JPH0149746B2 - - Google Patents
Info
- Publication number
- JPH0149746B2 JPH0149746B2 JP61202793A JP20279386A JPH0149746B2 JP H0149746 B2 JPH0149746 B2 JP H0149746B2 JP 61202793 A JP61202793 A JP 61202793A JP 20279386 A JP20279386 A JP 20279386A JP H0149746 B2 JPH0149746 B2 JP H0149746B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- pigment
- weight
- parts
- resistance
- 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
- 239000000049 pigment Substances 0.000 claims description 122
- 229920005989 resin Polymers 0.000 claims description 105
- 239000011347 resin Substances 0.000 claims description 105
- 229910052751 metal Inorganic materials 0.000 claims description 67
- 239000002184 metal Substances 0.000 claims description 67
- 239000000178 monomer Substances 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 238000013112 stability test Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 150000005690 diesters Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical group 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 79
- 229910052782 aluminium Inorganic materials 0.000 description 61
- 239000003973 paint Substances 0.000 description 45
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 36
- 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 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 16
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000002537 cosmetic Substances 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 235000015096 spirit Nutrition 0.000 description 8
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
- YRIOTLGRXFJRTJ-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)(COP(O)(=O)O)C1=CC=CC=C1 YRIOTLGRXFJRTJ-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- LHHMNJZNWUJFOC-UHFFFAOYSA-N 1-chloro-2-[2-chloroethoxy(ethenyl)phosphoryl]oxyethane Chemical compound ClCCOP(=O)(C=C)OCCCl LHHMNJZNWUJFOC-UHFFFAOYSA-N 0.000 description 1
- YENKRZXDJWBUIY-UHFFFAOYSA-N 1-phosphonooxypropan-2-yl 2-methylprop-2-enoate Chemical compound OP(=O)(O)OCC(C)OC(=O)C(C)=C YENKRZXDJWBUIY-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-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
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- MIGNNVYXEOGGRC-UHFFFAOYSA-N 5-(phosphonooxymethyl)nonan-5-yl 2-methylprop-2-enoate Chemical compound CCCCC(CCCC)(COP(O)(O)=O)OC(=O)C(C)=C MIGNNVYXEOGGRC-UHFFFAOYSA-N 0.000 description 1
- ZZTIQZXRIJXCPC-UHFFFAOYSA-N 5-(phosphonooxymethyl)nonan-5-yl prop-2-enoate Chemical compound CCCCC(CCCC)(COP(O)(O)=O)OC(=O)C=C ZZTIQZXRIJXCPC-UHFFFAOYSA-N 0.000 description 1
- PSMQLFYOBYVVRF-UHFFFAOYSA-N 9-(phosphonooxymethyl)heptadecan-9-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCC(OC(=O)C(C)=C)(COP(O)(O)=O)CCCCCCCC PSMQLFYOBYVVRF-UHFFFAOYSA-N 0.000 description 1
- DOBCIIMXGLLMKF-UHFFFAOYSA-N 9-(phosphonooxymethyl)heptadecan-9-yl prop-2-enoate Chemical compound CCCCCCCCC(OC(=O)C=C)(COP(O)(O)=O)CCCCCCCC DOBCIIMXGLLMKF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- 101100063818 Caenorhabditis elegans lig-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101100224228 Mus musculus Lig1 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-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
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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Description
〔産業上の利用分野〕
本発明は、新規な樹脂被覆金属顔料に関し、更
に詳しくは、塗料用顔料として使用した時、耐薬
品性、耐水性、耐化粧品性、耐指紋跡性等に優れ
たメタリツク塗膜を与える樹脂被覆金属顔料に関
するものである。又、プラスチツク練り込み用と
して従来にない耐熱安定性、貯蔵安定性を有する
樹脂被覆金属顔料に関するものである。
〔従来の技術とその問題点〕
従来、メタリツク塗料用、印刷インキ用、プラ
スチツク練り込み用等に、メタリツク感を重視す
る美粧効果を得る目的で金属顔料が使用されてい
る。
しかし、メタリツク塗料として使用した時、従
来の金属顔料では、塗料は貯蔵中に金属顔料分と
樹脂分が反応してゲル化し、使用できなくなる。
又、塗料中に含まれる水分と金属顔料分が反応し
てガスを発生し、容器を変形させるなどの欠点が
ある。このガス発生は酸又はアルカリ成分が存在
すると著しく促進されるなど、貯蔵安定上の問題
を残している。
更に、メタリツク塗料を用いて塗装して得られ
る塗膜は耐酸、耐アルカリ性等の耐薬品性及び耐
水性が十分ではなく、経時的に塗面が変色したり
光沢が低下する為に、メタリツク塗料の使用用途
が限定されている。
近年メタリツク塗膜の使用用途が広範囲にわた
り、従来に増して高い耐薬品性、耐水性が要求さ
れるばかりでなく、耐化粧品性、耐指紋跡性に優
れたメタリツク塗膜が望まれている。耐化粧品性
とは、メタリツク塗膜に付着した化粧品が塗膜に
シミを残す現象に対する性能であり、耐指紋跡性
とは、被塗物に付着した指紋の跡が塗膜上に黒斑
となつて浮き上がる現象に対する性能である。こ
れらは共にメタリツク塗膜の商品価値を大幅に低
下させる。又、従来の金属顔料では、プラスチツ
ク練り込み用、例えば、ポリエチレン、ポリ塩化
ビニル等の樹脂への練り込みに使用する時、金属
顔料と樹脂とが相溶性に乏しいため金属顔料が均
一に分散せず、目的とする均一なシートやフイル
ム等が得られない。又、ポリ塩化ビニルに配合す
ると、ポリ塩化ビニルから発生する塩化水素によ
り金属顔料表面が変色し金属光沢が失われる。
これらの課題の改善策として、金属顔料成分に
樹脂被覆を施す方法が提案されている。
樹脂被覆の一つの方法としては、予め製造した
樹脂を溶媒に溶解した溶液と顔料の懸濁液を混合
し、顔料上に樹脂を沈着せしめる方法（特公昭56
−43069号公報）が知られている。
しかし、この方法によつて顔料微粒子の表面に
均一に、かつ、強固に樹脂を付着せしめることは
困難である。この方法によつて作られた樹脂被覆
は樹脂層が金属表面に物理的に付着しているに過
ぎず、その付着力は弱い。従つて、塗料製造時の
顔料分散工程で加わる機械的な外力、又は樹脂被
覆顔料を用いて製造される塗料に含まれる溶媒に
よる溶解又は軟化により樹脂被覆層が剥離又は溶
解し、目的とする効果が著しく損なわれる。
又、熱を加えることにより、溶融又は軟化し易
く、プラスチツク練り込み用として、樹脂被覆の
効果が充分に得られない。
更に、金属顔料を分散した系において単量体の
重合を進行させ、樹脂の製造と顔料表面への被覆
を同時に行う方法も試みられており、この方法を
より確実なものにすることを目的として樹脂と金
属顔料表面との間に化学的な結合を持たせること
が試みられている（特開昭50−26837号公報）。し
かし、製造工程が煩雑で長い等の製造上の問題に
加えて顔料表面への樹脂層形成がコントロールさ
れない結果、十分な耐水性、耐薬品性の効果が発
揮されず、未だ工業的に実施されるに至つていな
い。
又、金属顔料を水中に分散した系において、重
合時正電荷を有するポリマーを生成する条件下で
重合を行なわせる方法が提案されている（特公昭
53−4029号公報）。しかし、この方法においても
十分な耐水性、耐アルカリ性、耐酸性等の効果が
得られず、工業的に実用化されていない。
更に、単量体は可溶であり、生成する重合物が
不溶である有機溶媒中で重合反応を進行させて得
た樹脂によつて金属粒子表面を被覆する方法が知
られている（特開昭56−161470号、特開昭51−
11818号公報）。しかし、これらの方法によつて製
造される樹脂被覆金属顔料も、未だ耐薬品性、耐
水性、特に耐化粧品性、耐指紋跡性等において実
用上充分な水準に達しておらず改良が必要であ
る。又、この樹脂被覆金属顔料も充分な耐熱安定
性がない為、練り込み用として使用し、高温下
（150℃以上）に置かれた時、金属顔料を被覆した
樹脂が軟化を起こし易く、顔料同士の結合が起こ
り、目的とした均一に分散したフイルム、シート
が得難い。
〔問題点を解決するための手段〕
本発明者らは、このような従来の金属顔料の問
題点を解決すべく鋭意研究を続けた結果、１分子
中にラジカル重合性二重結合とカルボキシル基を
有する単量体又はラジカル重合性二重結合を有す
る燐酸モノ又はジエステルの特性を生かし、金属
顔料表面に高度に三次元化した樹脂層を強固に密
着させることによつて目的を達成し得る事実を見
い出し、本発明に至つた。
即ち、本発明は、
(1) ラジカル重合性不飽和カルボン酸及び／又は
ラジカル重合性二重結合を有する燐酸モノ又は
ジエステル及びラジカル重合性二重結合を３個
