JPS6124407B2 - - Google Patents
Info
- Publication number
- JPS6124407B2 JPS6124407B2 JP2793576A JP2793576A JPS6124407B2 JP S6124407 B2 JPS6124407 B2 JP S6124407B2 JP 2793576 A JP2793576 A JP 2793576A JP 2793576 A JP2793576 A JP 2793576A JP S6124407 B2 JPS6124407 B2 JP S6124407B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin
- resin composition
- parts
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011342 resin composition Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 20
- 229920000180 alkyd Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 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 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920003180 amino resin Polymers 0.000 claims description 2
- 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 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 description 58
- 239000007788 liquid Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 31
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 13
- 239000000049 pigment Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000010306 acid treatment Methods 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000003472 neutralizing effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 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 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 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 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 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
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は熱硬化性固形樹脂組成物の製造方法、
更に詳しくは、スラリー状または粉末状の塗料を
調整するのに有利に使用できる熱硬化性固形樹脂
組成物の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for producing a thermosetting solid resin composition,
More specifically, the present invention relates to a method for producing a thermosetting solid resin composition that can be advantageously used to prepare slurry or powder coatings.
[従来技術]
近年、環境汚染の増大に伴なつて、塗料から逸
出する溶剤などの物質もその一因であるという見
地から、その解消のための種々努力がなされてい
る。かかる状況下で水溶性塗料、エマルシヨン塗
料などの水性塗料、粉体塗料、および固体状の塗
膜形成用樹脂を水中に分散してスラリー化したい
わゆるスラリー状塗料の開発がなされてきた。そ
の中でも、特に粉体塗料やスラリー状塗料は、塗
装工程における有害排出物質が極めて少なく、ま
たその後処理が簡単であり且つ塗料の回収使用が
可能であるという点で他の塗料に比し有利である
ところから、今後塗料の重要な分野を占めていく
ものと思われる。[Prior Art] In recent years, as environmental pollution has increased, various efforts have been made to eliminate it from the viewpoint that substances such as solvents escaping from paints are also a contributing factor. Under such circumstances, so-called slurry paints, in which water-based paints such as water-soluble paints and emulsion paints, powder paints, and solid film-forming resins are dispersed in water to form a slurry, have been developed. Among them, powder paints and slurry paints are particularly advantageous over other paints in that they emit extremely few harmful emissions during the painting process, are easy to dispose of afterwards, and can be recycled. From a certain point of view, it is thought that it will occupy an important field of paints in the future.
これらの粉体塗料やスラリー状塗料の製造方法
として従来知られているものに、固体状の樹脂を
顔料や架橋剤等と熱溶融混合した後粉砕して粉体
塗料とし、そして該粉体塗料をそのまま水中に懸
濁せしめスラリー状塗料とする方法(特開昭48−
45529号参照)がある。また、これ以外に(1)凝固
用液体と混和しうる液体部分を有する液体塗料に
凝固用液体を混合し、これにより沈澱した塗料粒
子をそのまま水中に懸濁せしめスラリー状塗料と
する方法および上記沈澱した塗料粒子を乾燥させ
て粉体塗料とする方法(特開昭48−52851号参
照)、および(2)顔料と重合性単量体および樹脂を
含む液状組成物を乳化重合後、重合生成物を噴霧
乾燥して粉体塗料とする方法(特開昭50−33821
号参照)が知られている。 Conventionally known methods for producing these powder paints and slurry paints include mixing a solid resin with pigments, crosslinking agents, etc. by hot melting, pulverizing the mixture to form a powder paint, and then producing the powder paint. A method of suspending it as it is in water to make a slurry paint
45529)). In addition to this, (1) a method of mixing a coagulating liquid with a liquid paint having a liquid portion that is miscible with the coagulating liquid, and thereby suspending the precipitated paint particles in water to form a slurry-like paint; A method of drying the precipitated paint particles to obtain a powder paint (see JP-A-48-52851), and (2) emulsion polymerization of a liquid composition containing a pigment, a polymerizable monomer, and a resin to form a polymer. Method of spray-drying materials to make powder coatings (Japanese Patent Application Laid-Open No. 50-33821
) is known.
しかしながら、これら従来法はいずれも技術上
あるいは経済上大きな難点を有し、故に広く実用
化されることを妨げられていた。例えば、上記(1)
法は、凝固用液体として液体塗料の非溶剤部分を
溶解しないものを使用し溶解力の差により沈澱析
出させる方法であることから、液体塗料の溶剤部
分と混和しうる凝固用液体は大量に必要である。
凝固用液体として例えば水を使用した場合、有効
な塗料成分に対して6〜73倍という大量の水が塗
料中の溶剤と混和して副生するので、これをその
まま排出したり蒸発させると、水質または大気の
汚染原因となり、しかも経済的にも著しく不利と
なる。また、閉サイクルで溶剤を回収再使用する
としても、そのための設備投資および運転のエネ
ルギーコストは膨大とならざるを得ず、且つ塗料
中の溶剤がアセトンの如き高引火性のものである
場合は、火災、爆発の危険も大であつて、そのた
めの安全、防護設備も厳重でなくてはならない。 However, all of these conventional methods have major technical or economical drawbacks, and have therefore been prevented from being widely put into practical use. For example, (1) above
This method uses a coagulating liquid that does not dissolve the non-solvent part of the liquid paint and causes precipitation to occur due to the difference in dissolving power, so a large amount of coagulating liquid that is miscible with the solvent part of the liquid paint is required. It is.
For example, when water is used as a coagulating liquid, a large amount of water, 6 to 73 times the amount of effective paint components, mixes with the solvent in the paint and forms a by-product, so if this water is simply discharged or evaporated, It causes water or air pollution, and is also extremely disadvantageous economically. Furthermore, even if the solvent is collected and reused in a closed cycle, the capital investment and operating energy costs for this would be enormous, and if the solvent in the paint is highly flammable such as acetone, There is also a great risk of fire and explosion, and the safety and protection equipment must be very strict.
そして上記(2)法では、顔料を重合性単量体およ
び樹脂の存在下通常の分散処理を行ない液状の顔
料分散組成物を得、更に開始剤、架橋剤その他乳
化剤、添加剤等を加え乳化重合した後、重合生成
物を噴霧乾燥して粉体塗料としていることから、
通常の溶液状樹脂と異なり、出発物質の液状の顔
料分散組成物の時点で溶剤としての機能を果して
いた重合性単量体のすべては、最終塗料において
実質的に樹脂に転化されているため、必然的に顔
料/樹脂比が小さくなり、高顔料濃度の塗料を得
ることが困難であり、また乳化重合時使用された
乳化剤はそのまま塗料中に残存する場合であり、
それによる塗膜外観あるいは性能の劣化は避け難
い。 In method (2) above, the pigment is subjected to a conventional dispersion treatment in the presence of a polymerizable monomer and a resin to obtain a liquid pigment dispersion composition, and then an initiator, crosslinking agent, emulsifier, additives, etc. are added to emulsify the pigment. After polymerization, the polymerization product is spray-dried to form a powder coating.
