JP2005336002A - Nitrite ion-type hydrotalcite powder, its manufacturing method, rust-preventive composition, and rust-preventive coating composition - Google Patents
Nitrite ion-type hydrotalcite powder, its manufacturing method, rust-preventive composition, and rust-preventive coating composition Download PDFInfo
- Publication number
- JP2005336002A JP2005336002A JP2004155732A JP2004155732A JP2005336002A JP 2005336002 A JP2005336002 A JP 2005336002A JP 2004155732 A JP2004155732 A JP 2004155732A JP 2004155732 A JP2004155732 A JP 2004155732A JP 2005336002 A JP2005336002 A JP 2005336002A
- Authority
- JP
- Japan
- Prior art keywords
- nitrite ion
- hydrotalcite powder
- rust
- nitrite
- hydrotalcite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 77
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000008199 coating composition Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229940005654 nitrite ion Drugs 0.000 claims abstract description 64
- -1 nitrite ions Chemical class 0.000 claims abstract description 44
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract 4
- 230000003449 preventive effect Effects 0.000 claims description 49
- 150000001450 anions Chemical class 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- 239000007769 metal material Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 40
- 239000002253 acid Substances 0.000 description 26
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 239000010452 phosphate Substances 0.000 description 22
- 239000011777 magnesium Substances 0.000 description 20
- 239000003973 paint Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 17
- 239000011701 zinc Substances 0.000 description 15
- 239000002131 composite material Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000011575 calcium Substances 0.000 description 13
- 229910052712 strontium Inorganic materials 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 230000002265 prevention Effects 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 9
- 229910052788 barium Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000005349 anion exchange Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000790 scattering method Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JJGGIYYGVKGMQZ-UHFFFAOYSA-N 1,2,4-triazole-3,4,5-triamine Chemical compound NC1=NN=C(N)N1N JJGGIYYGVKGMQZ-UHFFFAOYSA-N 0.000 description 1
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NBUGSEZNBDVRPG-UHFFFAOYSA-N B([O-])([O-])[O-].[Ca+2].[Ca+2] Chemical compound B([O-])([O-])[O-].[Ca+2].[Ca+2] NBUGSEZNBDVRPG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004132 Calcium polyphosphate Substances 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- JWPLVHLVNPVUKI-UHFFFAOYSA-N [1-[bis(2-phenyl-1-phosphonoethenyl)amino]-2-phenylethenyl]phosphonic acid Chemical compound C=1C=CC=CC=1C=C(P(O)(O)=O)N(C(=CC=1C=CC=CC=1)P(O)(O)=O)C(P(O)(=O)O)=CC1=CC=CC=C1 JWPLVHLVNPVUKI-UHFFFAOYSA-N 0.000 description 1
- VCQAIUIHXQEIHD-UHFFFAOYSA-N [Zn].[Sr] Chemical compound [Zn].[Sr] VCQAIUIHXQEIHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 description 1
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 description 1
- XNJIKBGDNBEQME-UHFFFAOYSA-L barium(2+);dioxido(oxo)phosphanium Chemical compound [Ba+2].[O-][P+]([O-])=O.[O-][P+]([O-])=O XNJIKBGDNBEQME-UHFFFAOYSA-L 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- FAARTQSZKSBAOS-UHFFFAOYSA-N barium(2+);diphosphite Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])[O-].[O-]P([O-])[O-] FAARTQSZKSBAOS-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000019827 calcium polyphosphate Nutrition 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical compound [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 description 1
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 1
- VSFBSEDSFCLXNI-UHFFFAOYSA-N calcium;zinc;phosphite Chemical compound [Ca+2].[Zn+2].[O-]P([O-])[O-] VSFBSEDSFCLXNI-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SPBMDAHKYSRJFO-UHFFFAOYSA-N didodecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)OCCCCCCCCCCCC SPBMDAHKYSRJFO-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- BSVSPZGXUSFFEG-UHFFFAOYSA-N dihydroxy(oxo)silane;tetrakis(2-hydroxyethyl)azanium Chemical compound O[Si](O)=O.OCC[N+](CCO)(CCO)CCO BSVSPZGXUSFFEG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- DXMRKRXRMGYFDG-UHFFFAOYSA-N dipotassium;hydrogen borate Chemical compound [K+].[K+].OB([O-])[O-] DXMRKRXRMGYFDG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLNZHTHIPQGEMX-UHFFFAOYSA-N ethane propane Chemical compound CCC.CCC.CC.CC XLNZHTHIPQGEMX-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- APURLPHDHPNUFL-UHFFFAOYSA-M fluoroaluminum Chemical compound [Al]F APURLPHDHPNUFL-UHFFFAOYSA-M 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- IJPPOBHVBIMQFD-UHFFFAOYSA-K magnesium;zinc;phosphate Chemical compound [Mg+2].[Zn+2].[O-]P([O-])([O-])=O IJPPOBHVBIMQFD-UHFFFAOYSA-K 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- STMLQIACVZOCHU-UHFFFAOYSA-N octan-2-yl dihydrogen phosphate Chemical compound CCCCCCC(C)OP(O)(O)=O STMLQIACVZOCHU-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- IDQWCBURUBJWFM-UHFFFAOYSA-N potassium;zinc;phosphite Chemical compound [K+].[Zn+2].[O-]P([O-])[O-] IDQWCBURUBJWFM-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical class F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JCDCUOAMVBQBTH-UHFFFAOYSA-N tetrabutoxy silicate Chemical compound CCCCOO[Si](OOCCCC)(OOCCCC)OOCCCC JCDCUOAMVBQBTH-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- LNSYCBFBTCINRL-UHFFFAOYSA-N tristrontium;diborate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]B([O-])[O-].[O-]B([O-])[O-] LNSYCBFBTCINRL-UHFFFAOYSA-N 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- GKTPAOCBXFIJAG-UHFFFAOYSA-N tristrontium;diphosphite Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])[O-].[O-]P([O-])[O-] GKTPAOCBXFIJAG-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
- VUDJAFZYSMINQA-UHFFFAOYSA-L zinc metaphosphate Chemical compound [Zn+2].[O-]P(=O)=O.[O-]P(=O)=O VUDJAFZYSMINQA-UHFFFAOYSA-L 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
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、金属材料に優れた防錆性を付与することができる亜硝酸イオン型ハイドロタルサイト粉末、その製造方法、これを用いた防錆剤組成物及び防錆塗料組成物に関するものである。 The present invention relates to a nitrite ion type hydrotalcite powder capable of imparting excellent rust prevention properties to a metal material, a method for producing the same, a rust preventive composition using the same, and a rust preventive coating composition. .
ハイドロタルサイトは、代表的には下記一般式（３） Hydrotalcite is typically represented by the following general formula (3)
（式中、Ａn-はｎ価のアニオンを表わし、ｘは０．２≦ｘ≦０．３３）で表わされる無機アニオン交換体で、主に塩化ビニル樹脂の安定剤として用いられているが、更なる用途が開発されている。 (Wherein, A n-represents an n-valent anion, x is 0.2 ≦ x ≦ 0.33) in an inorganic anion exchanger represented by, but is mainly used as a stabilizer for a vinyl chloride resin Further applications are being developed.
例えば、前記一般式（３）の式中のＡのアニオンがＮＯ2 -である亜硝酸イオン型ハイドロタルサイトを防錆顔料、或いは防錆塗料組成物として用いることも提案されている（例えば、特許文献１および特許文献２参照）。 For example, it has also been proposed to use a nitrite ion type hydrotalcite in which the anion of A in the formula of the general formula (3) is NO 2 − as a rust preventive pigment or a rust preventive coating composition (for example, (See Patent Document 1 and Patent Document 2).
従来、亜硝酸イオン型ハイドロタルサイトの製造方法は、例えば、アルカリの存在下に水溶性マグネシウム化合物と、水溶性アルミニウム化合物との反応により得る方法（例えば、特許文献１、特許文献３、特許文献４、特許文献５、特許文献６参照）、或いは特許文献２には、下記一般式（４） Conventionally, a method for producing a nitrite ion type hydrotalcite is, for example, a method obtained by a reaction between a water-soluble magnesium compound and a water-soluble aluminum compound in the presence of an alkali (for example, Patent Document 1, Patent Document 3, Patent Document). 4, Patent Document 5, and Patent Document 6), or Patent Document 2, the following general formula (4)
〔ただし、Ｍ1 はＺｎ、Ｐｂ、Ｃａ及びＳｒの少なくとも１種の元素、Ｍ2 はＡｌ及び／又はＦｅ、Ａn-はｎ価のアニオン、０＜ｘ≦０．５、０≦ｚ＜０．５、０．５≦ｙ＋ｚ＜１、０≦ｍ＜２〕
で表される固溶体を４００℃〜７００℃に加熱し、ｐＨ３〜１０で亜硝酸イオンを含有する水溶液に混合することにより製造する方法が提案されている。
The method of manufacturing by heating the solid solution represented by these to 400 to 700 degreeC and mixing with the aqueous solution containing nitrite ion by pH 3-10 is proposed.
しかしながら、特許文献２の方法において用いる原料のハイドロタルサイトは本発明の範囲外の組成のＭｇ4.5 Ａｌ2 （ＯＨ）13・ＣＯ3 ・３．５Ｈ2 Ｏ（一般式（２）中のｘが０．３１の組成に相当）を用いており、また、本発明者らによれば、特許文献２で得られる亜硝酸イオン型ハイドロタルサイト粉末に至っても、金属材料に長期に亘る防錆性能を付与することが難しく、更に優れた防錆性能を有するハイドロタルサイトの開発が望まれていた。 However, the raw hydrotalcite used in the method of Patent Document 2 is Mg 4.5 Al 2 (OH) 13 .CO 3 .3.5H 2 O having a composition outside the scope of the present invention (wherein x in the general formula (2) is Furthermore, according to the present inventors, even when the nitrite ion type hydrotalcite powder obtained in Patent Document 2 is reached, the metal material has a long-term antirust performance. It has been desired to develop a hydrotalcite that is difficult to impart and has excellent rust prevention performance.