以上有する単量体から生成した高度に三次元化
した樹脂によつて強固に密着して表面被覆され
てなり、かつ、耐アルカリ性が1.0以下で耐熱
安定試験で実質的に凝集しないことを特徴とす
る樹脂被覆金属顔料、
(2) 金属顔料を有機溶剤に分散し、ラジカル重合
性不飽和カルボン酸及び／又はラジカル重合性
二重結合を有する燐酸モノ又はジエステルを加
える第一工程、次いで、第一工程の液に、ラジ
カル重合性二重結合を３個以上有する単量体と
重合開始剤を加えて重合する第二工程を経るこ
とを特徴とする樹脂被覆金属顔料の製造方法、
に関するものである。
本発明による樹脂被覆金属顔料は、従来にない
耐熱安定性を示し、又顔料として長期間貯蔵した
時、顔料の凝集が見られず、その他の樹脂被覆に
より付与された特性（耐アルカリ性、耐水性等）
に変化がない貯蔵安定性の優れたものであり、メ
タリツク塗料用顔料として使用した時、塗料の貯
蔵安定性が優れ、かつ、卓越した耐薬品性、耐水
性、そして優れた耐化粧品性、耐指紋跡性を示す
塗膜を与える。
本発明におけるラジカル重合性不飽和カルボン
酸とは、アクリル酸、メタクリル酸、イタコン
酸、フマル酸等であり、その一種又は二種以上を
混合して使用される。使用される量は金属顔料の
種類と特性、特に表面積によつて異なるが、一般
に金属顔料100重量部に対して0.01重量部から10
重量部の間である。0.01重量部未満では、本発明
の効果、即ち、耐水性及び耐酸性などの耐薬品
性、耐指紋跡性等が良好に発揮されず、又、次の
１分子中に重合性二重結合を３個以上有する単量
体を重合する時、重合系がゲル化し、撹拌できな
くなる場合がある。又、10重量部を超えると耐水
性が低下する。これは、ラジカル重合性不飽和カ
ルボン酸に含まれるカルボキシル基の量が多すぎ
ることに起因すると推定される。
本発明におけるラジカル重合性二重結合を有す
る燐酸エステル単量体とは、２−メタクリロイロ
キシエチルホスフエート、ジ−２−メタクリロイ
ロキシエチルホスフエート、トリ−２−メタクリ
ロイロキシエチルホスフエート、２−アクリロイ
ロキシエチルホスフエート、ジ−２−アクリロイ
ロオキシエチルホスフエート、トリ−２−アクリ
ロイロキシエチルホスフエート、ジフエニル−２
−メタクリロイロキシエチルホスフエート、ジフ
エニル−２−アクリロイロキシエチルホスフエー
ト、ジブチル−２−メタクリロイロキシエチルホ
スフエート、ジブチル−２−アクリロイロキシエ
チルホスフエート、ジオクチル−２−メタクリロ
イロキシエチルホスフエート、ジオクチル−２−
アクリロイロキシエチルホスフエート、２−メタ
クリロイロキシプロピルホスフエート、ビス（２
−クロロエチル）ビニルホスホネート、ジアリル
ジブチルホスホノサクシネート等であり、その一
種又は二種以上を混合して使用される。
好ましいラジカル重合性二重結合を有する燐酸
エステルとして、燐酸モノエステルを挙げること
ができる。これは燐酸基の持つOH基が２個ある
ことにより、より強固にアルミニウム粒子表面に
固定されることに起因すると推定される。より好
ましい燐酸モノエステルとして、メタクロイロキ
シ基及びアクロイロキシ基を有したモノエステル
が挙げられ、例えば、２−メタクロイロキシエチ
ルホスフエート、２−アクロイロキシエチルホス
フエートが挙げられる。これらのモノエステル
は、一般の重合用溶媒に不溶の場合が多い。
使用される量は、金属顔料の種類と特性特に表
面積によつて異なるが、一般に金属顔料100重量
部に対して0.01重量部から30重量部の間である。
0.01重量部未満では、本発明の効果、即ち、耐水
性及び耐酸性などの耐薬品性、耐指紋跡性等が良
好に発揮されず、又、30重量部を超えて使用して
も、効果の増加は殆どない。
本発明に使用される１分子中に重合性二重結合
を３個以上有する単量体として、トリメチロール
プロパントリアクリレート、トリメチロールプロ
パントリメタクリレート、テトラメチロールメタ
ントリアクリレート、テトラメチロールメタンテ
トラアクリレート等を挙げることが出来、これら
の一種又は二種以上が使用される。
その使用量は金属顔料の金属分100重量部に対
して２重量部から50重量部の間であり、２重量部
未満では、本発明の効果、即ち、耐薬品性が低下
し、100重量部を超えると、効果の増加は期待さ
れず、光輝性、光沢、金属感などのメタリツク塗
料としての基本特性が低下し実用に供し難い。
本発明の効果を損なわない範囲、即ち、金属顔
料の金属分100重量部に対して０重量部から10重
量部の間で１分子中に重合性二重結合を１ないし
２個有する単量体を使用してもよい。使用量が10
重量部を超えると、本発明の効果、即ち、得られ
る樹脂被覆金属顔料を使用しメタリツク塗膜を作
成した時、特性が低下し、又、金属顔料の耐熱安
定性も低下し、実用に供し難い。
本発明に使用される１分子中に１ないし２個の
重合性二重結合を有する単量体としては、スチレ
ン、α−メチルスチレン、アクリル酸メチル等の
アクリル酸エステル類、メタクリル酸メチル等の
メタクリル酸エステル類、アクリロニトリル、メ
タクリロニトリル、酢酸ビニル、プロピオン酸ビ
ニル、エチレングリコールジメタクリレート、ジ
エチレングリコールジメタクリレート、トリエチ
レングリコールジメタクリレート、１，３−ブチ
レングリコールジメタクリレート、ネオペンチル
グリコールジアクリレート、ジビニルベンゼン等
を挙げることができ、これらの一種又は二種以上
が使用される。
本発明に使用される重合開始剤は、一般にラジ
カル発生剤として知られているものであり、ベン
ゾイルパーオキサイド、ラウロイルパーオキサイ
ド、イソブチルパーオキサイド、メチルエチルケ
トンパーオキサイド等のパーオキサイド類、及び
アゾビスイソブチロニトリル等である。
重合開始剤は、１分子中に重合性二重結合を３
個以上有する単量体100重量部に対して0.1重量部
から50重量部用いる。好ましくは、１重量部から
20重量部用いる。１分子中に重合性二重結合を３
個以上有する単量体100重量部に対して0.1重量部
未満では重合に長時間を要し実用的でない。50重
量部を超えると、重合速度が速すぎる為コントロ
ールができず実用的でない。
本発明の耐アルカリ性とは、所定の塗料を配合
し塗装して得られた塗膜を0.1N−NaOH水溶液
で55℃で４時間浸漬し、浸漬前後の塗膜の状態を
JIS−Ｚ−8722（1982）の条件ｄ（９−ｄ方法）に
より測色し、JIS−Ｚ−8730 6.3.2により求めた
色差（ΔEH）を言う。
所定の塗料とは、焼付型のアクリル・メラミン
樹脂を用いた塗料で、顔料濃度は、アクリル・メ
ラミン樹脂（不揮発分）100重量部に対し、15重
量部になるように配合し、必要な量のシンナーを
加えたものである。ここで使用されるアクリル樹
脂は、一般に市販されている焼付用アクリル樹脂
であり、メラミン樹脂は一般に市販されているブ
チル化メラミン樹脂である。その混合割合は、ア
クリル樹脂70〜90重量部に対し、メラミン樹脂30
〜10重量部である。
本発明の樹脂被覆金属顔料は、耐アルカリ性が
1.0以下であり、好ましくは0.8以下である。1.0を
超えると、目視で塗膜の変色が認められ、充分な
耐アルカリ性を持つたものでなく、本発明に含ま
れない。
本発明で言う耐熱安定性試験で実質的に凝集し
ない樹脂被覆金属顔料とは、所定の温度を所定の
時間樹脂被覆金属顔料に加えた時、粒度に殆ど変
化が見られないものである。即ち、JIS−Ｋ−
5400 8.2.1の温度を150℃に、時間を１時間、試
料の取得量を10ｇに変える以外同様にして熱を加
える耐熱安定性試験を行い、試験前の粒度d1′と
試験後の粒度d2′の比で凝集を測定する。
本発明の樹脂被覆金属顔料はd2′／d1′が1.5以下
であり、より好ましくは1.3以下である。1.5を超
えると、練り込み等の高温成形時に、金属顔料の
均一な分散が得られないため好ましくない。
ラジカル重合性不飽和カルボン酸及び／又はラ
ジカル重合性二重結合を有する燐酸モノ又はジエ
ステル及びラジカル重合性二重結合を３個以上有
する単量体を反応させて、生成した樹脂によつて
表面被覆した本発明の金属顔料を好ましく製造す
る方法は、まず金属顔料を有機溶剤に分散し、ラ
ジカル重合性不飽和カルボン酸及び／又はラジカ
ル重合性二重結合を有する燐酸モノ又はジエステ
ルを加える第一段工程、ラジカル重合性二重結合
を３個以上有する単量体と開始剤を加えて重合す
る第二段工程を経て製造する方法である。
第一工程は、金属顔料粒子を有機溶媒中に分散
し、次に撹拌を続けながらラジカル重合性不飽和
カルボン酸又はラジカル重合性二重結合を有する
燐酸モノ又はジエステルを添加し撹拌を続けるこ
とによつてなされる。
第一工程の処理温度は常温でも良いが、30〜80
℃に加温することが好ましい。
処理時間は、溶媒中に残存する不飽和カルボン
酸又は燐酸エステルの濃度が一定になる時点をも
つて第一工程を終了するが、一般に５分以上、好
ましくは10分以上である。
第一工程に行うに当たり、第二工程で添加され
るラジカル重合性二重結合を３個以上有する単量
体の一部又はすべてを既に添加し、実施する方法
もある。
しかし、第一工程の完結を早期に、かつ、確実
に終了させるために、又、第一工程の完結以前に
第二工程で添加されるラジカル重合性二重結合を
３個以上有する単量体の重合の開始を完全に停止
せしめるために、第一工程は、第二工程で添加す
るラジカル重合性二重結合を３個以上有する単量
体を含まない方が好ましい。無論第二工程で使用
する開始剤を第一工程で添加すると、得られる樹
脂被覆金属顔料の性能は著しく低下し、実用に供
し難い。
これにより、金属顔料表面にラジカル重合性不
飽和カルボン酸のカルボキシル基又はラジカル重
合性二重結合を有した燐酸エステルの燐酸基が固
定され、ラジカル重合性二重結合を表面に持つ顔
料粒子が得られると推定される。
この推定は、第一工程終了後、金属顔料を濾別
し、溶媒中に残存するラジカル重合性不飽和カル
ボン酸又はラジカル重合性二重結合を有する燐酸
モノ又はジエステルを定量すると、初期に加えた
量に比較して大幅な減少が認められる点よりも裏
付けられる。
第二工程は、第一工程終了後、１分子中に重合
性二重結合を３個以上有する単量体と開始剤を加
え、加熱、撹拌することによつて進行する。
この操作により、前もつて金属顔料表面に固定
された不飽和カルボン酸に基づく二重結合と１分
子中に重合性二重結合を３個以上有する単量体が
共重合し金属顔料表面に高度に架橋し、網目密度
の高い樹脂層が金属顔料表面と化学結合を持つ形
で形成されることにより、始めて本発明の優れた
効果が発現されると推定される。この推定は、本
発明の樹脂被覆金属顔料の耐熱安定性が大幅に良
くなり、試験後の凝集が殆どないことで裏付けら
れると考える。
反応系を窒素、アルゴン等の不活性ガスにて置
換することが好ましく、又、温度は開始剤の種類
によつて変化するが、一般には30℃から150℃の
間である。反応時間は30分から10時間の間であ
る。
反応は、単量体及び／又は開始剤を一括して添
加しても、分割して添加して行つてもよい。
第二工程の実施に当つて、ラジカル重合性不飽
和カルボン酸、又はラジカル重合性二重結合を有
する燐酸エステル、１分子中に重合性二重結合を
３個以上有する単量体と開始剤を一括して同時に
添加し、直ちに重合反応を開始せしめると、本発
明の効果が発揮されない。
又、ラジカル重合性不飽和カルボン酸、又はラ
ジカル重合性二重結合を有する燐酸エステルを使
用せず、１分子中に重合性二重結合を３個以上有
する単量体のみを有機溶媒に分散した金属顔料粒
子の存在下に重合する場合、即ち、第一工程を省
き、第二工程に入ると、重合系が増粘し、撹拌が
出来なくなる場合があるばかりでなく、得られる
樹脂被覆金属顔料の性能は非常に劣るものであ
る。この事実は、金属表面が充分に樹脂層によて
被覆されていない事を示している。これらの知見
は、第二工程に先立ち第一工程の必要性を明らか
にしている。
本発明に使用される金属顔料には、アルミニウ
ム、銅、亜鉛、鉄、ニツケル、及び／又はこれら
の合金が用いられ、好ましい例としてアルミニウ
ムを挙げることができる。その形状はフレーク
状、球状、針状等の粒状である。金属顔料の粒度
は用途により異なる。塗料用、印刷用としては、
平均径が約１〜100μ程度が良く、プラスチツク
練り込み用としては、約１〜200μ程度が良いが、
特に限定されず、本発明に適用できる。
本発明に使用されるアルミニウム顔料について
詳述すると、アルミニウムの細片、又は粒状粉を
機械的方法、例えばスタンプミル法、乾式ボール
ミル法、湿式ボールミル法、アトライター法、振
動ボールミル法等により数％の磨砕助剤と共に磨
砕して造られる。この磨砕助剤は磨砕助剤として
の機能と同時に、アルミニウム顔料の物性に影響
を与える。この磨砕助剤として従来からステアリ