Unlike ordinary solution resins, all of the polymerizable monomers that functioned as solvents in the starting liquid pigment dispersion composition are substantially converted to resins in the final coating. The pigment/resin ratio inevitably becomes small, making it difficult to obtain a paint with a high pigment concentration, and the emulsifier used during emulsion polymerization remains in the paint as it is.
Deterioration in the appearance or performance of the coating film due to this is unavoidable.
[発明の目的]
本発明の目的は、上記従来のスラリー状塗料や
粉体塗料の製造方法に対し、実質的に水性の樹脂
組成物液を用いるため特に従来法(1)のように溶剤
を必須とせず、またかりに組成物液中に溶剤を含
んでいても極めて僅かであり、しかも水溶化また
は水分散時に水中に分配される溶剤の量は更に少
ないため、その除去等の処理は省略または大幅に
簡略化できる等塗料製造時や塗装時の環境汚染の
防止または軽減が図られ、且つその処理等のコス
トダウンも行える他、要すれば顔料濃度の調整が
容易で、且つ顔料分散あるいは調色が従来の液状
塗料と同様に容易である、スラリー状または粉末
状塗料調整用の熱硬化性固形樹脂組成物の製造方
法であつて、比較的簡単な操作および設備で且つ
安全に実施できる方法を提供することにある。[Objective of the Invention] The object of the present invention is to improve the above-mentioned conventional method for producing slurry paints and powder paints by using a substantially water-based resin composition liquid, in particular, by using a solvent as in the conventional method (1). It is not necessary, and even if the composition contains a solvent, it is extremely small, and the amount of solvent distributed in water during water solubilization or water dispersion is even smaller, so treatments such as its removal may be omitted or It is possible to prevent or reduce environmental pollution during paint manufacturing and painting, and to reduce the cost of processing, etc., and it is easy to adjust the pigment concentration if necessary, and it is easy to disperse or adjust the pigment. A method for producing a thermosetting solid resin composition for preparing slurry-like or powder-like paints, which has the same color as conventional liquid paints, and which can be carried out safely with relatively simple operations and equipment. Our goal is to provide the following.
本発明者らは、かかる目的を達成するため鋭意
研究を進めた結果、中和されたカルボキシル基の
アニオン活性により水中に安定に保持されている
樹脂を含む水性組成物液に、酸性物質を作用させ
と当該樹脂組成物の全部または一部が凝集を来た
す場合でも酸性物質の適用と同時またはその前後
において撹拌または噴霧などの機械的造粒処理に
より、上記アニオン活性が失なわれ均一粒径の微
細な樹脂組成物粒子が析出されることを見出し
た。 As a result of intensive research to achieve this objective, the present inventors have discovered that an acidic substance acts on an aqueous composition containing a resin that is stably retained in water due to the anionic activity of the neutralized carboxyl group. Even if all or part of the resin composition is agglomerated, mechanical granulation treatment such as stirring or spraying at the same time as or before or after the application of the acidic substance will cause the anion activity to be lost and the particle size to be uniform. It has been found that fine resin composition particles are precipitated.
[発明の構成]
本発明は、上述の知見に基づいて完成されたも
のであつて、その要旨は、モノマーおよび樹脂の
両者を溶解し且つ水混和性のある溶剤を含む系で
の反応により得られるアルキド樹脂、アクリル樹
脂およびアクリル変性アルキド樹脂から選ばれる
樹脂の中和物と、エポキシ樹脂、アミノプラスト
樹脂およびブロツクポリイソシアナート化合物か
ら選ばれる架橋剤を含む水性樹脂組成物液に、酸
性物質を作用させると同時またはその前後におい
て造粒処理を施して、上記樹脂組成物の粒子を析
出させることを特徴とする熱硬化性固形樹脂組成
物の製造方法に存する。[Structure of the Invention] The present invention has been completed based on the above-mentioned findings, and the gist thereof is to dissolve monomers and resins by a reaction in a system containing a water-miscible solvent. An acidic substance is added to an aqueous resin composition liquid containing a neutralized resin selected from alkyd resins, acrylic resins, and acrylic modified alkyd resins, and a crosslinking agent selected from epoxy resins, aminoplast resins, and blocked polyisocyanate compounds. The method of producing a thermosetting solid resin composition is characterized in that the particles of the resin composition are precipitated by performing granulation treatment at the same time or before or after the reaction.
本発明におけるアルキド樹脂、アクリル樹脂ま
たはアクリル変性アルキド樹脂は、溶剤の存在下
に樹脂合成を行なう通常の方法によつて得られる
ものでよい。アクリル変性アルキド樹脂にあつて
は、重合性不飽和基やメルカプト基のようなグラ
フト化し得る活性点を有するアルキド樹脂にアク
リル重合性単量体を共重合させることにより得る
ことができる。溶剤としては、モノマーおよび樹
脂の両者を溶解し且つ水混和性のある例えばアル
コール系(例、イソプロパノール)、エーテル系
(例、エチルセロソルブ、ブチルセロソルブ)が
使用されてよい。これらの樹脂のカルボキシル基
を常法に従い中和して中和物とすることにより、
当該樹脂を水に溶解または分解させることができ
る。上記中和に使用する剤(以下、中和剤と称
す)としては、無機塩基性化合物(水酸化カリウ
ム、水酸化ナトリウム、炭酸カリウムなど)アン
モニアまたは有機アミン類(モノメチルアミン、
トリエチルアミン、モノエタノールアミン、ジメ
チルエタノールアミン、トリエタノールアミン、
エチレンジアミン、ジエチレントリアミンなど)
が挙げられる。 The alkyd resin, acrylic resin, or acrylic-modified alkyd resin in the present invention may be obtained by a conventional method of resin synthesis in the presence of a solvent. The acrylic-modified alkyd resin can be obtained by copolymerizing an acrylic polymerizable monomer with an alkyd resin having an active site that can be grafted, such as a polymerizable unsaturated group or a mercapto group. As the solvent, an alcohol-based solvent (eg, isopropanol) or an ether-based solvent (eg, ethyl cellosolve, butyl cellosolve) that dissolves both the monomer and the resin and is miscible with water may be used. By neutralizing the carboxyl groups of these resins according to conventional methods,
The resin can be dissolved or decomposed in water. Agents used for the above neutralization (hereinafter referred to as neutralizing agents) include inorganic basic compounds (potassium hydroxide, sodium hydroxide, potassium carbonate, etc.) ammonia or organic amines (monomethylamine,
triethylamine, monoethanolamine, dimethylethanolamine, triethanolamine,
(ethylenediamine, diethylenetriamine, etc.)
can be mentioned.
