JPH0229478A - Coating resin composition - Google Patents
Coating resin compositionInfo
- Publication number
- JPH0229478A JPH0229478A JP17840288A JP17840288A JPH0229478A JP H0229478 A JPH0229478 A JP H0229478A JP 17840288 A JP17840288 A JP 17840288A JP 17840288 A JP17840288 A JP 17840288A JP H0229478 A JPH0229478 A JP H0229478A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- acid
- weight
- amino
- butanol
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 title abstract description 16
- 239000011248 coating agent Substances 0.000 title abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 40
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920003180 amino resin Polymers 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims abstract description 8
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000003973 paint Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 150000003918 triazines Chemical class 0.000 claims description 5
- FNNFAYGKUXMHSH-UHFFFAOYSA-N 6-[2-(4,6-diamino-1,3,5-triazin-2-yl)phenyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C(=CC=CC=2)C=2N=C(N)N=C(N)N=2)=N1 FNNFAYGKUXMHSH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- -1 amino compound Chemical class 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 239000008199 coating composition Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 238000010992 reflux Methods 0.000 description 11
- 229920000180 alkyd Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 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 2
- 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 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000005028 tinplate Substances 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
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical group CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical group CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ZZAGLMPBQOKGGT-UHFFFAOYSA-N [4-[4-(4-prop-2-enoyloxybutoxy)benzoyl]oxyphenyl] 4-(4-prop-2-enoyloxybutoxy)benzoate Chemical compound C1=CC(OCCCCOC(=O)C=C)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCOC(=O)C=C)C=C1 ZZAGLMPBQOKGGT-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルキルエーテル化アミノ樹脂を含有してな
る塗料用樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition for paint containing an alkyl etherified amino resin.
(従来の技術)
従来からアルキルエーテル化アミノ樹脂とアルキド樹脂
、アクリル樹脂、エポキシ樹脂等を組合せてなる熱硬化
性樹脂組成物が、塗料に用いられている。最近、自動車
、産業機械、鋼製家具、電気製品、建築物等の被覆用塗
料に対して省力、省資源、省エネルギー、作業合理化等
の要求が強い。(Prior Art) Thermosetting resin compositions made by combining alkyl etherified amino resins with alkyd resins, acrylic resins, epoxy resins, etc. have been used for paints. Recently, there has been a strong demand for labor-saving, resource-saving, energy-saving, work rationalization, etc. for coating paints for automobiles, industrial machinery, steel furniture, electrical appliances, buildings, etc.
これらの問題を解決するには90〜110°Cの低温で
20分間硬化すること、あるいは200〜250°C等
の高温で短時間焼付は可能なことが望ましい。To solve these problems, it is desirable to be able to cure at a low temperature of 90 to 110°C for 20 minutes, or to be able to bake for a short time at a high temperature such as 200 to 250°C.
従来のアミノアルキド樹脂或いはアミノエポキシ樹脂に
おいて、使用されるアルキルエーテル化アミノ樹脂は、
数平均分子量が比較的小さ(、該樹脂中に結合ホルムア
ルデヒド及びブチルエーテル基が比較的多く含有される
ものであり、分子内にトリアジン核を一個〜数十個有す
るものの混合物であり、1核体及び2核体の低分子量体
の含を率が比較的高いのが一般的である。In conventional aminoalkyd resins or aminoepoxy resins, the alkyl etherified amino resins used are:
The number average molecular weight is relatively small (the resin contains a relatively large amount of bonded formaldehyde and butyl ether groups, and it is a mixture of one to several dozen triazine nuclei in the molecule, mononuclear and Generally, the content of low molecular weight dinuclear bodies is relatively high.
また、特開昭62−101666号公報に示されるアミ
ノ樹脂には、1核体及び2核体を有する割合が10重量
%以下というものもある。Furthermore, some amino resins disclosed in JP-A-62-101666 have a proportion of mononuclear bodies and dinuclear bodies of 10% by weight or less.
〔発明が解決しようとする課題]
低分子量体の含有割合が多いアルキルエーテル化アミノ
樹脂を用いた塗料は、硬化反応時に有機溶剤と共に低分
子部分が揮敗し、乾燥炉内に付着し或いは炉の出入口、
ダスト内壁、ダクト漏れ部等の低温雰囲気との接触によ
って凝集・固化する。[Problems to be Solved by the Invention] Paints using alkyl etherified amino resins with a high content of low molecular weight substances volatilize the low molecular weight parts together with the organic solvent during the curing reaction, and may adhere to the inside of the drying oven or dry in the oven. entrance and exit,
Dust coagulates and solidifies when it comes into contact with low-temperature atmospheres such as inside dust walls and duct leaks.