ン酸、オレイン酸等の高級飽和、又は不飽和脂肪
酸、ステアリルアミン等の高級脂肪族アミンをよ
く使用するが、これらの磨砕助剤に関係なく、本
発明の効果は得られる。ステアリン酸を使用して
得られたアルミニウム顔料は、一般にリーフイン
グタイプアルミペーストとしてよく知られてお
り、タンク等のシルバーペイントとして金属の防
錆用途に使用されている。又、オレイン酸、ステ
アリルアミン等を使用して得られたアルミニウム
顔料は、一般にノンリーフイングタイプアルミペ
ーストとしてよく知られ、自動車、家具等のメタ
リツク塗料として、美粧用途に使用されている。
本発明の重合に使用される有機溶剤は、脂肪族
炭化水素（例えばヘキサン、ヘプタン、オクタ
ン、ミネラルスピリツト等）、芳香族炭化水素
（例えば、ベンゼン、トルエン、ソルベントナフ
サ、キシレン等）、エステル（酢酸エチル、酢酸
ブチル等）、エーテル（テトラヒドロフラン、ジ
エチルエーテル等）が挙げられ、金属顔料100重
量部に対し50重量部から3000重量部用いる。好ま
しくは250重量部から1000重量部の間である。金
属顔料100重量部に対し50重量部未満ではペース
ト状となりラジカル重合性不飽和カルボン酸、及
び１分子中に重合性二重結合を３個以上有する単
量体、及び重合開始剤の均一拡散に長時間を要し
好ましくない。3000重量部を超えると重合時間が
長くなり好ましくない。
以上のようにして有機溶剤中で金属顔料表面に
樹脂被覆層を形成せしめた後、有機溶剤を濾別
し、不揮発分を30〜80％に調製し、必要に応じて
他の溶剤、添加剤等を加えた本発明の樹脂被覆金
属顔料を含むペーストを得る。
本発明の樹脂被覆金属顔料は、(イ)塗料用樹脂
100重量部に対し、(ロ)本発明の樹脂被覆金属顔料
0.1重量部〜100重量部、(ハ)希釈シンナーによりメ
タリツク塗料が得られる。
塗料用樹脂としては、従来メタリツク塗料で用
いられている塗料用樹脂の中の任意のものを用い
ることが出来、更に、金属と反応を起こし、ゲル
化を起こし易い官能基を多量に持つ従来のメタリ
ツク塗料に使用されていなかつた樹脂にも用いる
ことが出来る。これらの樹脂としては、アクリル
樹脂、アルキツド樹脂、オイルフリーアルキツド
樹脂、塩化ビニル樹脂、ウレタン樹脂、メラミン
樹脂、不飽和ポリエステル樹脂、尿素樹脂、セル
ロース系樹脂、エポキシ樹脂等が挙げられ、これ
らは単独で用いてもよいし混合して用いてもよ
い。
本発明の樹脂被覆金属顔料は、塗料用樹脂100
重量部に対して0.1重量部〜100重量部である。特
に１重量部〜50重量部用いることが好ましい。こ
の樹脂被覆金属顔料が0.1重量部未満であると、
メタリツク塗料として必要な金属光沢が不充分で
あり、又、100重量部を超えて用いると、塗料中
の金属顔料の量が多くなり過ぎて、塗装作業性が
悪くなるばかりでなく、物性も劣つた塗膜となり
実用的でない。
希釈シンナーとしては、トルエン、キシレン等
の芳香族系化合物、ヘキサン、ヘプタン、オクタ
ン等の脂肪族系化合物、エタノール、ブタノール
等のアルコール類、酢酸エチル、酢酸ブチル等の
エステル類、メチルエチルケトン等のケトン類、
トリクロロエチレン等の塩素化合物、エチレング
リコールモノエチルエーテル等のセロソルブ類等
の一般的有機溶剤で、これらの溶剤は二種以上混
合して使用するのが好ましく、この組成は塗料用
樹脂に対する溶解性、塗膜形成特性、塗装作業性
等を考慮して決定される。
なお、塗料業界で一般に使用されている顔料、
染料、湿潤剤、分散剤、色分れ防止剤、レベリン
グ剤、スリツプ剤、皮張り防止剤、ゲル化防止
剤、消泡剤等の添加剤等を加えることが可能であ
る。
〔実施例〕
次に、本発明の実施例を示す。まず実施例で用
いる試験方法及び測定方法を詳述する。
〔アルミニウム金属分100重量部に対する被覆樹
脂量〕
本発明の樹脂被覆アルミニウム顔料を含むペー
スト10ｇをクロロホルム（試薬）100mlによく分
散し、可溶分を抽出する。次いで、抽出残渣の樹
脂被覆アルミニウム顔料を80℃で１時間真空乾燥
して粉末化し、1.0ｇをとり、6N−HCl（試薬）
200mlで金属アルミニウム部分を少しずつ溶解す
る。残つた不溶樹脂分を濾過し、80℃で14時間真
空乾燥後、重量を測定し、アルミニウム金属分
100重量部に対する樹脂分を算出する。
〔耐アルカリ性〕
樹脂被覆アルミニウム顔料を使用し、下記の塗
料配合を行い、耐アルカリ性評価用のメタリツク
塗料を調製する。
〔塗料配合〕
（重量部）
樹脂被覆アルミニウム顔料（不揮発分換算）
7.5
アクリル・メラミン樹脂※１ 100 混合シンナー※２ 180
※１：アクリデイツク47−712（不揮発分：50
％）80部、スーパーベツカミンＪ−820（不揮
発分：50％）20部で混合したもの（日本ライ
ヒホールド(株)製）
※２：トルエン（70部）、酢酸エチル（20部）、
ブチルセロソルブ（10部）で混合したもの
次いで、該塗料をエアースプレー塗装で、アル
ミニウム板（70×150×１mm：日本テストパネル
(株)製）に膜厚が20μになるように塗装し、この塗
装板を140℃で30分乾燥し、耐アルカリ性を求め
るための試験塗膜とする。この塗膜に、内径34
mm、高さ15mmの塩化ビニル製円筒を金具で固定
し、0.1N−NaOH5mlを入れ、55℃で４時間放置
する。４時間放置後、塩化ビニル製円筒をはず
し、試験塗膜を水でよく洗い、塗膜を乾燥する。
この塗膜の試験前後の塗膜をJIS−Ｚ−8722
（1982）の条件ｄ（９−ｄ方法）により測色し、
JIS−Ｚ−8730（1980）の6.3.2により色差△EHを
求める（測定機：スガ試験機(株)製SH−４−
MCH型）。
〔耐酸性〕
0.1N−NaOHを0.1N−H2SO4に変える以外耐
アルカリ性と同様にして行う。
〔耐熱安定性試験による凝集〕
樹脂被覆アルミニウム顔料を含むペースト10ｇ
を計り、ビンに取り、温度150℃に保つた乾燥器
に入れて１時間加熱する。この樹脂被覆アルミニ
ウム顔料の粒度特性数をミネラルスピリツトを分
散媒とし、湿式ふるい分けし、その分析結果をド
イツ工業規格DIN−4190のRRS粒度線図（Rosin
−Rammler−Spering粒度線図）に基づいて求め
る。この値をd2′とする。次に加熱前の樹脂被覆
アルミニウム顔料についても同様に粒度特性数を
求める。この値をd1′とする。計算によりd2′／
d1′の値を得る。
ここで使用する篩は、44μ以上はJIS標準ふる
いを用い、44μ未満はマイクロメツシユシーブ
（Buckbee−mears Company製品）を用いる。
〔耐化粧品性〕
樹脂被覆アルミニウム顔料を使用し、下記の塗
料配合を行い、プラスチツク塗装用塗料を調製す
る。
〔塗料配合〕
〔重量部〕
樹脂被覆アルミニウム顔料を含むペースト（不揮
発分換算） ９
シンナー※１ 40
アクリル樹脂※２ 100 硝化綿樹脂溶液※３ 50
※１：酢酸ブチル（30部）、トルエン（45部）、
イソプロピルアルコール（20部）、エチルセ
ロソルブ（５部）を混合したもの
※２：アクリデイツクＡ−166（不揮発分；45
％）日本ライヒホールド(株)製、常乾型アクリ
ル樹脂
※３：LIG １／２（不揮発分70％）（旭化成工
業(株)製、工業用硝化綿）をシンナー※１で不
揮発分が16％になるように溶解したもの
該塗料をシンナー（※１）で粘度を13秒（FC
＃４、20℃）に調整し、ABS板に吹き付け塗装
し（膜厚10μ）、常温で３日乾燥し、耐化粧品性
試験に用いる。
試験塗膜の半分に化粧品（アトリツクスハンド
クリーム：花王石鹸株式会社製）を厚さ１mm程度
に塗る。次いで、この塗膜を温度60℃、湿度90％
に調整した恒温恒湿槽に５日間放置する。
試験後の塗膜を水洗し、水分をふき取り、１時
間室温で乾燥後、化粧品を付けた部分と付けない
部分の塗膜の外観を目視で比較する。
〔耐指紋跡性〕
予めABS板に指先を押さえ指紋の跡を付けて
置く以外、耐化粧品性と同様にして塗膜を作成す
る。
試験塗膜を60℃の温水を入れたビーカーに全部
漬け、３時間放置する。
試験後の塗膜を水洗し、水分をふき取り、１時
間室温で乾燥後、指紋跡の出方を目視判定する。
実施例 １
1000mlの三つ口フラスコに、アルミニウムペー
スト（旭化成工業株式会社製M601、金属分65.2
％、平均粒子径11μ、形状フレーク状）115ｇ及
びミネラルスピリツト400ｇを加え、窒素ガスを
導入しながら撹拌し、系内の温度を80℃に昇温し
た。次いで、アクリル酸（試薬）を0.375ｇを添
加し80℃で30分撹拌を続けた。次いでトリメチロ
ールプロパントリメタクリレート（試薬）7.5ｇ
とアゾビスイソブチロニトリル（試薬）0.75ｇを
添加し、80℃で５時間重合した。重合終了後、常
温まで放冷し、このスラリーを濾過し、樹脂被覆
アルミニウム顔料を含むペーストを得た。このペ
ーストの不揮発分（JIS−Ｋ−5910による）は
51.0重量％であつた。アルミニウム金属分100重
量部に対する被覆樹脂量は11.4重量部であつた。
これは、アクリル酸、トリメチロールプロパント
リメタクリレート、アゾビスイソブチロニトリル
の99％以上がアルミニウム金属表面上に付着した
ものと推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.3、耐酸性（ΔEH）も0.3であり、殆ど
変色せず良好な塗膜を得た。
又、塗膜を60℃の温水に７日間浸漬したところ
殆ど変色せず良好な塗膜であつた。塗料を50℃で
１カ月貯蔵したが、ゲル化等がなく良好な塗料で
あつた。
耐熱安定性試験後の凝集（d2′／d1′）は1.05で
あり、外観も均一なパウダーであり、実質的に凝
集は認められなかつた。
実施例 ２
1000mlの三つ口フラスコに、アルミニウムペー
スト（旭化成工業株式会社製MB−21、金属分
72.0％、平均粒子径24μ、形状フレーク状）118ｇ
及びミネラルスピリツト325ｇを加え、窒素ガス
を導入しながら撹拌し、系内の温度を80℃に昇温
した。次いで、アクリル酸（試薬）を0.255ｇを
添加し80℃で30分撹拌を続けた。次いでトリメチ
ロールプロパントリメタクリレート（試薬）4.25
ｇとアゾビスイソブチロニトリル（試薬）0.43ｇ
を添加し、80℃で５時間重合した。重合終了後、
常温まで放冷し、このスラリーを濾過し、樹脂被
覆アルミニウム顔料を含むペーストを得た。この
ペーストの不揮発分（JIS−Ｋ−5910による）は
60.2重量％であつた。アルミニウム金属分100重
量部に対する被覆樹脂量は5.7重量部であつた。
これは、アクリル酸、トリメチロールプロパント
リメタクリレート、アゾビスイソブチロニトリル
の98％以上がアルミニウム金属表面上に付着した
ものと推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.2、耐酸性（ΔEH）は0.1、耐熱安定性
試験後の凝集（d2′／d1′）は1.05であり、本発明
の樹脂被覆アルミニウム顔料が得られた。
実施例 ３
1000mlの三つ口フラスコに、アルミニウムペー
スト（旭化成工業株式会社製４／62、金属分67.3
％、平均粒子径9μ、形状フレーク状）104ｇ及び
ミネラルスピリツト400ｇを加え、窒素ガスを導
入しながら撹拌し、系内の温度を80℃に昇温し
た。次いで、アクリル酸（試薬）を0.525ｇを添
加し80℃で30分撹拌を続けた。次いでトリメチロ
ールプロパントリメタクリレート（試薬）10.5ｇ
とアゾビスイソブチロニトリル（試薬）0.525ｇ
を添加し、80℃で６時間重合した。重合終了後、
常温まで放冷し、このスラリーを濾過し、樹脂被
覆アルミニウム顔料を含むペーストを得た。この
ペーストの不揮発分（JIS−Ｋ−5910による）は
53.0重量％であつた。アルミニウム金属分100重
量部に対する被覆樹脂量は16.4重量部であつた。
これは、アクリル酸、トリメチロールプロパント
リメタクリレート、アゾビスイソブチロニトリル
の99％以上がアルミニウム金属表面上に付着した
ものと推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.6、耐酸性（ΔEH）は0.1、耐熱安定性
試験後の凝集（d2′／d1′）は1.10であり、本発明
の樹脂被覆アルミニウム顔料が得られた。
実施例 ４
1000mlの三つ口フラスコに、実施例１で使用し
たアルミニウムペーストＭ−601 115ｇ及びミネ
ラルスピリツト400ｇを加え、窒素ガスを導入し
ながら撹拌し、系内の温度を65℃に昇温した。次
いでメタクリル酸（試薬）を0.375ｇを添加し65
℃で60分撹拌を続けた。次いでトリメチロールプ
ロパントリアクリレート（試薬）7.5ｇとアゾビ
スイソブチロニトリル（試薬）0.75ｇを添加し、
65℃で７時間重合した。重合終了後、常温まで放