理論上、亜硝酸イオン型ハイドロタルサイト（例えば、Ｍｇ9.5Ａｌ2（ＯＨ）13・ＣＯ3・３．５Ｈ2Ｏ）は亜硝酸イオンを該化合物１ｇに対して１７９．５ｍｇ／ｇ含有し、この含有された亜硝酸イオンはアニオン交換により全量放出可能であると考えられるが、従来の亜硝酸イオン型ハイドロタルサイトは、この亜硝酸イオンの放出量が多くとも３２．７ｍｇ／ｇ程度である。 Theoretically, nitrite ion type hydrotalcite (for example, Mg 9.5 Al 2 (OH) 13 .CO 3 .3.5H 2 O) contains 179.5 mg / g of nitrite ion with respect to 1 g of the compound, It is considered that the total amount of the contained nitrite ion can be released by anion exchange, but the conventional nitrite ion type hydrotalcite has a release amount of this nitrite ion of at most 32.7 mg / g. .
本発明者は、かかる実情において、防錆効果に優れたハイドロタルサイト型化合物について鋭意研究を重ねた結果、特定の一般式で表されるハイドロタルサイトを原料として用い、これを特定温度範囲で焼成し、該ハイドロタルサイトからアニオンを脱離させて複合酸化物となし、次いで該複合酸化物を亜硝酸イオンを含む水溶液に浸漬してハイドロタルサイト構造を再生させて得られる亜硝酸イオン型ハイドロタルサイト粉末は、従来の亜硝酸イオン型ハイドロタルサイトに比べ、アニオン交換により放出される亜硝酸イオンの量が多く、更に該ハイドロタルサイトを含有する防錆剤組成物は優れた防錆性能を発揮し、特に金属材料に長期に亘って優れた防錆性能を付与することができることを見出し本発明を完成するに至った。 In this situation, the present inventor has conducted extensive research on hydrotalcite-type compounds having an excellent rust-preventing effect, and as a result, used hydrotalcite represented by a specific general formula as a raw material. Nitrite ion type obtained by firing, desorbing anions from the hydrotalcite to form a complex oxide, and then regenerating the hydrotalcite structure by immersing the complex oxide in an aqueous solution containing nitrite ions Hydrotalcite powder has a larger amount of nitrite ions released by anion exchange compared to conventional nitrite ion type hydrotalcite, and the rust inhibitor composition containing the hydrotalcite is excellent in rust prevention. The present inventors have found that the present invention can exhibit performance, and in particular, can impart excellent rust prevention performance to a metal material over a long period of time.
即ち、本発明の目的は、金属材料に優れた防錆性を付与することができる亜硝酸イオン型ハイドロタルサイト粉末、その製造方法、それを用いた防錆剤組成物及び防錆塗料組成物を提供することにある。 That is, an object of the present invention is to provide a nitrite ion type hydrotalcite powder capable of imparting excellent rust prevention properties to a metal material, a production method thereof, a rust preventive composition and a rust preventive coating composition using the same. Is to provide.
本発明が提供しようとする第１の発明は、亜硝酸イオンを含有するハイドロタルサイト粉末であって、該ハイドロタルサイト粉末５ｇを０．２モル／Ｌの塩化ナトリウム水溶液１００ｍＬに加え２５℃で４時間放置した時に溶出する亜硝酸イオンの量が３５ｍｇ／ｇ以上であることを特徴とする亜硝酸イオン型ハイドロタルサイト粉末である。 A first invention to be provided by the present invention is a hydrotalcite powder containing nitrite ions, and 5 g of the hydrotalcite powder is added to 100 mL of a 0.2 mol / L sodium chloride aqueous solution at 25 ° C. A nitrite ion-type hydrotalcite powder characterized in that the amount of nitrite ions eluted when left for 4 hours is 35 mg / g or more.
また、本発明が提供しようとする第２の発明は、下記一般式（２） The second invention to be provided by the present invention is the following general formula (2).
（式中、ＭはＭｇ、Ｃａ、Ｎｉ、Ｃｕ及びＺｎからなる群から選ばれた少なくとも１種以上の２価金属イオン、Ａはアニオン、ｘは０．１８≦ｘ≦０．２８、ｔは０．５≦ｔ≦２、ｎはアニオンの価数を示す。）
で表わされるハイドロタルサイトを４００〜７００℃で焼成し、前記一般式（２）中のアニオンＡを脱離させる第１工程、次いで前記第１工程で得られた生成物を亜硝酸イオンを含む水溶液に浸漬する第２工程を有することを特徴とする亜硝酸イオン型ハイドロタルサイト粉末の製造方法である。
(Wherein M is at least one divalent metal ion selected from the group consisting of Mg, Ca, Ni, Cu and Zn, A is an anion, x is 0.18 ≦ x ≦ 0.28, and t is 0.5 ≦ t ≦ 2, n represents the valence of the anion.)
The first step of calcining the hydrotalcite represented by the formula (2) to desorb the anion A in the general formula (2), and then the product obtained in the first step contains nitrite ions. It is a manufacturing method of the nitrite ion type hydrotalcite powder characterized by having the 2nd process immersed in aqueous solution.
また、本発明が提供しようとする第３の発明は、前記亜硝酸イオン型ハイドロタルサイトを含有する防錆剤組成物である。
また、本発明が提供しようとする第４の発明は、前記防錆剤組成物を含有する防錆塗料組成物である。
A third invention to be provided by the present invention is a rust preventive composition containing the nitrite ion type hydrotalcite.
Moreover, 4th invention which this invention tends to provide is the rust preventive coating composition containing the said rust preventive composition.
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、従来の亜硝酸イオン型ハイドロタルサイト粉末と比べ、アニオン交換により放出される亜硝酸イオンの量が多く、更に該亜硝酸イオン型ハイドロタルサイトを含有する防錆剤組成物及び防錆塗料組成物は金属材料に優れた防錆性能を付与することができる。 The nitrite ion type hydrotalcite powder of the present invention has a larger amount of nitrite ions released by anion exchange than the conventional nitrite ion type hydrotalcite powder. The contained rust preventive composition and rust preventive coating composition can impart excellent rust prevention performance to metal materials.
以下、本発明を好ましい実施形態に基づき詳細に説明する。
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、従来の亜硝酸イオン型ハイドロタルサイト粉末に比べて、特にアニオン交換により放出される亜硝酸イオンの量が多いことにおいて異なるものである。
Hereinafter, the present invention will be described in detail based on preferred embodiments.
The nitrite ion type hydrotalcite powder of the present invention is different from the conventional nitrite ion type hydrotalcite powder in that the amount of nitrite ions released by anion exchange is particularly large.
即ち、本発明の亜硝酸イオン型ハイドロタルサイト粉末は、該亜硝酸イオン型ハイドロタルサイト粉末５ｇをガラス瓶に入れ、０．２モル／Ｌの塩化ナトリウム水溶液１００ｍＬを加え、３００ｒｐｍ、２５℃、４時間攪拌した後のろ液中の亜硝酸イオン濃度をイオンクロマトグラフ法で求めた値（以下、「亜硝酸イオン放出量」と呼ぶ。）が３５ｍｇ／ｇ以上、好ましくは４０ｍｇ／ｇ以上で、その上限値は１４０ｍｇ／ｇであるのに対して、従来の亜硝酸イオン型ハイドロタルサイト粉末はこの亜硝酸イオン放出量が多くても３２．７ｍｇ／ｇで、本発明の亜硝酸イオン型ハイドロタルサイト粉末は従来の亜硝酸イオン型ハイドロタルサイト粉末に比べアニオン交換により放出される亜硝酸イオンの量が極めて多いところに特徴があり、従来品とは区別される。 That is, in the nitrite ion type hydrotalcite powder of the present invention, 5 g of the nitrite ion type hydrotalcite powder is put in a glass bottle, 100 mL of 0.2 mol / L sodium chloride aqueous solution is added, 300 rpm, 25 ° C., 4 ° C. The value obtained by ion chromatography (hereinafter referred to as “nitrite ion release amount”) of the nitrite ion concentration in the filtrate after stirring for a period of time is 35 mg / g or more, preferably 40 mg / g or more. The upper limit is 140 mg / g, whereas the conventional nitrite ion type hydrotalcite powder has a maximum release amount of 32.7 mg / g. The talcite powder is characterized in that the amount of nitrite ions released by anion exchange is extremely large compared to the conventional nitrite ion type hydrotalcite powder, It is distinguished from the coming goods.
本発明にかかる亜硝酸イオン型ハイドロタルサイト粉末は前記亜硝酸イオン放出量の多い特性を有することにより、該ハイドロタルサイト粉末を含有する防錆剤組成物は金属材料に長期に亘って優れた防錆性能を付与することができる。 The nitrite ion type hydrotalcite powder according to the present invention has a characteristic that the nitrite ion release amount is large, and thus the rust preventive composition containing the hydrotalcite powder is excellent for a metal material for a long time. Rust prevention performance can be imparted.
さらに、本発明の亜硝酸イオン型ハイドロタルサイト粉末は、前記した亜硝酸イオン放出量であることに加え、塩化物イオン吸着量が２０ｍｇ／ｇ以上、好ましくは２５〜１００ｍｇ／ｇであり、防錆性などの様々な効果を発現することができる。 Further, the nitrite ion type hydrotalcite powder of the present invention has a chloride ion adsorption amount of 20 mg / g or more, preferably 25 to 100 mg / g, in addition to the above-mentioned nitrite ion release amount. Various effects such as rusting can be exhibited.
なお、本発明において塩化物イオン吸着量は、亜硝酸イオン型ハイドロタルサイト粉末５ｇをガラス瓶に入れ、０．２モル／Ｌの塩化ナトリウム水溶液１００ｍＬを加え、３００ｒｐｍ、２５℃、４時間攪拌後のろ液中の塩化物イオン濃度をイオンクロマトグラフ法で求めた値から、下記計算式（１） In the present invention, the amount of chloride ion adsorption is 5 g of nitrite ion type hydrotalcite powder in a glass bottle, added with 100 mL of 0.2 mol / L sodium chloride aqueous solution, and stirred at 300 rpm, 25 ° C. for 4 hours. From the value obtained by ion chromatography for the chloride ion concentration in the filtrate, the following formula (1)
（Ｑは塩化物イオン吸着量（ｍｇ／ｇ）、Ｃ0 は吸着前の塩化物イオン濃度（ｍｇ／Ｌ）、Ｃ1 は吸着後の塩化物イオン濃度（ｍｇ／Ｌ）を示す）
により求められる値である。
(Q is chloride ion adsorption amount (mg / g), C 0 is chloride ion concentration (mg / L) before adsorption, and C 1 is chloride ion concentration (mg / L) after adsorption)
Is a value obtained by
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、アニオン成分として亜硝酸イオンを含有するハイドロタルサイトであり、該亜硝酸イオン型ハイドロタルサイト粉末の組成は、後述する原料のハイドロタルサイトの組成に大きく依存することから、その組成は多くの場合、下記一般式（５） The nitrite ion type hydrotalcite powder of the present invention is a hydrotalcite containing nitrite ions as an anion component, and the composition of the nitrite ion type hydrotalcite powder is the composition of the raw material hydrotalcite described later. In many cases, the composition thereof is represented by the following general formula (5).
