JP6786819B2 - Bright color resin composition, bright color article and its manufacturing method - Google Patents
Bright color resin composition, bright color article and its manufacturing method Download PDFInfo
- Publication number
- JP6786819B2 JP6786819B2 JP2016043143A JP2016043143A JP6786819B2 JP 6786819 B2 JP6786819 B2 JP 6786819B2 JP 2016043143 A JP2016043143 A JP 2016043143A JP 2016043143 A JP2016043143 A JP 2016043143A JP 6786819 B2 JP6786819 B2 JP 6786819B2
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- Prior art keywords
- acid
- resin composition
- metal
- reflective material
- color
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000002082 metal nanoparticle Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 239000010408 film Substances 0.000 description 47
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 37
- 239000006185 dispersion Substances 0.000 description 24
- -1 undecylene Chemical group 0.000 description 24
- 238000009500 colour coating Methods 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000010445 mica Substances 0.000 description 10
- 229910052618 mica group Inorganic materials 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- VARHPXNXWDIUTR-UHFFFAOYSA-N 2-(8-methylnonyl)dodecanoic acid Chemical compound CCCCCCCCCCC(C(O)=O)CCCCCCCC(C)C VARHPXNXWDIUTR-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 2
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- FYYGCTQPBDNICZ-UHFFFAOYSA-N 2-tetradecyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CCCCCCCCCCCCCC FYYGCTQPBDNICZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HKUFIYBZNQSHQS-UHFFFAOYSA-O dioctadecylazanium Chemical compound CCCCCCCCCCCCCCCCCC[NH2+]CCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-O 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- RGTIBVZDHOMOKC-UHFFFAOYSA-N stearolic acid Chemical compound CCCCCCCCC#CCCCCCCCC(O)=O RGTIBVZDHOMOKC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
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- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 239000011162 core material Substances 0.000 description 1
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- 239000004148 curcumin Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- LXSFGVACVWCFRS-UHFFFAOYSA-N dibutylazanium;n,n-dibutylcarbamate Chemical compound CCCC[NH2+]CCCC.CCCCN(C([O-])=O)CCCC LXSFGVACVWCFRS-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 239000003759 ester based solvent Substances 0.000 description 1
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- NZYYSSZGIPELSX-UHFFFAOYSA-N hydrogen carbonate;pyridin-1-ium Chemical compound OC(O)=O.C1=CC=NC=C1 NZYYSSZGIPELSX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
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- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
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- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- XIVQMBJJCVVPCF-UHFFFAOYSA-N methylcyclohexane;toluene Chemical compound CC1CCCCC1.CC1=CC=CC=C1 XIVQMBJJCVVPCF-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BEVIPXZYSPERIE-UHFFFAOYSA-N morpholine;morpholin-4-ium;carbamate Chemical compound NC([O-])=O.C1COCCN1.C1COCC[NH2+]1 BEVIPXZYSPERIE-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- WCVVIGQKJZLJDB-UHFFFAOYSA-N o-butylhydroxylamine Chemical compound CCCCON WCVVIGQKJZLJDB-UHFFFAOYSA-N 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- ZCYWLWVJCJEYPJ-UHFFFAOYSA-N o-hexan-2-ylhydroxylamine Chemical compound CCCCC(C)ON ZCYWLWVJCJEYPJ-UHFFFAOYSA-N 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical class CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- WBFJLQYCLUOFRY-UHFFFAOYSA-N octadecylazanium;n-octadecylcarbamate Chemical compound CCCCCCCCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCCNC([O-])=O WBFJLQYCLUOFRY-UHFFFAOYSA-N 0.000 description 1
- XKFXSYSPQZRVOY-UHFFFAOYSA-N octadecylazanium;octadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCCOC([O-])=O XKFXSYSPQZRVOY-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- IGMQODZGDORXEN-UHFFFAOYSA-N pentadecane-1-thiol Chemical class CCCCCCCCCCCCCCCS IGMQODZGDORXEN-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- WSQPMYJWTYRPQR-UHFFFAOYSA-N propan-2-amine;propan-2-yl carbamate Chemical compound CC(C)N.CC(C)OC(N)=O WSQPMYJWTYRPQR-UHFFFAOYSA-N 0.000 description 1
- AHIHJODVQGBOND-UHFFFAOYSA-M propan-2-yl carbonate Chemical compound CC(C)OC([O-])=O AHIHJODVQGBOND-UHFFFAOYSA-M 0.000 description 1
- TZRORHHMAGATLL-UHFFFAOYSA-N propan-2-ylazanium;propan-2-yl carbonate Chemical compound CC(C)[NH3+].CC(C)OC([O-])=O TZRORHHMAGATLL-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- LLISFGHXLYQOBX-UHFFFAOYSA-M silver;hexanoate Chemical compound [Ag+].CCCCCC([O-])=O LLISFGHXLYQOBX-UHFFFAOYSA-M 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical compound CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 0.000 description 1
- XBXCNNQPRYLIDE-UHFFFAOYSA-N tert-butylcarbamic acid Chemical compound CC(C)(C)NC(O)=O XBXCNNQPRYLIDE-UHFFFAOYSA-N 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical class CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、金属ナノ粒子を含有する光輝性呈色樹脂組成物に関する。また、本発明は、金属ナノ粒子を含有する光輝性呈色樹脂組成物を用いてなる光輝性呈色物品およびその製造方法に関する。 The present invention relates to a glittering color resin composition containing metal nanoparticles. The present invention also relates to a brightly colored article and a method for producing the same, which comprises using a brightly colored resin composition containing metal nanoparticles.
一般にメタリック感、パール感のような光輝性呈色塗膜を作製する場合、顔料と反射材を混合した塗料を基材に塗布、乾燥することが知られている。しかし、求められる塗膜の色に応じて、顔料種の変更、それに伴う分散剤やバインダー樹脂などの変更が必須のため、様々な材料を用意し、多くの塗料を使用する必要がある。 Generally, when producing a brilliant color coating film having a metallic feeling or a pearly feeling, it is known that a coating film in which a pigment and a reflective material are mixed is applied to a base material and dried. However, since it is essential to change the pigment type and the dispersant, binder resin, etc. according to the required color of the coating film, it is necessary to prepare various materials and use many paints.
特許文献1には、芯材と金属コロイド粒子とからなる金属コロイド光輝剤を含む塗料から塗膜を形成する旨、記載されている(請求項1、13、14)。
特許文献2には、金属ナノ粒子を有機溶媒中に分散させ、前記金属ナノ粒子を含む前記有機溶媒を水面上に展開させ、前記有機溶媒を揮発させて、前記金属ナノ粒子を二次元方向に自己組織化させて二次元結晶膜を形成し、水面上に形成された前記金属ナノ粒子の前記二次元結晶膜に前記金属反射面を接触させて転写し、前記金属ナノ粒子層を前記金属反射面の上に形成する、呈色方法が記載されている(請求項9)。前記呈色方法は、LB膜(Langmuir−Blodgett膜)の手法を利用するものであり、金属反射面に転写する金属ナノ粒子層の積層数を変更することでオレンジ〜赤〜ピンク〜紫〜青の鮮やかな金属光沢を有する発色が出ることを報告している。
Patent Document 1 describes that a coating film is formed from a coating material containing a metal colloidal luminescent agent composed of a core material and metal colloidal particles (claims 1, 13, and 14).
In Patent Document 2, metal nanoparticles are dispersed in an organic solvent, the organic solvent containing the metal nanoparticles is developed on a water surface, the organic solvent is volatilized, and the metal nanoparticles are displaced in a two-dimensional direction. A two-dimensional crystal film is formed by self-assembling, the metal reflecting surface is brought into contact with the two-dimensional crystal film of the metal nanoparticles formed on the water surface and transferred, and the metal nanoparticle layer is transferred to the metal reflecting. A coloring method for forming on a surface is described (claim 9). The coloring method utilizes the method of LB film (Langmuir-Blodgett film), and orange-red-pink-purple-blue by changing the number of layers of metal nanoparticle layers transferred to the metal reflecting surface. It has been reported that a color with a bright metallic luster appears.
特許文献1記載の塗料では、求められる塗膜の色に応じて、種類の異なる金属コロイド粒子や粒子径の異なる金属コロイド粒子が必要となり、様々な金属コロイド粒子を用意する必要がある。
また、特許文献2記載の呈色方法は、LB膜の転写を利用するものであり、工業的に大量生産の不向きな製法のため、汎用的な用途に使用することができない。
In the paint described in Patent Document 1, different types of metal colloidal particles and metal colloidal particles having different particle diameters are required according to the required color of the coating film, and it is necessary to prepare various metal colloidal particles.
Further, the coloration method described in Patent Document 2 utilizes transfer of an LB film, and cannot be used for general purposes because it is an industrially unsuitable manufacturing method for mass production.
本発明は、金属種やその大きさを特に変更することなく、多種多様な光輝性呈色塗膜を、塗布、乾燥工程といった簡易的な方法、即ち工業的生産にも適用できる方法で形成できる、光輝性呈色樹脂組成物を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention can form a wide variety of brilliant color coating films by a simple method such as a coating and drying process, that is, a method applicable to industrial production, without particularly changing the metal type and its size. , A brilliant color-developing resin composition.
本発明者らは、前記問題を解決するため鋭意検討した結果、本発明に達した。
本発明は、金属ナノ粒子(A)、反射材(B)、セルロース系樹脂(C)および溶剤(D)を含有する光輝性呈色樹脂組成物に関する。
前記金属ナノ粒子(A)の金属種は、金、銀、銅およびアルミニウムからなる群より選ばれる少なくとも1種であることが好ましい。
The present inventors have reached the present invention as a result of diligent studies to solve the above problems.
The present invention relates to a brilliant color resin composition containing metal nanoparticles (A), a reflective material (B), a cellulosic resin (C) and a solvent (D).
The metal species of the metal nanoparticles (A) is preferably at least one selected from the group consisting of gold, silver, copper and aluminum.
前記反射材(B)は、フレーク状であり、平均粒子径が1〜100μm、平均厚みが0.01〜1μmであることが好ましく、
前記反射材(B)は、アルミニウムであることが好ましい。
The reflective material (B) is in the form of flakes, preferably having an average particle diameter of 1 to 100 μm and an average thickness of 0.01 to 1 μm.
The reflective material (B) is preferably aluminum.
