisting of 41.5 parts of diethylamine and 8.5 parts of ethylenediamine was added dropwise over 30 minutes, followed by further reaction at 100° C. for 2 hours to obtain a modified epoxy resin composition. . This composition had poor uniformity and layer separation was observed.
これに予じめトリレンジイソシアー） （２，４−１２
，６−異性体比８０／２０）９４部に、ｎ−ブタノール
４３．５部を６０℃で１時間反応して得た部分ブロック
ジイソシアネート１３７．５部を加え、８０°Ｃで１時
間反応した。更にブチルセロソルブ１４４．６部を加え
、固型分７０％、アミン価６０ （ｍｇ−ＫＯＨ／ｇ）
の組成物を得た。Tolylene diisocyanate (2,4-12
, 6-isomer ratio 80/20) were added with 137.5 parts of partially blocked diisocyanate obtained by reacting 43.5 parts of n-butanol at 60°C for 1 hour, and the mixture was reacted at 80°C for 1 hour. . Furthermore, 144.6 parts of butyl cellosolve was added to give a solid content of 70% and an amine value of 60 (mg-KOH/g).
A composition was obtained.
この組成物に酢酸を加えＰＨ５，８となるよう中和し、
脱イオン水を加え固型分１０％とした。この水分散液は
不均一であり、水不溶物が一部浮遊していた。これを電
着浴として、２００Ｖで３分間型着し、更に１８０℃で
、３０分焼付け、厚さ２０１１．の塗膜を得た。Add acetic acid to this composition to neutralize it to pH 5.8,
Deionized water was added to make the solids content 10%. This aqueous dispersion was non-uniform, with some water-insoluble substances floating therein. Using this as an electrodeposition bath, mold was applied at 200V for 3 minutes, and then baked at 180°C for 30 minutes to a thickness of 2011. A coating film was obtained.
得られた塗膜の性能は以下の通りであった。The properties of the resulting coating film were as follows.
鉛筆硬度 ３Ｈ耐衝撃性（坏イ
ンチ、 ５００ｇ、５０ａＩ）微少割れ耐蝕性（１，２
００時間） 異常ありエリクセン
６＋１１１１１以上塗面平滑性 不良（ピン
ホール、ハジキ）以上の如く、本発明の電着塗料組成物
は、塗面平滑性、つきまわり性、浴安定性等の電着実用
性が良好であり、得られた塗膜性能は、比較例に比して
優れた耐蝕性、耐衝撃性等を有することが明白である。Pencil hardness: 3H Impact resistance (inches, 500g, 50aI) Micro-cracking corrosion resistance (1,2
00 hours) Eriksen with abnormality
6+11111 or more Poor coated surface smoothness (pinholes, repellency) As described above, the electrodeposition coating composition of the present invention has good electrodeposition practicality such as coated surface smoothness, throwing power, bath stability, etc. It is clear that the resulting coating film has superior corrosion resistance, impact resistance, etc. compared to the comparative example.
Claims (1)
体とするカチオン電着塗料用樹脂組成物において、塩基
性アミノ化合物の少なくとも、一部に、分子末端に第一
級アミノ基を含有するポリウレタンポリアミンを配合し
てなることを特徴とするカチオン電着塗料用樹脂組成物
。[Scope of Claims] A resin composition for a cationic electrodeposition coating based on a modified epoxy resin obtained by reacting an epoxy resin and a basic amino compound as essential components, in which at least a part of the basic amino compound is 1. A resin composition for cationic electrodeposition paint, comprising a polyurethane polyamine containing a primary amino group at the end of the molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14316184A JPS6121167A (en) | 1984-07-09 | 1984-07-09 | Resin composition for cationic electroplating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14316184A JPS6121167A (en) | 1984-07-09 | 1984-07-09 | Resin composition for cationic electroplating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6121167A true JPS6121167A (en) | 1986-01-29 |
| JPH0439506B2 JPH0439506B2 (en) | 1992-06-29 |
Family
ID=15332333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14316184A Granted JPS6121167A (en) | 1984-07-09 | 1984-07-09 | Resin composition for cationic electroplating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6121167A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6422917A (en) * | 1987-06-25 | 1989-01-25 | Basf Lacke & Farben | Synthetic resin having nitrogen basic group, and its production and use |
| CN103717686A (en) * | 2011-07-19 | 2014-04-09 | 日本帕卡濑精股份有限公司 | Aqueous composition for metal surface treatment, method for metal surface treatment using composition, and method for producing metal material having film, as well as metal surface treatment film using same |
-
1984
- 1984-07-09 JP JP14316184A patent/JPS6121167A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6422917A (en) * | 1987-06-25 | 1989-01-25 | Basf Lacke & Farben | Synthetic resin having nitrogen basic group, and its production and use |
| CN103717686A (en) * | 2011-07-19 | 2014-04-09 | 日本帕卡濑精股份有限公司 | Aqueous composition for metal surface treatment, method for metal surface treatment using composition, and method for producing metal material having film, as well as metal surface treatment film using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0439506B2 (en) | 1992-06-29 |
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