JP2022075610A - 水性塗料組成物及び塗装物品 - Google Patents
水性塗料組成物及び塗装物品 Download PDFInfo
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- JP2022075610A JP2022075610A JP2021180038A JP2021180038A JP2022075610A JP 2022075610 A JP2022075610 A JP 2022075610A JP 2021180038 A JP2021180038 A JP 2021180038A JP 2021180038 A JP2021180038 A JP 2021180038A JP 2022075610 A JP2022075610 A JP 2022075610A
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- fluororesin
- mass
- aqueous coating
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- 239000008199 coating composition Substances 0.000 title claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- 239000011247 coating layer Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011889 copper foil Substances 0.000 abstract description 8
- 229920002313 fluoropolymer Polymers 0.000 abstract description 2
- 239000004811 fluoropolymer Substances 0.000 abstract description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 description 22
- 239000010408 film Substances 0.000 description 21
- -1 fluoroalkyl vinyl ether Chemical compound 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 239000003973 paint Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000003021 water soluble solvent Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910021653 sulphate ion Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
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- 230000002411 adverse Effects 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
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- 125000000962 organic group Chemical group 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
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- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ODYWKGZHVSUTKO-UHFFFAOYSA-N 2-ethylhexan-1-ol;oxirane Chemical class C1CO1.CCCCC(CC)CO ODYWKGZHVSUTKO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 229920006015 heat resistant resin Polymers 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