また、本発明は、基材(E)と、前記本発明のいずれかに記載される光輝性呈色樹脂組成物の乾燥塗膜である光輝性呈色塗膜とを有する光輝性呈色物品に関する。 Further, the present invention is a brightly colored article having a base material (E) and a brightly colored coating film which is a dry coating film of the brightly colored resin composition according to any one of the present inventions. Regarding.
さらに、本発明は、基材(E)に、前記本発明のいずれかに記載される光輝性呈色樹脂組成物を塗布し、乾燥する、光輝性呈色物品の製造方法に関する。 Furthermore, the present invention relates to a method for producing a brightly colored article, wherein the base material (E) is coated with the brightly colored resin composition according to any one of the present inventions and dried.
本発明は、金属種やその大きさを特に変更することなく、多種多様な光輝性呈色塗膜を、塗布、乾燥工程といった簡易的な方法、即ち工業的生産にも適用できる方法で形成可能な、光輝性呈色樹脂組成物を提供できる。 INDUSTRIAL APPLICABILITY The present invention can form a wide variety of bright color coating films by a simple method such as a coating and drying process, that is, a method applicable to industrial production, without particularly changing the metal type and its size. A bright color-developing resin composition can be provided.
以下に本発明の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例(代表例)であり、本発明はその要旨を超えない限りこれらの内容に特定されない。 The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described as long as the gist of the present invention is not exceeded. Not specified in the content.
本発明における金属ナノ粒子(A)としては、局在プラズモンを形成可能な金属種を採用することができる。このような金属種として、例えば金、銀、銅、アルミニウム、白金、パラジウム、ロジウム、イリジウム、ルテニウム、オスニウムを挙げることができる。このなかでも特に、局在プラズモン吸収の大きい金、銀、銅、アルミニウムなどの貴金属が好ましい。また、多種類の金属種を混在させて金属ナノ粒子層を構成してもよい。金属ナノ粒子の粒径は、1nm以上60nm以下とすることが好ましく、さらに5nm以上20nm以下とすることが好ましい。
また、前記金属ナノ粒子は、インキ中で安定に存在するために分散剤で覆われていてもよい。分散剤とは、粒子表面に親和性のある官能基を有する化合物もしくは樹脂である。親和性のある官能基とは、例えば、アミノ基、4 級アンモニウム、水酸基、シアノ基、カルボキシル基、チオール基、スルホン酸基等の極性基が挙げられるが、これに限定されるものではない。親和性基は、化合物の主鎖に含まれていても、側鎖もしくは側鎖と主鎖の双方に含まれていてもよい。粒子表面に親和性のある官能基を有する化合物としては、有機脂肪酸、有機アミン、アルカンチオール、無機物、無機酸化物のいずれかであってもよい。粒子表面に親和性のある官能基を有する樹脂としては、一般に顔料分散剤として市販されているものを使用することができる。
As the metal nanoparticles (A) in the present invention, a metal species capable of forming localized plasmons can be adopted. Examples of such metal species include gold, silver, copper, aluminum, platinum, palladium, rhodium, iridium, ruthenium, and osnium. Of these, precious metals such as gold, silver, copper, and aluminum, which absorb a large amount of localized plasmon, are particularly preferable. Further, a metal nanoparticle layer may be formed by mixing many kinds of metal species. The particle size of the metal nanoparticles is preferably 1 nm or more and 60 nm or less, and more preferably 5 nm or more and 20 nm or less.
Further, the metal nanoparticles may be covered with a dispersant so that they can be stably present in the ink. The dispersant is a compound or resin having a functional group having an affinity for the particle surface. Examples of the functional group having an affinity include, but are not limited to, polar groups such as amino group, quaternary ammonium, hydroxyl group, cyano group, carboxyl group, thiol group and sulfonic acid group. The affinity group may be contained in the main chain of the compound, or may be contained in the side chain or both the side chain and the main chain. The compound having a functional group having an affinity for the particle surface may be any of an organic fatty acid, an organic amine, an alkanethiol, an inorganic substance, and an inorganic oxide. As the resin having a functional group having an affinity for the particle surface, a resin commercially available as a pigment dispersant can be generally used.
有機脂肪酸としては、特に限定されないが、例えば、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸、アクリル酸、クロトン酸、イソクロトン酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、ブラシジン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸、プロピオール酸、ステアロール酸等があげられる。中でも、安定性や低温分解性を考慮するとカプロン酸、エナント酸、カプリル酸、ミリスチン酸、オレイン酸、ステアリン酸、2−エチルヘキサン酸、2−エチルイソヘキサン酸、2−プロピルヘプタン酸、2−ブチルオクタン酸、2−イソブチルイソオクタン酸、2−ペンチルノナン酸、2−イソペンチルノナン酸、2−ヘキシルデカン酸、2−ヘキシルイソデカン酸、2−ブチルドデカン酸、2−イソブチルドデカン酸、2−ヘプチルウンデカン酸、2−イソヘプチルウンデカン酸、2−イソペプチルイソウンデカン酸、2−ドデシルヘキサン酸、2−イソドデシルヘキサン酸、2−オクチルドデカン酸、2−イソオクチルドデカン酸、2 − オクチルイソドデカン酸、2−ノニルトリデカン酸、2−イソノニルイソトリデカン酸、2−デシルドデカン酸、2−イソデシルドデカン酸、2−デシルイソドデカン酸、2−デシルテトラデカン酸、2−オクチルヘキサデカン酸、2−イソオクチルヘキサデカン酸、2−ウンデシルペンタデカン酸、2−イソウンデシルペンタデカン酸、2−ドデシルヘプタデカン酸、2−イソドデシルイソヘプタデカン酸、2−デシルオクタデカン酸、2−デシルイソオクタデカン酸、2−トリデシルヘプタデカン酸、2−イソトリデシルイソヘプタデカン酸、2−テトラデシルオクタデカン酸、2−イソテトラデシルオクタデカン酸、2−ヘキサデシルヘキサデカン酸、2−ヘキサデシルテトラデカン酸、2−ヘキサデシルイソヘキサデカン酸、2 − イソヘキサデシルイソヘキサデカン酸、2−ペンタデシルノナデカン酸、2−イソペンタデシルイソノナデカン酸、2−テトラデシルベヘン酸、2−イソテトラデシルベヘン酸、2−テトラデシルイソベヘン酸、2−イソテトラデシルイソベヘン酸、ピバリン酸、ネオノナン酸、ネオデカン酸、エクアシッド9(出光石油化学製)、エクアシッド13(出光石油化学製)などがあげられる。かかる脂肪酸のうち、脂肪酸の炭素数が3〜22の直鎖脂肪酸であると、親油性に優れ非水性溶剤中での安定性が向上するほか、分解温度が低く、低温焼結性に優れるため好ましい。これらは一種類で用いても複数種を混合して用いても良い。 The organic fatty acid is not particularly limited, but for example, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, Palmitic acid, heptadecylic acid, stearic acid, nonadecanic acid, araquinic acid, behenic acid, lignoseric acid, cellotic acid, heptacosanoic acid, montanic acid, melicic acid, laxelic acid, acrylic acid, crotonic acid, isocrotonic acid, undecylene acid, oleic acid , Elaidic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiole acid, stearolic acid and the like. Among them, caproic acid, enanthic acid, caproic acid, myristic acid, oleic acid, stearic acid, 2-ethylcaproic acid, 2-ethylisohexanoic acid, 2-propylcaproic acid, 2-, considering stability and low-temperature degradability. Butyloctanoic acid, 2-isobutylisooctanoic acid, 2-pentylnonanoic acid, 2-isopentylnonanoic acid, 2-hexyldecanoic acid, 2-hexylisodecanoic acid, 2-butyldodecanoic acid, 2-isobutyldodecanoic acid, 2-heptylundecane Acid, 2-isoheptyl undecanoic acid, 2-isopentadecylic acid, 2-dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanic acid , 2-Nonyltridecanoic acid, 2-Isononylisotridecanoic acid, 2-decyldodecanoic acid, 2-isodecyldodecanoic acid, 2-decylisododecanoic acid, 2-decyltetradecanoic acid, 2-octylhexadecanoic acid, 2- Isooctyl hexadecanoic acid, 2-undecyl pentadecanoic acid, 2-isoundecyl pentadecanoic acid, 2-dodecyl heptadecanoic acid, 2-isododecyl isoheptadecanoic acid, 2-decyl octadecanoic acid, 2-decyl isooctadecanoic acid, 2 -Tridecyl heptadecanoic acid, 2-isotridecyl isoheptadecanoic acid, 2-tetradecyl octadecanoic acid, 2-isotetradecyl octadecanoic acid, 2-hexadecyl hexadecanoic acid, 2-hexadecyl tetradecanoic acid, 2-hexadecyl Isohexadecanoic acid, 2-isohexadecylisohexadecanoic acid, 2-pentadecylic nonadecanoic acid, 2-isopentadecylic isononadecanoic acid, 2-tetradecylbechenic acid, 2-isotetradecylbechenic acid, 2-tetradecyl Examples thereof include isobehenic acid, 2-isotetradecyl isobehenic acid, pivalic acid, neononanic acid, neodecanoic acid, equiacid 9 (manufactured by Idemitsu Petrochemical), and equicad 13 (manufactured by Idemitsu Petrochemical). Among such fatty acids, linear fatty acids having 3 to 22 carbon atoms are excellent in lipophilicity, stability in non-aqueous solvents, low decomposition temperature, and excellent low-temperature sinterability. preferable. These may be used alone or in combination of two or more.