（式中、ＭはＭｇ、Ｃａ、Ｎｉ、Ｃｕ及びＺｎからなる群から選ばれた少なくとも１種以上の２価金属イオン、ｘは０＜ｘ≦０．５、ｔは０≦ｔ≦２、ｎはアニオンの価数を示す。）で表わされるハイドロタルサイト粉末である。 (Wherein, M is at least one divalent metal ion selected from the group consisting of Mg, Ca, Ni, Cu and Zn, x is 0 <x ≦ 0.5, t is 0 ≦ t ≦ 2, n represents a valence of an anion.)
さらに、好ましい本発明の亜硝酸イオン型ハイドロタルサイト粉末は、下記一般式（１） Furthermore, a preferable nitrite ion type hydrotalcite powder of the present invention is represented by the following general formula (1).
（式中、ｘは０．１５＜ｘ＜０．２５、ｔは０．５≦ｔ≦２を示す。）
で表わされる亜硝酸イオン型ハイドロタルサイト粉末であることが、複合酸化物からのハイドロタルサイト構造の再生効率に優れる点で特に好ましい。
(In the formula, x represents 0.15 <x <0.25, and t represents 0.5 ≦ t ≦ 2.)
The nitrite ion type hydrotalcite powder represented by the formula is particularly preferred from the viewpoint of excellent regeneration efficiency of the hydrotalcite structure from the composite oxide.
本発明の亜硝酸イオン型ハイドロタルサイト粉末のＭｇとＡｌの比は、ＭｇＯ／Ａｌ2 Ｏ3 のモル比として６．０〜６．５、好ましくは６．２〜６．５が望ましく、６．０〜６．５であると亜硝酸イオンの放出量が多く、また防錆性能に優れたものとなる。 The ratio of Mg to Al in the nitrite ion type hydrotalcite powder of the present invention is 6.0 to 6.5, preferably 6.2 to 6.5 as the molar ratio of MgO / Al 2 O 3. When it is from 0.0 to 6.5, the amount of nitrite ions released is large and the rust prevention performance is excellent.
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、上記特性に加え、レーザー散乱法により求められる平均粒径が５０μｍ以下、好ましくは２０μｍ以下、特に好ましくは０．０１〜２０μｍであると分散媒への分散性が良好且つコントロールしやすいので好ましい。 In addition to the above characteristics, the nitrite ion type hydrotalcite powder of the present invention has an average particle size determined by a laser scattering method of 50 μm or less, preferably 20 μm or less, particularly preferably 0.01 to 20 μm. The dispersibility is preferable because it is good and easy to control.
また、本発明の亜硝酸イオン型ハイドロタルサイト粉末は、組成と共にＢＥＴ比表面積が大きいことに特徴を有し、具体的にはＢＥＴ比表面積が３０ｍ2 ／ｇ以上、好ましくは３５ｍ2 ／ｇ以上、特に好ましくは３５〜５０ｍ2 ／ｇであり、このＢＥＴ比表面積であるのでイオン交換効率が向上し、イオン吸着・放出量が理論値に近づくため特に好ましい。 The nitrite ion type hydrotalcite powder of the present invention is characterized by a large BET specific surface area as well as the composition. Specifically, the BET specific surface area is 30 m 2 / g or more, preferably 35 m 2 / g or more. Particularly preferred is 35 to 50 m 2 / g, and since this BET specific surface area improves ion exchange efficiency, the ion adsorption / release amount approaches the theoretical value, which is particularly preferred.
次いで、本発明の亜硝酸イオン型ハイドロタルサイト粉末の製造方法について説明する。
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、下記一般式（２）
Subsequently, the manufacturing method of the nitrite ion type hydrotalcite powder of this invention is demonstrated.
The nitrite ion type hydrotalcite powder of the present invention has the following general formula (2)
（式中、ＭはＭｇ、Ｃａ、Ｎｉ、Ｃｕ及びＺｎからなる群から選ばれた少なくとも１種以上の２価金属イオン、Ａはアニオン、ｘは０．１８≦ｘ≦０．２８、ｔは０．５≦ｔ≦２、ｎはアニオンの価数を示す。）
で表わされるハイドロタルサイトを４００〜７００℃で焼成し、前記一般式（２）中のアニオンＡを脱離させる第１工程、次いで前記第１工程で得られた生成物を亜硝酸イオンを含む水溶液に浸漬する第２工程を実施することにより製造することができる。
(Wherein M is at least one divalent metal ion selected from the group consisting of Mg, Ca, Ni, Cu and Zn, A is an anion, x is 0.18 ≦ x ≦ 0.28, and t is 0.5 ≦ t ≦ 2, n represents the valence of the anion.)
The first step of calcining the hydrotalcite represented by the formula (2) to desorb the anion A in the general formula (2), and then the product obtained in the first step contains nitrite ions. It can manufacture by implementing the 2nd process immersed in aqueous solution.
前記第１工程は、前記一般式（２）で表わされるハイドロタルサイトを原料として用い、これを特定温度範囲で焼成を行って、該ハイドロタルサイトを脱アニオン化して複合酸化物を得る。即ち、この第１工程では、前記一般式（２）で表わされる特定の化学組成のハイドロタルサイトを用いること及び焼成温度を４００〜７００℃、好ましくは４５０〜６００℃で行うことが重要な要件の一つとなる。 In the first step, the hydrotalcite represented by the general formula (2) is used as a raw material, which is fired in a specific temperature range, and the hydrotalcite is deanionized to obtain a composite oxide. That is, in this first step, it is important to use hydrotalcite having a specific chemical composition represented by the general formula (2) and to perform the firing temperature at 400 to 700 ° C., preferably 450 to 600 ° C. It becomes one of.
原料の前記一般式（２）で表わされるハイドロタルサイトは、公知の方法により容易に製造することができる。その一例を示せば、アルカリの存在下、好ましくはｐＨ９〜１３で、水溶性の２価金属塩（Ｍ）と水溶性アルミニウム塩（Ａｌ）とをＭとＡｌのモル比（Ｍ／Ａｌ）が２．０〜８．０となるように０〜１００℃で０．５〜６時間反応させる方法により容易に製造することができる（例えば、特公昭４６−２２８０号公報、特公昭５０−３００３９号公報、特公昭４７−３２１９８号公報、特公昭５６−２９８９３号公報参照）。また、前記一般式（２）の式中のＭがＭｇで、ＡがＣＯ3 2- のハイドロタルサイトは、市販品、例えば、協和化学工業社製の商品名ＤＨＴ−６を用いることができることから工業的に特に有利である。 The hydrotalcite represented by the general formula (2) as a raw material can be easily produced by a known method. For example, the molar ratio of M to Al (M / Al) between a water-soluble divalent metal salt (M) and a water-soluble aluminum salt (Al) is preferably 9 to 13 in the presence of alkali. It can be easily produced by a method of reacting at 0 to 100 ° C. for 0.5 to 6 hours so that it becomes 2.0 to 8.0 (for example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039). Gazette, Japanese Patent Publication No. 47-32198, Japanese Patent Publication No. 56-29893). Moreover, as for the hydrotalcite in which M in the formula of the general formula (2) is Mg and A is CO 3 2- , a commercially available product, for example, trade name DHT-6 manufactured by Kyowa Chemical Industry Co., Ltd. can be used. It is particularly advantageous industrially.
かかる原料のハイドロタルサイトの諸物性は、前記組成の範囲内のものであれば特に制限されるものではないが、得られる亜硝酸イオン型ハイドロタルサイトの粒径は原料のハイドロタルサイトの粒径に大きく依存することから、原料のハイドロタルサイトの粒径は、レーザー散乱法により求められる平均粒径が５０μｍ以下、好ましくは２０μｍ以下、特に好ましくは０．０１〜２０μｍであると上記した平均粒径の亜硝酸イオン型ハイドロタルサイトが容易に得られることから好ましい。 The physical properties of the hydrotalcite of the raw material are not particularly limited as long as they are within the above-mentioned composition range, but the particle size of the obtained nitrite ion type hydrotalcite is the particle size of the raw hydrotalcite. Since the particle size of the raw hydrotalcite is greatly dependent on the diameter, the average particle diameter determined by the laser scattering method is 50 μm or less, preferably 20 μm or less, and particularly preferably 0.01 to 20 μm. Nitrite ion-type hydrotalcite having a particle size is preferable because it can be easily obtained.
本発明では、前記したハイドロタルサイトを焼成し、ハイドロタルサイトの構造中からアニオンが脱離した複合酸化物を得る。
この第１工程では焼成によりハイドロタルサイトからアニオンを完全に除去した複合酸化物を得ることが不純物含量が少なく、イオン交換容量を大きく取ることが出来る上で重要であり、通常は複合酸化物に含有されるアニオンの量が２０００ｐｐｍ以下、好ましくは１００ｐｐｍ以下となるまで十分に焼成を行うことが好ましい。
In the present invention, the above-mentioned hydrotalcite is fired to obtain a composite oxide from which anions are eliminated from the hydrotalcite structure.
In this first step, it is important to obtain a composite oxide in which anions are completely removed from hydrotalcite by calcination in order to reduce the impurity content and increase the ion exchange capacity. It is preferable to perform sufficient firing until the amount of anions contained is 2000 ppm or less, preferably 100 ppm or less.
焼成温度は４００〜７００℃、好ましくは４５０〜６００℃である。焼成温度が４００℃未満ではアニオンの脱離が不十分となり、不純物の量が多くなり、一方、７００℃を越えると複合酸化物の結晶化が進行し、ハイドロタルサイト構造の再生が進行しにくくなるからである。 The firing temperature is 400 to 700 ° C, preferably 450 to 600 ° C. When the calcination temperature is less than 400 ° C., the desorption of anions becomes insufficient and the amount of impurities increases. On the other hand, when the calcination temperature exceeds 700 ° C., the crystallization of the composite oxide proceeds and the regeneration of the hydrotalcite structure is difficult to proceed. Because it becomes.
