JP5008399B2 - 有機チタン化物及び/又は有機ジルコン化物を含有する水性分散液の形態である防錆塗料組成物 - Google Patents
有機チタン化物及び/又は有機ジルコン化物を含有する水性分散液の形態である防錆塗料組成物 Download PDFInfo
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- JP5008399B2 JP5008399B2 JP2006552720A JP2006552720A JP5008399B2 JP 5008399 B2 JP5008399 B2 JP 5008399B2 JP 2006552720 A JP2006552720 A JP 2006552720A JP 2006552720 A JP2006552720 A JP 2006552720A JP 5008399 B2 JP5008399 B2 JP 5008399B2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 85
- 239000008199 coating composition Substances 0.000 title claims description 47
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 26
- 230000003449 preventive effect Effects 0.000 title claims description 13
- 239000006185 dispersion Substances 0.000 title claims description 7
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- 229910052751 metal Inorganic materials 0.000 claims description 71
- 239000002184 metal Substances 0.000 claims description 71
- 229910000077 silane Inorganic materials 0.000 claims description 57
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 45
- 239000012074 organic phase Substances 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 15
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 11
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 10
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- 229910000831 Steel Inorganic materials 0.000 claims description 8
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
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- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011135 tin Substances 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims 3
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 claims 1
- QPLNUHHRGZVCLQ-UHFFFAOYSA-K aluminum;[oxido(phosphonooxy)phosphoryl] phosphate Chemical group [Al+3].OP([O-])(=O)OP([O-])(=O)OP(O)([O-])=O QPLNUHHRGZVCLQ-UHFFFAOYSA-K 0.000 claims 1
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- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 description 26
- -1 zircon compound Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- JPJZHBHNQJPGSG-UHFFFAOYSA-N titanium;zirconium;tetrahydrate Chemical compound O.O.O.O.[Ti].[Zr] JPJZHBHNQJPGSG-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