これら飛散物質は、炉の出入口部等での被塗物への落下
による製品不良の発生及び堆積物の着火、発火等の問題
、更に炉管理にあたり清掃管理費の増大等の問題が生じ
る。These scattered substances cause problems such as product defects and ignition of deposits due to falling onto objects to be coated at the entrance and exit of the furnace, as well as increased cleaning and management costs for furnace management.
一方、特開昭62−101666号公報に示されるよう
な、低分子量体の含有割合が比較的少ないアルキルエー
テル化アミノ樹脂は、上記問題点については改良されて
いるが、樹脂製造時或いは塗料作成時の作業性が悪いと
いう欠点を有している。On the other hand, alkyl etherified amino resins with a relatively low content of low molecular weight substances, as shown in JP-A-62-101666, have been improved with respect to the above-mentioned problems; It has the disadvantage of poor workability.
本発明は、樹脂製造時及び塗料作成時の作業性が良く、
塗膜の焼付時に加熱減量が小さく、飛散物も少ない塗料
用樹脂組成物を提供するものである。The present invention has good workability during resin production and paint preparation,
The present invention provides a resin composition for coatings which has a small heating loss during baking of a coating film and has few scattered substances.
本発明は、(A)アミノ樹脂原料(ベンゾグアナミンを
必須成分とし、他にメラミン、アセトグアナミン、フタ
ログアナミン、ジシアンジアミド又は尿素からなる群か
ら選ばれる1種以上のアミノ化合物を含んでもよい。)
とホルムアルデヒドとの付加縮合及びアルコールによる
エーテル化反応を行って得られ、分子内にトリアジン核
を1個有するもの及び2個有するものの割合がそれぞれ
10〜25重量%であり、ガードナー粘度(不揮発分6
0%、希釈溶剤n−ブタノール)がU以下、遊離のホル
ムアルデヒドカ月、5重量%以下であるアルキルエーテ
ル化アミノ樹脂及び
(B)該アルキルエーテル化アミノ樹脂と反応して硬化
可能な樹脂を含有してなる塗料用樹脂組成物に関する。The present invention provides (A) amino resin raw material (benzoguanamine is an essential component, and may also contain one or more amino compounds selected from the group consisting of melamine, acetoguanamine, phthaloguanamine, dicyandiamide, or urea).
is obtained by addition condensation with formaldehyde and etherification reaction with alcohol, and the ratio of those having one triazine nucleus and those having two triazine nuclei in the molecule is 10 to 25% by weight, respectively, and the Gardner viscosity (nonvolatile content 6
0%, diluent solvent n-butanol) is less than U, free formaldehyde is less than 5% by weight, and (B) a resin that can be cured by reacting with the alkyl etherified amino resin. The present invention relates to a resin composition for a coating material.
本発明の樹脂組成物に用いる(A)成分であるアルキル
エーテル化アミノ樹脂の製造法は、既に公知であり、条
件を適宜選択することにより容易に合成できる。アミノ
樹脂原料は、ベンゾグアナミンを必須成分とするが、他
にメラミン、アセトグアナミン、フタログアナミン、ジ
シアンジアミド、尿素からなる群から選ばれる1種以上
のアミノ化合物を併用してもよい。他のアミノ化合物を
併用する場合は、ベンゾグアナミンの使用量をアミノ樹
脂原料の総量に対して10重量%以上使用するのが好ま
しい。30重量%以上使用するのがより好ましい。(A
)成分であるアルキルエーテル化アミノ樹脂は、分子内
にトリアジン核を1個有するもの及び2個有するものの
割合がそれぞれ10〜25重世%である樹脂である。前
記割合は、より好ましくは10〜17重量%である。The method for producing the alkyl etherified amino resin, component (A), used in the resin composition of the present invention is already known, and can be easily synthesized by appropriately selecting conditions. The amino resin raw material contains benzoguanamine as an essential component, but may also contain one or more amino compounds selected from the group consisting of melamine, acetoguanamine, phthaloguanamine, dicyandiamide, and urea. When other amino compounds are used in combination, the amount of benzoguanamine used is preferably 10% by weight or more based on the total amount of amino resin raw materials. It is more preferable to use 30% by weight or more. (A
The alkyl etherified amino resin which is the component () is a resin in which the ratio of one triazine nucleus and two triazine nuclei in the molecule is 10 to 25%, respectively. The proportion is more preferably 10 to 17% by weight.