焼成時間は、上記範囲内のアニオン含有量となるまで十分に行う必要があり、多くの場合１時間以上、好ましくは２時間以上である。
焼成雰囲気は、特に制限されるものではなく、空気中或いは不活性ガス雰囲気中であってもよい。
The firing time must be sufficient until the anion content is within the above range, and in many cases is 1 hour or longer, preferably 2 hours or longer.
The firing atmosphere is not particularly limited, and may be in air or in an inert gas atmosphere.
なお、本発明において、前記焼成は必要により繰り返し行うことができる。
次いで、第２工程では、前記第１工程で得られた複合酸化物を亜硝酸イオンを含む溶液に浸漬し、ハイドロタルサイト構造を再生させ、ハイドロタルサイト構造中に亜硝酸イオンを含有させる。
In the present invention, the firing can be repeated as necessary.
Next, in the second step, the composite oxide obtained in the first step is immersed in a solution containing nitrite ions to regenerate the hydrotalcite structure, and nitrite ions are contained in the hydrotalcite structure.
前記亜硝酸イオンを含む溶液は、亜硝酸又は亜硝酸塩を溶解した水溶液であり、用いることができる亜硝酸塩としては、水に溶解するものであれば特に制限はなく、例えば、亜硝酸リチウム、亜硝酸ナトリウム、亜硝酸カリウム、亜硝酸バリウム、亜硝酸カルシウム、亜硝酸マグネシウム、亜硝酸亜鉛等が挙げられ、これらは１種又は２種以上で用いることができる。 The solution containing nitrite ions is an aqueous solution in which nitrite or nitrite is dissolved, and nitrite that can be used is not particularly limited as long as it is soluble in water. Examples thereof include sodium nitrate, potassium nitrite, barium nitrite, calcium nitrite, magnesium nitrite, zinc nitrite and the like, and these can be used alone or in combination of two or more.
亜硝酸イオンを含む溶液は、多くの場合、亜硝酸イオンを５〜４０重量％、好ましくは５〜２０重量％含む溶液として調製する。
前記複合酸化物１ｇは理論上亜硝酸イオンを多くの場合０．２７ｇまで取り込むことが可能であるが、本発明では、亜硝酸イオンを含む溶液の添加量は、複合酸化物１００重量部に対して亜硝酸イオンとして理論量以上の２７重量部以上、好ましくは３０重量部以上、特に好ましくは５０〜１５０重量部とすることが亜硝酸イオンを理論値に近い量まで取り込ませることが出来るので好ましい。
The solution containing nitrite ions is often prepared as a solution containing 5 to 40% by weight, preferably 5 to 20% by weight of nitrite ions.
1 g of the composite oxide can theoretically incorporate nitrite ions up to 0.27 g in many cases. In the present invention, the amount of the solution containing nitrite ions is 100 parts by weight of the composite oxide. It is preferable that the amount of nitrite ions is 27 parts by weight or more, preferably 30 parts by weight or more, particularly preferably 50 to 150 parts by weight, because the nitrite ions can be taken up to an amount close to the theoretical value. .
第２工程の具体的な操作は、所定量の複合酸化物と亜硝酸イオンを含む溶液とを０〜１００℃、好ましくは１０〜６０℃で２時間以上、好ましくは４時間以上、特に好ましくは４〜２４時間、攪拌下に反応を行って、ハイドロタルサイト構造の再生と亜硝酸イオンの導入を行う。 The specific operation of the second step is that a solution containing a predetermined amount of complex oxide and nitrite ions is 0 to 100 ° C., preferably 10 to 60 ° C. for 2 hours or longer, preferably 4 hours or longer, particularly preferably. The reaction is carried out with stirring for 4 to 24 hours to regenerate the hydrotalcite structure and introduce nitrite ions.
反応終了後、濾過、水洗、乾燥、必要により粉砕、分級して、製品とする。
かくして得られる亜硝酸イオン型ハイドロタルサイト粉末は、前記亜硝酸イオン放出量が３５ｍｇ／ｇ以上、好ましくは４０ｍｇ／ｇ以上で、その上限値は１４０ｍｇ／ｇであり、塩化物イオン吸着量が２０ｍｇ／ｇ以上、好ましくは２５〜１００ｍｇ／ｇである。
After completion of the reaction, the product is filtered, washed with water, dried, and pulverized and classified as necessary to obtain a product.
The nitrite ion-type hydrotalcite powder thus obtained has a release amount of nitrite ions of 35 mg / g or more, preferably 40 mg / g or more, an upper limit of 140 mg / g, and a chloride ion adsorption amount of 20 mg. / G or more, preferably 25 to 100 mg / g.
また、亜硝酸イオン型ハイドロタルサイト粉末の好ましい物性として、レーザー散乱法により求められる平均粒径が５０μｍ以下、好ましくは２０μｍ以下、特に好ましくは０．０１〜２０μｍである。また、ＢＥＴ比表面積が３０ｍ2 ／ｇ以上、好ましくは３５ｍ2 ／ｇ以上、特に好ましくは３５〜５０ｍ2 ／ｇであることが好ましい。 Further, as a preferable physical property of the nitrite ion type hydrotalcite powder, an average particle size determined by a laser scattering method is 50 μm or less, preferably 20 μm or less, particularly preferably 0.01 to 20 μm. Further, BET specific surface area of 30 m 2 / g or more, preferably 35m 2 / g or more, particularly preferably preferably 35~50m 2 / g.
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、優れたアニオン交換能を利用した、例えば、塩化ビニル樹脂の安定剤、砒素、セレン化合物などの有害なアニオンに対する吸着剤等の従来の無機アニオン交換体の用途に使用することができる。また、特に金属材料の防錆剤組成物として好適に使用することができる。 The nitrite ion type hydrotalcite powder of the present invention utilizes an excellent anion exchange ability, for example, a conventional inorganic anion exchange such as a stabilizer for vinyl chloride resin, an adsorbent for harmful anions such as arsenic and selenium compounds. Can be used for body applications. In particular, it can be suitably used as a rust preventive composition for metallic materials.
次いで、本発明の防錆剤組成物について説明する。
本発明の防錆剤組成物は、前記亜硝酸イオン型ハイドロタルサイト粉末を含有することを特徴とする。
かかる防錆剤組成物は、金属製支持体の表面に断熱部材、耐火物を接触させて用いる際の金属製支持体の防錆剤、特にセメント混和剤として使用してコンクリート構造物における鉄筋の防錆剤や、塗料分野における金属材料用の防錆剤として好適に用いることができる。
Next, the rust inhibitor composition of the present invention will be described.
The rust inhibitor composition of the present invention contains the nitrite ion type hydrotalcite powder.
Such a rust preventive composition is used as a rust preventive agent for a metal support, particularly as a cement admixture, when a heat-insulating member or a refractory is brought into contact with the surface of the metal support. It can be suitably used as a rust inhibitor and a rust inhibitor for metal materials in the paint field.
本発明の防錆剤組成物は、前記亜硝酸イオン型ハイドロタルサイト粉末を単独で使用することができることは勿論であるが、防錆顔料と併用することにより一層防錆効果を高めることができる。
併用することができる防錆顔料としては、特に制限はなく、例えば有機質顔料及び無機質顔料のいずれにでも適用できる。例えば、ニトリル系有機化合物顔料等の有機質防錆顔料、Ｍｇ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ又はＡｌの１種又は２種以上から選ばれたリンのオキシ酸塩、モリブデン酸塩、リンモリブデン酸塩、ホウ酸塩、ホウ珪酸塩及びリン珪酸塩、クロム酸塩及び鉛酸塩の１種又は２種以上の無機質防錆顔料が挙げられるが、本発明では環境上の問題からＭｇ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ又はＡｌの１種又は２種以上から選ばれたリンのオキシ酸塩、モリブデン酸塩、リンモリブデン酸塩、ホウ酸塩、ホウ珪酸塩及びリン珪酸塩の白色系の防錆顔料が好ましく用いられる。
In the rust inhibitor composition of the present invention, the nitrite ion type hydrotalcite powder can be used alone, but the rust preventive effect can be further enhanced by using it together with a rust preventive pigment. .
There is no restriction | limiting in particular as a rust preventive pigment which can be used together, For example, it can apply to any of an organic pigment and an inorganic pigment. For example, organic rust preventive pigments such as nitrile organic compound pigments, phosphorus oxyacid salts, molybdates and phosphomolybdates selected from one or more of Mg, Ca, Ba, Sr, Zn or Al , Borate, borosilicate and phosphosilicate, chromate and lead salt include one or more inorganic rust preventive pigments. In the present invention, Mg, Ca, Ba are used due to environmental problems. , Sr, Zn or Al phosphorous oxyacid salt, molybdate, phosphomolybdate, borate, borosilicate and phosphosilicate white rust preventive pigments selected from one or more Is preferably used.
具体的には、リンのオキシ酸塩としては、Ｍｇ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ又はＡｌの１種又は２種以上から選ばれた亜リン酸塩、リン酸塩及び／又は縮合リン酸塩であって、亜リン酸塩としては、例えば亜リン酸マグネシウム、亜リン酸カルシウム、亜リン酸バリウム、亜リン酸ストロンチウム、亜リン酸亜鉛、亜リン酸アルミニウム、亜リン酸亜鉛カルシウム、亜リン酸亜鉛カリウム等が挙げられる。リン酸塩としては、例えば、リン酸マグネシウム、リン酸カルシウム、リン酸バリウム、リン酸ストロンチウム、リン酸亜鉛、リン酸アルミニウム、リン酸亜鉛マグネシウム、リン酸亜鉛カルシウム、リン酸亜鉛カリウム等が挙げられる。縮合リン酸塩としては、ポリリン酸マグネシウム、ポリリン酸カルシウム、ポリリン酸亜鉛、ポリリン酸アルミニウム、メタリン酸マグネシウム、メタリン酸カルシウム、メタリン酸バリウム、メタリン酸ストロンチウム、メタリン酸亜鉛、メタリン酸アルミニウム等が挙げられる。モリブデン酸塩としては、モリブデン酸亜鉛、モリブデン酸カルシウム、モリブデン酸バリウム、モリブデン酸アルミニウム、モリブデン酸マグネシウム、モリブデン酸ストロンチウム、モリブデン酸亜鉛カルシウム等及びモリブデン酸亜鉛カリウム等が挙げられる。 Specifically, as the oxyacid salt of phosphorus, phosphite, phosphate and / or condensed phosphate selected from one or more of Mg, Ca, Ba, Sr, Zn or Al As the phosphite, for example, magnesium phosphite, calcium phosphite, barium phosphite, strontium phosphite, zinc phosphite, aluminum phosphite, zinc calcium phosphite, zinc phosphite Potassium etc. are mentioned. Examples of the phosphate include magnesium phosphate, calcium phosphate, barium phosphate, strontium phosphate, zinc phosphate, aluminum phosphate, zinc magnesium phosphate, zinc calcium phosphate, and potassium potassium phosphate. Examples of the condensed phosphate include magnesium polyphosphate, calcium polyphosphate, zinc polyphosphate, aluminum polyphosphate, magnesium metaphosphate, calcium metaphosphate, barium metaphosphate, strontium metaphosphate, zinc metaphosphate, aluminum metaphosphate, and the like. Examples of molybdate include zinc molybdate, calcium molybdate, barium molybdate, aluminum molybdate, magnesium molybdate, strontium molybdate, calcium calcium molybdate, and zinc potassium molybdate.