上記架橋剤としては、アルキド樹脂、アクリル
樹脂またはアクリル変性アルキド樹脂の分子中に
存在する官能基(カルボキシル基、ヒドロキシル
基など)と反応しうるものであれば通常の架橋性
の樹脂または化合物が使用されてよく、特にそれ
自体上述の樹脂と相溶性を有するか、または少な
くとも焼付時に相溶して均一な塗膜を与えるもの
が望ましい。具体的に例えばカルボキシル基と反
応しうるものとしては2個以上のエポキシ基を有
するエポキシ樹脂、ヒドロキシル基と反応しうる
ものとしては尿素樹脂、メラミン樹脂(ヘキサメ
トキシメチロールメラミンなど)、ベンゾグアナ
ミンなどのアミノプラスト樹脂およびブロツクさ
れたイソシアナート基を有するポリイソシアナー
ト化合物等が挙げられる。 As the above-mentioned crosslinking agent, ordinary crosslinking resins or compounds can be used as long as they can react with the functional groups (carboxyl group, hydroxyl group, etc.) present in the molecules of alkyd resin, acrylic resin, or acrylic modified alkyd resin. In particular, it is desirable to use a resin that is itself compatible with the above-mentioned resin, or at least is compatible with the resin during baking to provide a uniform coating film. Specifically, examples of compounds that can react with carboxyl groups include epoxy resins having two or more epoxy groups; examples of compounds that can react with hydroxyl groups include urea resins, melamine resins (such as hexamethoxymethylolmelamine), and amino acids such as benzoguanamine. Examples include plasto resins and polyisocyanate compounds having blocked isocyanate groups.
上記架橋剤は、溶剤または水に対する性質に応
じて、合成により得られた樹脂溶剤溶液そのも
の、その中和処理物、または中和物を水に溶解ま
たは分散させた系のいずれかに混合されてよい。
また、混合困難の場合は適宜溶融状態で混合する
か、乳化混合するかあるいは溶剤に溶解して混合
するなど必要に応じ種々の混合方法が採用されて
よい。 The above-mentioned crosslinking agent may be mixed into either the resin solvent solution itself obtained by synthesis, its neutralized product, or a system in which the neutralized product is dissolved or dispersed in water, depending on its property against solvents or water. good.
In addition, if mixing is difficult, various mixing methods may be adopted as necessary, such as mixing in a molten state, emulsification mixing, or dissolving in a solvent and mixing.
以上の樹脂中和物と架橋剤を含む水性樹脂組成
物液にあつては、更に必要に応じて顔料、着色
剤、改質剤(例、天然樹脂、セルロースアセテー
トブチレート等のセルロース誘導体、アルキド樹
脂、アクリル樹脂、ビニル樹脂)が配合されてよ
い。かかる水性樹脂組成物液の不揮発分は、通常
5〜80重量%、好ましくは10〜60重量%に設定さ
れる。 In the case of the aqueous resin composition liquid containing the above resin neutralized product and crosslinking agent, pigments, colorants, modifiers (e.g., natural resins, cellulose derivatives such as cellulose acetate butyrate, alkyds, etc.) may be added as necessary. resin, acrylic resin, vinyl resin) may be blended. The nonvolatile content of such aqueous resin composition liquid is usually set at 5 to 80% by weight, preferably 10 to 60% by weight.
このようにして調製された水性樹脂組成物液
は、多くの場合酸性物質を作用させることにより
その全部または大部分が凝集を起こすため、その
酸性物質による処理と、その処理と同時または前
後において機械的な造粒処理(以下、酸処理と称
す)に付す。ここで使用する酸性物質としては、
水に溶解して水素イオンを供給しうるものであれ
ばよく、例えば硫酸、塩酸、リン酸、炭酸などの
無機酸水溶液、蟻酸、酢酸、モノクロル酢酸、ジ
クロル酢酸、トリクロル酢酸、乳酸、酪酸、グリ
コール酢酸などの有機酸水溶液、および炭酸ガ
ス、亜硫酸ガスなどの酸性ガスが挙げられる。無
機酸水溶液や有機酸水溶液の濃度は、該酸処理で
析出する粒状樹脂組成物の粒子状態(粒径、粒子
形状など)に応じて選定すればよく、通常1N以
下、好ましくは0.2N以下が望ましい。また、酸
性ガスの場合はそれ単独で使用されても何ら差支
えないが、必要に応じ空気、窒素などの非反応性
気体と適宜混合して使用することができる。かか
る酸性物質の使用量は、通常上記樹脂中和物の中
和されたカルボキシル基に対して約当量以上とな
るように設定されればよい。 In many cases, all or most of the aqueous resin composition liquid prepared in this way causes agglomeration when exposed to an acidic substance. granulation treatment (hereinafter referred to as acid treatment). The acidic substances used here are:
Any material that can dissolve in water and supply hydrogen ions may be used, such as inorganic acid aqueous solutions such as sulfuric acid, hydrochloric acid, phosphoric acid, and carbonic acid, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, butyric acid, and glycol. Examples include aqueous organic acids such as acetic acid, and acid gases such as carbon dioxide gas and sulfur dioxide gas. The concentration of the inorganic acid aqueous solution or organic acid aqueous solution may be selected depending on the particle state (particle size, particle shape, etc.) of the granular resin composition precipitated by the acid treatment, and is usually 1N or less, preferably 0.2N or less. desirable. In addition, in the case of acidic gas, there is no problem even if it is used alone, but it can be used by appropriately mixing it with a non-reactive gas such as air or nitrogen if necessary. The amount of such an acidic substance to be used may be generally set to be about equivalent or more to the neutralized carboxyl group of the above-mentioned resin neutralized product.
当該酸処理は、得られる樹脂組成物の粒子の形
状、大きさ等に基づき適宜実施されてよく、例え
ば以下に示す方法が採用されてよい。 The acid treatment may be carried out as appropriate based on the shape, size, etc. of the particles of the resulting resin composition, and for example, the method described below may be employed.