分子内にトリアジン核を1個有するもの又は2個有する
ものの割合がどちらか一方でも25重量%を越えると、
熱硬化時に揮発する低分子物質が多くなり、乾燥炉内に
付着するものの割合が大きくなる。また、未反応のメラ
ミン、ベンゾグアナミン等のアミノ化合物或いはホルム
アルデヒド低付加体のメラミン、グアナミン等の含有率
も多くなり、揮発・付着する割合も多くなる。更に遊離
ホルムアルデヒド、アミノ樹脂より脱離するホルムアル
デヒドも悪影響を与える。一方、分子内にトリアジン核
を1個有するもの又は2個有するものの割合が、どちら
か一方が10重量%未満の場合は、塗料とするとき、多
量の溶剤を必要とし、塗装固形分が低下し、塗膜の鮮映
性が劣る。また、塗料化する前の樹脂自体も粘度が高く
、取り扱い上、非常な困難を生じ、作業能率の低下が起
こる。If the proportion of either one or two triazine nuclei in the molecule exceeds 25% by weight,
The amount of low-molecular substances that volatilize during heat curing increases, and the proportion of substances that adhere to the inside of the drying oven increases. In addition, the content of unreacted amino compounds such as melamine and benzoguanamine, or low formaldehyde adducts such as melamine and guanamine increases, and the proportion of volatilization and adhesion also increases. Furthermore, free formaldehyde and formaldehyde released from the amino resin also have an adverse effect. On the other hand, if the proportion of either one or two triazine nuclei in the molecule is less than 10% by weight, a large amount of solvent will be required to form a paint, and the solid content of the coating will decrease. , the sharpness of the coating film is poor. In addition, the resin itself has a high viscosity before being made into a paint, making it extremely difficult to handle and reducing work efficiency.
じる。Jiru.
本発明のアルキルエーテル化アミノ樹脂は、べンゾグア
ナミンを含有するアミノ樹脂原料をブタノール、メタノ
ール等のアルコール中でホルムアルデヒドと付加反応さ
せ、次いで酸性領域で縮合反応及びアルキルエーテル化
反応を行う。その後、再度ブタノール、メタノール等の
アルコールを添加し、再アルキルエーテル化反応を行い
、粘度を下げ、最後に目的の固形分になるように脱溶剤
を行うことにより製造できる。或いは縮合反応及びアル
キルエーテル化反応後、脱溶剤を行った後、再度アルコ
ールを添加し、再アルキルエーテル化反応を行い、粘度
を下げ、再び目的の固形分になるように脱溶剤を行って
もよい。この際、例えば300mmHg以下の減圧下で
、温度125〜150°Cで1〜3時間脱溶剤を行うこ
とにより遊離ホルムアルデヒドの含有量を1.5重量%
以下とすることができる。より好ましい条件は、250
mmHg以下の減圧下で他は同じ条件とすることである
。The alkyl etherified amino resin of the present invention is produced by subjecting an amino resin raw material containing benzoguanamine to an addition reaction with formaldehyde in an alcohol such as butanol or methanol, followed by a condensation reaction and an alkyl etherification reaction in an acidic region. Thereafter, alcohol such as butanol or methanol is added again to perform a re-alkyl etherification reaction to lower the viscosity, and finally, the solvent can be removed to reach the desired solid content. Alternatively, after the condensation reaction and the alkyl etherification reaction, the solvent may be removed, alcohol may be added again, the alkyl etherification reaction may be performed again, the viscosity may be lowered, and the solvent may be removed to achieve the desired solid content again. good. At this time, the content of free formaldehyde is reduced to 1.5% by weight by desolventizing for 1 to 3 hours at a temperature of 125 to 150°C under reduced pressure of, for example, 300 mmHg or less.
It can be as follows. More preferable conditions are 250
The other conditions are the same under reduced pressure of mmHg or less.
以上の反応でホルムアルデヒドの付加反応工程以外は、
塩酸、硫酸、リン酸、硝酸、フタル酸、マレイン酸、シ
ュウ酸、ギ酸等の酸性触媒を添加し、酸性条件下(好ま
しくはpH4〜6)で行うのが好ましい。反応温度は合
成時間等の観点から還流温度が好ましく、ブタノールを
用いる場合を例にあげれば90〜120″Cにするのが
好ましい。In the above reaction, except for the formaldehyde addition reaction step,
It is preferable to add an acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, phthalic acid, maleic acid, oxalic acid, or formic acid, and carry out the reaction under acidic conditions (preferably pH 4 to 6). The reaction temperature is preferably reflux temperature from the viewpoint of synthesis time, etc., and in the case of using butanol, for example, it is preferably 90 to 120''C.
また、原料の仕込みは、例えばアミノ樹脂原料1モルに
対し、ホルムアルデヒド4〜7モル及びアルコール4〜
8モル、更に追加するアルコール0.5〜4モル使用す
るのが好ましく、ベンゾグアナミン1モルに対し、ホル
ムアルデヒド1.8〜4.0モル及びアルコール2〜5
モル、追加するアルコール0.5〜4.0モルを使用す
るのが好ましい。In addition, the raw materials may be charged, for example, 4 to 7 moles of formaldehyde and 4 to 7 moles of alcohol to 1 mole of amino resin raw material.