リンモリブデン酸塩としては、例えばリンモリブデン酸亜鉛、リンモリブデン酸カルシウム、リンモリブデン酸バリウム、リンモリブデン酸アルミニウム、リンモリブデン酸マグネシウム、リンモリブデン酸ストロンチウム及びモリブデン酸亜鉛カリウム等が挙げられる。 Examples of the phosphomolybdate include zinc phosphomolybdate, calcium phosphomolybdate, barium phosphomolybdate, aluminum phosphomolybdate, magnesium phosphomolybdate, strontium phosphomolybdate, and potassium potassium molybdate.
ホウ酸塩としては、例えばホウ酸亜鉛、ホウ酸カルシウム、ホウ酸バリウム、ホウ酸アルミニウム、ホウ酸マグネシウム、ホウ酸ストロンチウム、ホウ酸亜鉛カルシウム及びホウ酸亜鉛カリウム等が挙げられる。 Examples of the borate include zinc borate, calcium borate, barium borate, aluminum borate, magnesium borate, strontium borate, calcium calcium borate, and potassium potassium borate.
ホウ珪酸塩としては、例えばホウ珪酸亜鉛、ホウ珪酸カルシウム、ホウ珪酸バリウム、ホウ珪酸アルミニウム、ホウ珪酸マグネシウム、ホウ珪酸ストロンチウム、ホウ珪酸亜鉛カリウム、ホウ珪酸亜鉛カルシウムストロンチウム等が挙げられる。 Examples of the borosilicate include zinc borosilicate, calcium borosilicate, barium borosilicate, aluminum borosilicate, magnesium borosilicate, strontium borosilicate, zinc potassium borosilicate, zinc calcium borosilicate, and strontium borosilicate.
リン珪酸塩としては、例えばリン珪酸亜鉛、リン珪酸カルシウム、リン珪酸バリウム、リン珪酸アルミニウム、リン珪酸マグネシウム、リン珪酸ストロンチウム、リン珪酸亜鉛カリウム、リン珪酸亜鉛カルシウム、リン珪酸亜鉛ストロンチウム及びリン珪酸カルシウムストロンチウム亜鉛等が挙げられる。 Examples of phosphosilicates include zinc phosphosilicate, calcium phosphosilicate, barium phosphosilicate, aluminum phosphosilicate, magnesium phosphosilicate, strontium phosphosilicate, potassium phosphosilicate zinc, zinc calcium phosphosilicate, zinc strontium phosphosilicate, and calcium strontium phosphosilicate. Zinc etc. are mentioned.
これらの防錆顔料は、１種又は２種以上で用いられ、また、正塩、塩基性塩又は複合塩のいずれであってもよく、また、含水物又は無水物のいずれであってもよい。また、これらの防錆顔料は、レーザー散乱法により求められる平均粒径が２０μｍ以下、好ましくは０．０１〜１０μｍであると塗料分散性が良好となる点で好ましい。 These rust preventive pigments are used alone or in combination of two or more thereof, and may be any of a normal salt, a basic salt, or a complex salt, and may be either a hydrate or an anhydride. . Further, these rust preventive pigments are preferable in that the average particle size obtained by the laser scattering method is 20 μm or less, preferably 0.01 to 10 μm, in that the paint dispersibility is good.
本発明では、上記した防錆顔料を所望により酸性リン酸エステル又は／及びキレート能を有するホスホン酸、又はその誘導体から選ばれた有機リン酸化合物で表面処理したものであっても差し支えない。酸性リン酸エステルとしては、例えばメチルアシッドホスフェート、ジメチルアシッドホスフェート、エチルアシッドホスフェート、ジエチルアシッドホスフェート、メチルエチルアシッドホスフェート、正−またはイソープロピルアシッドホスフェート、正−またはイソ−ジプロピルアシッドホスフェート、メチルブチルアシッドホスフェート、エチルブチルアシッドホスフェート、プロピルブチルアシッドホスフェート、正−またはイソ−オクチルアシッドホスフェート、正−またはイソ−ジオクチルアシッドホスフェート、正−デシルアシッドホスフェート、正−ジデシルアシッドホスフェート、正−ラウリルアシッドホスフェート、正−ジラウリルアシッドホスフェート、正−またはイソ−セシルアシッドホスフェート、正−またはイソ−ジセシルアシッドホスフェート、正−ステアリルアシッドホスフェート、正−またはイソ−ジステアリルアシッドホスフェート、アリルアシッドホスフェート、ジアリルアシッドホスフェートなどが挙げられ、これら化合物のＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ又はＡｌから選ばれた１種又は２以上の金属塩、アミン塩等が挙げられる。 In the present invention, the above-mentioned rust preventive pigment may be surface-treated with an organic phosphate compound selected from acidic phosphate esters and / or phosphonic acids having chelating ability, or derivatives thereof as desired. Acid phosphate esters include, for example, methyl acid phosphate, dimethyl acid phosphate, ethyl acid phosphate, diethyl acid phosphate, methyl ethyl acid phosphate, positive- or iso-propyl acid phosphate, positive- or iso-dipropyl acid phosphate, methyl butyl acid Phosphate, ethyl butyl acid phosphate, propyl butyl acid phosphate, positive- or iso-octyl acid phosphate, positive- or iso-dioctyl acid phosphate, positive-decyl acid phosphate, positive-didecyl acid phosphate, positive-lauryl acid phosphate, positive -Dilauryl acid phosphate, positive- or iso- ceyl acid phosphate, positive- or And so-dicesyl acid phosphate, normal-stearyl acid phosphate, positive- or iso-distearyl acid phosphate, allyl acid phosphate, diallyl acid phosphate, and the like, and from these compounds Mg, Ca, Sr, Ba, Zn or Al One or two or more selected metal salts, amine salts and the like can be mentioned.
キレート能を有するホスホン酸の化合物としては、例えばアミノアルキレンホスホン酸、エチレンジアミンテトラアルキレンホスホン酸、アルキルメタン−１−ヒドロキシ−１，１−ジホスホン酸又は、２−ヒドロキシホスホノ酢酸などが代表的な化合物として挙げられる。このうちアミノアルキレンホスホン酸としては、例えば、ニトリロトリスチレンホスホン酸、ニトリロトリスプロピレンホスホン酸、ニトリロジエチルメチレンホスホン酸、ニトリロプロピルビスメチレンホスホン酸等が挙げられる。エチレンジアミンテトラアルキレンホスホン酸としては、例えば、エチレンジアミンテトラメチレンホスホン酸、エチレンジアミンテトラエチレンホスホン酸、エチレンジアミンテトラプロピレンホスホン酸等が挙げられる。アルキレン−１−ヒドロキシ−１，１−ジホスホン酸としては、例えば、メタン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、プロパン−１−ヒドロキシ−１，１−ジホスホン酸等が挙げられ、これら化合物のＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ又はＡｌから選ばれた１種又は２種以上の複合塩であってもよいが、これら化合物に限定されるものではない。また、上記の酸性リン酸エステルとキレート能を有するホスホン酸の化合物を１種または２種以上を組み合わせて用いてもよい。リンのオキシ酸塩に対する酸性リン酸エステル又は／およびキレート能を有するホスホン酸の配合量は、用いる化合物の物性や種類等によって一様ではないが、通常０．１〜３０重量％、好ましくは、１〜１０重量％である。 Typical examples of the phosphonic acid compound having chelating ability include aminoalkylenephosphonic acid, ethylenediaminetetraalkylenephosphonic acid, alkylmethane-1-hydroxy-1,1-diphosphonic acid, and 2-hydroxyphosphonoacetic acid. As mentioned. Among these, examples of the aminoalkylenephosphonic acid include nitrilotristyrenephosphonic acid, nitrilotrispropylenephosphonic acid, nitrilodiethylmethylenephosphonic acid, nitrilopropylbismethylenephosphonic acid, and the like. Examples of the ethylenediaminetetraalkylenephosphonic acid include ethylenediaminetetramethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, ethylenediaminetetrapropylenephosphonic acid, and the like. Examples of the alkylene-1-hydroxy-1,1-diphosphonic acid include methane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, and propane-1-hydroxy-1 , 1-diphosphonic acid, and the like. These compounds may be one or two or more complex salts selected from Mg, Ca, Sr, Ba, Zn, or Al, but are limited to these compounds. It is not a thing. Moreover, you may use 1 type or in combination of 2 or more types of the compound of said phosphoric acid which has chelate ability with acidic phosphate ester. The amount of acidic phosphoric acid ester or / and phosphonic acid having chelating ability relative to the oxyacid salt of phosphorus is not uniform depending on the physical properties and type of the compound used, but is usually 0.1 to 30% by weight, preferably, 1 to 10% by weight.
本発明にかかる防錆剤組成物に含有される亜硝酸イオン型ハイドロタルサイト粉末の含有量は、０．０１〜３０重量％、好ましくは０．１〜２０重量％の範囲が望ましい。
また、亜硝酸イオン型ハイドロタルサイト粉末と防錆顔料の配合割合は特に制限されるものではないが、多くの場合、亜硝酸イオン型ハイドロタルサイト粉末１００重量部に対して防錆顔料３〜３０００重量部、好ましくは５〜２０００重量部とすることが防錆効果の設計自由度と経済性の面で好ましい。
The content of the nitrite ion type hydrotalcite powder contained in the rust preventive composition according to the present invention is 0.01 to 30% by weight, preferably 0.1 to 20% by weight.
Further, the mixing ratio of the nitrite ion type hydrotalcite powder and the rust preventive pigment is not particularly limited, but in many cases, the rust preventive pigment 3 to 100 parts by weight of the nitrite ion type hydrotalcite powder is not limited. 3000 parts by weight, preferably 5 to 2000 parts by weight, is preferable from the viewpoint of the degree of freedom in designing the rust-proofing effect and the economy.