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- 238000005476 soldering Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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Abstract
Description
数十ギガヘルツレベルの高周波領域の用途で用いられるプリント配線基板にも、誘電特性や吸湿性の観点から、フッ素樹脂の絶縁層を形成した積層体が主に用いられている。
特許文献2には、金属基材上にフッ素樹脂による被覆層を形成するための塗料組成物が開示され、更に、シリカを配合することも開示されている。
特許文献3~5には、フッ素樹脂粒子を含有する水性塗料組成物が開示されている。
さらに、シリカ粒子(B)、非フッ素系界面活性剤(C)及び水(D)を含有し、
上記フッ素樹脂粒子(A)は、平均粒子径が0.05~1000μmであり、
上記シリカ粒子(B)は、平均粒子径が0.1~20μmであり、
上記フッ素樹脂粒子(A)と上記シリカ粒子(B)の配合比は、フッ素樹脂粒子(A):シリカ粒子(B)=10:90~90:10(質量比)であり、
上記フッ素樹脂粒子(A)を塗料固形分100質量%に対して15~80質量%含む
ことを特徴とする水性塗料組成物に関する。
上記グリコール系溶媒(E)は、フッ素樹脂粒子(A)の焼成後に残留しないことが好ましい。
上記シリカ粒子(B)は、水分散性が30質量%以上であることが好ましい。
上記フッ素樹脂粒子(A)は、体積基準累積50%径が0.05~40μmであることが好ましい。
上記非フッ素系界面活性剤(C)は、シリコーン系界面活性剤であることが好ましい。
上記塗装物品は、金属基材上に上述の水性塗料組成物を塗装することによって形成された被覆層を有する塗装物品であってもよい。
上記塗装物品は、プリント基板、基板用誘電材料又は積層回路基板であってもよい。
上記水分散性は、シリカ、水を容器に秤量し、十分にせん断をかけて分散させた後、撹拌を止めた際にシリカ表面が濡れ、数分間沈殿が生じ無いことを確認した。
上記シリコーン化合物としては特に限定されず、従来公知のシリコーン化合物を使用することができる。例えば、シランカップリング剤及びオルガノシラザンからなる群より選択される少なくとも一種を含むことが好ましい。
上記シリコーン化合物の表面処理量は、シリカ粒子表面への表面処理剤の反応量が単位表面積(nm2)あたり0.1~10個であることが好ましく、0.3~7個であることがより好ましい。
また、シリカ粒子(B)は粉体をそのまま使用してもよく、樹脂中に分散させたものを用いてもよい。
一般式(110):CF2=CF-ORf111
(式中、Rf111は、パーフルオロ有機基を表す。)で表されるフルオロモノマー、
一般式(120):CF2=CF-OCH2-Rf121
(式中、Rf121は、炭素数1~5のパーフルオロアルキル基)で表されるフルオロモ
ノマー、
一般式(130):CF2=CFOCF2ORf131
(式中、Rf131は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5
~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は
分岐状パーフルオロオキシアルキル基である。)で表されるフルオロモノマー、
一般式(140):CF2=CFO(CF2CF(Y141)O)m(CF2)nF
(式中、Y141はフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数であ
る。nは1~4の整数である。)で表されるフルオロモノマー、及び、
一般式(150):CF2=CF-O-(CF2CFY151-O)n-(CFY152
)m-A151
(式中、Y151は、フッ素原子、塩素原子、-SO2F基又はパーフルオロアルキル基を表す。パーフルオロアルキル基は、エーテル性の酸素及び-SO2F基を含んでもよい。nは、0~3の整数を表す。n個のY151は、同一であってもよいし異なっていてもよい。Y152は、フッ素原子、塩素原子又は-SO2F基を表す。mは、1~5の整数を表す。m個のY152は、同一であってもよいし異なっていてもよい。A151は、-SO2X151、-COZ151又は-POZ152Z153を表す。X151は、F、Cl、Br、I、-OR151又は-NR152R153を表す。Z151、Z152及びZ153は、同一又は異なって、-NR154R155又は-OR156を表す。R151、R152、R153、R154、R155及びR156は、同一又は異なって、H、アンモニウム、アルカリ金属、フッ素原子を含んでも良いアルキル基、アリール基、若しくはスルホニル含有基を表す。)で表されるフルオロモノマーからなる群より選択される少なくとも1種であることが好ましい。