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Description
1) この有機チタン化物の水和酸化チタンTi(OH)4への転化:
Ti(OC4H9)4 + 4H2O → Ti(OH)4 + 4C4H9OH
2) 次いで、二酸化チタンTiO2の形成:
Ti(OH)4 → TiO2 + 2H2O
したがって、二酸化チタンの形成を避けるためには、有機相と相溶性のあるチタン化物とジルコン化物とは、高度に無水の状況下で使用されなければならない。その結果、空気、湿気、又は微量の水分と接触することによって有機チタン化物が二酸化チタンへと加水分解されることを避けたいのであれば、有機相と相溶性のあるチタン化物又はジルコン化物を含有する無水組成物の調製は、非常に規制の多い慎重な取り扱いが要求される。
−有機チタン化物及び/又は有機ジルコン化物:0.3〜24%
−微粒子状金属、又は複数種の微粒子状金属の混合物:10〜40%
−シラン基材のバインダー:1〜25%
−水:全量を100%にする量
ここにおいて、有機チタン化物及び/又は有機ジルコン化物とシラン基材のバインダーとの合計が5〜25%である。
−水に可溶な有機溶媒:0〜20%
−シラン基材のバインダー:20〜50%
−C1〜C8テトラアルキルチタネート及び/又はジルコネート:5〜25%
−水:40〜70%。
(1) シランの加水分解:
R-Si(OR')3+3H2O ←→ R-Si(OH)3+3R'OH
(2) 有機チタン化物又は有機ジルコン化物の水和酸化チタン又は水和酸化ジルコニウムへの転換
X-(OR”)4+4H2O ←→ X(OH)4+4R”OH
(3) 水和酸化チタン又は水和酸化ジルコニウムと加水分解シランとの反応
2R-Si(OH)3+X(OH)4 ←→ X(OH)2・[R-SiO(OH)2]。
以下の実施例はこの発明を使用する方法を示すが、この発明をいかなる形態においても制限することはない。
他に表示されない限り、通常、試験板は冷間でラミネートされた低炭素含有量のステンレス鋼板である。これらの試験板の製作は、まず、洗浄溶液への浸漬から始めることができる。そして、試験板を洗浄パッドで拭き取り、次いで水ですすぎ、さらに洗浄溶液に浸漬することができる。洗浄溶液を除去した後に、試験板を水道水ですすいで乾燥する。
洗浄した板を塗料組成物に浸漬し、板を引き上げて過剰量の組成物を排出する。緩やかに撹拌しながらこの操作を何度か繰り返した後、直ちに焼き付けるか、又は塗料が手で触って乾いている程度まで周囲温度で乾燥するか、低めの温度で予備硬化させ、その後に焼き付ける、という通常の方法で被覆を行う。塗膜重量(mg/cm2)は、被覆の前後で計量して、その差によって求める。
被覆された板の耐腐蝕性を、ISO 9227に規定の塗料及びワニス用の標準塩水噴霧(塩水霧)試験によって測定した。この試験において、試験板は一定温度に保たれたチャンバに置かれ、そこで所定時間5%の塩水の微細な噴霧(ミスト)に曝され、水ですすがれて乾燥される。試験に付された板の腐蝕の程度は赤錆のパーセンテージで表現することができる。
2 エカルト・ヴェルケ(Eckart Werke)によって販売されているAlu Chromal III粉末
3 γ-グリシドオキシプロピルトリメトキシシラン(クランプトン(Crompton))
4 珪酸ナトリウム(ローディア(Rhodia))
5 R40のエトキシル化ノニルフェノール、販売会社:オキシテーノ・エス・アー(Oxiteno SA)(ブラジル)
6 R95のエトキシル化ノニルフェノール、販売会社:オキシテーノ・エス・アー(Oxiteno SA)(ブラジル)
7 ローディア(Rhodia)が販売するKelzan/Rhodopol 23
8 販売会社:デュポン・ドゥ・ヌムール(Dupont de Nemours)
9 販売会社:ラヴォレー(Lavollee)
10 販売会社:コグニス・エス・アー
以下の薬剤をこの順番に混合する。
b) 50.00gのSilane A-187
c) 20.00gのTBT(テトラブチルチタネート)
得られた溶液を24時間放置する。TnBTの前にDPGへ導入されるシランは、DPG中に任意に存在する水と反応する。DPG中に任意に存在する水と有機チタン化物との制御されない反応は、このようにして避けることができる。
i) 0.125 mlの水を滴下し、溶液を10分間放置する。
ii) ステップi)を5回繰り返す。
iii) 残量の水を0.25 ml/分/3回で、又は20秒ごとに約0.083 mlずつ添加する。
導入されるTnBTの量が30.00gである外は、実施例4と同様にプロセスを進める。無色の、場合によってはわずかに黄色がかった有機チタン化物の水性組成物が得られる。
導入されるTnBTの量が40.00gである外は、実施例4と同様にプロセスを進める。無色の、場合によってはわずかに黄色がかった有機チタン化物の水性組成物が得られる。
導入されるTnBTの量が40.00g、Silane A 187の量が70.00gである外は、実施例4と同様にプロセスを進める。無色の、場合によってはわずかに黄色がかった有機チタン化物の水性組成物が得られる。