なお、本発明の亜硝酸イオン型ハイドロタルサイト粉末は必要に応じて分散性を改善する目的で高級脂肪酸またはその誘導体、界面活性剤、シランカップリング剤でさらに表面処理したものであってもよい。 The nitrite ion-type hydrotalcite powder of the present invention may be further surface-treated with a higher fatty acid or a derivative thereof, a surfactant or a silane coupling agent for the purpose of improving dispersibility, if necessary. .
本発明にかかる防錆剤組成物は、セメント混和剤として、普通、早強、超早強等の各種ポルトランドセメント、これらポルトランドセメントに高炉スラグ、フライアッシュ、及びシリカを混合した各種混合セメント、中庸熱セメント、ビ−ライトセメント、並びに、アルミナセメント等のセメント成分に含有させて用いることができる。この場合、防錆剤組成物の使用量は特に限定されるものではないが、通常、セメント成分１００重量部に対して０．５〜３０重量部、好ましくは１〜１０重量部とすることが好ましい。 The rust preventive composition according to the present invention includes, as cement admixtures, various portland cements such as ordinary, early strength, and ultra-early strength, various mixed cements obtained by mixing blast furnace slag, fly ash, and silica with these portland cements, medium cocoons It can be used by containing in cement components such as thermal cement, belite cement, and alumina cement. In this case, although the usage-amount of a rust preventive composition is not specifically limited, Usually, it is 0.5-30 weight part with respect to 100 weight part of cement components, Preferably it is 1-10 weight part. preferable.
また、セメント成分と防錆剤組成物の他に、減水剤、消泡剤、防凍剤、凝結促進剤や凝結遅延剤等の凝結調整剤、セメント膨張材、セメント急硬材、無機硫酸塩、ベントナイトやゼオライト等の粘土鉱物、ハイドロドカルマイト等のアニオン交換体等を、本発明の目的を実質的に阻害しない範囲で併用することができる。
また、本発明の防錆剤組成物は、塗料の一成分として塗料組成物中に含有させた防錆塗料として好適に用いることができる。
In addition to cement components and rust preventive compositions, water reducing agents, antifoaming agents, antifreeze agents, setting modifiers such as setting accelerators and setting retarders, cement expansion materials, cement rapid hardening materials, inorganic sulfates, Clay minerals such as bentonite and zeolite, anion exchangers such as hydrocalumite, and the like can be used in combination as long as the object of the present invention is not substantially inhibited.
Moreover, the rust preventive composition of the present invention can be suitably used as a rust preventive paint contained in the paint composition as one component of the paint.
次いで、本発明の防錆塗料組成物について説明する。
本発明の防錆塗料組成物は、前記防錆剤組成物と塗料ビヒクルを含有するものである。塗料ビヒクルとは、塗料成分を分散させる媒体をいう。即ち、塗膜形成成分である重合油、天然または合成樹脂、無機系結合剤、繊維素やゴムの誘導体等の高分子物質やそれらを溶剤に溶解させたものである。
Next, the rust preventive coating composition of the present invention will be described.
The rust preventive coating composition of the present invention contains the rust preventive composition and a paint vehicle. A paint vehicle refers to a medium in which paint components are dispersed. That is, a polymer material that is a coating film forming component, a natural or synthetic resin, an inorganic binder, a high-molecular substance such as a fiber or rubber derivative, or the like is dissolved in a solvent.
前記合成樹脂としては、例えばフェノール樹脂、アルキド樹脂、メラミン樹脂、グアナジン樹脂、ビニル樹脂、エポキシ樹脂、ポリアミン樹脂、アクリル樹脂、ポリブタジエン樹脂、ポリエステル樹脂、ウレタン樹脂、ケイ素樹脂、含フッ素樹脂等が挙げられ、これらは必要に応じ、混合系または変性された樹脂であっても差し支えない。 Examples of the synthetic resin include phenol resin, alkyd resin, melamine resin, guanazine resin, vinyl resin, epoxy resin, polyamine resin, acrylic resin, polybutadiene resin, polyester resin, urethane resin, silicon resin, and fluorine-containing resin. These may be mixed systems or modified resins as required.
また、前記無機系結合剤としては、水溶性珪酸塩、変性水溶液珪酸塩、アルキルシリケート、アルコキシシリケート、カップリング剤、コロイダルシリカ等が挙げられる。
前記水溶性珪酸塩としては、一般式Ｍ2 Ｏ・ｘＳｉＯ2 ・ｙＨ2 Ｏで表され、Ｍはナトリウム、リチウム、カリウム等のアルカリ金属、Ｎ（Ｃ2 Ｈ4 ＯＨ）2 、Ｎ（ＣＨ2 ＯＨ）4 、Ｎ（Ｃ2 Ｈ4 ＯＨ）4 、Ｃ（ＮＨ2 ）3 ＮＨを示し、式中のｘ及びｙは整数を示し、具体的な化合物としては例えば、珪酸ナトリウム、珪酸カリウム、珪酸リチウム等の珪酸アルカリ金属塩、珪酸トリエタノールアミン、珪酸テトラメタノールアンモニウム、珪酸テトラエタノールアンモニウム等が挙げられる。
Examples of the inorganic binder include water-soluble silicate, modified aqueous silicate, alkyl silicate, alkoxy silicate, coupling agent, colloidal silica, and the like.
The water-soluble silicate of the general formula represented by M 2 O · xSiO 2 · yH 2 O, M is sodium, lithium, an alkali metal such as potassium, N (C 2 H 4 OH ) 2, N (CH 2 OH) 4 , N (C 2 H 4 OH) 4 , C (NH 2 ) 3 NH, wherein x and y are integers, and specific compounds include, for example, sodium silicate, potassium silicate, silicic acid Examples thereof include alkali metal silicates such as lithium, triethanolamine silicate, tetramethanol ammonium silicate, tetraethanol ammonium silicate and the like.
前記変性水溶性珪酸塩としては、前記水溶性珪酸塩をアルミニウム、マグネシウム、カルシウム、バリウム、ストロンチウム、亜鉛、ジルコニウム、バナジウムから選ばれる金属の酸化物、水酸化物、弗化物、珪弗化物の１種又は２種以上で変性させたもの、或いは珪弗化ナトリウム、トリ珪弗化亜鉛酸カリウム、フルオロアルミニウム錯塩、フルオロ亜鉛錯塩等で変性させたもの（特開昭５３−１８６３６号参照。）等が挙げられる。 As the modified water-soluble silicate, the water-soluble silicate is selected from the group consisting of oxides, hydroxides, fluorides, and silicon fluorides of metals selected from aluminum, magnesium, calcium, barium, strontium, zinc, zirconium, and vanadium. Modified with seeds or two or more, or modified with sodium silicofluoride, potassium trisilicofluorinated zincate, fluoroaluminum complex salt, fluorozinc complex salt, etc. (see JP-A-53-18636), etc. Is mentioned.
前記アルキルシリケートとしては、一般式；ＳｉＲ4 又はＳｉＸＲ3 で表され、式中のＲはアルキル基を示し、Ｘはアルコキシ基、ビニル基、エポキシ基、アミノ基、メタクリル基、メルカプト基を示す。前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜５の直鎖状又は分岐状のアルキル基が挙げられ、具体的な化合物として、例えば、テトラメチルシリケート、テトラエチルシリケート、テトラプロピルシリケート、テトラブチルシリケート等が挙げられる。 The alkyl silicate is represented by the general formula; SiR 4 or SiXR 3 , wherein R represents an alkyl group, and X represents an alkoxy group, a vinyl group, an epoxy group, an amino group, a methacryl group, or a mercapto group. Examples of the alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Specific examples of the alkyl group include tetramethyl Examples thereof include silicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate and the like.
前記アルコキシシランとしては、一般式；Ｓｉ（ＯＲ）4 又はＳｉＸ（ＯＲ）3 、ＳｉＲ（ＯＲ）3 で表され、式中のＲはアルキル基を示し、Ｘはビニル基、エポキシ基、アミノ基、メタクリル基、メルカプト基を示す。前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜５の直鎖状又は分岐状のアルキル基が挙げられ、具体的な化合物として、例えば、テトラメチルキシシリケート、テトラエトキシシリケート、テトラプロポキシシリケート、テトラブトキシシリケート等が挙げられる。 The alkoxysilane is represented by the general formula; Si (OR) 4 or SiX (OR) 3 , SiR (OR) 3 , wherein R represents an alkyl group, and X represents a vinyl group, an epoxy group, or an amino group. , A methacryl group and a mercapto group. Examples of the alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Specific examples of the alkyl group include tetramethyl Examples thereof include xyl silicate, tetraethoxy silicate, tetrapropoxy silicate, tetrabutoxy silicate and the like.
前記カップリング剤としては、例えば、γ−グリシドキシプロピルトリメトキシシランや、γ−グリシドキシプロピルメチルジエトキシシラン、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、ビニルトリエトキシシラン、γ−メタクリロキシトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等のシラン系カップリング剤、イソプロピルトリイソステアロイルチタネートや、テトラオクチルビス（ジドデシル）ホスファイトチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート等のチタン系カップリング剤、アルミニウム系カップリング剤、ジルコニウム系カップリング剤等が挙げられる。 Examples of the coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and vinyltriethoxysilane. Silane coupling agents such as γ-methacryloxytrimethoxysilane and γ-mercaptopropyltrimethoxysilane, isopropyltriisostearoyl titanate, tetraoctylbis (didodecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyltridodecyl Examples include titanium coupling agents such as benzenesulfonyl titanate, aluminum coupling agents, and zirconium coupling agents.
前記コロイダルシリカとしては、粒径が通常２〜１００ｎｍ程度のもので、固形分２０〜４０％程度で０．７％以下のＮａ2 Ｏを含むもので、特に好ましくはｐＨ８〜１０でアルカリで安定化されたコロイダルシリカを用いることができる。 The colloidal silica usually has a particle size of about 2 to 100 nm, contains 20 to 40% solids and contains 0.7% or less Na 2 O, and is particularly preferably stable at pH 8 to 10 with alkali. Colloidal silica can be used.
前記塗膜成分は１種又は２種以上で適宜組み合わせて用いることができる。
また、希釈剤としては、水、アルコール類、ケトン類、ベンゼン類、トルエン、キシレンの如き芳香族炭化水素類、液化パラフィンの如き脂肪族炭化水素類など、一般的に塗料で用いられている溶剤が適用できる。
The coating film components can be used alone or in combination of two or more.