It is preferable to use 8 moles of alcohol and 0.5 to 4 moles of additional alcohol, and 1.8 to 4.0 moles of formaldehyde and 2 to 5 moles of alcohol per mole of benzoguanamine.
mol, preferably from 0.5 to 4.0 mol of additional alcohol.
このようにして得られたアルキルエーテル化アミノ樹脂
は、ゲルパーミェーションクロマトグラフィーにより分
子量分布の測定を行い、分子内にトリアジン核1個有す
るもの及び2個有するものの割合をクロマトグラムから
対応する成分の面積比を算出することによって求めるこ
とができる。The molecular weight distribution of the alkyl etherified amino resin thus obtained is measured by gel permeation chromatography, and the proportion of those having one triazine nucleus and those having two triazine nuclei in the molecule is determined from the chromatogram. It can be determined by calculating the area ratio of the components.
本発明に用いるアルキルエーテル化アミノ樹脂は、n−
ブタノールに不揮発分が60重量%になるように溶解し
たときの粘度(ガードナー 25’c >がU以下であ
る。Ut棒jj&−r%掌f’lhゞ湯3゜7本発明に
おいて(B)成分として用いる、上記アルキルエーテル
化アミノ樹脂と反応して硬化可能な樹脂としては、アク
リル樹脂、アルキド樹脂、アルキド変性アクリル樹脂、
エポキシ樹脂、エポキシ変性アルキド樹脂等、従来公知
のものが使用できる。これらは上記アルキルエーテル化
アミノ樹脂と反応するために水酸基価が15〜200の
ものが好ましい。The alkyl etherified amino resin used in the present invention is n-
Viscosity when dissolved in butanol so that the non-volatile content is 60% by weight (Gardner 25'c > is less than U. Ut rod jj & -r% palm f'lh ゞ 3゜7 In the present invention (B) Examples of resins that can be cured by reacting with the alkyl etherified amino resin used as components include acrylic resins, alkyd resins, alkyd-modified acrylic resins,
Conventionally known resins such as epoxy resins and epoxy-modified alkyd resins can be used. These preferably have a hydroxyl value of 15 to 200 in order to react with the alkyl etherified amino resin.
上記アルキド樹脂は、例えば多価カルボン酸、多価アル
コール及び必要に応じて油脂若しくはこれの脂肪酸を反
応させて得られる樹脂である。多価カルボン酸としては
、フタル酸、イソフタル酸、テレフタル酸、テトラビト
ロフタル酸、マレイン酸、フマル酸、コハク酸、アジピ
ン酸、セパシン酸、トリメリット酸、ピロメリット酸等
がある。The alkyd resin is a resin obtained by reacting, for example, a polyhydric carboxylic acid, a polyhydric alcohol, and, if necessary, oil or fat or a fatty acid thereof. Examples of polyhydric carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrabitrophthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sepacic acid, trimellitic acid, and pyromellitic acid.
これらは、酸無水物、酸ハライド等のエステル形成性誘
導体の形で使用してもよい。多価アルコールとしては、
エチレングリコール、ジエチレングリコール、トリエチ
レングリコール、プロピレングリコール、ジプロピレン
グリコール、ネオペンチルグリコール、■、4−ブタン
ジオール、16−ヘキサンジオール、トリメチレングリ
コール、グリセリン、トリメチロールプロパン、トリメ
チロールエタン、ペンタエリドリフト等がある。油とし
ては、桐油、亜麻仁油、大豆油、脱水ヒマシ油、サフラ
ワー油、ヒマシ油、ヤシ油、トール油等がある。These may be used in the form of ester-forming derivatives such as acid anhydrides and acid halides. As a polyhydric alcohol,
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, ■, 4-butanediol, 16-hexanediol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerydrift, etc. There is. Examples of the oil include tung oil, linseed oil, soybean oil, dehydrated castor oil, safflower oil, castor oil, coconut oil, and tall oil.
アルキド樹脂の製造は、公知の方法により行うことがで
き、油を使用するときは、油と多価アルコールを水酸化
リチウム等のエステル交換触媒の存在下に200〜26
0°Cで反応させた後、多塩基酸及び残りの多価アルコ
ールを加えて180〜250°Cで反応させる方法、油
を使用しないときは、原料を混合して180〜250°
Cで反応させる方法等がある。The alkyd resin can be produced by a known method, and when oil is used, the oil and polyhydric alcohol are mixed in the presence of a transesterification catalyst such as lithium hydroxide.
After reacting at 0°C, add the polybasic acid and remaining polyhydric alcohol and react at 180 to 250°C. If oil is not used, mix the raw materials and heat at 180 to 250°C.
There is a method of reacting with C, etc.