冷し、このスラリーを濾過し、樹脂被覆アルミニ
ウム顔料を含むペーストを得た。このペーストの
不揮発分（JIS−Ｋ−5910による）は47.5重量％
であつた。アルミニウム金属分100重量部に対す
る被覆樹脂量は11.2重量部であつた。これは、メ
タクリル酸、トリメチロールプロパントリアクリ
レート、アゾビスイソブチロニトリルの97.4％が
アルミニウム金属表面上に付着したものと推定さ
れる。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.4、耐酸性（ΔEH）は0.5、耐熱安定性
試験後の凝集（d2′／d1′）は1.08であり、本発明
の樹脂被覆アルミニウム顔料が得られた。
実施例５〜７、比較例１〜２
実施例２で使用したアルミニウムペーストMG
−21を用いて、実施例２の樹脂被覆アルミニウム
顔料の調製と同様に表１に示す重合を行い、樹脂
被覆アルミニウム顔料を含むペーストを得た。
比較例１は、トリメチロールプロパントリメタ
クリレートのみを重合したが、重合開始後１時間
で系内のスラリー粘度が上がり撹拌が困難となつ
た。これは、アクリル酸処理を行わなかつたた
め、アルミニウム粒子表面に付着せず、有機溶剤
（ミネラルスピリツト）内で重合が進んだものと
推察される。
結果を表１に示したように、実施例５〜７は極
めて良好な性能を示したが、比較例１は耐アルカ
リ性が劣り、樹脂が被覆していないものと推察さ
れる。比較例２も実施例５〜７に比べ劣る性能を
示した。これはアクリル酸に含まれるカルボキシ
ル基の量が多すぎたためと推定される。
[Field of Industrial Application] The present invention relates to a novel resin-coated metal pigment, and more specifically, when used as a paint pigment, it exhibits excellent chemical resistance, water resistance, cosmetic resistance, fingerprint resistance, etc. This invention relates to resin-coated metallic pigments that provide metallic coatings. The present invention also relates to a resin-coated metal pigment for use in plastic kneading, which has unprecedented heat resistance stability and storage stability. [Prior art and its problems] Metallic pigments have been used in metallic paints, printing inks, plastic kneading, etc. for the purpose of obtaining cosmetic effects emphasizing metallic appearance. However, when used as a metallic paint, the metal pigment and resin components of the paint react with each other during storage, causing the paint to gel and become unusable.
In addition, there is a drawback that the water contained in the paint and the metal pigment react with each other to generate gas, which deforms the container. This gas generation is significantly accelerated in the presence of acid or alkaline components, leaving problems with storage stability. Furthermore, the paint film obtained by painting with metallic paint does not have sufficient chemical resistance such as acid resistance and alkali resistance, and water resistance, and the painted surface changes color and loses gloss over time. has limited uses. In recent years, metallic coatings have been used in a wide range of applications, and not only are higher chemical resistance and water resistance than ever before required, but also metallic coatings with excellent cosmetic resistance and fingerprint resistance are desired. Cosmetic resistance refers to the performance against the phenomenon in which cosmetics adhering to a metallic paint film leaves stains on the paint film, and fingerprint resistance refers to the performance against the phenomenon that cosmetics adhering to the metallic paint film leave stains on the paint film.Fingerprint resistance refers to the performance against the phenomenon that the marks of fingerprints attached to the coated object cause black spots on the paint film. This is the performance against the phenomenon of rolling and rising. Both of these significantly reduce the commercial value of metallic coatings. Furthermore, when conventional metal pigments are used for kneading into plastics, for example, into resins such as polyethylene and polyvinyl chloride, the metal pigments are not uniformly dispersed due to poor compatibility between the metal pigment and the resin. However, the desired uniform sheet or film cannot be obtained. Furthermore, when blended with polyvinyl chloride, the surface of the metal pigment changes color due to hydrogen chloride generated from the polyvinyl chloride, causing loss of metallic luster. As a solution to these problems, a method has been proposed in which the metal pigment component is coated with a resin. One method for resin coating is to mix a suspension of pigment with a solution prepared in advance by dissolving the resin in a solvent, and deposit the resin on the pigment.
-43069) is known. However, it is difficult to uniformly and firmly adhere the resin to the surface of the pigment fine particles using this method. In the resin coating made by this method, the resin layer is merely physically attached to the metal surface, and its adhesion is weak. Therefore, the resin coating layer peels off or dissolves due to mechanical external force applied during the pigment dispersion process during paint manufacturing, or by dissolution or softening by the solvent contained in the paint manufactured using resin-coated pigments, resulting in the desired effect. is significantly impaired. Furthermore, it is easily melted or softened by applying heat, and the effect of resin coating cannot be obtained sufficiently when used for kneading into plastics. Furthermore, attempts have been made to proceed with the polymerization of monomers in a system in which metal pigments are dispersed, and simultaneously manufacture the resin and coat the pigment surface. Attempts have been made to create a chemical bond between the resin and the surface of the metal pigment (Japanese Unexamined Patent Publication No. 50-26837). However, in addition to manufacturing problems such as the complicated and long manufacturing process, the formation of a resin layer on the pigment surface is not controlled, and as a result, sufficient water and chemical resistance effects cannot be achieved, and it has not yet been implemented industrially. It has not yet been reached. In addition, a method has been proposed in which a metal pigment is dispersed in water and the polymerization is carried out under conditions that produce a positively charged polymer during polymerization (Tokuko Sho et al.