有機脂肪アミンとしては、特に限定されないが、例えば、メチルアミン、エチルアミン、n−プロピルアミン、イソプロピルアミン、n−ブチルアミン、イソブチルアミン、イソアミルアミン、n−ヘキシルアミン、2−エチルヘキシルアミン、n−ヘプチルアミン、n−オクチルアミン、イソオクチルアミン、ノニルアミン、デシルアミン、ドデシルアミン、ヘキサデシルアミン、オクタデシルアミン、ドコデシルアミン、シクロプロピルアミン、シクロペンチルアミン、シクロヘキシルアミン、アリールアミン、ヒドロキシアミン、アンモニウムヒドロキシド、メトキシアミン、2−エタノールアミン、メトキシエチルアミン、2-ヒドロキシプロピルアミン、メトキシプロピルアミン、シアノエチルアミン、エトキシアミン、n−ブトキシアミン、2−ヘキシルオキシアミン、メトキシエトキシエチルアミン、メトキシエトキシエトキシエチルアミン、ジエチルアミン、ジプロピルアミン、ジエタノールアミン、ヘキサメチレンイミン、モルホリン、ピペリジン、ピペラジン、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリエチレンジアミン、2,2−(エチレンジオキシ)ビスエチルアミン、トリエチルアミン、トリエタノールアミン、ピロール、イミダゾール、ピリジン、アミノアセトアルデヒドジメチルアセタール、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、アニリン、アニシジン、アミノベンゾニトリル、ベンジルアミン及びその誘導体、そしてポリアリールアミンやポリエチレンイミンのような高分子化合物及びその誘導体などのようなアミン化合物が挙げられて、アンモニウムカルバメート、カーボネート、バイカーボネート系化合物としては、具体的に例えば、アンモニウムカルバメート、アンモニウムカーボネート、アンモニウムバイカーボネート、エチルアンモニウムエチルカルバメート、イソプロピルアンモニウムイソプロピルカルバメート、n−ブチルアンモニウムn−ブチルカルバメート、イソブチルアンモニウムイソブチルカルバメート、t−ブチルアンモニウムt−ブチルカルバメート、2−エチルヘキシルアンモニウム2−エチルヘキシルカルバメート、オクタデシルアンモニウムオクタデシルカルバメート、2―メトキシエチルアンモニウム2−メトキシエチルカルバメート、2−シアノエチルアンモニウム2−シアノエチルカルバメート、ジブチルアンモニウムジブチルカルバメート、ジオクタデシルアンモニウムジオクタデシルカルバメート、メチルデシルアンモニウムメチルデシルカルバメート、ヘキサメチレンイミンアンモニウムヘキサメチレンイミンカルバメート、モルホリニウムモルホリンカルバメート、ピリジニウムエチルヘキシルカルバメート、トリエチレンジアミニウムイソプロピルバイカルバメート、ベンジルアンモニウムベンジルカルバメート、トリエトキシシリルプロピルアンモニウムトリエトキシシリルプロピルカルバメート、エチルアンモニウムエチルカーボネート、イソプロピルアンモニウムイソプロピルカーボネート、イソプロピルアンモニウムバイカーボネート、n−ブチルアンモニウムn−ブチルカーボネート、イソブチルアンモニウムイソブチルカーボネート、t−ブチルアンモニウムt−ブチルカーボネート、t−ブチルアンモニウムバイカーボネート、2−エチルヘキシルアンモニウム2−エチルヘキシルカーボネート、2−エチルヘキシルアンモニウムバイカーボネート、2−メトキシエチルアンモニウム2−メトキシエチルカーボネート、2−メトキシエチルアンモニウムバイカーボネート、2−シアノエチルアンモニウム2−シアノエチルカーボネート、2−シアノエチルアンモニウムバイカーボネート、オクタデシルアンモニウムオクタデシルカーボネート、ジブチルアンモニウムジブチルカーボネート、ジオクタデシルアンモニウムジオクタデシルカーボネート、ジオクタデシルアンモニウムバイカーボネート、メチルデシルアンモニウムメチルデシルカーボネート、ヘキサメチレンイミンアンモニウムヘキサメチレンイミンカーボネート、モルホリンアンモニウムモルホリンカーボネート、ベンジルアンモニウムベンジルカーボネート、トリエトキシシリルプロピルアンモニウムトリエトキシシリルプロピルカーボネート、ピリジニウムバイカーボネート、トリエチレンジアミニウムイソプロピルカーボネート、トリエチレンジアミニウムバイカーボネート、及びこれらの誘導体などが挙げられる。これらは一種類で用いても複数種を混合して用いても良い。 The organic fatty amine is not particularly limited, and is, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine. , N-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine , 2-Ethanolamine, methoxyethylamine, 2-hydroxypropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, diethylamine, dipropylamine , Diethanolamine, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, amino Acetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline, anicidin, aminobenzonitrile, benzylamine and its derivatives, and high molecular weight compounds such as polyarylamine and polyethyleneimine and their derivatives. Examples of amine compounds such as ammonium carbamate, carbonate, and carboxylate compounds include, for example, ammonium carbamate, ammonium carbonate, ammonium biocarbonate, ethylammonium ethyl carbamate, isopropylammonium isopropyl carbamate, n-. Butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylcarbamate 2- Cyanoethyl carbamate, dibutylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridinium ethylhexyl carbamate, triethylenediaminium isopropylbicarbamate, benzyl Ammonium benzyl carbamate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbamate, ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, isopropylammonium bicarbonate, n-butylammonium n-butyl carbonate, isobutylammonium isobutyl carbonate, t-butylammonium t- Butyl carbonate, t-butylammonium biocarbonate, 2-ethylhexylammonium 2-ethylhexyl carbonate, 2-ethylhexylammonium biocarbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium biocarbonate, 2-cyanoethylammonium 2 -Cyanoethyl carbonate, 2-cyanoethylammonium biocarbonate, octadecylammonium octadecyl carbonate, dibutylammonium dibutyl carbonate, dioctadecylammonium dioctadecyl carbonate, dioctadecylammonium biocarbonate, methyldecylammonium methyldecyl carbonate, hexamethyleneimine ammonium hexamethyleneimine carbonate Examples thereof include morpholine ammonium morpholine carbonate, benzylammonium benzyl carbonate, triethoxysilylpropylammonium triethoxysilylpropyl carbonate, pyridinium bicarbonate, triethylenediaminium isopropyl carbonate, triethylenediaminium biocarbonate, and derivatives thereof. These may be used alone or in combination of two or more.
アルカンチオールとしては、特に限定されないが、例えば、メタンチオール、エタンチオール、プロパンチオール、ブタンチオール、ペンタンチオール、ヘキサンチオール、ヘプタンチオール、オクタンチオール、ノナンチオール、デカンチオール、ウンデカンチオール、ドデカンチオール、トリデカンチオール、テトラデカンチオール、ペンタデカンチオール、ヘキサデカンチオール、ヘプタデカンチオール、オクタデカンチオール、ノナデカンチオール及びイコサンチオールなどが挙げられる。これらは一種類で用いても複数種を混合して用いても良い。 The alcan thiol is not particularly limited, but for example, methane thiol, ethane thiol, propane thiol, butane thiol, pentan thiol, hexane thiol, heptane thiol, octane thiol, nonan thiol, decane thiol, undecane thiol, dodecane thiol, tridecane. Examples thereof include thiols, tetradecanethiols, pentadecanethiols, hexadecanethiols, heptadecanethiols, octadecanethiols, nonadecanthiols and icosanthiols. These may be used alone or in combination of two or more.
分散樹脂としては、一般に市販されているものを使用することができ、例えば、日本ルーブリゾール株式会社製のソルスパース3000、ソルスパース9000、ソルスパース1 7000、ソルスパース24000 、ソルスパース28000 、ソルスパース32000、ソルスパース35100 、ソルスパース36000 、ソルスパース41000、エフカアディティブズ社製のEFKA4009、EFKA4046、EFKA4047、EFKA4080、EFKA4010、EFKA4015、EFKA4050、EFKA4055、EFKA4060、EFKA4330、EFKA4300、EFKA7462、味の素ファインテクノ株式会社製のアジスパーPB821、アジスパーPB711、アジスパーPB822、アジスパーPN411、アジスパーPA111、コグニスジャパン株式会社製のTEXAPHORUV20、TEXAPHORUV21、TEXAPHORP61、ビッグケミー・ジャパン株式会社製のDisperbyk−101 、Disperbyk−103、Disperbyk−106、Disperbyk−110、Disperbyk−111、Disperbyk−161、Disperbyk−162 、Disperbyk−163 、Disperbyk−164 、Disperbyk−166、Disperbyk−167、Disperbyk−168、Disperbyk−170 、Disperbyk−171、Disperbyk−174、Disperbyk−180、Disperbyk−182等が挙げられるがこれらに限定されるものではない。分散樹脂は、一種類でも複数種を組み合わせて用いても良い。 As the dispersion resin, commercially available ones can be used, for example, Solspurth 3000, Solsperse 9000, Solsperse 17000, Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse Co., Ltd. 36000, Solsperse 41000, EFKA4009, EFKA4046, EFKA4047, EFKA4080, EFKA4010, EFKA4015, EFKA4050, EFKA4055, EFKA4060, EFKA4055, EFKA4060, EFKA4530, EFKA4630, EFKA4330, EFKA4330 PB822, Ajispar PN411, Ajispar PA111, TEXAPHORUV20, TEXAPHORUV21, TEXAPHORP61, Dipperbak-101, Dipperbik-103, Dipperbik-106, Dipperbik-106, Dipperbik , Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-174, etc. It is not limited to. The dispersion resin may be used alone or in combination of two or more.