一般式(110)で表されるフルオロモノマーとしては、更に、上記一般式(110)において、Rf111が炭素数4~9のパーフルオロ(アルコキシアルキル)基であるもの、Rf111が下記式:
一般式(160):CF2=CF-ORf161
(式中、Rf161は、炭素数1~10のパーフルオロアルキル基を表す。)で表されるフルオロモノマーが好ましい。Rf161は、炭素数が1~5のパーフルオロアルキル基であることが好ましい。
ら1個の水素原子を除去して形成される基を意味する。
当該「有機基」の例は、
1個以上の置換基を有していてもよいアルキル基、
1個以上の置換基を有していてもよいアルケニル基、
1個以上の置換基を有していてもよいアルキニル基、
1個以上の置換基を有していてもよいシクロアルキル基、
1個以上の置換基を有していてもよいシクロアルケニル基、
1個以上の置換基を有していてもよいシクロアルカジエニル基、
1個以上の置換基を有していてもよいアリール基、
1個以上の置換基を有していてもよいアラルキル基、
1個以上の置換基を有していてもよい非芳香族複素環基、
1個以上の置換基を有していてもよいヘテロアリール基、
シアノ基、ホルミル基、RaO-、RaCO-、RaSO2-、RaCOO-、RaNR
aCO-、RaCONRa-、RaOCO-、RaOSO2-、及び、RaNRbSO2
-
(これらの式中、Raは、独立して、
1個以上の置換基を有していてもよいアルキル基、
1個以上の置換基を有していてもよいアルケニル基、
1個以上の置換基を有していてもよいアルキニル基、
1個以上の置換基を有していてもよいシクロアルキル基、
1個以上の置換基を有していてもよいシクロアルケニル基、
1個以上の置換基を有していてもよいシクロアルカジエニル基、
1個以上の置換基を有していてもよいアリール基、
1個以上の置換基を有していてもよいアラルキル基、
1個以上の置換基を有していてもよい非芳香族複素環基、又は、
1個以上の置換基を有していてもよいヘテロアリール基、
Rbは、独立して、H又は1個以上の置換基を有していてもよいアルキル基である)
を包含する。
上記有機基としては、1個以上の置換基を有していてもよいアルキル基が好ましい。
上記平均粒子径は、例えば、レーザー回折・散乱法によって測定した体積平均粒子径である。上記フッ素樹脂粒子(A)を所望の粒子径とするために、ふるいや風力による分級を行ってもよい。
本開示において、水性塗料組成物の固形分濃度は、加熱残存質量測定法により測定するものである。
具体例として、DBE‐712、DBE‐821(アヅマックス社製)、KPシリーズ、KF‐6015、KF‐6016、KF‐6017、KF‐6028(信越化学工業社製)、ABIL‐EM97(ゴールドシュミット社製)、ポリフローKL‐100、ポリフローKL‐401、ポリフローKL‐402、ポリフローKL‐700(共栄社化学製)、「FZ-77」(東レ・ダウコーニング株式会社製)、「BYK-333」(ビックケミー・ジャパン株式会社製)等が挙げられる。
さらに、本開示の水性塗料組成物は、水と併用して水溶性溶媒を含有することが好ましい。上記水溶性溶媒は、上記フッ素樹脂粒子(A)を濡らす働きを有し、更に高沸点のものは、塗装後の乾燥時に樹脂同士をつなぎ、クラックの発生を防止する乾燥遅延剤として作用する。高沸点溶媒でも、フッ素樹脂の焼成温度では蒸発するので、被覆膜に悪影響を及ぼすことはない。
上記物品基材は、表面加工されたものであってもよい。上記表面加工としては、サンドブラストを用いて所望の粗度まで粗面化するもの、粒子を付着させて粗面化したもの、金属酸化防止処理を施したものが挙げられる。
ステップ1.予備粉砕(乾式粉砕)
懸濁重合によりテトラフルオロエチレン(TFE)/パーフルオロビニルエーテル(PFVE)共重合体(PFA:融点=300℃、MFR=25g/10min)を製造し、得られた乾燥粉末をそのまま、エアジェットミル装置(アイエムマテリアル社製)により粉砕し、平均粒子径10μmの微粉末を得た。
ステップ1.により得られたPFA微粉末100質量部に対して、アセチレングリコール系分散剤(サーフィノール440、エアプロダクツジャパン社製)10質量部、シリコーン系界面活性剤(KP-106、信越化学工業社製)10質量部及びイオン交換水280質量部をPFA微粉末と十分に撹拌・混合し、PFA分散液を得た。
ステップ2.により得られたPFA分散液を100メッシュ金網で濾過した後、高圧乳化機(ナノマイザーNMII、吉田機械興業社製、粉砕圧力=200MPa)に通し、平均粒子径0.20μm(CAPA700:堀場製作所社製による測定)のPFA微粉末分散液(フッ素樹脂粒子(A-1)分散液)を得た。