(a) 上記酸性ガスを水性樹脂組成物液中に徐々に
吹込みながら高速撹拌する方法。(a) A method of stirring at high speed while gradually blowing the acidic gas into the aqueous resin composition liquid.
(b) 上記酸水溶液中に水性樹脂組成物液を徐々に
加えながら高速撹拌する方法、またはその逆の
方法。この際、酸水溶液中にポリエチレンオキ
サイド、ポバールなどの分散能を有する水溶性
高分子化合物、ヒドロキシセルロースなどのセ
ルロース誘導体、またはいわゆるカチオン系あ
るいはノニオン系界面活性剤で代表される低分
子分散剤等を存在させておくことにより、より
丸みを帯びた球状の樹脂組成物粒子が析出す
る。かかる粒子を使用して得られる塗料によれ
ば、塗装した場合被塗物表面により密な充填が
できるためより平滑で光沢の良好な塗膜が得ら
れる。(b) A method in which the aqueous resin composition liquid is gradually added to the acid aqueous solution while stirring at high speed, or vice versa. At this time, water-soluble polymer compounds with dispersibility such as polyethylene oxide and poval, cellulose derivatives such as hydroxycellulose, or low-molecular dispersants represented by so-called cationic or nonionic surfactants are added to the acid aqueous solution. By allowing it to exist, more rounded spherical resin composition particles are precipitated. According to the paint obtained using such particles, when coated, the surface of the object to be coated can be more densely filled, so that a smoother and glossier coating film can be obtained.
(c) 上記酸水溶液表面または酸水溶液中に要すれ
ば撹拌下、水性樹脂組成物液を噴霧する方法。
この場合も、上記(b)法と同様に酸水溶液中に分
散剤を存在させておくことも有利である。(c) A method of spraying the aqueous resin composition liquid on the surface of the acid aqueous solution or into the acid aqueous solution, with stirring if necessary.
In this case as well, it is advantageous to have a dispersant present in the acid aqueous solution as in the method (b) above.
(d) 上記酸性ガスの気流中に水性樹脂組成物液を
噴霧する方法。(d) A method of spraying an aqueous resin composition liquid into the acid gas stream.
(e) 上記酸水溶液と水性樹脂組成物液とをそれぞ
れ噴霧状態で接触させる方法。(e) A method in which the acid aqueous solution and the aqueous resin composition liquid are brought into contact with each other in a sprayed state.
かかる酸処理によつて、水性樹脂組成物液中の
樹脂中和物の中和されたカルボキシル基は酸性物
質の作用を受けて、遊離のカルボキシル基になる
と共に造粒作用を受けて、樹脂組成物の粒子が析
出する。一般に粒子の形状にあつては、上記(a)お
よび(b)法に比較して(c)、(d)および(e)法がより一層
真球に近い形状をもたらす。この粒子の粒径は、
上記酸処理の条件(例えば水性樹脂組成物液の粘
度、撹拌速度、噴霧ノズルの口径、噴霧粘度等)
によつて適宜に調整することができる。 Through this acid treatment, the neutralized carboxyl groups of the resin neutralized product in the aqueous resin composition liquid are affected by the acidic substance, become free carboxyl groups, and undergo a granulation action, resulting in a change in the resin composition. Particles of matter precipitate. In general, regarding the shape of particles, methods (c), (d), and (e) yield shapes that are much closer to true spheres than methods (a) and (b) above. The particle size of this particle is
Conditions for the above acid treatment (e.g. viscosity of the aqueous resin composition liquid, stirring speed, aperture of the spray nozzle, spray viscosity, etc.)
It can be adjusted as appropriate.
次に、上記酸処理後の系を、必要に応じ系中の
余剰の酸性物質を上述の中和剤で中和せしめた後
通常の分離処理(別、ふるい分け、遠心分離な
ど)に付して樹脂組成物の粒子を分取する。な
お、上記酸処理が(d)法および(e)法の場合では、当
該粒子を直接的に分取することできる。 Next, the system after the acid treatment is subjected to normal separation treatment (separation, sieving, centrifugation, etc.) after neutralizing excess acidic substances in the system with the above-mentioned neutralizing agent, if necessary. Particles of the resin composition are separated. In addition, when the above acid treatment is performed by method (d) or method (e), the particles can be directly separated.
このようにして得られる本発明の熱硬化性固形
樹脂組成物に、適当な後処理を施すことによりス
ラリー状塗料を得ることができる。 A slurry-like paint can be obtained by subjecting the thus obtained thermosetting solid resin composition of the present invention to an appropriate post-treatment.
即ち、当該樹脂組成物の粒子を水洗して酸処理
によつて副生する低分子塩、更にまた未反応の中
和剤や酸性物質を除去した後、要すれば粉砕処理
に付し、次いで所定不輝発分となるように水中に
再分散せしめて粗粒のない均一粒径のスラリー状
塗料を得る。当該スラリー状塗料を塗装に供する
に当り、特に一定以上の不揮発分とする場合に
は、かかる塗料を静止状態で放置せしめるか、あ
るいは遠心分離等の方法で分離し適宜上澄水を除
去すればよい。 That is, the particles of the resin composition are washed with water to remove low-molecular salts produced by acid treatment, as well as unreacted neutralizers and acidic substances, and then subjected to pulverization treatment if necessary. It is redispersed in water to a predetermined non-brightening content to obtain a slurry-like paint with uniform particle size and no coarse particles. When using the slurry paint for painting, especially if the non-volatile content exceeds a certain level, the paint may be left stationary or separated by a method such as centrifugation and the supernatant water removed as appropriate. .
上記塗装方法としては、例えばエアースプレー
塗装、静電塗装、浸漬塗装、ロールコータ塗装、
ハケ塗り等の方法が採用でき、塗布後適当な条件
で焼付乾燥することにより、平滑にして光沢ある
塗膜を得ることができる。 The above coating methods include, for example, air spray coating, electrostatic coating, dipping coating, roll coater coating,
A method such as brush painting can be employed, and by baking and drying under appropriate conditions after application, a smooth and glossy coating can be obtained.
当該スラリー状塗料を、通常のスプレー塗装法
いて塗装した場合、従来の水溶性あるいはエマル
シヨン等の水性焼付塗料に比し、塗装時の水分の
蒸発が早いため、より厚膜の塗膜を得ることが容
易となり、そのため塗装作業性も格段に向上す
る。更に、焼付乾燥後の形成塗膜にあつても、組
成的に類似の従来の粉体塗料の塗膜と比較して、
平滑性や光沢性の点で優れていることが認められ
ている。 When this slurry paint is applied using the normal spray coating method, water evaporates faster during application than with conventional water-based baking paints such as water-soluble or emulsion paints, so a thicker paint film can be obtained. As a result, painting work efficiency is greatly improved. Furthermore, the coating film formed after baking and drying has a higher
It is recognized that it has excellent smoothness and gloss.