本発明における反射材(B)は、アルミニウム、亜鉛、銅、ブロンズ、ニッケル、チタン、ステンレスなどの金属フレーク、または、ガラス、雲母チタン、酸化チタン被覆合成雲母、酸化チタン及び酸化ケイ素被覆雲母、酸化チタン被覆ガラスフレーク、酸化チタン被覆シリカフレーク、酸化チタン被覆アルミナフレーク、シリカ被覆雲母、シリカ被覆合成雲母、シリカ被覆ガラスフレーク、酸化チタンフレーク、シリカ被覆アルミニウム等があげられる。干渉光を持つことにより金属コロイドにより発せられる色を強調する効果がある。市販品では、例えば、雲母チタン、ベンガラ被覆雲母、ベンガラ被覆雲母チタン、カーミン被覆雲母チタン、紺青被覆雲母チタン、酸化チタン被覆合成金雲母、ベンガラ・酸化チタン被覆合成金雲母、酸化チタン被覆ガラスフレーク、酸化チタン被覆アルミナフレーク( メルク社製シローナシルバーなど) 、酸化チタン被覆シリカフレーク( メルク社製シローナマジックモーヴなど) 、酸化鉄・シリカ被覆アルミニウム、酸化鉄・シリカ被覆酸化鉄、酸化チタン及び酸化ケイ素被覆雲母( メルク社製チミロンスプレンディッドゴールド、同シローナカリビアンブルーなど) 、酸化チタン被覆ガラスフレーク( 日本板硝子社製メタシャインMC1080RR、エンゲルハード社製リフレックスシリーズなど) を用いることができる。
反射材がフレーク状であるとき、平均厚みが0.01〜1μm、平均粒径が1〜100μmのものが好ましい。更に平均厚みが0.1〜0.67μm 、平均粒径が5〜30μmが好ましく。更に、平均厚みが0.2〜0.4μm、平均粒径が9〜20μmが好ましい。また、上記平均粒子厚み(μm)は、〔4000/水面被覆面積(cm2/g)〕式により求められた値であり、その測定方法は例えば「アルミニウムハンドブック」(昭和47年4月15日発行第9版、社団法人 軽金属協会; 朝倉書店)第1243頁に記載されている。
The reflective material (B) in the present invention is metal flakes such as aluminum, zinc, copper, bronze, nickel, titanium, and stainless steel, or glass, titanium oxide, titanium oxide-coated synthetic mica, titanium oxide and silicon oxide-coated mica, and oxidation. Examples thereof include titanium-coated glass flakes, titanium oxide-coated silica flakes, titanium oxide-coated alumina flakes, silica-coated mica, silica-coated synthetic mica, silica-coated glass flakes, titanium oxide flakes, and silica-coated aluminum. Having interference light has the effect of emphasizing the color emitted by the metal colloid. Commercially available products include, for example, mica titanium, Bengala-coated mica, Bengala-coated mica titanium, Carmine-coated mica titanium, dark blue-coated mica titanium, titanium oxide-coated synthetic gold mica, Bengala / titanium oxide-coated synthetic gold mica, titanium oxide-coated glass flakes, Titanium oxide coated alumina flakes (such as Sirona Silver manufactured by Merck), titanium oxide coated silica flakes (such as Sirona Magic Move manufactured by Merck), iron oxide / silica coated aluminum, iron oxide / silica coated iron oxide, titanium oxide and oxidation Silicon-coated mica (Timilon splendid gold manufactured by Merck, Sirona Caribbean blue, etc.) and titanium oxide-coated glass flakes (Metashine MC1080RR manufactured by Nippon Plate Glass Co., Ltd., Reflex series manufactured by Engelhard Co., Ltd., etc.) can be used.
When the reflective material is flaky, it preferably has an average thickness of 0.01 to 1 μm and an average particle size of 1 to 100 μm. Further, the average thickness is preferably 0.1 to 0.67 μm, and the average particle size is preferably 5 to 30 μm. Further, the average thickness is preferably 0.2 to 0.4 μm, and the average particle size is preferably 9 to 20 μm. The average particle thickness (μm) is a value obtained by the formula [4000 / water surface coverage area (cm 2 / g)], and the measuring method is, for example, "Aluminum Handbook" (April 15, 1972). Published 9th Edition, Light Metal Association; Asakura Shoten), p. 1243.
本発明におけるセルロース系樹脂(C)としては、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ニトロセルロース、セルロースアセテートブチレート、セルロースアセテート、セルロースプロピオネート、セルロースブチレート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースアセテートベンゾエート、セルロースベンゾエート、ヒドロキシセルロース、セルロースアセテート、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロースおよびカルボキシメチルセルロース等が挙げられるがこれらに限定されない。
セルロース系樹脂は、単独または2種類以上併用できる。
Examples of the cellulosic resin (C) in the present invention include methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, nitrocellulose, cellulose acetate butyrate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate. Examples include, but are not limited to, cellulose acetate benzoate, cellulose benzoate, hydroxycellulose, cellulose acetate, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose.
The cellulosic resin can be used alone or in combination of two or more.
本発明における溶剤(D)としては、金属ナノ粒子(A)、反射材(B)及びセルロース系樹脂(C)を溶解、分散できる溶剤が好ましく。具体的には、アルコール系、エステル系溶剤、ケトン系溶剤、グリコールエーテル系溶剤、エーテル系溶剤、炭化水素系溶剤、およびカーボネート系溶剤等が好ましい。 As the solvent (D) in the present invention, a solvent capable of dissolving and dispersing the metal nanoparticles (A), the reflective material (B) and the cellulosic resin (C) is preferable. Specifically, alcohol-based solvents, ester-based solvents, ketone-based solvents, glycol ether-based solvents, ether-based solvents, hydrocarbon-based solvents, carbonate-based solvents and the like are preferable.
アルコール系溶剤は、例えば、メタノール、エタノール、イソプロピルアルコール、sec−ブタノール、イソブタノール、n−ブタノール、オクチル(2−エチルヘキシル)アルコール、シクロヘキサノール、フルフリルアルコール、メチルシクロヘキサノール、テトタヒドロフルフリルアルコール、ベンジルアルコール、フェニルエチルアルコール、Pine oil、エチレングリコール、ジエチレングリコール、グリセリンおよびトリエタノールアミン等が挙げられるがこれらに限定されない。 Alcohol-based solvents include, for example, methanol, ethanol, isopropyl alcohol, sec-butanol, isobutanol, n-butanol, octyl (2-ethylhexyl) alcohol, cyclohexanol, furfuryl alcohol, methylcyclohexanol, tetotahydrofurfuryl alcohol, etc. Examples thereof include, but are not limited to, benzyl alcohol, phenylethyl alcohol, Pine oil, ethylene glycol, diethylene glycol, glycerin and triethanolamine.
エステル系溶剤は、例えば酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸n−ブチル、酢酸イソブチル、酢酸−sec−ブチル、酢酸アミル、酢酸シクロヘキシル、グリコールジアセテート、乳酸エチル、および炭酸ジメチル等が挙げられるがこれらに限定されない。 Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, -sec-butyl acetate, amyl acetate, cyclohexyl acetate, glycol diacetate, ethyl lactate, and dimethyl carbonate. Not limited to these.
ケトン系溶剤は、例えばアセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、ジイソブチルケトン、メシチルオキシド、ジアセトンアルコール、イソホロン、メチルシクロヘキサノン、アセトフェノンおよびシクロヘキサノン等が挙げられるがこれらに限定されない。 Examples of the ketone solvent include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diisobutyl ketone, mesityl oxide, diacetone alcohol, isophorone, methylcyclohexanone, acetophenone and cyclohexanone.
グリコールエーテル系溶剤は、例えばエチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル、およびエチレングリコールモノブチルエーテル等のモノエーテル、ならびにこれらの酢酸エステル;ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、およびプロピレングリコールモノエチルエーテル等、ならびにこれらの酢酸エステル;等が挙げられるがこれらに限定されない。 Glycol ether solvents include monoethers such as, for example, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether, and acetates thereof; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like, and acetates thereof; and the like, but are not limited thereto.
エーテル系溶剤としては、エチルエーテル、イソプロピルエーテル、ジオキサン、モルフォリン、n−ブチルエーテル、フェニルエーテルおよびベンジルエーテル等が挙げられるがこれらに限定されない。 Examples of the ether solvent include, but are not limited to, ethyl ether, isopropyl ether, dioxane, morpholine, n-butyl ether, phenyl ether and benzyl ether.
炭化水素系溶剤は、例えばn−ヘキサン、シクロヘキサン、メチルシクロヘキサントルエン、キシレン、エチルベンゼン、イソプロピルベンゼン、ジエチルベンゼン、ジフェニルエタン、シクロヘキセン、ジペンテン、クロロホルム、四塩化炭素、プロピレンジクロライド、トリクロロエタン及びミネラルスピリット等が挙げられるがこれらに限定されない。 Examples of the hydrocarbon solvent include n-hexane, cyclohexane, methylcyclohexanetoluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, diphenylethane, cyclohexene, dipentene, chloroform, carbon tetrachloride, propylene dichloride, trichloroethane and mineral spirit. Is not limited to these.
カーボネート系溶剤は、例えばジメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート及びエチレンカーボネート等が挙げられるがこれらに限定されない。
溶剤は、単独または2種類以上併用できる。
Examples of the carbonate solvent include, but are not limited to, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate and the like.
The solvent can be used alone or in combination of two or more.
<光輝性呈色樹脂組成物の製造方法>
本発明における光輝性呈色樹脂組成物の製造方法は特に限定されるものではなく、金属ナノ粒子(A)、反射材(B)、セルロース系樹脂(C)、溶剤(D)を均一に混合するのに用いられる方法であれば良く、通常用いられる従来公知の方法で何ら構わない。
<Manufacturing method of bright color resin composition>
The method for producing the brilliant color resin composition in the present invention is not particularly limited, and the metal nanoparticles (A), the reflective material (B), the cellulosic resin (C), and the solvent (D) are uniformly mixed. Any method used for this purpose may be used, and any conventionally known method may be used.
すなわち、具体的には例えば、光輝性呈色樹脂組成物を構成する各成分を処方し、シェイカー、超音波撹拌、ディスパー、メカニカルスターラー、ペイントコンディショナー(レッドデビル社製)、ボールミル、サンドミル(シンマルエンタープライゼス社製「ダイノーミル」等)、アトライター、パールミル(アイリッヒ社製「DCPミル」等)、コボールミル、ホモミキサー、ホモジナイザー(エム・テクニック社製「クレアミックス」等)、湿式ジェットミル(ジーナス社製「ジーナスP Y 」、ナノマイザー社製「ナノマイザー」)、微小ビーズミル(寿工業(株)製「スーパーアペックミル」、「ウルトラアペックミル」)などで混合、混練あるいは分散する方法が挙げられる。 That is, specifically, for example, each component constituting the brilliant color resin composition is formulated, and a shaker, ultrasonic stirring, disper, mechanical stirrer, paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru) are formulated. Enterprises "Dyno Mill" etc.), Atwriter, Pearl Mill (Eirich "DCP Mill" etc.), Coball Mill, Homo Mixer, Homogenizer (M Technique "Claire Mix" etc.), Wet Jet Mill (Genus) Examples thereof include a method of mixing, kneading or dispersing with a fine bead mill (“Super Apec Mill” or “Ultra Apec Mill” manufactured by Kotobuki Kogyo Co., Ltd.), or “Genus P Y” manufactured by Nanomizer Co., Ltd.
また、本発明の光輝性呈色樹脂組成物には、その他必要に応じて単官能単量体、紫外線吸収剤、酸化防止剤、熱安定剤、光安定剤、帯電防止剤、界面活性剤、貯蔵安定剤、レベリング剤、光安定剤などを使用することもできる。 In addition, the bright color resin composition of the present invention includes, if necessary, a monofunctional monomer, an ultraviolet absorber, an antioxidant, a heat stabilizer, a light stabilizer, an antistatic agent, a surfactant, and the like. Storage stabilizers, leveling agents, light stabilizers and the like can also be used.