As diluents, solvents commonly used in paints such as water, alcohols, ketones, benzenes, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as liquefied paraffin Is applicable.
塗料ビヒクルに対する本発明の防錆剤組成物の配合量は、通常０．３〜４０重量％、好ましくは１〜３０重量％、更に好ましくは５〜１５重量％である。配合量が０．３重量％より小さくなると防錆力が低くなり、４０重量％より大きくなると、塗料粘性が高くなり、好ましい塗料特性が得られなくなる。 The blending amount of the rust inhibitor composition of the present invention with respect to the paint vehicle is usually 0.3 to 40% by weight, preferably 1 to 30% by weight, and more preferably 5 to 15% by weight. When the blending amount is less than 0.3% by weight, the rust preventive power is lowered, and when it is more than 40% by weight, the viscosity of the paint is increased, and preferable paint properties cannot be obtained.
本発明の防錆塗料組成物は上記以外の成分として塗料分野で一般的に用いられる各種の添加剤を含有させて用いることができる。
本発明に係る防錆塗料組成物は、刷毛やローラー塗り、スプレー塗装、静電気塗装、粉体塗装、ロールコーター、カーテンフローコーター、ディッピング塗装や電着塗装等に供することができる。
The anticorrosive coating composition of the present invention can be used by containing various additives generally used in the coating field as components other than those described above.
The rust preventive coating composition according to the present invention can be used for brush, roller coating, spray coating, electrostatic coating, powder coating, roll coater, curtain flow coater, dipping coating, electrodeposition coating, and the like.
以下、本発明を実施例により更に詳細に説明するが、本発明はこれらに限定されるものではない。
実施例１
組成がＭｇ6 Ａｌ2 （ＯＨ）16・ＣＯ3 ・３．５Ｈ2 Ｏ（協和化学工業社製；商品名ＤＨＴ−６、平均粒径０．８μｍ）であるハイドロタルサイト粉末１００ｇを５００℃で２時間保持し、冷却後、得られた複合酸化物をデシケータにて１日放置して複合酸化物５８．５ｇを得た。
次いで、亜硝酸ナトリウム１１４ｇを純水に溶解して１Ｌとした亜硝酸ナトリウム水溶液に複合酸化物５０ｇを攪拌下に２５℃で４時間浸漬した。
次いで、得られた試料を濾過、乾燥、粉砕して白色粉末９１．５ｇを得た。
得られた試料を粉末Ｘ線回折法により結晶構造を解析したところ、該試料はハイドロタルサイト構造を持つ化合物であることを確認した。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
Example 1
100 g of hydrotalcite powder having a composition of Mg 6 Al 2 (OH) 16 .CO 3 .3.5H 2 O (manufactured by Kyowa Chemical Industry Co., Ltd .; trade name DHT-6, average particle size 0.8 μm) at 500 ° C. After maintaining for 2 hours and cooling, the resulting composite oxide was left in a desiccator for 1 day to obtain 58.5 g of composite oxide.
Next, 50 g of the composite oxide was immersed in a sodium nitrite aqueous solution prepared by dissolving 114 g of sodium nitrite in pure water to 1 L at 25 ° C. for 4 hours with stirring.
Next, the obtained sample was filtered, dried and pulverized to obtain 91.5 g of a white powder.
When the crystal structure of the obtained sample was analyzed by a powder X-ray diffraction method, it was confirmed that the sample was a compound having a hydrotalcite structure.
比較例１
組成がＭｇ4.5 Ａｌ2 （ＯＨ）13・ＣＯ3 ・３．５Ｈ2 Ｏ（協和化学工業社製；商品名ＤＨＴ−４、平均粒径１．０μｍ）であるハイドロタルサイト粉末１００ｇを５００℃で２時間保持し、冷却後、得られた複合酸化物をデシケータにて１日放置して複合酸化物５６．８ｇを得た。
次いで、亜硝酸ナトリウム１１４ｇを純水に溶解して１Ｌとした亜硝酸ナトリウム水溶液に複合酸化物５０ｇを攪拌下に２５℃で４時間浸漬した。
次いで、得られた試料を濾過、乾燥、粉砕して白色粉末９６．７ｇを得た。
得られた試料を実施例１と同様、粉末Ｘ線回折法により結晶構造を解析したところ、該試料はハイドロタルサイト構造を持つ化合物であることを確認した。
Comparative Example 1
100 g of hydrotalcite powder having a composition of Mg 4.5 Al 2 (OH) 13 .CO 3 .3.5H 2 O (manufactured by Kyowa Chemical Industry Co., Ltd .; trade name DHT-4, average particle size 1.0 μm) at 500 ° C. After maintaining for 2 hours and cooling, the obtained composite oxide was left in a desiccator for 1 day to obtain 56.8 g of composite oxide.
Next, 50 g of the composite oxide was immersed in a sodium nitrite aqueous solution prepared by dissolving 114 g of sodium nitrite in pure water to 1 L at 25 ° C. for 4 hours with stirring.
Subsequently, the obtained sample was filtered, dried and pulverized to obtain 96.7 g of a white powder.
When the crystal structure of the obtained sample was analyzed by powder X-ray diffraction as in Example 1, it was confirmed that the sample was a compound having a hydrotalcite structure.
比較例２〜３
硫酸マグネシウム７水和物２４６．４８ｇ、亜硝酸カルシウム１３２．０９ｇ及び水５００ｍｌを仕込み、２５℃で１時間反応を行った。次いで、析出した石膏を濾過により除去し、１７．５重量％亜硝酸マグネシウム水溶液６６０ｇを得た。
次いで、前記亜硝酸マグネシウム水溶液１００ｇに、ＭｇＯ／Ａｌ2 Ｏ3 のモル比が６となるようにアルミン酸ソーダ４．１ｇを混合し、次いで、水酸化ナトリウムによりｐＨを８．５（比較例２）、１０．５（比較例３）となるように調製し、２５℃で４時間反応を行った。
次いで、濾過、洗浄、乾燥、粉砕し白色粉末を得た。得られた試料を粉末Ｘ線回折法により結晶構造を解析したところ、該試料はハイドロタルサイト構造を持つ化合物であることを確認した。
Comparative Examples 2-3
246.48 g of magnesium sulfate heptahydrate, 132.09 g of calcium nitrite, and 500 ml of water were charged and reacted at 25 ° C. for 1 hour. Next, the precipitated gypsum was removed by filtration to obtain 660 g of a 17.5 wt% magnesium nitrite aqueous solution.
Next, 4.1 g of sodium aluminate was mixed with 100 g of the magnesium nitrite aqueous solution so that the molar ratio of MgO / Al 2 O 3 was 6, and then the pH was adjusted to 8.5 with sodium hydroxide (Comparative Example 2). ) 10.5 (Comparative Example 3), and reacted at 25 ° C. for 4 hours.
Then, filtration, washing, drying and pulverization gave a white powder. When the crystal structure of the obtained sample was analyzed by a powder X-ray diffraction method, it was confirmed that the sample was a compound having a hydrotalcite structure.
＜化学組成の評価＞
実施例１及び比較例１〜３で得たハイドロタルサイトを硫酸で溶解、希釈した後、ＩＣＰ原子発光法によりＭｇとＡｌの濃度を測定し、そのモル比から組成式を求めた。その結果を表１に示す。
<Evaluation of chemical composition>
After dissolving and diluting the hydrotalcite obtained in Example 1 and Comparative Examples 1 to 3 with sulfuric acid, the concentrations of Mg and Al were measured by ICP atomic emission method, and the composition formula was determined from the molar ratio. The results are shown in Table 1.
＜物性評価＞
（１）亜硝酸イオン放出量
前記の実施例１及び比較例１〜３で得られた亜硝酸イオン型ハイドロタルサイト粉末５ｇをガラス瓶に入れ、０．２モル／Ｌの塩化ナトリウム水溶液１００ｍＬを加え、３００ｒｐｍ、２５℃、４時間攪拌後のろ液中の亜硝酸イオン濃度をイオンクロマトグラフ法で求めた。その結果を表２に示す。
（２）塩化物イオン吸着量
塩化物イオン吸着量は上記のろ液をイオンクロマトグラフ法で濃度を測定し，初期濃度から差し引いた値をサンプル量１ｇ当たりに換算して求めた。
（３）平均粒径
上記で得られた亜硝酸イオン型ハイドロタルサイト粉末の平均粒径をレーザー散乱法により求めた。
（４）ＢＥＴ比表面積
上記で得られた亜硝酸イオン型ハイドロタルサイト粉末の比表面積をＢＥＴ法で測定して求めた。
（５）理論上の亜硝酸イオン含有量
上記の化学組成から算出される理論上の亜硝酸イオン含有量を示す。
<Physical property evaluation>
(1) Amount of nitrite ion released 5 g of nitrite ion type hydrotalcite powder obtained in Example 1 and Comparative Examples 1 to 3 was put in a glass bottle, and 100 mL of 0.2 mol / L sodium chloride aqueous solution was added. The concentration of nitrite ions in the filtrate after stirring for 4 hours at 300 rpm, 25 ° C. was determined by ion chromatography. The results are shown in Table 2.
(2) Chloride ion adsorption amount Chloride ion adsorption amount was determined by measuring the concentration of the above filtrate by ion chromatography and subtracting it from the initial concentration per 1 g of sample amount.
(3) Average particle diameter The average particle diameter of the nitrite ion type hydrotalcite powder obtained above was determined by a laser scattering method.
(4) BET specific surface area The specific surface area of the nitrite ion type hydrotalcite powder obtained above was measured by the BET method.
(5) Theoretical nitrite ion content The theoretical nitrite ion content calculated from the above chemical composition is shown.
以上の評価の結果を表２に示す。 The results of the above evaluation are shown in Table 2.
＜防錆性能の評価＞
（１）防錆塗料の調製
下記組成の主剤に硬化剤を添加して、ペイントコンディショナー法にて常乾型エポキシ樹脂塗料を調製した。
<Evaluation of rust prevention performance>
(1) Preparation of rust preventive paint A curing agent was added to the main component having the following composition, and a normally dry epoxy resin paint was prepared by a paint conditioner method.