一方、上記水洗後の樹脂組成物粒子をそのまま
でまたはその再水分散体とした後通常の方法に従
い乾燥(熱風乾燥、噴霧乾燥、真空乾燥など)す
ることにより、粉末状塗料が得られる。かかる塗
料は、従来の粉体塗料と同様の塗装方法で同様に
使用することができる。このような粉末状塗料の
利点は、従来用いられている実質的に水を含まな
い固体樹脂組成物を粉砕する方法に比し、粉砕工
程における粉塵の飛散、粉塵爆発等の危険がな
く、また通常の騒音も少ない上、前述の如く、そ
の形状の選定や粒径の調節は容易であり、使用す
る樹脂の種類など広範囲にわたり、自由に選択す
ることができる。 On the other hand, a powdered coating material can be obtained by drying the washed resin composition particles as they are or by redispersing them in water according to a conventional method (hot air drying, spray drying, vacuum drying, etc.). Such coatings can be used in the same manner as conventional powder coatings in similar application methods. The advantage of such a powder coating is that, compared to the conventional method of pulverizing a solid resin composition that does not contain substantially water, there is no risk of dust scattering or dust explosion during the pulverization process, and there is no risk of dust explosion. Not only does it generate less noise, as mentioned above, it is easy to select the shape and adjust the particle size, and the type of resin used can be freely selected from a wide range of options.
[発明の効果]
以上の構成から成る本発明方法によれば、樹脂
成分に対する溶剤の溶解力の差を利用して沈殿さ
せて成る従来法(1)の如く大量の溶剤混合物を副生
することがないので、大気等の汚染の心配が少な
く、従つてその実施時にそれらの再循環使用、回
収、除去等の処理を省略できるので、経済性が優
れており、またアセトン等を使用した場合に懸念
される爆発等の危険が少ない。本発明方法におい
て、中和剤として一価金属の無機塩基性化合物が
望ましく、例えば水酸化ナトリウムを用い、これ
に酸性物質として塩酸水溶液を組わせること副生
する塩は無害の食塩であることから、従来法(1)に
比し廃棄物処理の点で有利で且つ経済的にも優れ
ている。なお、中和剤として二価金属の無機塩基
性化合物を使用した場合は一般に水不溶性塩が副
生されるが、この場合も形成塗膜に悪影響を及ぼ
さない程度のものであればそのまま残留させても
差支えない。[Effects of the Invention] According to the method of the present invention having the above-described structure, a large amount of a solvent mixture can be produced as a by-product, unlike the conventional method (1) in which the resin component is precipitated by utilizing the difference in the dissolving power of the solvent. There is no need to worry about contaminating the air, etc., and therefore, the process of recycling, collecting, removing, etc. can be omitted, making it highly economical, and when using acetone, etc. There is little risk of explosion, etc. In the method of the present invention, an inorganic basic compound of a monovalent metal is preferably used as a neutralizing agent, for example, sodium hydroxide is used, and an aqueous hydrochloric acid solution is combined with this as an acidic substance. The salt produced as a by-product is harmless common salt. Therefore, it is more advantageous and economically superior to the conventional method (1) in terms of waste treatment. Note that when an inorganic basic compound of a divalent metal is used as a neutralizing agent, a water-insoluble salt is generally produced as a by-product, but in this case as well, it can be allowed to remain as long as it does not adversely affect the formed coating film. There is no problem.
また、本発明方法では、酸処理前の水性樹脂組
成物液は通常の液状塗料と同じ形態であるため、
顔料分散を要する場合には従来の液状塗料の技術
をそのまま利用することができることから、本発
明方法を塗料製造に応用すると、従来の粉体塗料
あるいは粉体塗料を水中に分散したスラリー状塗
料に比し、顔料への樹脂の吸着も良好でそのため
光沢、平滑性に優れ、その上従来の調色法が使え
るため非常に容易で且つ高精度の調色が可能とい
える。 In addition, in the method of the present invention, since the aqueous resin composition liquid before acid treatment has the same form as a normal liquid paint,
When pigment dispersion is required, conventional liquid paint technology can be used as is, so if the method of the present invention is applied to paint production, it can be used to create conventional powder paints or slurry paints in which powder paints are dispersed in water. In comparison, the adsorption of the resin to the pigment is good, which results in excellent gloss and smoothness.Furthermore, since conventional color toning methods can be used, color toning can be done very easily and with high precision.
更に、本発明方法では、アルキド樹脂、アクリ
ル樹脂および/またはアクリル変性アルキド樹脂
の溶剤溶液から出発し、これを用いて水性樹脂組
成物液を得、該液に酸処理を施すというように、
当初より水系の樹脂組成物を使用することなく、
熱硬化性固形樹脂組成物を製造することができる
ので、該固形樹脂組成物の取得技術の拡張に大い
に寄与することができる。 Furthermore, in the method of the present invention, starting from a solvent solution of alkyd resin, acrylic resin and/or acrylic modified alkyd resin, using this to obtain an aqueous resin composition liquid, and subjecting the liquid to acid treatment,
From the beginning, without using water-based resin compositions,
Since a thermosetting solid resin composition can be produced, it can greatly contribute to the expansion of the technology for obtaining the solid resin composition.
[実施例]
次に、実施例および参考例を挙げて本発明を具
体的に説明するなお、実施例および参考例中
「部」とあるは「重量部」を意味する。[Examples] Next, the present invention will be specifically described with reference to Examples and Reference Examples. In the Examples and Reference Examples, "parts" means "parts by weight."
実施例 1
アクリル酸14.5部、アクリル部ヒドロキシプロ
ピル8.9部、メタクリル酸メチル14.9部、メタク
リル酸n−ブチル16.1部、スチレン26部およびア
クリル酸n−ブチル16.6部を構成モノマーとする
アクリル樹脂の不揮発分80重量%エチルセロソル
ブ溶液にジメチルエタノールアミン水溶液を作用
させ、中和率100%の水性アクリル樹脂液(不揮
発分38重量%)を得る。この樹脂液35部、ヘキサ
メトキシメチロールメラミン2.9部および表面が
親水性物質で被覆されたアルミニウム粉末0.71部
を分散混合せしめ、次いで水30部を添加混合して
水性樹脂組成物液を調整する。Example 1 Nonvolatile content of an acrylic resin whose constituent monomers are 14.5 parts of acrylic acid, 8.9 parts of hydroxypropyl acrylate, 14.9 parts of methyl methacrylate, 16.1 parts of n-butyl methacrylate, 26 parts of styrene, and 16.6 parts of n-butyl acrylate. A dimethylethanolamine aqueous solution is allowed to act on an 80% by weight ethyl cellosolve solution to obtain an aqueous acrylic resin liquid (non-volatile content: 38% by weight) with a neutralization rate of 100%. 35 parts of this resin liquid, 2.9 parts of hexamethoxymethylolmelamine, and 0.71 part of aluminum powder whose surface is coated with a hydrophilic substance are dispersed and mixed, and then 30 parts of water is added and mixed to prepare an aqueous resin composition liquid.