53-4029). However, even with this method, effects such as sufficient water resistance, alkali resistance, acid resistance, etc. cannot be obtained, and it has not been put into practical use industrially. Furthermore, a method is known in which the surface of metal particles is coated with a resin obtained by proceeding a polymerization reaction in an organic solvent in which the monomer is soluble and the resulting polymer is insoluble (Japanese Patent Application Laid-Open No. No. 161470, 1982, JP 51-
Publication No. 11818). However, the resin-coated metal pigments produced by these methods have not yet reached a practically sufficient level in terms of chemical resistance, water resistance, especially cosmetic resistance, fingerprint resistance, etc., and improvements are needed. be. In addition, this resin-coated metal pigment also does not have sufficient heat resistance stability, so when it is used for kneading and placed under high temperatures (150℃ or higher), the resin that coats the metal pigment tends to soften, causing the pigment to deteriorate. Bonding occurs, making it difficult to obtain the desired uniformly dispersed film or sheet. [Means for Solving the Problems] As a result of intensive research to solve the problems of conventional metal pigments, the present inventors found that a radically polymerizable double bond and a carboxyl group are present in one molecule. The fact that the objective can be achieved by firmly adhering a highly three-dimensional resin layer to the surface of a metal pigment by taking advantage of the characteristics of a monomer or diester of phosphoric acid having a radically polymerizable double bond. This discovery led to the present invention. That is, the present invention provides: (1) highly phosphoric acid mono- or diester having a radically polymerizable unsaturated carboxylic acid and/or a radically polymerizable double bond, and a monomer having three or more radically polymerizable double bonds; (2) A resin-coated metallic pigment whose surface is tightly adhered to and coated with a three-dimensional resin, and which has an alkali resistance of 1.0 or less and substantially does not agglomerate in a heat stability test. A first step in which a metal pigment is dispersed in an organic solvent and a radically polymerizable unsaturated carboxylic acid and/or a phosphoric acid mono- or diester having a radically polymerizable double bond is added. The present invention relates to a method for producing a resin-coated metal pigment, which comprises a second step of adding and polymerizing a monomer having three or more double bonds and a polymerization initiator. The resin-coated metal pigment of the present invention exhibits unprecedented heat resistance stability, and when stored as a pigment for a long period of time, pigment aggregation is not observed, and other properties imparted by the resin coating (alkali resistance, water resistance, etc)
When used as a pigment for metallic paints, it has excellent storage stability and has excellent chemical resistance, water resistance, and cosmetic resistance. Provides a coating film that exhibits fingerprint marks. The radically polymerizable unsaturated carboxylic acids in the present invention include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, etc., and one type thereof or a mixture of two or more types thereof are used. The amount used varies depending on the type and properties of the metal pigment, especially its surface area, but generally ranges from 0.01 parts by weight to 10 parts by weight per 100 parts by weight of metal pigment.
Between parts by weight. If it is less than 0.01 part by weight, the effects of the present invention, that is, chemical resistance such as water resistance and acid resistance, fingerprint resistance, etc., will not be exhibited well, and the polymerizable double bond will not be formed in the next molecule. When polymerizing monomers having three or more, the polymerization system may gel and become unstirable. Moreover, if it exceeds 10 parts by weight, water resistance will decrease. This is presumed to be because the amount of carboxyl groups contained in the radically polymerizable unsaturated carboxylic acid is too large. The phosphoric acid ester monomer having a radically polymerizable double bond in the present invention includes 2-methacryloyloxyethyl phosphate, di-2-methacryloyloxyethyl phosphate, tri-2-methacryloyloxyethyl phosphate, 2-acryloyloxyethyl phosphate, di-2-acryloyloxyethyl phosphate, tri-2-acryloyloxyethyl phosphate, diphenyl-2
-methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate ate, dioctyl-2-
Acryloyloxyethyl phosphate, 2-methacryloyloxypropyl phosphate, bis(2
-chloroethyl) vinyl phosphonate, diallyl dibutyl phosphonosuccinate, etc., and one type or a mixture of two or more types thereof are used. Phosphoric acid monoester can be mentioned as a preferable phosphoric ester having a radically polymerizable double bond. This is presumed to be due to the presence of two OH groups in the phosphoric acid group, which causes it to be more firmly fixed to the surface of the aluminum particles. More preferable phosphoric acid monoesters include monoesters having a methacroyloxy group and an acroyloxy group, such as 2-methacryloyloxyethyl phosphate and 2-acryloyloxyethyl phosphate. These monoesters are often insoluble in common polymerization solvents. The amount used varies depending on the type and properties of the metal pigment, especially its surface area, but is generally between 0.01 and 30 parts by weight per 100 parts by weight of metal pigment.
If the amount is less than 0.01 part by weight, the effects of the present invention, i.e., water resistance, chemical resistance such as acid resistance, fingerprint resistance, etc., will not be exhibited well, and even if it is used in excess of 30 parts by weight, the effect will not be achieved. There is almost no increase in Examples of monomers having three or more polymerizable double bonds in one molecule used in the present invention include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, and tetramethylolmethane tetraacrylate. One or more of these may be used. The amount used is between 2 parts by weight and 50 parts by weight based on 100 parts by weight of the metal content of the metal pigment. If it is less than 2 parts by weight, the effect of the present invention, that is, chemical resistance will decrease, If it exceeds this value, no increase in effectiveness is expected, and the basic properties of a metallic paint, such as glitter, luster, and metallic feel, deteriorate, making it difficult to put it into practical use. A monomer having 1 or 2 polymerizable double bonds in one molecule within a range that does not impair the effects of the present invention, that is, 0 to 10 parts by weight based on 100 parts by weight of the metal content of the metal pigment. may be used. usage is 10
If it exceeds the weight part, the effect of the present invention, that is, when a metallic coating film is created using the obtained resin-coated metallic pigment, the properties will decrease, and the heat resistance stability of the metallic pigment will also decrease, making it impossible to put it into practical use. hard. Examples of monomers having one or two polymerizable double bonds in one molecule used in the present invention include styrene, α-methylstyrene, acrylic esters such as methyl acrylate, and methyl methacrylate. Methacrylic acid esters, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene etc., and one or more of these may be used. The polymerization initiator used in the present invention is generally known as a radical generator, and includes peroxides such as benzoyl peroxide, lauroyl peroxide, isobutyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyl peroxide. Lonitrile and the like. The polymerization initiator has 3 polymerizable double bonds in one molecule.
It is used in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the monomer having at least 100 parts by weight. Preferably from 1 part by weight
Use 20 parts by weight. 3 polymerizable double bonds in one molecule
If the amount is less than 0.1 part by weight per 100 parts by weight of the monomer having at least 100 parts by weight, the polymerization will take a long time and is not practical. If it exceeds 50 parts by weight, the polymerization rate is too fast to be controlled and is not practical. The alkali resistance of the present invention refers to the condition of the coating film obtained by mixing and painting the specified paint by immersing it in a 0.1N-NaOH aqueous solution at 55°C for 4 hours, and observing the state of the coating film before and after dipping.
It refers to the color difference (ΔE H ) measured according to condition d (9-d method) of JIS-Z-8722 (1982) and determined according to JIS-Z-8730 6.3.2. The specified paint is a paint that uses baking-type acrylic/melamine resin, and the pigment concentration is 15 parts by weight per 100 parts by weight of acrylic/melamine resin (non-volatile content), and the required amount is with the addition of thinner. The acrylic resin used here is a commonly available acrylic resin for baking, and the melamine resin is a commonly available butylated melamine resin. The mixing ratio is 70 to 90 parts by weight of acrylic resin and 30 parts by weight of melamine resin.
~10 parts by weight. The resin-coated metal pigment of the present invention has alkali resistance.
It is 1.0 or less, preferably 0.8 or less. If it exceeds 1.0, discoloration of the coating film is visually observed, it does not have sufficient alkali resistance, and is not included in the present invention. In the present invention, a resin-coated metal pigment that does not substantially agglomerate in a heat stability test is one that shows almost no change in particle size when a predetermined temperature is applied to the resin-coated metal pigment for a predetermined period of time. That is, JIS-K-
5400 A heat resistance stability test was conducted in the same manner as in 8.2.1 except that the temperature was changed to 150°C, the time was changed to 1 hour, and the amount of sample obtained was changed to 10 g. Agglomeration is measured by the ratio of d 2 ′. The resin-coated metal pigment of the present invention has d 2 ′/d 1 ′ of 1.5 or less, more preferably 1.3 or less. If it exceeds 1.5, it is not preferable because uniform dispersion of the metal pigment cannot be obtained during high-temperature molding such as kneading. Surface coating with a resin produced by reacting a radically polymerizable unsaturated carboxylic acid and/or a phosphoric acid mono- or diester having a radically polymerizable double bond and a monomer having three or more radically polymerizable double bonds. The preferred method for producing the metal pigment of the present invention is to first disperse the metal pigment in an organic solvent, and then add a radically polymerizable unsaturated carboxylic acid and/or a phosphoric acid mono- or diester having a radically polymerizable double bond in the first step. This is a manufacturing method that involves a second stage step of adding a monomer having three or more radically polymerizable double bonds and an initiator and polymerizing it. The first step is to disperse metal pigment particles in an organic solvent, then add a radically polymerizable unsaturated carboxylic acid or a phosphoric acid mono- or diester having a radically polymerizable double bond while continuing to stir. It is done by hand. The processing temperature in the first step may be room temperature, but
Preferably, it is heated to ℃. The treatment time is generally 5 minutes or more, preferably 10 minutes or more, although the first step ends when the concentration of the unsaturated carboxylic acid or phosphoric acid ester remaining in the solvent becomes constant. There is also a method in which some or all of the monomers having three or more radically polymerizable double bonds to be added in the second step are already added before the first step. However, in order to quickly and reliably complete the first step, monomers having three or more radically polymerizable double bonds are added in the second step before the first step is completed. In order to completely stop the initiation of polymerization, the first step preferably does not contain the monomer having three or more radically polymerizable double bonds, which is added in the second step. Of course, if the initiator used in the second step is added in the first step, the performance of the resulting resin-coated metal pigment will be significantly reduced, making it difficult to put it into practical use. As a result, the carboxyl group of the radically polymerizable unsaturated carboxylic acid or the phosphoric acid group of the phosphoric acid ester having a radically polymerizable double bond is fixed on the surface of the metal pigment, and pigment particles having a radically polymerizable double bond on the surface are obtained. It is estimated that This estimation is based on the fact that after the first step, the metal pigment is filtered out and the amount of radically polymerizable unsaturated carboxylic acid or phosphoric acid mono- or diester having a radically polymerizable double bond remaining in the solvent is quantified. This is supported by the fact that there is a significant decrease compared to the amount. After the first step, the second step proceeds by adding a monomer having three or more polymerizable double bonds in one molecule and an initiator, followed by heating and stirring. Through this operation, the double bond based on the unsaturated carboxylic acid previously fixed on the surface of the metal pigment and the monomer having three or more polymerizable double bonds in one molecule copolymerize, and the surface of the metal pigment becomes highly concentrated. It is presumed that the excellent effects of the present invention are only manifested when a resin layer with a high network density is formed in a form that has chemical bonds with the surface of the metal pigment. This assumption is believed to be supported by the fact that the heat resistance stability of the resin-coated metal pigment of the present invention is significantly improved and there is almost no aggregation after the test. It is preferable to replace the reaction system with an inert gas such as nitrogen or argon, and the temperature varies depending on the type of initiator, but is generally between 30°C and 150°C. Reaction time is between 30 minutes and 10 hours. The reaction may be carried out by adding the monomer and/or initiator all at once or by adding them in portions. In carrying out the second step, a radically polymerizable unsaturated carboxylic acid or a phosphoric acid ester having a radically polymerizable double bond, a monomer having three or more polymerizable double bonds in one molecule, and an initiator are used. If they are added all at once and the polymerization reaction is started immediately, the effects of the present invention will not be exhibited. In addition, a radically polymerizable unsaturated carboxylic acid or a phosphoric acid ester having a radically polymerizable double bond is not used, and only a monomer having three or more polymerizable double bonds in one molecule is dispersed in an organic solvent. When polymerizing in the presence of metal pigment particles, that is, omitting the first step and entering the second step, not only does the polymerization system thicken and stirring may become impossible, but the resulting resin-coated metal pigment The performance of is very poor. This fact indicates that the metal surface is not sufficiently covered with the resin layer. These findings highlight the necessity of a first step prior to a second step. The metal pigment used in the present invention includes aluminum, copper, zinc, iron, nickel, and/or alloys thereof, and aluminum is a preferred example. Its shape is granular, such as flakes, spheres, and needles. The particle size of metal pigments varies depending on the application. For paint and printing,
It is best to have an average diameter of about 1 to 100μ, and for kneading into plastics, about 1 to 200μ is good.