得られたPFA微粉末の体積基準累積50%径は、0.20μmであった。
ステップ3.により得られたPFA微粉末分散液100質量部に対し、シリコーン系界面活性剤(KP-106、信越化学工業社製)2.5質量部、エチレングリコール(双葉化学社製)2.5質量部、シリカ粒子58質量部、更に、イオン交換水20質量部を加え塗料化した。
なお、使用したシリカ粒子は以下の通りである。
B-1:アドマテックス製アドマファインSC2500-SQ 平均粒子径0.5μm,比表面積6.1m2/g、最大粒子径1.7μm
B-2:アドマテックス製アドマファインSC6500-SQ 平均粒子径1.5μm,比表面積4.0m2/g、最大粒子径4.2μm
いずれのシリカも、70質量%で良い水分散性を示すことを確認した。
各配合成分を表1に示したように変更したこと以外は、実施例1と同様にして塗料化した。
平均粒子径25μmのPFA微粉末を用い、湿式粉砕を省略したこと以外は、実施例1と同様にして塗料化した(フッ素樹脂粒子(A-2)分散液)。
得られたPFA微粉末の体積基準累積50%径は、22.9μmであった。
各配合成分を表2に示したように変更したこと以外は、実施例9と同様にして塗料化した。
バインダー樹脂としてポリビニルアルコール(PVA、けん化度:78~82mol%富士フィルム和光純薬株式会社製)10wt%水溶液10質量部を加え、各配合成分を表3に示したように変更したこと以外は、実施例9と同様にして塗料化した。
各配合成分を表4に示したように変更したこと以外は、実施例1及び9と同様に塗料化した。
フッ素系界面活性剤として、フタージェント250(ネオス社製)2.5質量部を加えた。なお、比較例4は、エチレングリコールを添加せず塗料化した。
以下の方法にしたがって、樹脂被覆層を得た。
銅箔(福田金属箔粉工業製 CF-V9S-SV-18)上にバーコーター(No.40)を用いて塗料を塗工した。塗工後の銅箔を130℃で15分間乾燥させて粉落ちを評価した。さらに窒素ガス雰囲気下350℃15分間焼成し膜厚30μmの塗膜を作製した。焼成後の塗膜にはエチレングリコールは残留していなかった。
得られた銅張積層体について、反りの有無を目視で確認した。
×:円筒状に丸まった。
△:浮きが見られた。
〇:浮きが見られなかった。
指で撫でた場合と、指圧した場合とで、フッ素樹脂パウダーの脱落を目視で確認した。
×:脱落が見られた。
〇:脱落が見られなかった。
塗工表面をSEMで確認し、シリカ粒子の変形の有無を確認した。
×:変形あり。
〇:変形なし。
上記シリカ粒子(B)は、最大粒子径が10μm以下であることが好ましい。
Claims (11)
- 溶融成型可能なフッ素樹脂粒子(A)を含有する水性塗料組成物であって、
さらに、シリカ粒子(B)、非フッ素系界面活性剤(C)及び水(D)を含有し、
前記フッ素樹脂粒子(A)は、平均粒子径が0.05~1000μmであり、
前記シリカ粒子(B)は、平均粒子径が0.1~20μmであり、
前記フッ素樹脂粒子(A)と前記シリカ粒子(B)の配合比は、フッ素樹脂粒子(A):シリカ粒子(B)=10:90~90:10(質量比)であり、
前記フッ素樹脂粒子(A)を塗料固形分100質量%に対して15~80質量%含む
ことを特徴とする水性塗料組成物。 - さらに、グリコール系溶媒(E)を含有する請求項1記載の水性塗料組成物。
- グリコール系溶媒(E)は、フッ素樹脂粒子(A)の焼成後に残留しない請求項2記載の水性塗料組成物。
- シリカ粒子(B)は、最大粒子径が10μm以下である請求項1~3のいずれか記載の水性塗料組成物。
- シリカ粒子(B)は、水分散性が30質量%以上である請求項1~4のいずれか記載の水性塗料組成物。
- フッ素樹脂粒子(A)は、平均粒子径が0.1~100μmである請求項1~5のいずれか記載の水性塗料組成物。
- フッ素樹脂粒子(A)は、体積基準累積50%径が0.05~40μmである請求項1~6のいずれか記載の水性塗料組成物。
- 非フッ素系界面活性剤(C)は、シリコーン系界面活性剤である請求項1~7のいずれか記載の水性塗料組成物。
- 請求項1~8のいずれかに記載の水性塗料組成物を塗装することによって形成された被覆層を有することを特徴とする塗装物品。
- 金属基材上に請求項1~8のいずれかに記載の水性塗料組成物を塗装することによって形成された被覆層を有する請求項9記載の塗装物品。
- プリント基板、基板用誘電材料又は積層回路基板である請求項9又は10記載の塗装物品。
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