<光輝性呈色塗膜>
本発明の光輝性呈色樹脂組成物から形成される光輝性呈色塗膜は、基材(E)上に光輝性呈色樹脂組成物を塗布、乾燥することによって得られる。
塗工方法としては、公知の方法を用いることができ、例えばロットまたはワイヤーバーなどを用いた方法や、マイクログラビア、グラビア、ダイ、カーテン、リップ、スロット、スプレー、ロールコーター、シルクスクリーン、インクジェットまたはスピンなどの各種コーティング方法を用いることができる。
光輝性呈色塗膜の厚みは特に限定されないが、通常、0.5〜20μmであることが好ましい。
<Glittering color coating>
The bright color coating film formed from the bright color resin composition of the present invention can be obtained by applying the bright color resin composition on the substrate (E) and drying it.
As a coating method, a known method can be used, for example, a method using a lot or a wire bar, micro gravure, gravure, die, curtain, lip, slot, spray, roll coater, silk screen, inkjet or Various coating methods such as spin can be used.
The thickness of the brilliant color coating film is not particularly limited, but is usually preferably 0.5 to 20 μm.
本発明における基材(E)としては、特に限定されるものではなく、例えば、ポリイミドフィルム、ポリパラフェニレンテレフタルアミドフィルム、ポリエーテルニトリルフィルム、ポリエーテルサルホンフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリカーボネートフィルム、ポリ塩化ビニルフィルム、ポリアクリルフィルム、ガラス、セラミック、合金及び金属等が挙げられる。またこれらの基材上にITO(スズドープ酸化インジウム)層および金属層(アルミニウム、金、銀など)等を基材の全面または部分的に形成されていても良い。 The base material (E) in the present invention is not particularly limited, and for example, a polyimide film, a polyparaphenylene terephthalamide film, a polyether nitrile film, a polyether sulfone film, a polyethylene terephthalate film, and a polyethylene naphthalate film. , Polybutylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyacrylic film, glass, ceramics, alloys, metals and the like. Further, an ITO (tin-doped indium oxide) layer, a metal layer (aluminum, gold, silver, etc.) and the like may be formed on the entire surface or a part of the substrate on these substrates.
<光輝性呈色塗膜の乾燥工程>
基材(E)上に塗布された光輝性呈色樹脂組成物において、まず、反射材(B)が沈降し、その後、乾燥過程においての自己組織化により金属ナノ粒子(A)が反射材(B)上に積層する。
金属ナノ粒子(A)の積層数は金属ナノ粒子(A)またはセルロース系樹脂(C)比率によって制御できる。具体的には、金属ナノ粒子(A)比率が増えると積層数が増加し、減ると積層数が減少する。セルロース系樹脂(C)比率が増えると樹脂中へ分散する金属ナノ粒子(A)が増加し、反射材(B)上への積層数が減少し、セルロース系樹脂(C)比率が減ると塗液粘度が減少し、乾燥過程においての自己組織化がうまくいかず、反射材(B)上への積層数が減少する。
<Drying process of bright color coating film>
In the brilliant color-developing resin composition applied on the base material (E), the reflective material (B) first settles, and then the metal nanoparticles (A) become the reflective material (A) due to self-assembly in the drying process. B) Laminate on top.
The number of laminated metal nanoparticles (A) can be controlled by the ratio of the metal nanoparticles (A) or the cellulosic resin (C). Specifically, as the ratio of metal nanoparticles (A) increases, the number of layers increases, and as the ratio decreases, the number of layers decreases. When the ratio of the cellulosic resin (C) increases, the number of metal nanoparticles (A) dispersed in the resin increases, the number of layers on the reflector (B) decreases, and when the ratio of the cellulosic resin (C) decreases, the coating is applied. The liquid viscosity decreases, self-assembly in the drying process does not go well, and the number of layers on the reflector (B) decreases.
<呈色メカニズム>
(Near Field効果)
金属ナノ粒子(A)が積層した反射材(B)上に外部から光が照射されると、金属ナノ粒子(A)の周りには局在プラズモンが励起される。金属ナノ粒子層が平面状に規則的に配列されていると、二次元方向に隣接している個々の金属ナノ粒子(A)で励起された局在プラズモンは面方向に相互に結合し、単独の金属ナノ粒子(A)よりも長波長の光を吸収する。
<Coloring mechanism>
(Near Field effect)
When the reflective material (B) on which the metal nanoparticles (A) are laminated is irradiated with light from the outside, localized plasmons are excited around the metal nanoparticles (A). When the metal nanoparticles are regularly arranged in a plane, the localized plasmons excited by the individual metal nanoparticles (A) adjacent in the two-dimensional direction are bonded to each other in the plane direction and are alone. Absorbs light with a longer wavelength than the metal nanoparticles (A) of.
金属ナノ粒子層を透過した一部の光は、下地層の反射材(B)で反射され、再び背面から金属ナノ粒子層に入射する。これにより、外部からの直射光と、反射材面での反射光とが、わずかな時間差で金属ナノ粒子層に入射する。すると、個々の金属ナノ粒子層において励起された局在プラズモン間に複雑な相互作用が生まれる。これによって、金属ナノ粒子(A)の積層数に応じて共鳴吸収ピークはさらに長波長シフトを呈する。 A part of the light transmitted through the metal nanoparticle layer is reflected by the reflective material (B) of the base layer, and is again incident on the metal nanoparticle layer from the back surface. As a result, the direct light from the outside and the reflected light on the reflector surface are incident on the metal nanoparticle layer with a slight time difference. This creates complex interactions between the excited localized plasmons in the individual metal nanoparticle layers. As a result, the resonance absorption peak exhibits a longer wavelength shift depending on the number of layers of the metal nanoparticles (A).
(Far Field効果)
金属ナノ粒子(A)は、局在プラズモンが励起される波長においてのみ極めて大きな実効誘電率を有する。すなわち、狭い波長域において波長によって屈折率が大きく変化するメタマテリアル的性質を有する。このメタマテリアル的性質のために、金属ナノ粒子(A)の背面に反射材(B)での反射光が入射すると、特定の波長の光がその層数に応じて、金属ナノ粒子層の層構造の中に強く閉じ込められる。
(Far Field effect)
The metal nanoparticles (A) have an extremely large effective permittivity only at the wavelength at which the localized plasmon is excited. That is, it has a metamaterial property in which the refractive index changes greatly depending on the wavelength in a narrow wavelength range. Due to this metamaterial property, when the reflected light from the reflector (B) is incident on the back surface of the metal nanoparticles (A), the light of a specific wavelength is layered in the metal nanoparticles layer according to the number of layers. Strongly trapped in the structure.
このように、直射光と反射材(B)での反射光の両方によって局在プラズモンが励起されるNear Field 効果と、金属ナノ粒子層の層間への光閉じ込めのFar Field 効果によって、金属ナノ粒子層はその層数に応じて金属ナノ粒子(A)の本来の色とは異なる色に呈色する。 In this way, the Near Field effect in which the localized plasmon is excited by both the direct light and the reflected light in the reflector (B) and the Far Field effect in which the light is confined between the layers of the metal nanoparticle layer cause the metal nanoparticles. The layers are colored differently from the original color of the metal nanoparticles (A) according to the number of layers.
一般的に、金属ナノ粒子(A)の種類、大きさ、形状によっても局在プラズモンによる吸収を変更できることが知られており、上記メカニズムと合わせることで呈色の色域を拡げることができる。 In general, it is known that the absorption by localized plasmons can be changed depending on the type, size, and shape of the metal nanoparticles (A), and the color gamut of coloration can be expanded by combining with the above mechanism.
本発明の光輝性呈色樹脂組成物は、構成要素を任意の割合で変更することができ、それにより塗膜時の色や発色性が変わる。金属ナノ粒子(A)が少なすぎると、発色が弱くなり、多すぎると吸収がブロード化し発色性が悪くなる。よって、金属ナノ粒子(A)と反射材(B)とセルロース系樹脂(C)の合計100質量%中に、金属ナノ粒子(A)は0.6〜12.5質量%が好ましく、更に1.3〜9.4質量%とすることが好ましい。
反射材(B)が少なすぎると、基板を十分に覆う反射面が作ることができず、多すぎると基板との密着性が悪くなるため、金属ナノ粒子(A)と反射材(B)とセルロース系樹脂(C)の合計100質量%中に、反射材(B)は1〜98.4質量%が好ましく、更に30〜82質量%とすることが好ましく、更に30〜50質量%とすることが好ましい。
セルロース系樹脂(C)が少なすぎると、光輝性呈色樹脂組成物の粘度が低くなり、乾燥時の金属ナノ粒子の沈降、凝集が促進され、十分な発色が得られず、多すぎると金属ナノ粒子が樹脂中に分散してしまい反射材(B)上への集積ができなくなるため、十分な発色が得られず、分散色が出てしまう。したがって、光輝性呈色樹脂組成物の粘度が100〜25000mPa・sになるよう添加量を制御することが好ましく、更に300〜5000とすることが好ましい。もしくは、金属ナノ粒子(A)と反射材(B)とセルロース系樹脂(C)の合計100質量%中に、セルロース系樹脂(C)は1〜20質量%が好ましく、更に3〜15質量%とすることが好ましい。
In the brilliant color-developing resin composition of the present invention, the constituent elements can be changed at an arbitrary ratio, thereby changing the color and color-developing property at the time of coating film. If the amount of the metal nanoparticles (A) is too small, the color development becomes weak, and if the amount is too large, the absorption becomes broad and the color development property deteriorates. Therefore, the metal nanoparticles (A) are preferably 0.6 to 12.5% by mass in the total of 100% by mass of the metal nanoparticles (A), the reflective material (B), and the cellulosic resin (C), and further 1 It is preferably .3 to 9.4% by mass.
If the amount of the reflective material (B) is too small, a reflective surface that sufficiently covers the substrate cannot be formed, and if the amount of the reflective material (B) is too large, the adhesion to the substrate deteriorates. Therefore, the metal nanoparticles (A) and the reflective material (B) The reflective material (B) is preferably 1 to 98.4% by mass, more preferably 30 to 82% by mass, and further 30 to 50% by mass in the total 100% by mass of the cellulose resin (C). Is preferable.