実施例6で得られた有機チタン化物の水性組成物を、防錆塗料組成物に導入する。以下の表6は、このようにして得られた組成物の組成と、有機チタン化物を含有しない従来技術の防錆塗料組成物の組成とを示している。
少量(10, 20, 又は30 g/kg)の有機チタン化物を添加することによって、使用されるシランと酸化モリブデンの量を減らすことができ、これによって、良好な防錆結果を維持しながら経費を抑制することができる。
a) チタン化物
i) 水相の調製
10重量部のTYZOR(R) TEP(デュポン・ドゥ・ヌムールにより供給、60%乾燥抽出物)と25重量部のSilane A-187とを、電磁撹拌しながら1時間混合する。次いで、113重量部の水を素早く加え、電磁撹拌を1時間行う。
有機相は次の成分を含有する。
−ジプロピレングリコール 75重量部
−Remcopal N4 10012 14重量部
−Remcopal N9 100113 15.5重量部
−Silane A 187 70重量部
−亜鉛ペースト 235重量部
−Aluminium Stapa14 30重量部
−Schwego foam 832515 5.5重量部
−酸化イットリウム16 30重量部
−エアロジル 38017 0.4重量部
12 エトキシル化ノニルフェノール型の湿潤剤(CECA)
13 エトキシル化ノニルフェノール型の湿潤剤(CECA)
14 エカルト・ヴェルケ(Eckart Werke)によって市販されているジプロピレングリコールに溶解した80%Chromal VIII
15 炭化水素型の消泡剤(シュヴェクマン(Schwegman))
16 純度99.99%のY2O3
17 シリカ型の抗沈降剤(デグサ(Degussa))。
−本発明による浴:本発明による防錆塗料組成物:ステップi)とii)とでそれぞれ得られた油相と水相とを混合した。
−参照浴:参照組成物
参照組成物の水相は以下の成分を含有する。
珪酸ナトリウム20 N 32 8.8重量部
硼酸 8.2重量部
酸化モリブデン 9重量部
Silane A 187 31重量部
参照組成物の有機相は、本発明による浴の有機相(ステップii))と同じ組成を有している。
b2xG:スクリュー又はプレートをチッピング、即ち、衝撃のスパッタリング2回に付した後の塩水霧試験の結果。
c自己犠牲保護:金属への被覆に切り込みを入れた後、赤錆が発生することなく塩水霧に曝すことのできた時間数
d表示5:表面の1%未満に赤錆が発生する程度の結果
e表示4.8:表面の5%未満に赤錆が発生する程度の結果。
Claims (26)
- 下記の比率(質量%)で
−有機相と相容性を有する有機チタン化物及び/又は有機ジルコン化物:0.3〜24%
−微粒状金属又は複数種の微粒子状金属の混合物:10〜40%
−シラン基材のバインダー:1〜20%
−水:全量を100%にする量、
(ここにおいて、有機チタン化物及び/又は有機ジルコン化物とシラン基材のバインダーとの合計が5〜25%である。)を含有する水性分散液中の微粒子状金属を基材とする金属部品用の塗料組成物を得て、
スプレー法、浸漬排水法又は浸漬遠心分離法によって塗料層を形成し、
該塗料層を、熱エネルギーを供給して180℃〜350℃の温度で焼き付け操作に付し、それによって防錆被覆を形成することによって得られる防錆被覆を備えた金属製の基板。 - 前記有機相と相溶性を有する有機チタン化物がC 1 〜C 8 テトラアルキルチタネートであり、前記有機相と相溶性を有する有機ジルコン化物がC 1 〜C 8 テトラアルキルジルコネートであることを特徴とする、請求項1に記載の防錆被覆を備えた金属製の基板。
- 前記有機相と相溶性を有する有機チタン化物が、テトラエチルチタネート、テトラ-n-ブチルチタネート及びオクチレングリコールチタネートよりなる群から選択され、前記有機相と相溶性を有する有機ジルコン化物が、テトラ-n-プロピルジルコネート及びテトラ-n-ブチルジルコネートよりなる群から選択されることを特徴とする、請求項2に記載の防錆被覆を備えた金属製の基板。
- 前記微粒子状金属が、亜鉛及びアルミニウム、並びにこれらの合金及び混合物、又はマンガン、マグネシウム、錫、若しくはガルファンと前記金属との合金から選択されることを特徴とする、請求項1〜3のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記シラン基材のバインダーは、C 1 〜C 4 アルコキシルラジカルから選択される、ヒドロキシル機能を有する少なくとも1つの加水分解可能な官能基を有するシランであることを特徴とする、請求項1〜4のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記シランがエポキシ官能基をさらに有していることを特徴とする、請求項1〜5のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記シランがエポキシ官能基を有するジメトキシシラン若しくはトリメトキシシラン、エポキシ官能基を有するジエトキシシラン若しくはトリエトキシシラン、又はそれらの混合物から選択されることを特徴とする、請求項6に記載の防錆被覆を備えた金属製の基板。