主剤の成分 配合割合（重量部）
エピコート１００１Ｘ７５1) ４１．５
キシレン／メチルエチルケトン（１／１：Ｖ／Ｖ） ２１．０
防錆剤組成物 ７．８
炭酸カルシウム ５．０
酸化チタン ２．５
ガラスビーズ ８０．０
硬化剤の成分
トーマイド４１０−Ｎ2) ４８．１
キシレン／イソブタノール（７／３：Ｖ／Ｖ） １０．０
（注）
１）エピコート１００１Ｘ７５（ジャパンエポキシレジン社製）
２）トーマイド４１０−Ｎ（富士化成工業社製）
Main ingredient component ratio (parts by weight)
Epicoat 1001X75 1) 41.5
Xylene / Methyl ethyl ketone (1/1: V / V) 21.0
Rust preventive composition 7.8
Calcium carbonate 5.0
Titanium oxide 2.5
Glass beads 80.0
Ingredients of curing agent tomide 410-N 2) 48.1
Xylene / isobutanol (7/3: V / V) 10.0
(note)
1) Epicoat 1001X75 (Japan Epoxy Resin Co., Ltd.)
2) Tomide 410-N (Fuji Kasei Kogyo Co., Ltd.)
なお、防錆剤組成物は下記表３の組成のものを使用した。 In addition, the thing of the composition of following Table 3 was used for the rust preventive composition.
（注）亜燐酸亜鉛は市販の平均粒径が３μｍのものを使用した。 (Note) Zinc phosphite with a commercially available average particle size of 3 μm was used.
（２）塗料分散性の評価
（１）で調製した塗料をＪＩＳ Ｋ５１０１に準ずるグラインドゲージにて防錆剤組成物の分散度合を評価した。その結果を表４に示した。
良：１０μｍ以下の分散
可：１０〜５０μｍの分散
不可：５０μｍ以上の分散
(2) Evaluation of paint dispersibility The degree of dispersion of the rust inhibitor composition was evaluated using a grind gauge according to JIS K5101 for the paint prepared in (1). The results are shown in Table 4.
Good: Dispersion of 10 μm or less Possible: Dispersion of 10-50 μm Impossible: Dispersion of 50 μm or more
（３）塗装鋼板の調製
上記の防錆塗料を７０×１５０×０．７ｍｍの日本テストパネル製、ＳＰＣＣ−ＳＤ鋼板に乾燥塗装膜厚が３０〜３５μｍになるようにバーコーターにて塗布し、２５℃、湿度６０％の恒温恒湿器で１時間乾燥させて塗装鋼板を得た。
(3) Preparation of coated steel plate The above rust preventive coating was applied to a SPCC-SD steel plate made by Nippon Test Panel 70 x 150 x 0.7 mm with a bar coater so that the dry coating film thickness was 30 to 35 µm. The coated steel sheet was obtained by drying for 1 hour in a constant temperature and humidity chamber at 25 ° C. and a humidity of 60%.
（４）防錆試験
（３）で調製した塗装鋼板の裏面および端面を３Ｍ社製、スコッチブランドテープでマスキングした後、クロスカットして、塩水噴霧試験機にセットし、濃度５重量％の食塩水を噴霧して防錆試験を行った。
(4) Rust prevention test After masking the back and end surfaces of the coated steel plate prepared in (3) with 3M Co., Scotch brand tape, cross-cut, and set in a salt spray tester. Rust prevention test was conducted by spraying water.
（５）防錆性能の評価
塩水噴霧試験４００時間及び６００時間に於ける結果を下記の５段階評価法により評価し、防錆顔料の防錆効果を判定した。その結果を表４に示した。
５：クロスカット部以外の錆発生が全くなく、ブリスターもない。
４：クロスカット部から片側２ｍｍ以内に錆が発生、ブリスターもない。
３：クロスカット部から片側６ｍｍ以内に錆及び部分的にブリスターが発生
２：クロスカット部から片側１２ｍｍ以内に錆および部分的にブリスターが発生。
１：鋼板全体に錆およびブリスターが発生。
(5) Evaluation of rust preventive performance The results of the salt spray test at 400 hours and 600 hours were evaluated by the following five-step evaluation method, and the rust preventive effect of the rust preventive pigment was determined. The results are shown in Table 4.
5: There is no rust generation | occurrence | production other than a crosscut part, and there is no blister.
4: Rust is generated within 2 mm on one side from the crosscut part, and there is no blister.
3: Rust and partial blister occurred within 6 mm on one side from cross cut part 2: Rust and partial blister occurred within 12 mm on one side from cross cut part.
1: Rust and blister occur on the whole steel plate.
本発明の亜硝酸イオン型ハイドロタルサイト粉末は、アニオン交換により放出される亜硝酸イオンの量が多く、金属材料に優れた防錆性能を付与することができるので、防錆剤組成物及び防錆塗料組成物に利用することができる。 The nitrite ion type hydrotalcite powder of the present invention has a large amount of nitrite ions released by anion exchange and can impart excellent rust prevention performance to metal materials. It can be used for a rust coating composition.
Claims (11)
で表わされる請求項１乃至４のいずれかの項に記載の亜硝酸イオン型ハイドロタルサイト粉末。 The following general formula (1)
The nitrite ion type hydrotalcite powder according to any one of claims 1 to 4, represented by:
で表わされるハイドロタルサイトを４００〜７００℃で焼成し、前記一般式（２）中のアニオンＡを脱離させる第１工程、次いで前記第１工程で得られた生成物を亜硝酸イオンを含む水溶液に浸漬する第２工程を有することを特徴とする亜硝酸イオン型ハイドロタルサイト粉末の製造方法。 The following general formula (2)
The first step of calcining the hydrotalcite represented by the formula (2) to desorb the anion A in the general formula (2), and then the product obtained in the first step contains nitrite ions. The manufacturing method of the nitrite ion type hydrotalcite powder characterized by having the 2nd process immersed in aqueous solution.
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| KR101217140B1 (en) * | 2010-04-21 | 2012-12-31 | 한국세라믹기술원 | Inorganic filler for heavy duty paint and heavy duty paint composition using the same |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS462280B1 (en) * | 1966-07-25 | 1971-01-20 | ||
| JPS5030039B1 (en) * | 1967-07-17 | 1975-09-27 | ||
| JPS63273670A (en) * | 1987-05-02 | 1988-11-10 | Kyowa Chem Ind Co Ltd | Corrosion-resistant coating compound composition |
| JPH05306124A (en) * | 1992-04-30 | 1993-11-19 | Nippon Paint Co Ltd | Rust-preventing pigment, production of rust-preventing pigment and corrosion-resistant coating composition |
| JPH0733431A (en) * | 1993-07-21 | 1995-02-03 | Nippon Chem Ind Co Ltd | Production of hydrocalmite |
| JPH10508281A (en) * | 1994-07-16 | 1998-08-18 | メタルゲゼルシャフト・アクチエンゲゼルシャフト | Layered lattice compound and stabilizer for halogen-containing polymer containing this compound |
| JPH11148029A (en) * | 1997-11-18 | 1999-06-02 | Nippon Chem Ind Co Ltd | Rust-preventive pigment composition and rust-preventive paint containing the same |
| JP2000191943A (en) * | 1998-10-19 | 2000-07-11 | Nts:Kk | Film-forming composition and its production |
| JP2000313852A (en) * | 1999-04-30 | 2000-11-14 | Kansai Paint Co Ltd | Cationic electrodeposition coating material |
| JP2004352994A (en) * | 2004-06-28 | 2004-12-16 | Sumitomo Seika Chem Co Ltd | Polyolefin-based powder coating composition |
| JP2005112998A (en) * | 2003-10-07 | 2005-04-28 | Nippon Chem Ind Co Ltd | Inorganic coating composition |
-
2004
- 2004-05-26 JP JP2004155732A patent/JP4636587B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS462280B1 (en) * | 1966-07-25 | 1971-01-20 | ||
| JPS5030039B1 (en) * | 1967-07-17 | 1975-09-27 | ||
| JPS63273670A (en) * | 1987-05-02 | 1988-11-10 | Kyowa Chem Ind Co Ltd | Corrosion-resistant coating compound composition |
| JPH05306124A (en) * | 1992-04-30 | 1993-11-19 | Nippon Paint Co Ltd | Rust-preventing pigment, production of rust-preventing pigment and corrosion-resistant coating composition |
| JPH0733431A (en) * | 1993-07-21 | 1995-02-03 | Nippon Chem Ind Co Ltd | Production of hydrocalmite |
| JPH10508281A (en) * | 1994-07-16 | 1998-08-18 | メタルゲゼルシャフト・アクチエンゲゼルシャフト | Layered lattice compound and stabilizer for halogen-containing polymer containing this compound |
| JPH11148029A (en) * | 1997-11-18 | 1999-06-02 | Nippon Chem Ind Co Ltd | Rust-preventive pigment composition and rust-preventive paint containing the same |
| JP2000191943A (en) * | 1998-10-19 | 2000-07-11 | Nts:Kk | Film-forming composition and its production |
| JP2000313852A (en) * | 1999-04-30 | 2000-11-14 | Kansai Paint Co Ltd | Cationic electrodeposition coating material |
| JP2005112998A (en) * | 2003-10-07 | 2005-04-28 | Nippon Chem Ind Co Ltd | Inorganic coating composition |
| JP2004352994A (en) * | 2004-06-28 | 2004-12-16 | Sumitomo Seika Chem Co Ltd | Polyolefin-based powder coating composition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101217140B1 (en) * | 2010-04-21 | 2012-12-31 | 한국세라믹기술원 | Inorganic filler for heavy duty paint and heavy duty paint composition using the same |
| JP2015520018A (en) * | 2012-04-17 | 2015-07-16 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングＣｈｅｍｅｔａｌｌ ＧｍｂＨ | Method of coating a metal surface with a coating composition containing layered double hydroxide particles |
| US9903037B2 (en) | 2012-04-17 | 2018-02-27 | Chemetall Gmbh | Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide |
| JP2016511300A (en) * | 2013-01-17 | 2016-04-14 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Method for producing anticorrosion coating |
| JP2016108427A (en) * | 2014-12-05 | 2016-06-20 | 丸尾カルシウム株式会社 | Hydrotalcite composition, resin composition containing the composition and molded body thereof |
| CN107986661A (en) * | 2017-11-29 | 2018-05-04 | 中国科学院海洋研究所 | A kind of triazole corrosion inhibitor compound of active group containing salicylide of hydrotalcite intercalation chlorion probe modification and its application |
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| CN111204782A (en) * | 2020-01-19 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Nitrite intercalation hydrotalcite material, aqueous resin composite coating and preparation method thereof |
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