If the amount of the cellulosic resin (C) is too small, the viscosity of the brilliant coloring resin composition becomes low, the precipitation and aggregation of the metal nanoparticles during drying are promoted, and sufficient color development cannot be obtained. Since the nanoparticles are dispersed in the resin and cannot be accumulated on the reflective material (B), sufficient color development cannot be obtained and dispersed colors are produced. Therefore, it is preferable to control the addition amount so that the viscosity of the bright color resin composition is 100 to 25,000 mPa · s, and further preferably 300 to 5,000. Alternatively, the cellulosic resin (C) is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, in the total of 100% by mass of the metal nanoparticles (A), the reflective material (B), and the cellulosic resin (C). Is preferable.
溶剤(E)が少なすぎると分散しにくくなり、多すぎると光輝性呈色樹脂組成物の粘度が低くなり、乾燥時の金属ナノ粒子の沈降、凝集が促進されにくくなり、発色性が低下する。したがって、光輝性呈色樹脂組成物の粘度が100〜25000mPa・sになるよう添加量を制御することが好ましく、更に300〜5000mPa・sとすることが好ましい。もしくは、光輝性呈色樹脂組成物中の質量%濃度で50〜97質量%が好ましく、更に72〜90質量%とすることが好ましい。 If the amount of the solvent (E) is too small, it becomes difficult to disperse, and if it is too large, the viscosity of the bright color resin composition becomes low, and the precipitation and aggregation of metal nanoparticles during drying are difficult to be promoted, and the color development property is lowered. .. Therefore, it is preferable to control the addition amount so that the viscosity of the bright color resin composition is 100 to 25,000 mPa · s, and further preferably 300 to 5000 mPa · s. Alternatively, the mass% concentration in the bright color-developing resin composition is preferably 50 to 97% by mass, and more preferably 72 to 90% by mass.
このように、本発明の光輝性呈色塗膜によれば、光輝性呈色樹脂組成物を塗布乾燥といった簡易的な方法で、反射材(B)上への金属ナノ粒子(A)の積層を可能とし、層数を変更することにより、異なる色に呈色させることができる。したがって、単一の金属種を用いて光輝性呈色塗膜を複数の異なる色に呈色させることができ、従来のように異なる色ごとに異なる種類の金属、顔料を用意する必要が無い。また、このようにして得られる光輝性呈色塗膜の表面は金属光沢を有する鮮やかな色に呈色されているので、様々な物品の表面の意匠性を高めることができる。 As described above, according to the bright color coating film of the present invention, the metal nanoparticles (A) are laminated on the reflective material (B) by a simple method such as applying and drying the bright color resin composition. By changing the number of layers, it is possible to develop different colors. Therefore, the brilliant color coating film can be colored into a plurality of different colors by using a single metal type, and it is not necessary to prepare different types of metals and pigments for each different color as in the conventional case. Further, since the surface of the brilliant color coating film thus obtained is colored in a vivid color having a metallic luster, the design of the surface of various articles can be enhanced.
次に実施例により本発明を具体的に説明する。実施例において部及び%とあるのは、特に指定のない限り、すべて質量基準であるものとする。 Next, the present invention will be specifically described with reference to Examples. Unless otherwise specified, the terms "part" and "%" in the examples are all based on mass.
<金属ナノ粒子(A)の製造法>
金属ナノ粒子(A)について説明する。金属ナノ粒子の平均粒子径は、透過型電子顕微鏡(TEM)により、100個のナノ粒子を観察し、平均値を出したものである。
<Manufacturing method of metal nanoparticles (A)>
The metal nanoparticles (A) will be described. The average particle size of the metal nanoparticles is obtained by observing 100 nanoparticles with a transmission electron microscope (TEM) and calculating the average value.
製造例1 銀ナノ粒子1の製造
セパラブル4口フラスコに冷却管、温度計、窒素ガス導入管、攪拌装置を取り付け、窒素雰囲気下、室温で攪拌しながらトルエン200部およびヘキサン酸銀22.3部を仕込み、0.5Mの溶液とした後に、分散剤としてジエチルアミノエタノール2.3部(金属1molに対し0.2mol倍)、オレイン酸2.8部(金属1molに対し0.1mol倍)を添加し溶解させた。その後、20%のコハク酸ジヒドラジド(以下、SUDHと略す)水溶液73.1部(金属1molに対しヒドラジド基2mol倍)を滴下すると液色が淡黄色から濃茶色に変化した。さらに反応を促進させるために40℃に昇温し、反応を進行させた。静置、分離した後、水相を取り出すことで過剰の還元剤や不純物を除去し、さらにトルエン層に数回蒸留水を加え、洗浄、分離を繰り返した後、乾燥させて銀ナノ粒子1を得た。銀ナノ粒子1の平均粒子径は13nmであった。
Production Example 1 Production of silver nanoparticles 1 A cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer are attached to a separable 4-neck flask, and 200 parts of toluene and 22.3 parts of silver hexanoate are stirred at room temperature in a nitrogen atmosphere. To make a 0.5 M solution, 2.3 parts of diethylaminoethanol (0.2 mol times with respect to 1 mol of metal) and 2.8 parts of oleic acid (0.1 mol times with respect to 1 mol of metal) were added as dispersants. And dissolved. Then, when 73.1 parts (2 mol times of hydrazide group with respect to 1 mol of metal) of a 20% aqueous solution of dihydrazide succinate (hereinafter abbreviated as SUDH) was added dropwise, the liquid color changed from pale yellow to dark brown. The temperature was raised to 40 ° C. to further promote the reaction, and the reaction was allowed to proceed. After standing and separating, excess reducing agent and impurities are removed by taking out the aqueous phase, distilled water is added to the toluene layer several times, washing and separation are repeated, and then dried to obtain silver nanoparticles 1. Obtained. The average particle size of the silver nanoparticles 1 was 13 nm.
製造例2 銀ナノ粒子2の製造
ジエチルアミノエタノール2.3部の代わりに分散剤としてトリエチルアミン2.62部(金属1molに対し0.2mol倍)を用いた以外は製造例2と同様にして、銀ナノ粒子2を得た。銀ナノ粒子2の平均粒子径は5nmであった。
Production Example 2 Production of silver nanoparticles 2 Silver in the same manner as in Production Example 2 except that 2.62 parts of triethylamine (0.2 mol times with respect to 1 mol of metal) was used as a dispersant instead of 2.3 parts of diethylaminoethanol. Nanoparticles 2 were obtained. The average particle size of the silver nanoparticles 2 was 5 nm.
製造例3 銀ナノ粒子3の製造
フラスコに銀ナノ粒子水分散液(品名:730785、粒子径:10nm、ALDRICH社製)を100ml入れ、1−デカンチオールの20%エタノール溶液:270部を20分かけて加え、3時間撹拌した。その後、水600部を20分かけて加え、一晩静置した。析出した固体を水、エタノールにて、洗浄濾過を行い、得られた固体を真空乾燥し、0.99部の銀ナノ粒子3を得た。銀ナノ粒子3の平均粒子径は10nmであった。
Production Example 3 Production of silver nanoparticles 3 Put 100 ml of an aqueous dispersion of silver nanoparticles (product name: 730785, particle diameter: 10 nm, manufactured by ALDRICH) in a flask, and add 1-decanothiol 20% ethanol solution: 270 parts for 20 minutes. The mixture was added over and stirred for 3 hours. Then, 600 parts of water was added over 20 minutes, and the mixture was allowed to stand overnight. The precipitated solid was washed and filtered with water and ethanol, and the obtained solid was vacuum dried to obtain 0.99 parts of silver nanoparticles 3. The average particle size of the silver nanoparticles 3 was 10 nm.
製造例4 銀ナノ粒子4の製造
銀ナノ粒子水分散液として銀ナノ粒子水分散液(品名:730793、粒子径:20nm、ALDRICH社製)を用いた以外は製造例3と同様にして、1.03部の銀ナノ粒子4を得た。銀ナノ粒子4の平均粒子径は20nmであった。
Production Example 4 Production of silver nanoparticles 4 Similar to Production Example 3 except that a silver nanoparticles aqueous dispersion (product name: 730793, particle diameter: 20 nm, manufactured by ALDRICH) was used as the silver nanoparticle aqueous dispersion. 0.03 parts of silver nanoparticles 4 were obtained. The average particle size of the silver nanoparticles 4 was 20 nm.
製造例5 銀ナノ粒子5の製造
銀ナノ粒子水分散液として銀ナノ粒子水分散液(品名:730807、粒子径:40nm、ALDRICH社製)を用いた以外は製造例3と同様にして、1.01部の銀ナノ粒子5を得た。銀ナノ粒子5の平均粒子径は20nmであった。
Production Example 5 Production of Silver Nanoparticles 5 Similar to Production Example 3 except that a silver nanoparticles aqueous dispersion (product name: 730807, particle diameter: 40 nm, manufactured by ALDRICH) was used as the silver nanoparticles aqueous dispersion. 0.01 parts of silver nanoparticles 5 were obtained. The average particle size of the silver nanoparticles 5 was 20 nm.
製造例6 銀ナノ粒子6の製造
銀ナノ粒子水分散液として銀ナノ粒子水分散液(品名:730815、粒子径:60nm、ALDRICH社製)を用いた以外は製造例3と同様にして、0.88部の銀ナノ粒子6を得た。銀ナノ粒子6の平均粒子径は60nmであった。
Production Example 6 Production of silver nanoparticles 6 In the same manner as in Production Example 3, 0, except that a silver nanoparticles aqueous dispersion (product name: 73815, particle diameter: 60 nm, manufactured by ALDRICH) was used as the silver nanoparticles aqueous dispersion. .88 parts of silver nanoparticles 6 were obtained. The average particle size of the silver nanoparticles 6 was 60 nm.
製造例7 銀ナノ粒子7の製造
銀ナノ粒子水分散液として銀ナノ粒子水分散液(品名:730777、粒子径:100nm、ALDRICH社製)を用いた以外は製造例3と同様にして、0.92部の銀ナノ粒子7を得た。銀ナノ粒子7の平均粒子径は100nmであった。
Production Example 7 Production of silver nanoparticles 7 In the same manner as in Production Example 3, 0, except that a silver nanoparticles aqueous dispersion (product name: 730777, particle diameter: 100 nm, manufactured by ALDRICH) was used as the silver nanoparticles aqueous dispersion. .92 parts of silver nanoparticles 7 were obtained. The average particle size of the silver nanoparticles 7 was 100 nm.