また、アクリル樹脂は、アクリル酸2−ヒドロキシエチ
ル、アクリル酸2−ヒドロキシプロピル、メタクリル酸
2−ヒドロキシエチル、メタクリル酸2−ヒドロキシプ
ロピル等のヒドロキシ基ヲをするα、β−エチレン性不
飽和単量体及びその他の不飽和単量体を共重合させて得
られるものである。その他の不飽和単量体としては、ア
クリル酸、メタクリル酸、マレイン酸、イタコン酸等の
αβ−モノエチレン性不飽和カルボン酸、アクリル酸メ
チル、アクリル酸エチル、アクリル酸n−フチル、アク
リル酸2−エチルヘキシル、メタクリル酸メチル、メタ
クリル酸n−ブチル等のα、βモノエチレン性不飽和カ
ルボン酸のアルキルエステル、アクリルアミド、メタク
リルアミド、N−メチロールアクリルアミド、N−メチ
ロールメタクリルアミド、ジアセトンアクリルアミド等
のアクリルアミド誘導体、アクリル酸グリシジル、メタ
クリル酸グリシジル等のα、β−モノエチレン性不性用
飽和カルボン酸リシジルエステル、酢酸ビニル、プロピ
オン酸ビニル等の飽和カルボン酸のビニルエステル、ス
チレン、α−メチルスチレン、ビニルトルエン等の芳香
族不飽和単量体等がある。Acrylic resins also contain α,β-ethylenically unsaturated monomers having hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. It is obtained by copolymerizing monomers and other unsaturated monomers. Other unsaturated monomers include αβ-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, methyl acrylate, ethyl acrylate, n-phthyl acrylate, and diacrylic acid. - Alkyl esters of α, β monoethylenically unsaturated carboxylic acids such as ethylhexyl, methyl methacrylate, and n-butyl methacrylate; acrylamides such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and diacetone acrylamide; derivatives, lycidyl esters of α, β-monoethylenically saturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate, styrene, α-methylstyrene, Examples include aromatic unsaturated monomers such as vinyltoluene.
上記共重合は、アゾビスイソブチロニトリル、過酸化ベ
ンゾイル、過酸化ジブチル、クメンヒドロペルオキシド
等のラジカル触媒の存在下に90〜160 ’Cに加熱
して行うことができる。The above copolymerization can be carried out by heating to 90 to 160'C in the presence of a radical catalyst such as azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, cumene hydroperoxide.
上記アルキド樹脂変性アクリル樹脂は、上記アルキド樹
脂の存在下に上記アクリル樹脂の原料であるモノマーを
重合させて得ることができる。The alkyd resin-modified acrylic resin can be obtained by polymerizing monomers that are raw materials for the acrylic resin in the presence of the alkyd resin.
上記アルキド樹脂、アクリル樹脂及びアルキド樹脂変性
アクリル樹脂の原料配合は、水酸基価が15〜200に
なるように調整されるのが好ましい。なお、水酸基価が
小さすぎると、硬化性が劣り、大きすぎると、塗膜の耐
水性が劣る傾向となる。The raw material composition of the alkyd resin, acrylic resin, and alkyd resin-modified acrylic resin is preferably adjusted so that the hydroxyl value is 15 to 200. Note that if the hydroxyl value is too small, the curability tends to be poor, and if it is too large, the water resistance of the coating film tends to be poor.
本発明において、アルキルエーテル化アミノ樹脂樹脂及
び該樹脂と反応して硬化可能な樹脂は、前者/後者が重
量比で10/90〜70/30になるように配合される
のが好ましい。この重量比が10/90未満では、硬化
性能が劣る傾向があり、70/30を越えると、塗膜の
可撓性が劣る傾向がある。In the present invention, the alkyl etherified amino resin and the resin that can be cured by reacting with the alkyl etherified amino resin are preferably blended so that the weight ratio of the former to the latter is 10/90 to 70/30. When this weight ratio is less than 10/90, the curing performance tends to be poor, and when it exceeds 70/30, the flexibility of the coating film tends to be poor.
本発明に係る塗料用樹脂組成物には、塩酸、リン酸、p
−トルエンスルホン酸等の触媒を添加してもよい。使用
量はアルキルエーテル化アミノ樹脂に対して1重量%以
下が好ましい。The resin composition for paint according to the present invention includes hydrochloric acid, phosphoric acid, p
- A catalyst such as toluenesulfonic acid may be added. The amount used is preferably 1% by weight or less based on the alkyl etherified amino resin.
また、本発明に係る塗料用樹脂組成物は、キシレン、ト
ルエン、ブチルセロソルブ、エチルセロソルブ、n−ブ
タノール、イソブタノール、イソプロパツール、メタノ
ール等の有機溶剤により、適当な固形分にして使用する
ことができる。Furthermore, the resin composition for paint according to the present invention can be used by adjusting the solid content to an appropriate level with an organic solvent such as xylene, toluene, butyl cellosolve, ethyl cellosolve, n-butanol, isobutanol, isopropanol, or methanol. can.