It is not particularly limited and can be applied to the present invention. To explain in detail about the aluminum pigment used in the present invention, aluminum flakes or granular powder are processed by a mechanical method such as a stamp mill method, a dry ball mill method, a wet ball mill method, an attritor method, a vibrating ball mill method, etc. It is made by grinding with a grinding aid. This grinding aid functions as a grinding aid and at the same time influences the physical properties of the aluminum pigment. Conventionally, higher saturated or unsaturated fatty acids such as stearic acid and oleic acid, and higher aliphatic amines such as stearylamine are often used as the grinding aid, but regardless of these grinding aids, the present invention You can get the effect. Aluminum pigments obtained using stearic acid are generally well known as leafing type aluminum pastes, and are used as silver paints for tanks and other metal rust prevention applications. Aluminum pigments obtained using oleic acid, stearylamine, etc. are generally well known as non-leafing type aluminum pastes, and are used for cosmetic purposes as metallic paints for automobiles, furniture, etc. Organic solvents used in the polymerization of the present invention include aliphatic hydrocarbons (e.g., hexane, heptane, octane, mineral spirits, etc.), aromatic hydrocarbons (e.g., benzene, toluene, solvent naphtha, xylene, etc.), esters (e.g., benzene, toluene, solvent naphtha, xylene, etc.), ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, diethyl ether, etc.), and are used in an amount of 50 to 3000 parts by weight per 100 parts by weight of the metal pigment. Preferably it is between 250 and 1000 parts by weight. If it is less than 50 parts by weight per 100 parts by weight of the metal pigment, it will become paste-like and will not uniformly diffuse radically polymerizable unsaturated carboxylic acids, monomers having three or more polymerizable double bonds in one molecule, and polymerization initiators. This is not desirable as it takes a long time. If it exceeds 3000 parts by weight, the polymerization time will become longer, which is not preferable. After forming a resin coating layer on the surface of the metal pigment in an organic solvent as described above, the organic solvent is filtered off, the nonvolatile content is adjusted to 30 to 80%, and other solvents and additives are added as necessary. A paste containing the resin-coated metal pigment of the present invention is obtained. The resin-coated metal pigment of the present invention is characterized by (a) resin for paints;
For 100 parts by weight, (b) the resin-coated metal pigment of the present invention
A metallic paint can be obtained by using 0.1 parts by weight to 100 parts by weight and (c) diluting thinner. As the paint resin, any of the paint resins conventionally used in metallic paints can be used. It can also be used with resins not used in metallic paints. These resins include acrylic resins, alkyd resins, oil-free alkyd resins, vinyl chloride resins, urethane resins, melamine resins, unsaturated polyester resins, urea resins, cellulose resins, epoxy resins, etc. They may be used alone or in combination. The resin-coated metal pigment of the present invention has a coating resin of 100%
The amount is 0.1 parts by weight to 100 parts by weight. In particular, it is preferable to use 1 part by weight to 50 parts by weight. When this resin-coated metal pigment is less than 0.1 part by weight,
The metallic luster necessary for a metallic paint is insufficient, and if more than 100 parts by weight is used, the amount of metal pigment in the paint becomes too large, which not only worsens painting workability but also deteriorates physical properties. It becomes a sticky coating and is not practical. Examples of diluent thinners include aromatic compounds such as toluene and xylene, aliphatic compounds such as hexane, heptane, and octane, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone. ,
General organic solvents such as chlorine compounds such as trichlorethylene, cellosolves such as ethylene glycol monoethyl ether, etc. It is preferable to use a mixture of two or more of these solvents, and this composition has a It is determined by taking into account film formation characteristics, painting workability, etc. In addition, pigments commonly used in the paint industry,
Additives such as dyes, wetting agents, dispersants, anti-color separation agents, leveling agents, slip agents, anti-skinning agents, anti-gelling agents, antifoaming agents, etc. can be added. [Example] Next, an example of the present invention will be shown. First, the test methods and measurement methods used in Examples will be explained in detail. [Amount of coating resin per 100 parts by weight of aluminum metal] 10 g of the paste containing the resin-coated aluminum pigment of the present invention is well dispersed in 100 ml of chloroform (reagent), and the soluble content is extracted. Next, the resin-coated aluminum pigment as the extraction residue was vacuum dried at 80°C for 1 hour and powdered. 1.0g was taken and 6N-HCl (reagent) was added.
Dissolve the metal aluminum part little by little with 200ml. The remaining insoluble resin content was filtered, and after vacuum drying at 80°C for 14 hours, the weight was measured and the aluminum metal content was determined.
Calculate the resin content per 100 parts by weight. [Alkali Resistance] A metallic paint for alkali resistance evaluation is prepared by using the resin-coated aluminum pigment and formulating the paint as shown below. [Paint formulation] (Parts by weight) Resin-coated aluminum pigment (non-volatile content equivalent)
7.5 Acrylic/melamine resin *1 100 mixed thinner *2 180 *1: Acrylic 47-712 (non-volatile content: 50
%), 20 parts of Super Betsucomin J-820 (non-volatile content: 50%) (manufactured by Nippon Reichhold Co., Ltd.) *2: Toluene (70 parts), ethyl acetate (20 parts),
Mixed with butyl cellosolve (10 parts) Next, the paint was applied to an aluminum plate (70 x 150 x 1 mm: Japan Test Panel) by air spray painting.
Co., Ltd.) to a film thickness of 20 μm, and this coated board was dried at 140°C for 30 minutes and used as a test coating to determine alkali resistance. This coating has an inner diameter of 34
Fix a vinyl chloride cylinder with a diameter of 15 mm and a height of 15 mm with metal fittings, add 5 ml of 0.1N NaOH, and leave at 55°C for 4 hours. After standing for 4 hours, the vinyl chloride cylinder is removed, the test coating is thoroughly washed with water, and the coating is dried. The coating film before and after the test is JIS-Z-8722
(1982) under condition d (method 9-d),
Calculate color difference △E H according to 6.3.2 of JIS-Z-8730 (1980) (Measuring device: SH-4- manufactured by Suga Test Instruments Co., Ltd.
MCH type). [Acid resistance] Performed in the same manner as alkali resistance except that 0.1N-NaOH was changed to 0.1N-H 2 SO 4 . [Agglutination by heat stability test] 10 g of paste containing resin-coated aluminum pigment
Measure it out, put it in a jar, put it in a dryer kept at a temperature of 150℃, and heat it for 1 hour. The particle size characteristic number of this resin-coated aluminum pigment was determined by wet sieving using mineral spirits as a dispersion medium, and the analysis results were calculated using the RRS particle size diagram of the German industrial standard DIN-4190.
-Rammler-Spering grain size diagram). Let this value be d 2 ′. Next, the particle size characteristic number is similarly determined for the resin-coated aluminum pigment before heating. Let this value be d 1 ′. By calculation, d 2 ′/
Obtain the value of d 1 ′. The sieve used here is a JIS standard sieve for 44μ or more, and a micromesh sieve (manufactured by Buckbee-mears Company) for less than 44μ. [Cosmetic resistance] Using the resin-coated aluminum pigment, prepare a paint for plastic coating by formulating the paint as shown below. [Paint formulation] [Parts by weight] Paste containing resin-coated aluminum pigment (non-volatile content equivalent) 9 Thinner *1 40 Acrylic resin *2 100 nitrified cotton resin solution *3 50 *1: Butyl acetate (30 parts), toluene (45 parts) Department),
A mixture of isopropyl alcohol (20 parts) and ethyl cellosolve (5 parts) *2: Acridik A-166 (non-volatile content; 45
%) Manufactured by Nippon Reichhold Co., Ltd., air-drying acrylic resin *3: LIG 1/2 (70% non-volatile content) (manufactured by Asahi Kasei Industries, Ltd., industrial nitrified cotton) with thinner*1 to reduce the non-volatile content to 16 %.The paint was diluted with thinner (*1) to reduce the viscosity to 13 seconds (FC
#4, adjusted to 20℃), spray painted on an ABS board (film thickness 10μ), dried for 3 days at room temperature, and used for cosmetic resistance test. Cosmetics (Atrix Hand Cream: manufactured by Kao Soap Co., Ltd.) are applied to half of the test coating to a thickness of approximately 1 mm. Next, this coating film is heated to a temperature of 60℃ and a humidity of 90%.
Leave it in a constant temperature and humidity chamber for 5 days. After the test, the paint film is washed with water, the moisture is wiped off, and after drying at room temperature for 1 hour, the appearance of the paint film on the areas with and without cosmetics applied is visually compared. [Fingerprint resistance] A coating film is created in the same manner as for cosmetic resistance, except that the fingertip is pressed onto an ABS board in advance to leave fingerprint marks on it. The entire test coating was immersed in a beaker containing warm water at 60°C and left for 3 hours. After the test, the coating film is washed with water, the moisture is wiped off, and after drying at room temperature for 1 hour, the appearance of fingerprint marks is visually judged. Example 1 Aluminum paste (M601 manufactured by Asahi Kasei Corporation, metal content 65.2
%, average particle size 11 μm, flake-like shape) and 400 g of mineral spirits were added, and the mixture was stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C. Next, 0.375 g of acrylic acid (reagent) was added and stirring was continued at 80° C. for 30 minutes. Next, 7.5 g of trimethylolpropane trimethacrylate (reagent)
and 0.75 g of azobisisobutyronitrile (reagent) were added and polymerized at 80°C for 5 hours. After the polymerization was completed, the slurry was allowed to cool to room temperature and filtered to obtain a paste containing a resin-coated aluminum pigment. The nonvolatile content of this paste (according to JIS-K-5910) is
It was 51.0% by weight. The amount of coating resin was 11.4 parts by weight based on 100 parts by weight of aluminum metal.
It is estimated that more than 99% of acrylic acid, trimethylolpropane trimethacrylate, and azobisisobutyronitrile were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.3, and the acid resistance (ΔE H ) was also 0.3, and a good coating film was obtained with almost no discoloration. Furthermore, when the coating film was immersed in hot water at 60°C for 7 days, there was almost no discoloration and the coating film remained in good condition. The paint was stored at 50°C for one month, but it remained in good condition with no gelation. The aggregation (d 2 ′/d 1 ′) after the heat resistance stability test was 1.05, and the powder had a uniform appearance, with virtually no aggregation observed. Example 2 Aluminum paste (MB-21 manufactured by Asahi Kasei Corporation, metal content) was placed in a 1000 ml three-necked flask.