次にかかる水性樹脂組成物液63.61部を、500ml
の1/20N−塩酸水溶液中に高速ラボミキサーにて
撹拌しながら滴下(時間:約15分)する。滴下後
系中の余剰の酸を1N−水酸化カリウム水溶液で
中和した後、250メツシユのふるい分けに供して
粒径10〜30μの熱硬化性固形樹脂組成物を得る。 Next, add 63.61 parts of the aqueous resin composition liquid to 500ml.
Add dropwise to a 1/20N aqueous hydrochloric acid solution while stirring using a high-speed lab mixer (time: approximately 15 minutes). After dropping, the excess acid in the system is neutralized with a 1N potassium hydroxide aqueous solution, and then sieved through a 250-mesh sieve to obtain a thermosetting solid resin composition with a particle size of 10 to 30 μm.
参考例 1
実施例1で得られた固形樹脂組成物を、水洗後
不揮発分50重量%となるように水中に再分散せし
めてスラリー状塗料を製造する。かかるスラリー
状塗料を、磨鋼板にエアースプレー塗装した後
160℃で30分間焼付乾燥した所、得られた塗膜
は、平滑で良好な光沢を示しメタリツク感も良好
であつた。更に、該塗膜をデユポン式衝撃試験に
供した所20cm以上(500g)を示し、充分架橋し
ていることが認められた。Reference Example 1 After washing with water, the solid resin composition obtained in Example 1 is redispersed in water so that the nonvolatile content is 50% by weight to produce a slurry paint. After applying this slurry paint to a polished steel plate by air spraying,
After baking and drying at 160° C. for 30 minutes, the resulting coating film was smooth and had good gloss and a good metallic feel. Furthermore, when the coating film was subjected to a DuPont impact test, it showed an impact strength of 20 cm or more (500 g), indicating that it was sufficiently crosslinked.
参考例 2
実施例1で得られた固形樹脂組成物を水洗後、
流動層式乾燥機で50℃で3時間乾燥せしめて粉末
状塗料を製造する。かかる粉末状塗料を、梨地鋼
板に静電塗装した後160℃で30分間焼付乾燥した
所、平滑で良好な光沢を示しメタリツク感もよく
充分架橋した塗膜が得られた。Reference Example 2 After washing the solid resin composition obtained in Example 1 with water,
A powder coating is produced by drying in a fluidized bed dryer at 50°C for 3 hours. When this powdered paint was applied electrostatically to a matte steel plate and then baked and dried at 160°C for 30 minutes, a well-crosslinked coating film was obtained that was smooth, had good gloss, had a good metallic feel, and was fully crosslinked.
実施例 2
アルキド樹脂(数平均分子量1500、酸価56、水
酸基価30、モノマー構成:大豆油35重量%、ネオ
ペンチルグリコール25重量%、イソフタル酸15重
量%、トリメリツト酸25重量%)の不揮発分70重
量%イソプロパノール溶液にトリエチルアミンを
作用させて得られる中和樹脂液100部、架橋剤と
してのベンゾグアナミン30部、酸化チタン(石原
産業社製商品名「タイペークR−820チタン」)60
部および水640部を分散混合して水性樹脂組成物
液を調製する。Example 2 Nonvolatile content of alkyd resin (number average molecular weight 1500, acid value 56, hydroxyl value 30, monomer composition: soybean oil 35% by weight, neopentyl glycol 25% by weight, isophthalic acid 15% by weight, trimellitic acid 25% by weight) 100 parts of a neutralized resin solution obtained by reacting triethylamine with a 70% by weight isopropanol solution, 30 parts of benzoguanamine as a crosslinking agent, 60 parts of titanium oxide (product name: "Tipaque R-820 Titanium" manufactured by Ishihara Sangyo Co., Ltd.)
1 part and 640 parts of water are dispersed and mixed to prepare an aqueous resin composition liquid.
次に、かかる水性樹脂組成物液を、1/20N−塩
酸水溶液を満たした容器の水面に向つてエアース
プレーする(この際、塩酸水溶液は撹拌してお
く)。析出した粒子を遠心分離機にて分取して、
50μ以下の真球状の熱硬化性固形樹脂組成物を得
る。 Next, the aqueous resin composition liquid is air-sprayed onto the water surface of a container filled with a 1/20 N hydrochloric acid aqueous solution (at this time, the hydrochloric acid aqueous solution is stirred). Separate the precipitated particles using a centrifuge,
A thermosetting solid resin composition having a true spherical shape of 50μ or less is obtained.
参考例 3
実施例2で得られた固形樹脂組成物を、水洗後
不揮発分50重量%となるように水中に再分散せし
めてスラリー状塗料を製造する。かかるスラリー
状塗料を、磨鋼板にエアースプレー塗装した後
160℃で30分間焼付乾燥した所、得られる塗膜
は、平滑で良好な光沢を示した。更に、該塗膜を
エリクセン試験に供した所3mm以上を示し充分架
橋していることが認められた。Reference Example 3 After washing with water, the solid resin composition obtained in Example 2 is redispersed in water so that the nonvolatile content becomes 50% by weight to produce a slurry paint. After applying this slurry paint to a polished steel plate by air spraying,
After baking and drying at 160°C for 30 minutes, the resulting coating film was smooth and had good gloss. Furthermore, when the coating film was subjected to an Erichsen test, it was found to be 3 mm or more, indicating sufficient crosslinking.
参考例 4
実施例2で得られた固形樹脂組成物を水洗後、
流動層式乾燥機で50℃で3時間乾燥せしめて粉末
状塗料を製造する。かかる粉末状塗料を、梨地鋼
板に静電塗装した後160℃で30分間焼付乾燥した
所、平滑で良好な光沢を示し充分架橋した塗膜が
得られた。Reference Example 4 After washing the solid resin composition obtained in Example 2 with water,
A powder coating is produced by drying in a fluidized bed dryer at 50°C for 3 hours. When this powdered paint was electrostatically applied to a matte steel plate and then baked and dried at 160°C for 30 minutes, a smooth and well-crosslinked coating film was obtained that exhibited good gloss.