本発明に係る塗料用樹脂組成物には、目的に応じて、チ
タン白等の顔料、その他の添加剤を添加してもよい。Pigments such as titanium white and other additives may be added to the coating resin composition according to the present invention, depending on the purpose.
また、塗装方法としては、スプレー塗装、ディッピング
等が採用できる。Further, as a coating method, spray painting, dipping, etc. can be adopted.
次に本発明に関する製造例及び実施例を示す。 Next, production examples and examples related to the present invention will be shown.
以下、「部」及び1%」は、それぞれ「重量部」及び「
重量%」を示す。Hereinafter, "part" and "1%" refer to "part by weight" and "1%," respectively.
% by weight.
製造例1
かきまぜ機、還流冷却器及び温度計を装着したフラスコ
にメラミン63g、ベンゾグアナミン93.5g、n−
ブタノール370g及び80%パラホルムアルデヒド1
87.5 gを秤り取り、還流下(95°C)で1時間
付加反応を行った。その後、硝酸でp)15〜5.5に
調整し、再び加熱し、還流しながら脱水を3時間行った
。その後、n−ブタノールを144g追加し、再び還流
しながら脱水を1時間行った。その後、冷却し、減圧下
(250mm 11 g )で脱溶剤をはじめ、フラス
コ内容物の温度が135°Cになった時点で脱溶剤の終
点とした。Production Example 1 Melamine 63g, benzoguanamine 93.5g, n-
370 g of butanol and 1 part of 80% paraformaldehyde
87.5 g was weighed out and an addition reaction was carried out under reflux (95°C) for 1 hour. Thereafter, p) was adjusted to 15 to 5.5 with nitric acid, heated again, and dehydrated for 3 hours under reflux. Thereafter, 144 g of n-butanol was added, and dehydration was performed for 1 hour while refluxing again. Thereafter, the flask was cooled, and solvent removal was started under reduced pressure (250 mm 11 g), and the end point of solvent removal was when the temperature of the contents of the flask reached 135°C.
この時の脱溶時間は1時間30分であった。その後不揮
発分が60%になるようにn−ブタノールで希釈した。The desolution time at this time was 1 hour and 30 minutes. Thereafter, it was diluted with n-butanol so that the nonvolatile content was 60%.
この時のガードナー粘度(25°C)は、Mであった。The Gardner viscosity (25°C) at this time was M.
製造例2
製造例1と同様の装置を用い、メラミン37.8g1ベ
ンゾグアナミン130.9g、n−ブタノール370g
、80%パラホルムアルデヒド150gを秤り取り、還
流下(95°C)で1時間付加反応を行った。その後、
硝酸でpH5〜5.5に調整し、再び加熱し、還流しな
がら脱水を3時間行った。Production Example 2 Using the same equipment as Production Example 1, melamine 37.8g1 benzoguanamine 130.9g, n-butanol 370g
, 150 g of 80% paraformaldehyde was weighed out and an addition reaction was carried out under reflux (95°C) for 1 hour. after that,
The pH was adjusted to 5 to 5.5 with nitric acid, heated again, and dehydrated for 3 hours under reflux.
その後、冷却し、減圧下(220mmHg)で脱溶剤を
はじめ、フラスコ内容物の温度が135°Cになった時
点で脱溶剤の終点とした。n−ブタノールを144g追
加し、再びエーテル化反応を1時間還流下で行った。そ
の後、再び脱溶剤を減圧下(250mm)Ig)で行い
、125°Cになった時点で終点とした。その後不揮発
分が60%になるようにn−ブタノールで希釈した。こ
の時のガードナー粘度(25°C)は、Hであった。Thereafter, the flask was cooled, and solvent removal was started under reduced pressure (220 mmHg), and the end point of solvent removal was when the temperature of the contents of the flask reached 135°C. 144 g of n-butanol was added and the etherification reaction was carried out again under reflux for 1 hour. Thereafter, the solvent was again removed under reduced pressure (250 mm) (Ig), and the temperature reached 125°C, which was defined as the end point. Thereafter, it was diluted with n-butanol so that the nonvolatile content was 60%. The Gardner viscosity (25°C) at this time was H.
製造例3
製造例1と同様の装置を用い、ベンゾグアナミン187
g、n−ブタノール296g及びバラホルムアルデヒド
112.5gを秤り取り、還流下(94°C)で1時間
30分付加反応を行った。その後、硝酸でPHを4.0
〜4.5に調整し、再び加熱し、還流しながら脱水を5
時間行った。その後、n−ブタノールを144g追加し
、再び還流しながら脱水を1時間行った。その後冷却し
、減圧下(200mmtlg)で脱溶剤を行い、135
°Cになった時点で脱溶剤の終点とした。その後不揮発
分が60%になるようにn−ブタノールで希釈した。Production Example 3 Using the same equipment as Production Example 1, benzoguanamine 187
296 g of n-butanol and 112.5 g of paraformaldehyde were weighed out, and an addition reaction was carried out under reflux (94°C) for 1 hour and 30 minutes. Then, adjust the pH to 4.0 with nitric acid.