72.0%, average particle size 24μ, flake shape) 118g
and 325 g of mineral spirits were added, stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C. Next, 0.255 g of acrylic acid (reagent) was added and stirring was continued at 80° C. for 30 minutes. Then trimethylolpropane trimethacrylate (reagent) 4.25
g and azobisisobutyronitrile (reagent) 0.43g
was added and polymerized at 80°C for 5 hours. After polymerization,
The slurry was allowed to cool to room temperature and filtered to obtain a paste containing a resin-coated aluminum pigment. The nonvolatile content of this paste (according to JIS-K-5910) is
It was 60.2% by weight. The amount of coating resin was 5.7 parts by weight based on 100 parts by weight of aluminum metal.
It is estimated that more than 98% of acrylic acid, trimethylolpropane trimethacrylate, and azobisisobutyronitrile were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.2, the acid resistance (ΔE H ) was 0.1, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.05. An aluminum pigment was obtained. Example 3 Aluminum paste (manufactured by Asahi Kasei Corporation 4/62, metal content 67.3
%, average particle size 9 μm, flake-like shape) and 400 g of mineral spirits were added, and the mixture was stirred while introducing nitrogen gas, and the temperature in the system was raised to 80°C. Next, 0.525 g of acrylic acid (reagent) was added and stirring was continued at 80° C. for 30 minutes. Next, 10.5 g of trimethylolpropane trimethacrylate (reagent)
and azobisisobutyronitrile (reagent) 0.525g
was added and polymerized at 80°C for 6 hours. After polymerization,
The slurry was allowed to cool to room temperature and filtered to obtain a paste containing a resin-coated aluminum pigment. The nonvolatile content of this paste (according to JIS-K-5910) is
It was 53.0% by weight. The amount of coating resin was 16.4 parts by weight based on 100 parts by weight of aluminum metal.
It is estimated that more than 99% of acrylic acid, trimethylolpropane trimethacrylate, and azobisisobutyronitrile were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.6, the acid resistance (ΔE H ) was 0.1, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.10. An aluminum pigment was obtained. Example 4 Add 115 g of aluminum paste M-601 used in Example 1 and 400 g of mineral spirits to a 1000 ml three-necked flask, stir while introducing nitrogen gas, and raise the temperature in the system to 65°C. did. Next, 0.375g of methacrylic acid (reagent) was added to 65
Stirring was continued for 60 minutes at °C. Next, 7.5 g of trimethylolpropane triacrylate (reagent) and 0.75 g of azobisisobutyronitrile (reagent) were added,
Polymerization was carried out at 65°C for 7 hours. After the polymerization was completed, the slurry was allowed to cool to room temperature and filtered to obtain a paste containing a resin-coated aluminum pigment. The non-volatile content of this paste (according to JIS-K-5910) is 47.5% by weight
It was hot. The amount of coating resin was 11.2 parts by weight based on 100 parts by weight of the aluminum metal content. It is estimated that 97.4% of methacrylic acid, trimethylolpropane triacrylate, and azobisisobutyronitrile were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.4, the acid resistance (ΔE H ) was 0.5, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.08. An aluminum pigment was obtained. Examples 5-7, Comparative Examples 1-2 Aluminum paste MG used in Example 2
-21, the polymerization shown in Table 1 was carried out in the same manner as in the preparation of the resin-coated aluminum pigment in Example 2 to obtain a paste containing the resin-coated aluminum pigment. In Comparative Example 1, only trimethylolpropane trimethacrylate was polymerized, but the viscosity of the slurry in the system increased 1 hour after the start of polymerization, making stirring difficult. This is presumed to be because the acrylic acid treatment was not performed, so the aluminum particles did not adhere to the surface and polymerization progressed in the organic solvent (mineral spirits). As shown in Table 1, Examples 5 to 7 showed extremely good performance, but Comparative Example 1 had poor alkali resistance, presumably because it was not coated with resin. Comparative Example 2 also showed inferior performance compared to Examples 5-7. This is presumed to be because the amount of carboxyl groups contained in acrylic acid was too large.
【表】【table】
【表】
実施例８〜９、比較例３
実施例１で使用したアルミニウムペーストＭ−
601を用いて、実施例１の樹脂被覆アルミニウム
顔料の調製と同様に表２に示す重合を行い、樹脂
被覆アルミニウム顔料を含むペーストを得た。
比較例３は、トリメチロールプロパントリメタ
クリレート、アクリル酸、開始剤を同時に添加し
て重合した。重合開始後１時間で系内のスラリー
粘度が上がつた。これは、アルミニウム粒子表面
に充分付着せず、有機溶剤（ミネラルスピリツ
ト）内で重合が進んだものと推察される。
結果を表２に示したように、実施例８〜９は極
めて良好な性能を示したが、比較例３は劣つた耐
アルカリ性を示し、樹脂が被覆していないものと
推察される。[Table] Examples 8 to 9, Comparative Example 3 Aluminum paste M- used in Example 1
601, the polymerization shown in Table 2 was carried out in the same manner as in the preparation of the resin-coated aluminum pigment in Example 1 to obtain a paste containing the resin-coated aluminum pigment. In Comparative Example 3, trimethylolpropane trimethacrylate, acrylic acid, and an initiator were simultaneously added and polymerized. One hour after the start of polymerization, the viscosity of the slurry in the system increased. It is presumed that this is because the aluminum particles did not adhere sufficiently to the surface of the aluminum particles, and polymerization proceeded in the organic solvent (mineral spirits). As the results are shown in Table 2, Examples 8 and 9 showed extremely good performance, but Comparative Example 3 showed poor alkali resistance, presumably because it was not coated with resin.
【表】【table】
【表】
実施例 10
実施例１のアクリル酸を２−メタクリロイロキ
シエチルホスフエートに変える以外同様にして、
樹脂被覆アルミニウム顔料を含むペーストを得
た。このペーストの不揮発分（JIS−Ｋ−5910に
よる）は54.0重量％であつた。アルミニウム金属
分100重量部に対する被覆樹脂量は11.4重量部で
あつた。これは、２−メタクリロイロキシエチル
ホスフエート、トリメチロールプロパントリメタ
クリレート、アゾビスイソブチロニトリルの99％
以上がアルミニウム金属表面上に付着したものと
推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.2、耐酸性（ΔEH）は0.1であり、殆ど
変色せず良好な塗膜を得た。又、塗膜を60℃の温
水に７日間浸漬したところ、殆ど変色せず良好な
塗膜であつた。塗料を50℃で１カ月貯蔵したが、
ゲル化等がなく良好な塗料であつた。
耐熱安定性試験後の凝集（d2′／d1′）は1.03で
あり、外観も均一な粉末であり、実質的に凝集は
認められなかつた。
実施例 11
実施例２のアクリル酸を２−メタクリロイロキ
シエチルホスフエートに変える以外同様にして、
本発明の樹脂被覆アルミニウム顔料を含むペース
トを得た。このペーストの不揮発分（JIS−Ｋ−
5910による）は59.0重量％であつた。アルミニウ
ム金属分100重量部に対する被覆樹脂量は5.8重量
部であつた。これは、２−メタクリロイロキシエ
チルホスフエート、トリメチロールプロパントリ
メタクリレート、アゾビスイソブチロニトリルの
99％以上がアルミニウム金属表面上に付着したも
のと推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.3、耐酸性（ΔEH）は0.2、及び耐熱安
定性試験後の凝集（d2′／d1′）は1.10であり、本
発明の樹脂被覆アルミニウム顔料が得られた。
実施例 12
実施例１のアクリル酸を２−アクリロイロキシ
エチルホスフエートに変える以外同様にして、本
発明の樹脂被覆アルミニウム顔料を含むペースト
を得た。このペーストの不揮発分（JIS−Ｋ−
5910による）は51.0重量％であつた。アルミニウ
ム金属分100重量部に対する被覆樹脂量は5.8重量
部であつた。これは、２−アクリロイロキシエチ
ルホスフエート、トリメチロールプロパントリメ
タクリレート、アゾビスイソブチロニトリルの99
％以上がアルミニウム金属表面上に付着したもの
と推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.5、耐酸性（ΔEH）は0.3、及び耐熱安
定性試験後の凝集（d2′／d1′）は1.05であり、本
発明の樹脂被覆アルミニウム顔料が得られた。
実施例 13
実施例２のアクリル酸0.255ｇを２−メタクリ
ロイロキシホスフエート2.55ｇに、トリメチロー
ルプロパントリメタクリレート4.25ｇを8.5ｇに
変える以外同様にして、本発明の樹脂被覆アルミ
ニウム顔料を含むペーストを得た。このペースト
の不揮発分（JIS−Ｋ−5910による）は57.9重量
％であつた。アルミニウム金属分100重量部に対
する被覆樹脂量は13.4重量部であつた。これは、
２−メタクリロイロキシエチルホスフエート、ト
リメチロールプロパントリメタクリレート、アゾ
ビスイソブチロニトリルの99％以上がアルミニウ
ム金属表面上に付着したものと推定される。
この樹脂被覆アルミニウム顔料の耐アルカリ性
（ΔEH）は0.1、耐酸性（ΔEH）は0.1、及び耐熱安
定性試験後の凝集（d2′／d1′）は1.15であり、本
発明の樹脂被覆アルミニウム顔料が得られた。
実施例 14
(1) 比較例４の樹脂被覆アルミニウム顔料の調製
実施例１のトリメチロールプロパントリメタ
クリレートをエチレングリコールジメタクリレ
ート（試薬）に変える以外同様にして、樹脂被
覆アルミニウム顔料を含むペーストを得た。こ
のペーストの不揮発分（JIS−Ｋ−5910による）
は51.5重量％であつた。
(2) 比較例５の樹脂被覆アルミニウム顔料の調製
実施例10のトリメチロールプロパントリメタ
クリレートをエチレングリコールジメタクリレ
ート（試薬）に変える以外同様にして、樹脂被
覆アルミニウム顔料を含むペーストを得た。こ
のペーストの不揮発物（JIS−Ｋ−5910による）
は49.5重量％であつた。
比較例４及び５の樹脂被覆アルミニウム顔料と
実施例１及び実施例10の樹脂被覆アルミニウム顔
料の性能〔耐アルカリ性、耐酸性、耐指紋跡性、
耐化粧品性、耐熱安定性試験後の凝集（d2′／d1′）
を比較した。
その結果を表３に示したように、比較例４及び
５に比べ実施例１及び10は極めて優れた性能を示
した。[Table] Example 10 Same procedure as in Example 1 except that acrylic acid was changed to 2-methacryloyloxyethyl phosphate.
A paste containing resin-coated aluminum pigment was obtained. The nonvolatile content (according to JIS-K-5910) of this paste was 54.0% by weight. The amount of coating resin was 11.4 parts by weight based on 100 parts by weight of aluminum metal. This is 99% of 2-methacryloyloxyethyl phosphate, trimethylolpropane trimethacrylate, and azobisisobutyronitrile.