実施例 3
実施例2のアルキド樹脂溶剤溶液100部、およ
びエタノールでブロツクされたトリレンジイソシ
アナート樹脂14部の50重量%メチルエチルケトン
溶液を混合し、混合物にジメチルエタノールアミ
ンを作用させて中和率70%の樹脂混合液を得る。
この混合液114部、実施例2の酸化チタン30部お
よび水350部を分散混合して水性樹脂組成物液を
調製する。Example 3 100 parts of the alkyd resin solvent solution of Example 2 and a 50% by weight methyl ethyl ketone solution of 14 parts of tolylene diisocyanate resin blocked with ethanol were mixed, and the mixture was treated with dimethylethanolamine to achieve a neutralization rate of 70. % resin mixture is obtained.
114 parts of this mixed solution, 30 parts of the titanium oxide of Example 2, and 350 parts of water are dispersed and mixed to prepare an aqueous resin composition liquid.
次に、かかる水性樹脂組成物液を、炭酸ガス気
流中にエアースプレーして真球状の粒子を得、こ
れを採取して熱硬化性固形樹脂組成物を得る。 Next, the aqueous resin composition liquid is air-sprayed into a carbon dioxide gas stream to obtain true spherical particles, which are collected to obtain a thermosetting solid resin composition.
参考例 5
実施例3で得られた固形樹脂組成物を、水洗後
不揮発分50重量%となるように水中に再分散せし
めてスラリー状塗料、そして上記固形樹脂組成物
を水洗後乾燥せしめて粉末状塗料とする。Reference Example 5 The solid resin composition obtained in Example 3 was washed with water and redispersed in water to a non-volatile content of 50% by weight to obtain a slurry paint, and the solid resin composition was washed with water and dried to obtain a powder. Paint.
実施例 4
下記組成および特数値のメルカプト基を有する
アルキド樹脂10部、アクリル酸15部、メタクリル
酸2−ヒドロキシエチル15部、メタクリル酸メチ
ル38部、スチレン19部、アクリル酸n−ブチル8
部およびブチルセロソルブ30部を混合して液状組
成物を得る。Example 4 10 parts of alkyd resin having a mercapto group with the following composition and special values, 15 parts of acrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 38 parts of methyl methacrylate, 19 parts of styrene, 8 parts of n-butyl acrylate.
and 30 parts of butyl cellosolve to obtain a liquid composition.
アルキド樹脂の組成および特数値
モノマー構成
ネオペンチルアルコール 69.4部
トリメチロールプロパン 33.4部
イソフタル酸 119.7部
アジピン酸 13.2部
チオグリコール酸 16.6部
酸 価 10 以下
数平均分子量 1800
重量平均分子量 4500
粘度(不揮発分60重量%、ガードナー気泡粘度
計) L〜R
上記液状組成物25部をコルベンに仕込み130℃
に保持しながら撹拌下、これに上記液状組成物
110部およびアゾビスイソブチロニトリル1.5部の
混合物を3時間要して滴下する。滴下後同温度で
1時間撹拌する。次いで、110℃にて水酸化ナト
リウムの10重量%水溶液36部を加えた後30分間撹
拌し、更に100℃以下で水150部を加えて中和アク
リル変性アルキド樹脂水性液を得る。この樹脂液
130部に、ヘキサメチロールメラミン10部および
アルミニウム粉末(東洋アルミ社製商品名「アル
ペースト5105WA」)30部を加え分散混合して水
性樹脂組成物液を調製する。Composition and special values of alkyd resin Monomer composition Neopentyl alcohol 69.4 parts Trimethylolpropane 33.4 parts Isophthalic acid 119.7 parts Adipic acid 13.2 parts Thioglycolic acid 16.6 parts Acid number 10 or less Number average molecular weight 1800 Weight average molecular weight 4500 Viscosity (nonvolatile content 60 weight %, Gardner bubble viscometer) L~R 25 parts of the above liquid composition was placed in a Kolben and heated to 130°C.
Add the above liquid composition to this while stirring while maintaining the
A mixture of 110 parts of azobisisobutyronitrile and 1.5 parts of azobisisobutyronitrile is added dropwise over a period of 3 hours. After dropping, stir at the same temperature for 1 hour. Next, 36 parts of a 10% by weight aqueous solution of sodium hydroxide was added at 110°C, followed by stirring for 30 minutes, and further 150 parts of water was added at 100°C or lower to obtain a neutralized acrylic-modified alkyd resin aqueous solution. This resin liquid
To 130 parts, 10 parts of hexamethylol melamine and 30 parts of aluminum powder (trade name "Alpaste 5105WA" manufactured by Toyo Aluminum Co., Ltd.) are added and dispersed to prepare an aqueous resin composition liquid.
次に、かかる水性樹脂組成物液130部を水200部
で希釈した後、これに1/10N−塩酸水溶液700部
を加えラボミキサーで充分撹拌して造粒する。次
に、余剰の酸を1/10N−水酸化ナトリウム水溶液
で中和した後、水性媒体を除去して粒径10〜20μ
の熱硬化性固形樹脂組成物を得る。 Next, 130 parts of the aqueous resin composition liquid is diluted with 200 parts of water, and then 700 parts of a 1/10N hydrochloric acid aqueous solution is added thereto and thoroughly stirred with a lab mixer to form granules. Next, after neutralizing the excess acid with a 1/10N aqueous sodium hydroxide solution, the aqueous medium was removed and the particle size was 10 to 20 μm.
A thermosetting solid resin composition is obtained.
参考例 6
実施例4で得られた固形樹脂組成物を充分水洗
(この場合、副成する塩は無害の塩化ナトリウム
であり、水洗により完全に除去される)後不揮発
分50重量%となるように水中に再分散せしめてス
ラリー状塗料を製造する。かかるスラリー状塗料
を、磨鋼板にエアースプレー塗装した後160℃で
30分間焼付乾燥した所、平滑で良好な光沢を示す
塗膜が得られた。Reference Example 6 The solid resin composition obtained in Example 4 was thoroughly washed with water (in this case, the by-formed salt is harmless sodium chloride and is completely removed by washing with water), and then the nonvolatile content was adjusted to 50% by weight. The slurry is then redispersed in water to produce a slurry paint. This slurry paint is air-sprayed onto a polished steel plate and then heated to 160°C.