- 前記シランがγ−グリシドオキシプロピルトリメトキシシラン、又はβ-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランから選択されることを特徴とする、請求項7に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、該塗料組成物の全重量に対して1〜30重量%の有機溶媒、又は有機溶媒の混合物をさらに含有することを特徴とする、請求項1〜8のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記有機溶媒が、グリコール溶媒、アセテート、プロピレングリコール、ポリプロピレングリコール、ニトロプロパン、アルコール、ケトン、プロピレングリコールメチルエーテル、2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート(テクサノール)、ホワイトスピリット、及びこれらの混合物よりなる群から選択されることを特徴とする、請求項9に記載の防錆被覆を備えた金属製の基板。
- 前記グリコール溶媒がグリコールエーテルであることを特徴とする、請求項10に記載の防錆被覆を備えた金属製の基板。
- 前記グリコールエーテルが、ジエチレングリコール、トリエチレングリコール及びジプロピレングリコールよりなる群から選択されることを特徴とする、請求項11に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、該塗料組成物の全重量に対して0.1〜7重量%の酸化モリブデンをさらに含有することを特徴とする、請求項1〜12のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、酸化物又は塩の形態のイットリウム、ジルコニウム、ランタン、セリウム、プラセオジウムよりなる群から選択される該塗料組成物の防錆性の強化剤を、塗料組成物の全重量に対して0.5〜10重量%の割合でさらに含有し、又は、組成物の全重量に対して0.2〜4重量%の腐蝕抑制顔料をさらに含有することを特徴とする、請求項1〜13のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記防錆性の強化剤が酸化イットリウムY 2 O 3 であり、前記腐蝕抑制顔料がアルミニウムトリホスフェートであることを特徴とする、請求項14に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、増粘剤及び/又は湿潤剤をさらに含有することを特徴とする、請求項1〜15のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、該塗料組成物の全重量に対して0.005〜7重量%の前記増粘剤、及び/又は該塗料組成物の全重量に対して0.1〜4重量%の前記湿潤剤を含有することを特徴とする、請求項16に記載の防錆被覆を備えた金属製の基板。
- 前記焼き付け操作が、対流、赤外、又は誘導によって行われることを特徴とする、請求項1に記載の防錆被覆を備えた金属製の基板。
- 前記焼き付け操作が、対流又は赤外の場合は10分〜60分間、誘導の場合は30秒〜5分間行われることを特徴とする、請求項18に記載の防錆被覆を備えた金属製の基板。
- 焼き付け操作の前に、熱エネルギーを供給することによって被覆された金属部品を乾燥操作に付すことを特徴とする、請求項1〜請求項19のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記乾燥操作が、対流、赤外、又は誘導によって行われることを特徴とする、請求項20に記載の防錆被覆を備えた金属製の基板。
- 前記乾燥操作が、対流又は赤外の場合は作動状態で約10分〜30分間、誘導の場合は30秒〜5分間、30〜250℃の温度で行われることを特徴とする、請求項21に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、乾燥被覆膜の厚さが3μm〜30μmとなるように、保護される金属部品に塗布されることを特徴とする、請求項1〜22のいずれか一項に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、乾燥被覆膜の厚さが4μm〜12μmとなるように、保護される金属部品に塗布されることを特徴とする、請求項23に記載の防錆被覆を備えた金属製の基板。
- 前記塗料組成物が、乾燥被覆膜の厚さが5μm〜10μmとなるように、保護される金属部品に塗布されることを特徴とする、請求項24に記載の防錆被覆を備えた金属製の基板。
- 前記金属製の基板が、鋼鉄、亜鉛で被覆された鋼鉄、若しくは亜鉛の基材層を有する鋼鉄、鋳鉄、又はアルミニウムで出来ていることを特徴とする、請求項1に記載の防錆被覆を備えた金属製の基板。
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