製造例8 金ナノ粒子1の製造
セパラブル4口フラスコに冷却管、温度計、窒素ガス導入管、攪拌装置を取り付け、窒素ガスを導入しながらトルエン91.1部、および顔料分散剤としてソルスパース32000(日本ルーブリゾール株式会社製、重量平均分子量約50000)5.9部を仕込み、溶解させた後、20%コハク酸ジヒドラジド水溶液73.1部( 金属1molに対してヒドラジド基2molの比率)を50℃で攪拌しながら滴下し、均一な液滴を生成させた。ビーカーに1M塩化金酸水溶液100部秤取り、攪拌しながら25% アンモニア水27.3部( 金属1molに対してアンモニア4molの比率)滴下した後上記トルエン溶液中に滴下し、30℃ で反応を進行させた。静置、分離した後、水相を取り出すことで過剰の還元剤や不純物を除去し、さらにトルエン層に数回蒸留水を加え、洗浄、分離を繰り返した後、乾燥させて金ナノ粒子1を得た。得られた金ナノ粒子1の平均粒子径は5nmであった。
Production Example 8 Production of gold nanoparticles 1 A cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer are attached to a separable 4-neck flask, and 91.1 parts of toluene while introducing nitrogen gas, and Solsperse 32000 as a pigment dispersant ( 5.9 parts by weight average molecular weight of about 50,000) manufactured by Nippon Lubrizol Co., Ltd. was charged and dissolved, and then 73.1 parts of a 20% dihydrazide succinate aqueous solution (ratio of 2 mol of hydrazide groups to 1 mol of metal) was added at 50 ° C. The mixture was added dropwise with stirring to generate uniform droplets. Weigh 100 parts of a 1M aqueous solution of chloroauric acid in a beaker, add 27.3 parts of 25% ammonia water (ratio of 4 mol of ammonia to 1 mol of metal) while stirring, add dropwise to the above toluene solution, and react at 30 ° C. I made it progress. After allowing to stand and separating, excess reducing agent and impurities are removed by taking out the aqueous phase, distilled water is added to the toluene layer several times, washing and separation are repeated, and then the gold nanoparticles 1 are dried. Obtained. The average particle size of the obtained gold nanoparticles 1 was 5 nm.
製造例9 銅ナノ粒子1の製造
製造例8のペンタン酸金をペンタン酸銅26.6部、還元剤を20%SUDH水溶液292.3部(金属1molに対しヒドラジド基4mol倍)に変更した以外は製造例8と同様にして赤色の銅ナノ粒子1を得た。得られた銅ナノ粒子1の平均粒子径は7nmであった。
Production Example 9 Production of Copper Nanoparticles 1 Except that the gold pentanate in Production Example 8 was changed to 26.6 parts of copper pentanate and the reducing agent was changed to 292.3 parts of a 20% SUDH aqueous solution (4 mol times of hydrazide group with respect to 1 mol of metal). Obtained red copper nanoparticles 1 in the same manner as in Production Example 8. The average particle size of the obtained copper nanoparticles 1 was 7 nm.
その他実施例に使用した金属ナノ粒子(A)を下記に示す。
アルミナノ粒子1:ビックケミー社製 NANOBYK−3610(平均粒子径20nm)
The metal nanoparticles (A) used in other examples are shown below.
Alumino particles 1: NANOBYK-3610 manufactured by Big Chemie (average particle diameter 20 nm )
実施例に使用した反射材(B)を下記に列挙する。
反射材1:福田金属箔粉工業(株)製 XF301(銀フレーク、平均粒子径4〜7μm)
反射材2:東洋アルミニウム(株)製 1260M-S(平均粒子径9μmのアルミフレークをミネラルスピリットに分散した、濃度64%の分散体)。
反射材3:東洋アルミニウム(株)製 1700ML(平均粒子径19μmのアルミフレークをミネラルスピリットに分散した、濃度65%の分散体)。
反射材4:東洋アルミニウム(株)製 5620NS(平均粒子径19μmのアルミフレークをミネラルスピリットに分散した、濃度71%の分散体)。
反射材5:東洋アルミニウム(株)製 5660NS(平均粒子径9μmのアルミフレークをミネラルスピリットに分散した、濃度70%の分散体)。
反射材6:東洋アルミニウム(株)製 WXM5660(平均粒子径9μmのアルミフレークをミネラルスピリットに分散した、濃度63%の分散体)。
反射材7:東洋アルミ社製 54−497(平均粒子径62μmのアルミフレークをミネラルスピリットに分散した、濃度65%の分散体)。
反射材8:トピー工業社製 PDM-20L (合成マイカ、平均粒子径20μm)
The reflective material (B) used in the examples is listed below.
Reflective material 1: Made by Fukuda Metal Foil Powder Industry Co., Ltd. XF301 (silver flakes, average particle size 4-7 μm)
Reflective material 2: 1260M-S manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 9 μm are dispersed in a mineral spirit and having a concentration of 64%).
Reflective material 3: 1700 ML manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 19 μm are dispersed in a mineral spirit and having a concentration of 65%).
Reflective material 4: 5620NS manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 19 μm are dispersed in a mineral spirit and having a concentration of 71%).
Reflective material 5: 5660NS manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 9 μm are dispersed in a mineral spirit and having a concentration of 70%).
Reflective material 6: WXM5660 manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 9 μm are dispersed in a mineral spirit and having a concentration of 63%).
Reflective material 7: 54-497 manufactured by Toyo Aluminum Co., Ltd. (a dispersion in which aluminum flakes having an average particle diameter of 62 μm are dispersed in a mineral spirit and having a concentration of 65%).
Reflective material 8: PDM-20L manufactured by Topy Industries, Ltd. (synthetic mica, average particle size 20 μm)
[実施例1]
銀ナノ粒子1をトルエンに分散し、1.81%濃度の金属ナノ粒子の分散液1を得た。
セルロース系樹脂(C)である「エトセル300(日新化成(株)製)」を溶剤(D)であるトルエンに溶解し、7.5%濃度の樹脂溶液1を得た。
前記金属ナノ粒子の分散液1:9.6部(金属ナノ粒子を0.174部を含む)、反射材1:6部、前記樹脂溶液1:3.84部(セルロース系樹脂を0.288部含む)に溶剤(D)としてトルエン:10.56部を加え、ディスパーにおいて1分撹拌し、光輝性呈色樹脂組成物(固形分濃度20%)を得た。
得られた光輝性呈色樹脂組成物を2g、PETフィルム(100μm 東洋紡工業社製)に滴下し、No.15のアプリケータで塗布し、室温(24℃)で塗膜を十分に乾燥させ光輝性呈色塗膜を得た。後述する方法に従い、色調、発色強さ、色相均一感、光沢感を評価した。
[Example 1]
The silver nanoparticles 1 were dispersed in toluene to obtain a dispersion liquid 1 of metal nanoparticles having a concentration of 1.81%.
"Etocell 300 (manufactured by Nissin Kasei Co., Ltd.)" which is a cellulosic resin (C) was dissolved in toluene which is a solvent (D) to obtain a resin solution 1 having a concentration of 7.5%.
Dispersion of the metal nanoparticles 1: 9.6 parts (including 0.174 parts of metal nanoparticles), reflective material 1: 6 parts, resin solution 1: 3.84 parts (cellulosic resin 0.288 parts) Toluene (10.56 parts) was added as a solvent (D) to (including parts), and the mixture was stirred in a disper for 1 minute to obtain a brilliant colored resin composition (solid content concentration: 20%).
2 g of the obtained brilliant color-developing resin composition was dropped onto a PET film (100 μm manufactured by Toyobo Kogyo Co., Ltd.), applied with an applicator of No. 15, and the coating film was sufficiently dried at room temperature (24 ° C.) to shine. A sex-colored coating film was obtained. The color tone, color development intensity, hue uniformity, and glossiness were evaluated according to the methods described later.
[実施例2〜6]
実施例1で用いた反射材1の代わりに、各分散体に含まれるアルミニウムフレークの量が約6部となるように反射材2、3、5、6、7を用いた以外は、実施例1と同様にして、光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[実施例7]
実施例1で用いた反射材1の代わりに、反射材8を用いた以外は、実施例1と同様にして、光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Examples 2 to 6]
Examples except that the reflectors 2, 3, 5, 6, and 7 were used instead of the reflector 1 used in the first embodiment so that the amount of aluminum flakes contained in each dispersion was about 6 parts. A bright color resin composition and a bright color coating film were obtained in the same manner as in 1, and evaluated in the same manner.
[Example 7]
A bright color resin composition and a bright color coating film were obtained in the same manner as in Example 1 except that the reflective material 8 was used instead of the reflective material 1 used in Example 1. evaluated.
[実施例8]
0.043部の銀ナノ粒子1を含む金属ナノ粒子のトルエンの分散液、6部のアルミニウムフレークを含む反射材4、「エトセル300」を0.288部含むトルエン溶液、および希釈用のトルエンを用い、実施例1と同様にして固形分約20%の光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Example 8]
Toluene dispersion of metal nanoparticles containing 0.043 parts of silver nanoparticles 1, reflective material 4 containing 6 parts of aluminum flakes, toluene solution containing 0.288 parts of "Etocell 300", and toluene for dilution. In the same manner as in Example 1, a brilliant coloring resin composition having a solid content of about 20% and a brilliant coloring coating film were obtained and evaluated in the same manner.
[実施例9〜14]
表1に示すように銀ナノ粒子1の量を代えた以外は、実施例8と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Examples 9 to 14]
A brilliant color resin composition and a brilliant color coating film were obtained in the same manner as in Example 8 except that the amount of silver nanoparticles 1 was changed as shown in Table 1, and evaluated in the same manner.
[実施例15]
0.022部の銀ナノ粒子1を含む金属ナノ粒子のトルエンの分散液、0.75部のアルミニウムフレークを含む反射材4、「エトセル300」を0.008部含むトルエン溶液を用い、トルエンで希釈し、実施例1と同様にして固形分濃度19%の光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Example 15]
Using a toluene dispersion of metal nanoparticles containing 0.022 parts of silver nanoparticles, a reflective material 4 containing 0.75 parts of aluminum flakes, and a toluene solution containing 0.008 parts of "Etocell 300", with toluene. The mixture was diluted to obtain a brightly colored resin composition having a solid content concentration of 19% and a brightly colored coating film in the same manner as in Example 1, and evaluated in the same manner.