After baking and drying for 30 minutes, a smooth coating film with good gloss was obtained.
また、上記固形樹脂組成物を水洗後参考例2と
同様に乾燥して粉末状塗料とした時の、得られる
焼付塗膜も充分な性能を有することが認められ
た。 Furthermore, when the solid resin composition was washed with water and then dried to form a powder coating in the same manner as in Reference Example 2, the baked coating film obtained was also found to have sufficient performance.
実施例 5
アルキド樹脂(数平均分子量1410、酸価55、水
酸基価20、モノマー構成:大豆油30重量%、ネオ
ペンチルグリコール25重量%、イソフタル酸15重
量%、アヂピン酸5重量%、トリメリツト酸25重
量%)の不揮発分80重量%イソプロパノール/ブ
チルセロソルブ(1:1)溶液100部とエピクロ
ルヒドリン・ビスフエノールAエポキシ樹脂(シ
エル化学社製商品名「エピコート#828」)18部を
含む組成物にジメチルエタノールアミンを作用さ
せて中和樹脂液を得、これに水640部および実施
例2の酸化チタン60部を分散混合して水性樹脂組
成物液を調製する。Example 5 Alkyd resin (number average molecular weight 1410, acid value 55, hydroxyl value 20, monomer composition: 30% by weight of soybean oil, 25% by weight of neopentyl glycol, 15% by weight of isophthalic acid, 5% by weight of adipic acid, 25% by weight of trimellitic acid) A composition containing 100 parts of isopropanol/butyl cellosolve (1:1) solution with a nonvolatile content of 80% by weight) and 18 parts of epichlorohydrin bisphenol A epoxy resin (trade name "Epicote #828" manufactured by Ciel Chemical Co., Ltd.) was added with dimethyl ethanol. A neutralized resin liquid is obtained by the action of an amine, and 640 parts of water and 60 parts of the titanium oxide of Example 2 are dispersed and mixed to prepare an aqueous resin composition liquid.
次に、かかる水性樹脂組成物液を実施例2と同
様に処理して熱硬化性固形樹脂組成物を得る。 Next, this aqueous resin composition liquid is treated in the same manner as in Example 2 to obtain a thermosetting solid resin composition.
参考例 7
実施例5で得られた固形樹脂組成物を参考例3
と同様に処理してスラリー状塗料を得、これを磨
鋼板にエアースプレー塗装した後130℃で30分間
焼付乾燥した所、得られた塗膜は良好な光沢を示
し、かつ表面をキシレンで20回ラビングした所ツ
ヤヒケもなく、充分に硬化していた。Reference Example 7 The solid resin composition obtained in Example 5 was prepared as Reference Example 3.
A slurry-like paint was obtained by processing in the same manner as above, and this was air-sprayed onto a polished steel plate, and then baked and dried at 130℃ for 30 minutes.The resulting coating showed good gloss, and the surface was coated with xylene for 20 minutes. After rubbing twice, there was no shine or sink and it was sufficiently cured.
Claims (1)
和性のある溶剤中でモノマーを反応させて得られ
たアルキド樹脂、アクリル樹脂およびアクリル変
性アルキド樹脂から選ばれた分子中にカルボキシ
ル基を有する樹脂を含有する反応混合物に塩基を
加えて前記カルボキシル基を中和せしめ、ここに
得られた中和混合物と、エポキシ樹脂、アミノプ
ラスト樹脂およびブロツクポリイソシアナート化
合物から選ばれた架橋剤と、必要に応じ他の任意
成分とを水と混合して得られた水性液に、酸性物
質を作用させると同時またはその前後において造
粒処理を施して、前記樹脂と架橋剤を含有する粒
子を析出させることを特徴とする熱硬化性固形樹
脂組成物の製造方法。1 Contains a resin having a carboxyl group in the molecule selected from alkyd resins, acrylic resins, and acrylic-modified alkyd resins obtained by dissolving both monomers and resin and reacting the monomers in a water-miscible solvent. A base is added to the reaction mixture to neutralize the carboxyl groups, and the resulting neutralized mixture is mixed with a crosslinking agent selected from epoxy resins, aminoplast resins and blocked polyisocyanate compounds, and other substances as necessary. An aqueous solution obtained by mixing an optional component of with water is subjected to a granulation treatment at the same time or before or after the action of an acidic substance to precipitate particles containing the resin and a crosslinking agent. A method for producing a thermosetting solid resin composition.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2793576A JPS52110732A (en) | 1976-03-12 | 1976-03-12 | Method of manufacturing coating composition |
DE19772710421 DE2710421A1 (en) | 1976-03-12 | 1977-03-10 | RESIN PARTICLES FOR PAINT AND COATING COMPOUNDS, THEIR PRODUCTION AND THE COATING COMPOUNDS CONTAINING THEM |
GB10151/77A GB1579299A (en) | 1976-03-12 | 1977-03-10 | Resinous particles for coating composition |
FR7707387A FR2343773A1 (en) | 1976-03-12 | 1977-03-11 | PROCESS FOR THE PREPARATION OF RESINOUS PARTICLES THAT CAN BE USED IN ITSELF AS COATING PRODUCTS OR IN THE PREPARATION OF SOLVENT-FREE COATING PRODUCTS |
CA273,814A CA1105183A (en) | 1976-03-12 | 1977-03-11 | Resinous particles for coating composition and its production |
US05/777,548 US4365043A (en) | 1976-03-12 | 1977-03-14 | Resinous particles for coating composition and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2793576A JPS52110732A (en) | 1976-03-12 | 1976-03-12 | Method of manufacturing coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS52110732A JPS52110732A (en) | 1977-09-17 |
JPS6124407B2 true JPS6124407B2 (en) | 1986-06-11 |
Family
ID=12234741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2793576A Granted JPS52110732A (en) | 1976-03-12 | 1976-03-12 | Method of manufacturing coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS52110732A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0428580Y2 (en) * | 1986-05-12 | 1992-07-10 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6596790B2 (en) * | 2001-09-25 | 2003-07-22 | Solvay Solexis, Inc. | Precipitation process for making polyvinylidene fluoride powder coatings and coatings made by the process |
JP4656930B2 (en) * | 2004-07-28 | 2011-03-23 | 積水化学工業株式会社 | Suspension manufacturing method |
-
1976
- 1976-03-12 JP JP2793576A patent/JPS52110732A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0428580Y2 (en) * | 1986-05-12 | 1992-07-10 |
Also Published As
Publication number | Publication date |
---|---|
JPS52110732A (en) | 1977-09-17 |
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