It is presumed that the above substances adhered to the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.2, and the acid resistance (ΔE H ) was 0.1, and a good coating film was obtained with almost no discoloration. Furthermore, when the coating film was immersed in hot water at 60°C for 7 days, it remained in good condition with almost no discoloration. The paint was stored at 50℃ for one month,
It was a good paint with no gelation. The agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.03, and the powder had a uniform appearance, with virtually no aggregation observed. Example 11 Same procedure as in Example 2 except that acrylic acid was changed to 2-methacryloyloxyethyl phosphate,
A paste containing the resin-coated aluminum pigment of the present invention was obtained. Non-volatile content of this paste (JIS-K-
5910) was 59.0% by weight. The amount of coating resin was 5.8 parts by weight based on 100 parts by weight of aluminum metal. This includes 2-methacryloyloxyethyl phosphate, trimethylolpropane trimethacrylate, and azobisisobutyronitrile.
It is estimated that more than 99% of the particles were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.3, the acid resistance (ΔE H ) was 0.2, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.10. A coated aluminum pigment was obtained. Example 12 A paste containing the resin-coated aluminum pigment of the present invention was obtained in the same manner as in Example 1 except that acrylic acid was changed to 2-acryloyloxyethyl phosphate. Non-volatile content of this paste (JIS-K-
5910) was 51.0% by weight. The amount of coating resin was 5.8 parts by weight based on 100 parts by weight of aluminum metal. This is 99% of 2-acryloyloxyethyl phosphate, trimethylolpropane trimethacrylate, azobisisobutyronitrile.
It is estimated that more than % of the aluminum particles were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.5, the acid resistance (ΔE H ) was 0.3, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.05. A coated aluminum pigment was obtained. Example 13 A paste containing the resin-coated aluminum pigment of the present invention was prepared in the same manner as in Example 2 except that 0.255 g of acrylic acid was changed to 2.55 g of 2-methacryloyloxyphosphate and 4.25 g of trimethylolpropane trimethacrylate was changed to 8.5 g. I got it. The nonvolatile content of this paste (according to JIS-K-5910) was 57.9% by weight. The amount of coating resin was 13.4 parts by weight based on 100 parts by weight of aluminum metal. this is,
It is estimated that more than 99% of 2-methacryloyloxyethyl phosphate, trimethylolpropane trimethacrylate, and azobisisobutyronitrile were deposited on the aluminum metal surface. The alkali resistance (ΔE H ) of this resin-coated aluminum pigment was 0.1, the acid resistance (ΔE H ) was 0.1, and the agglomeration (d 2 ′/d 1 ′) after the heat resistance stability test was 1.15. A coated aluminum pigment was obtained. Example 14 (1) Preparation of resin-coated aluminum pigment of Comparative Example 4 A paste containing a resin-coated aluminum pigment was obtained in the same manner as in Example 1 except that trimethylolpropane trimethacrylate was replaced with ethylene glycol dimethacrylate (reagent). . Nonvolatile content of this paste (according to JIS-K-5910)
was 51.5% by weight. (2) Preparation of resin-coated aluminum pigment of Comparative Example 5 A paste containing a resin-coated aluminum pigment was obtained in the same manner as in Example 10 except that trimethylolpropane trimethacrylate was replaced with ethylene glycol dimethacrylate (reagent). Nonvolatile matter of this paste (according to JIS-K-5910)
was 49.5% by weight. Performance of the resin-coated aluminum pigments of Comparative Examples 4 and 5 and the resin-coated aluminum pigments of Examples 1 and 10 [alkali resistance, acid resistance, fingerprint resistance,
Cosmetic resistance, agglomeration after heat stability test (d 2 ′/d 1 ′)
compared. As shown in Table 3, Examples 1 and 10 exhibited extremely superior performance compared to Comparative Examples 4 and 5.
Claims (1)
ラジカル重合性二重結合を有する燐酸モノ又はジ
エステル及びラジカル重合性二重結合を３個以上
有する単量体から生成した高度に三次元化した樹
脂によつて強固に密着して表面被覆されてなり、
かつ、耐アルカリ性が1.0以下で耐熱安定試験で
実質的に凝集しないことを特徴とする樹脂被覆金
属顔料。 ２ 金属顔料を有機溶剤に分散し、ラジカル重合
性不飽和カルボン酸及び／又はラジカル重合性二
重結合を有する燐酸モノ又はジエステルを加える
第一工程、次いで、第一工程の液に、ラジカル重
合性二重結合を３個以上有する単量体と重合開始
剤を加えて重合する第二工程を経ることを特徴と
する樹脂被覆金属顔料の製造方法。[Scope of Claims] 1. A highly tertiary compound produced from a radically polymerizable unsaturated carboxylic acid and/or a phosphoric acid mono- or diester having a radically polymerizable double bond, and a monomer having three or more radically polymerizable double bonds. The surface is tightly adhered and coated with the original resin,
A resin-coated metal pigment characterized by having an alkali resistance of 1.0 or less and substantially not agglomerating in a heat resistance stability test. 2 A first step in which a metal pigment is dispersed in an organic solvent and a radically polymerizable unsaturated carboxylic acid and/or a phosphoric acid mono- or diester having a radically polymerizable double bond is added. A method for producing a resin-coated metal pigment, comprising a second step of adding and polymerizing a monomer having three or more double bonds and a polymerization initiator.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-198387 | 1985-09-07 | ||
| JP19838785 | 1985-09-07 | ||
| JP61-897 | 1986-01-07 | ||
| JP61-1908 | 1986-01-08 | ||
| JP61-1329 | 1986-01-09 | ||
| JP61-11795 | 1986-01-22 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11323089A Division JPH0249076A (en) | 1989-05-02 | 1989-05-02 | Metallic paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62253668A JPS62253668A (en) | 1987-11-05 |
| JPH0149746B2 true JPH0149746B2 (en) | 1989-10-25 |
Family
ID=16390278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61202793A Granted JPS62253668A (en) | 1985-09-07 | 1986-08-29 | Novel resin-coated metallic pigment and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62253668A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996038506A1 (en) * | 1995-05-30 | 1996-12-05 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and metallic coating material containing the pigment |
| WO2004089591A1 (en) * | 2003-04-01 | 2004-10-21 | Suzuka Fuji Xerox Co., Ltd. | Molded article of reclaimed thermoplastic resin |
| US8283397B2 (en) | 2005-10-31 | 2012-10-09 | Toyo Aluminium Kabushiki Kaisha | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2668536B2 (en) * | 1987-11-13 | 1997-10-27 | 旭化成メタルズ株式会社 | Novel metal powder pigment |
| JPH0692546B2 (en) * | 1988-06-16 | 1994-11-16 | 昭和アルミパウダー株式会社 | Colored metallic pigment and method for producing the same |
| JPH07258581A (en) * | 1994-03-18 | 1995-10-09 | Nippon Paint Co Ltd | Photochromic brilliant pigment and coating composition containing the same |
| JP2001115061A (en) * | 1999-10-14 | 2001-04-24 | Showa Aluminum Powder Kk | Metal pigment and its production |
| JP4684429B2 (en) * | 2001-02-02 | 2011-05-18 | 旭化成メタルズ株式会社 | New aluminum pigment |
| JP2003020413A (en) * | 2001-07-10 | 2003-01-24 | Cemedine Co Ltd | Highly designable composition |
| KR101285519B1 (en) | 2005-10-13 | 2013-07-17 | 도요 알루미늄 가부시키가이샤 | Coated metal pigment, method for production of the pigment, and coating composition comprising the pigment |
| JP2008050486A (en) * | 2006-08-25 | 2008-03-06 | Dainippon Ink & Chem Inc | Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition |
| JP5153160B2 (en) * | 2007-02-16 | 2013-02-27 | 旭化成ケミカルズ株式会社 | Metal pigment composition |
| JP4734360B2 (en) * | 2008-03-03 | 2011-07-27 | 株式会社東芝 | Nanoparticle thin film, method for producing nanoparticle thin film, nanoparticle thin film pattern forming method, and circuit pattern forming method |
| JP5242290B2 (en) * | 2008-08-18 | 2013-07-24 | 東洋アルミニウム株式会社 | Resin-coated aluminum pigment, metallic paint and ink |
| JP5196432B2 (en) | 2008-09-17 | 2013-05-15 | 東洋アルミニウム株式会社 | Resin-coated metallic pigment, water-based paint containing the same, coated material coated with the same, and method for producing the same |
| SG178543A1 (en) | 2009-09-18 | 2012-03-29 | Asahi Kasei Chemicals Corp | Resin-coated metal pigment, and process for producing same |
| US20120183775A1 (en) * | 2009-10-15 | 2012-07-19 | Yoichi Shinba | Process for production of core-shell particles, core-shell particles, and paste composition and sheet composition which contain same |
| JP5652095B2 (en) * | 2010-09-30 | 2015-01-14 | 大日本印刷株式会社 | Decorative sheet |
| JP6218281B2 (en) * | 2014-03-12 | 2017-10-25 | 旭化成株式会社 | Resin-attached metal pigment |
| CN106133050B (en) * | 2014-03-31 | 2018-06-12 | 旭硝子株式会社 | Fluororesin composition and laminated body |
| WO2018047359A1 (en) | 2016-09-06 | 2018-03-15 | Dic株式会社 | Resin coated inorganic or metallic pigment |
| JP6766154B2 (en) * | 2016-09-06 | 2020-10-07 | Dic株式会社 | Resin coated aluminum pigment |
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|---|---|---|---|---|
| JPS49123981A (en) * | 1973-03-07 | 1974-11-27 | ||
| JPS5017450A (en) * | 1973-06-19 | 1975-02-24 | ||
| JPS5154624A (en) * | 1974-11-08 | 1976-05-13 | Sinloihi Co Ltd | JUGOTAIDEHIFUKUSARETA BISAIRYUSHI OYOBI SONOSEIZOHOHO |
-
1986
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49123981A (en) * | 1973-03-07 | 1974-11-27 | ||
| JPS5017450A (en) * | 1973-06-19 | 1975-02-24 | ||
| JPS5154624A (en) * | 1974-11-08 | 1976-05-13 | Sinloihi Co Ltd | JUGOTAIDEHIFUKUSARETA BISAIRYUSHI OYOBI SONOSEIZOHOHO |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996038506A1 (en) * | 1995-05-30 | 1996-12-05 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and metallic coating material containing the pigment |
| WO2004089591A1 (en) * | 2003-04-01 | 2004-10-21 | Suzuka Fuji Xerox Co., Ltd. | Molded article of reclaimed thermoplastic resin |
| US8283397B2 (en) | 2005-10-31 | 2012-10-09 | Toyo Aluminium Kabushiki Kaisha | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
| US8734908B2 (en) | 2005-10-31 | 2014-05-27 | Toyo Aluminium Kabushiki Kaisha | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62253668A (en) | 1987-11-05 |
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