[実施例16〜20]
表2に示すように「エトセル300」の量を代えた以外は、実施例15と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Examples 16 to 20]
A bright color resin composition and a bright color coating film were obtained in the same manner as in Example 15 except that the amount of "Etocell 300" was changed as shown in Table 2, and evaluated in the same manner.
[実施例21]
0.005部の銀ナノ粒子1を含む金属ナノ粒子のトルエンの分散液、0.75部のアルミニウムフレークを含む反射材4、「エトセル300」を0.135部含むトルエン溶液を用い、実施例1と同様にして固形分濃度28%の光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[実施例22〜24]
表2に示すように銀ナノ粒子1の量を代えた以外は、実施例21と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Example 21]
Example using a toluene dispersion of metal nanoparticles containing 0.005 parts of silver nanoparticles, a reflective material 4 containing 0.75 parts of aluminum flakes, and a toluene solution containing 0.135 parts of "Etocell 300". A bright color resin composition having a solid content concentration of 28% and a bright color coating film were obtained in the same manner as in No. 1, and evaluated in the same manner.
[Examples 22 to 24]
A bright color resin composition and a bright color coating film were obtained in the same manner as in Example 21 except that the amount of silver nanoparticles 1 was changed as shown in Table 2, and evaluated in the same manner.
[実施例25〜28]
0.022部の銀ナノ粒子1を含む金属ナノ粒子のトルエンの分散液、0.75部のアルミニウムフレークを含む反射材4、「エトセル300」を0.135部含むトルエン溶液を用い、希釈用のトルエンの量を変えた以外は実施例24と同様にして固形分濃度3%(実施例25)、6%(実施例26)、10%(実施例27)、16%(実施例28)の光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Examples 25 to 28]
Dilution using a toluene dispersion of metal nanoparticles containing 0.022 parts of silver nanoparticles 1, a reflective material 4 containing 0.75 parts of aluminum flakes, and a toluene solution containing 0.135 parts of "Etocell 300". Solid content concentration 3% (Example 25), 6% (Example 26), 10% (Example 27), 16% (Example 28) in the same manner as in Example 24 except that the amount of toluene was changed. A brightly colored resin composition and a brightly colored coating film were obtained and evaluated in the same manner.
[実施例29〜37]
表3に示すように金属ナノ粒子の種類と量を代えた以外は実施例10と同様にして、光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Examples 29 to 37]
A bright color resin composition and a bright color coating film were obtained in the same manner as in Example 10 except that the types and amounts of the metal nanoparticles were changed as shown in Table 3, and evaluated in the same manner.
[実施例38〜43]
表3に示すようにセロース樹脂(C)の種類と量、銀ナノ粒子1の量、反射材4の量を代えた以外は、実施例10と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。使用したセルロース系樹脂(C)を下記に列挙する。
エトセル100:日新化成(株)製
エトセル10:日新化成(株)製
MCE−1500:信越化学工業(株)製
PMC−50U:巴工業(株)製
[Examples 38 to 43]
As shown in Table 3, the brilliant color-developing resin composition and brilliance were the same as in Example 10, except that the type and amount of the celose resin (C), the amount of silver nanoparticles 1, and the amount of the reflective material 4 were changed. A color-developing coating film was obtained and evaluated in the same manner. The cellulosic resin (C) used is listed below.
Etocell 100: Nissin Kasei Co., Ltd. Etocell 10: Nissin Kasei Co., Ltd. MCE-1500: Shin-Etsu Chemical Co., Ltd. PMC-50U: Tomoe Engineering Co., Ltd.
[比較例1〜2]
比較例1は反射材を用いなかった以外は、比較例2はセルロース系樹脂を用いなかった以外は、それぞれ実施例1と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Comparative Examples 1-2]
A bright color resin composition and a bright color coating film were used in the same manner as in Example 1, except that Comparative Example 1 did not use a reflective material and Comparative Example 2 did not use a cellulosic resin. Obtained and evaluated in the same manner.
[比較例3〜20]
表4に示すように、セロース樹脂(C)「エトセル300(日新化成(株)製)」に代えて、
比較例3〜6ではポリエステル樹脂「バイロン200(東洋紡(株)製)」を用い、
比較例7〜10ではフェノール樹脂「JER1256(三菱化学(株)製)」を用い、
比較例11〜14ではアクリル樹脂「フォレットGS−1000(綜研化学(株)製)」を用い、
比較例15〜18ではエポキシ樹脂「パウダックスE100(日本ペイント(株)製)」を用い、
比較例19ではアクリル樹脂「VS−1057(星光PMC(株)製)」を用い、
比較例20ではスチレン−アクリル樹脂「US−1071(星光PMC(株)製)」を用い、
各樹脂の量および銀ナノ粒子1の量を代えた以外は、実施例1と同様にして光輝性呈色樹脂組成物、光輝性呈色塗膜を得、同様にして評価した。
[Comparative Examples 3 to 20]
As shown in Table 4, instead of the cerose resin (C) "Etocell 300 (manufactured by Nissin Kasei Co., Ltd.)"
In Comparative Examples 3 to 6, the polyester resin "Byron 200 (manufactured by Toyobo Co., Ltd.)" was used.
In Comparative Examples 7 to 10, the phenol resin "JER1256 (manufactured by Mitsubishi Chemical Corporation)" was used.
In Comparative Examples 11 to 14, the acrylic resin "Foret GS-1000 (manufactured by Soken Chemical Co., Ltd.)" was used.
In Comparative Examples 15 to 18, the epoxy resin "Powdax E100 (manufactured by Nippon Paint Co., Ltd.)" was used.
In Comparative Example 19, acrylic resin "VS-1057 (manufactured by Seiko PMC Corporation)" was used.
In Comparative Example 20, a styrene-acrylic resin "US-1071 (manufactured by Seiko PMC Corporation)" was used.
A bright color resin composition and a bright color coating film were obtained in the same manner as in Example 1 except that the amount of each resin and the amount of silver nanoparticles 1 were changed, and evaluated in the same manner.
色調:目視による色判断およびと吸収スペクトルのピーク位置により判断した。
機種:日立製作所社製U−4100 spectrophotometer
スキャン速度:300nm/min
測定範囲:250〜800nm
Color tone: Judgment was made by visual color judgment and peak position of absorption spectrum.
Model: Hitachi, Ltd. U-4100 spectrophotometer
Scan speed: 300 nm / min
Measuring range: 250-800 nm
発色強さ:光輝性呈色塗膜の外観を目視で評価した。
○:明らかに呈色している。
△:わずかに呈色している。
×:ほぼ呈色していない。(反射材である金属自体の色)
Color development intensity: The appearance of the brilliant color coating film was visually evaluated.
◯: Clearly colored.
Δ: Slightly colored.
X: Almost no coloration. (The color of the metal itself, which is a reflective material)
色相均一感:光輝性呈色塗膜の外観を目視で評価した。
○:色相ムラが観察されなかった。
△:わずかに色相ムラが観察された。
×:色相ムラが観察された。
Hue uniformity: The appearance of the brilliant color coating film was visually evaluated.
◯: No hue unevenness was observed.
Δ: Slight hue unevenness was observed.
X: Hue unevenness was observed.
光沢感:光輝性呈色塗膜の反射光沢感を目視で評価した。
○:光沢感を強く感じた。
△:光沢感を感じた。
×:光沢感を感じなかった。
Glossiness: The reflected glossiness of the brilliant color coating film was visually evaluated.
◯: I felt a strong luster.
Δ: I felt a glossy feeling.
X: No glossiness was felt.
表1〜3の実施例1〜43に示すように、すべての実施例において、発色、色相の均一感、光沢感ともに良好な結果を得た。
実施例8〜14に示すように、金属ナノ粒子の含有量の違いにより色調が変化することを確認した。
実施例15〜24に示すように、セルロース系樹脂の含有量の違いにより色調が変化することを確認した。
実施例29、30、31に示すように、金属種の違いにより色調が変化することを確認した。
実施例13、32〜37、に示されるように、金属ナノ粒子の粒子径の違いにより色調が変化することを確認した
As shown in Examples 1 to 43 of Tables 1 to 3, good results were obtained in all of the examples in terms of color development, hue uniformity, and glossiness.
As shown in Examples 8 to 14, it was confirmed that the color tone changed depending on the difference in the content of the metal nanoparticles.
As shown in Examples 15 to 24, it was confirmed that the color tone changed depending on the difference in the content of the cellulosic resin.
As shown in Examples 29, 30, and 31, it was confirmed that the color tone changed depending on the metal type.
As shown in Examples 13, 32 to 37, it was confirmed that the color tone changes due to the difference in the particle size of the metal nanoparticles.
一方、表4の比較例1〜20に示すように、反射材を含まない組成、セルロース系樹脂を含まない組成、セルロース系樹脂の代わりに他の樹脂を含む組成においては、発色が見られなかった。 On the other hand, as shown in Comparative Examples 1 to 20 in Table 4, no color development was observed in the composition not containing the reflective material, the composition not containing the cellulosic resin, and the composition containing another resin instead of the cellulosic resin. It was.
以上のことより、本発明の光輝性呈色樹脂組成物とそれを塗布、乾燥工程といった簡易的な方法で得られる光輝性呈色塗膜は、発色強度、色相均一感、光沢感といった点で優れた高意匠性を提供でき、更に、金属ナノ粒子の濃度、樹脂濃度、金属種、金属ナノ粒子の粒子径といったパラメータを制御することで多数の色に対応することを提供することができる。 From the above, the brilliant color-developing resin composition of the present invention and the brilliant color-forming coating film obtained by a simple method such as a coating and drying steps thereof are in terms of color development strength, hue uniformity, and glossiness. It is possible to provide excellent designability, and further, it is possible to provide support for a large number of colors by controlling parameters such as the concentration of metal nanoparticles, the resin concentration, the metal species, and the particle size of metal nanoparticles.
Claims (4)
A method for producing a brightly colored article, wherein the brightly colored resin composition according to claim 1 or 2 is applied to the base material (E) and dried.
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