Adjust to ~4.5, heat again, and dehydrate under reflux for 5
Time went. Thereafter, 144 g of n-butanol was added, and dehydration was performed for 1 hour while refluxing again. After that, it was cooled and the solvent was removed under reduced pressure (200 mm tlg).
When the temperature reached °C, it was considered as the end point of solvent removal. Thereafter, it was diluted with n-butanol so that the nonvolatile content was 60%.
この時のガードナー粘度(25°C)は、Gであった。The Gardner viscosity (25°C) at this time was G.
製造比較例1
製造例1と同様の装置を用い、メラミン126g、n−
ブタノール444g及びパラホルムアルデヒド375g
を秤り取り、90°Cで1時間付加反応を行い、その後
、硝酸でPH6〜6.5に調整し、再び加熱し、還流し
ながら3時間脱水工程を行った。その後同温度で脱溶剤
をはじめ、フラスコ内容物の温度が130°Cになった
時点で脱溶剤の終点とした。その後不揮発分が60%に
なるようにn−ブタノールで希釈した。この時のガード
ナー粘度(25°C)は、Aであった。Comparative Production Example 1 Using the same equipment as Production Example 1, 126 g of melamine, n-
444g butanol and 375g paraformaldehyde
was weighed and subjected to an addition reaction at 90° C. for 1 hour, then adjusted to pH 6 to 6.5 with nitric acid, heated again, and subjected to a dehydration step for 3 hours under reflux. Thereafter, desolvation was started at the same temperature, and the end point of the desolvation was when the temperature of the contents of the flask reached 130°C. Thereafter, it was diluted with n-butanol so that the nonvolatile content was 60%. The Gardner viscosity (25°C) at this time was A.
製造例1〜3及び製造比較例1で得られたアルキルエー
テル化アミノ樹脂について、分子内にトリアジン核を1
個及び2個有するものの割合及び分子量を第1表に示す
。これらは、下記の測定条件によるゲルパーミェーショ
ンクロマトグラフィーにより標準ポリスチレンの検量線
を用いてクロマトグラムの対応する各成分を決定し、そ
の各成分のクロマトグラムの面積比により求めた。Regarding the alkyl etherified amino resins obtained in Production Examples 1 to 3 and Production Comparative Example 1, one triazine nucleus was added in the molecule.
Table 1 shows the proportions and molecular weights of those having 1 and 2 atoms. These were determined by gel permeation chromatography under the following measurement conditions using a standard polystyrene calibration curve to determine each component corresponding to the chromatogram, and by the area ratio of the chromatogram of each component.
測定条件
カラム:日立化成工業■商品名、ゲルパック(Gelp
ack) R−420、R−430,R−440,3木
を直列に結合、理論段数17000段/木溶媒:テトラ
ヒド口フラン
流量: 1.77 ml/ min
温度:40°C
サンプル濃度: 600mg15m1
注入量:200μ!
検出器;示差屈折計
(以下余白)
第1表 アルキルエーテル化アミノ樹脂の特性実施例1
製造例1のブチルエーテル化メラミン樹脂溶液50重量
部及びアルキド樹脂(日立化成工業σ勾商品名、フタル
キッド804−70A、固形分の水酸基価80、固形分
70%)40重量部を秤り取り、ツルペッツ10oを1
5.5 g加え、塗装固形分55%になるように調整し
た。この塗料をブリキ板(10cmX 10cm)に重
量測定後にバーコータ#60で塗布した。このブリキ板
を108°Cで30分乾燥させ、冷却後、塗膜重量を測
定する。Measurement conditions Column: Hitachi Chemical ■Product name: Gelpak
ack) R-420, R-430, R-440, 3 trees connected in series, number of theoretical plates 17,000/wood Solvent: Tetrahydride Furan Flow rate: 1.77 ml/min Temperature: 40°C Sample concentration: 600 mg 15 m1 Injection Amount: 200μ! Detector: Differential refractometer (blank below) Table 1 Characteristics of alkyl etherified amino resin Example 1 50 parts by weight of the butyl etherified melamine resin solution of Production Example 1 and alkyd resin (Hitachi Chemical Co., Ltd. Sigma product name, Phthalkyd 804- Weigh out 40 parts by weight of 70A, solid content hydroxyl value 80, solid content 70%, and add 1
5.5 g was added to adjust the coating solid content to 55%. This paint was applied to a tin plate (10 cm x 10 cm) using a bar coater #60 after measuring its weight. This tin plate is dried at 108°C for 30 minutes, and after cooling, the weight of the coating film is measured.
その後、150°Cで20分、180°Cで10分、2
00″Cで3分及び200°Cで10分別々に焼付けを
行い、冷却後再び重量を測定した。加熱減量は、各々同
一の試験を5回行い、その平均値を求めた。結果を第3
表に示す。なお、加熱減量は、下記の式により求めた。After that, 20 minutes at 150°C, 10 minutes at 180°C, 2
Baking was performed separately at 00"C for 3 minutes and at 200°C for 10 minutes, and the weight was measured again after cooling. The same test was performed five times for each heat loss, and the average value was determined. 3
Shown in the table. In addition, the heating loss was calculated|required by the following formula.
加熱減量(%)一
実施例2〜3及び比較例1
第2表に示す配合で実施例1と同様にして加熱減量を求
めた。その結果を第3表に示す。Loss on heating (%) - Examples 2 to 3 and Comparative Example 1 The loss on heating was determined in the same manner as in Example 1 using the formulations shown in Table 2. The results are shown in Table 3.
以下余白
〔発明の効果〕
本発明に係る塗料用樹脂組成物は、樹脂製造時或いは塗
料作成時の作業性が良く、しかも塗膜の焼付時に加熱減
量が小さく、飛散物が少ない。Margins below [Effects of the Invention] The resin composition for paints according to the present invention has good workability during resin production or paint preparation, and also has a small heating loss and less scattering during baking of the paint film.
第2表 塗料配合 単位:部 第3表 加熱減量測定結果Table 2 Paint formulation Unit: parts Table 3 Heating loss measurement results
Claims (1)
分とし、他にメラミン、アセトグアナミン、フタログア
ナミン、ジシアンジアミド又は尿素からなる群から選ば
れる1種以上のアミノ化合物を含んでもよい。)とホル
ムアルデヒドとの付加縮合及びアルコールによるエーテ
ル化反応を行って得られ、分子内にトリアジン核を1個
有するもの及び2個有するものの割合がそれぞれ10〜
25重量%であり、ガードナー粘度(不揮発分60%、
希釈溶剤n−ブタノール)がU以下、遊離のホルムアル
デヒド含有量が1.5重量%以下であるアルキルエーテ
ル化アミノ樹脂及び (B)該アルキルエーテル化アミノ樹脂と反応して硬化
可能な樹脂 を含有してなる塗料用樹脂組成物。[Claims] 1. (A) Amino resin raw material (contains benzoguanamine as an essential component, and may also contain one or more amino compounds selected from the group consisting of melamine, acetoguanamine, phthaloguanamine, dicyandiamide, or urea) ) with formaldehyde and etherification reaction with alcohol, and the ratio of those having one triazine nucleus and those having two triazine nuclei in the molecule is 10 to 10, respectively.
25% by weight, Gardner viscosity (non-volatile content 60%,
an alkyl etherified amino resin in which the dilution solvent (n-butanol) is U or less and a free formaldehyde content is 1.5% by weight or less; and (B) a resin that can be cured by reacting with the alkyl etherified amino resin. Resin composition for paint.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63178402A JP2590369B2 (en) | 1988-07-18 | 1988-07-18 | Resin composition for paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63178402A JP2590369B2 (en) | 1988-07-18 | 1988-07-18 | Resin composition for paint |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0229478A true JPH0229478A (en) | 1990-01-31 |
JP2590369B2 JP2590369B2 (en) | 1997-03-12 |
Family
ID=16047872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63178402A Expired - Lifetime JP2590369B2 (en) | 1988-07-18 | 1988-07-18 | Resin composition for paint |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2590369B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5021906A (en) * | 1989-10-31 | 1991-06-04 | International Business Machines Corporation | Programmable air bearing slider including magnetic read/write element |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59147060A (en) * | 1983-02-09 | 1984-08-23 | Hitachi Chem Co Ltd | Resin composition for water-based paint |
JPS60221471A (en) * | 1984-04-18 | 1985-11-06 | Nissan Motor Co Ltd | Matte coating material composition |
-
1988
- 1988-07-18 JP JP63178402A patent/JP2590369B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59147060A (en) * | 1983-02-09 | 1984-08-23 | Hitachi Chem Co Ltd | Resin composition for water-based paint |
JPS60221471A (en) * | 1984-04-18 | 1985-11-06 | Nissan Motor Co Ltd | Matte coating material composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5021906A (en) * | 1989-10-31 | 1991-06-04 | International Business Machines Corporation | Programmable air bearing slider including magnetic read/write element |
Also Published As
Publication number | Publication date |
---|---|
JP2590369B2 (en) | 1997-03-12 |
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