JPH0256377B2 - - Google Patents
Info
- Publication number
- JPH0256377B2 JPH0256377B2 JP23267683A JP23267683A JPH0256377B2 JP H0256377 B2 JPH0256377 B2 JP H0256377B2 JP 23267683 A JP23267683 A JP 23267683A JP 23267683 A JP23267683 A JP 23267683A JP H0256377 B2 JPH0256377 B2 JP H0256377B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- zinc
- formula
- potassium
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000049 pigment Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 22
- -1 phosphorous acid compound Chemical class 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 150000003752 zinc compounds Chemical class 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 150000003112 potassium compounds Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- AVUCOJBTHOYKFN-UHFFFAOYSA-K potassium zinc phosphorous acid phosphate Chemical group [K+].P(=O)([O-])([O-])[O-].[Zn+2].P(O)(O)O AVUCOJBTHOYKFN-UHFFFAOYSA-K 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000002265 prevention Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000011118 potassium hydroxide Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 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 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- 239000005819 Potassium phosphonate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- IDQWCBURUBJWFM-UHFFFAOYSA-N potassium;zinc;phosphite Chemical compound [K+].[Zn+2].[O-]P([O-])[O-] IDQWCBURUBJWFM-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000011161 development 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
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- CXDLXIMRJLZPDZ-UHFFFAOYSA-K potassium;zinc;phosphate Chemical compound [K+].[Zn+2].[O-]P([O-])([O-])=O CXDLXIMRJLZPDZ-UHFFFAOYSA-K 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- KDWVHRNGTQBVEN-UHFFFAOYSA-N tripotassium;phosphite Chemical class [K+].[K+].[K+].[O-]P([O-])[O-] KDWVHRNGTQBVEN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
Description
本発明は改良された亜リン酸リン酸亜鉛カリウ
ム系化合物を有効成分とする防錆顔料に関するも
のである。
従来、防錆顔料として、最も代表的なものとし
て鉛丹、あるいはジンククロメートが広範囲に使
用されている。これ等の防錆顔料は極めて優れた
防錆力を示すが、その組成中に有毒金属である
鉛、クロムなどを含有しているためにその毒性が
最近問題として取り上げられ、これに対する新し
い低毒性あるいは無公害性の防錆顔料の開発が要
請されていた。この要望に応じて無公害性の防錆
顔料として多くの提案がなされている。
これまでに無公害防錆顔料として(a)金属縮合リ
ン酸塩系例えば縮合リン酸アルミニウム、(b)金属
リン酸塩系例えばリン酸ケイ素、リン酸チタニウ
ム、(C)金属亜リン酸塩系例えば亜リン酸亜鉛、バ
リウム塩、マグネシウム塩、マンガン塩、(d)金属
次亜リン酸塩系例えば次亜リン酸カルシウムまた
は次亜リン酸鉄、および(e)金属モリブデン酸塩例
えば亜鉛塩、カルシウム塩など数多くの提案がな
されたが、これらの無公害防錆顔料は、防錆力が
鉛系、クロメート系に及ばす防錆顔料として決定
的なものでない。従つて、これらの提案された顔
料は必要な防錆性を得るために２〜３種組合せて
使用されているのが現状である。
ところで本出願人は、前記従来の防錆顔料と異
り、無公害で優れた防錆力のある白色の亜リン酸
リン酸カリウム亜鉛系顔料を開発し、既に特許出
願（特願昭58−80090号）をしている。
本発明は、上記顔料の防錆性を更に向上すべく
研究を行つた結果、亜リン酸に一部分有機ホスホ
ン酸（塩）を用いることにより、その効果が著し
いことを知見し、完成したものである。
即ち、本発明は、亜鉛化合物、カリウム化合
物、亜リン酸化合物、リン酸化合物および、亜リ
ン酸に対して少なくとも２重量％以上の
一般式
RmN［（CH2）nP（Ｏ）（OZ）2］3-o
［式中Ｒは低級アルキル基、ｍは０〜３、ｎ＝１
〜２、Ｚは水素、アルカリ金属又はアンモニウム
基を示す］
で表わされるアミノアルキレンホスホン酸、
一般式
［式中ｎは１〜３の整数、Ｚは前式と同義であ
る］
で表わされるエチレンジアミンテトラアルキレン
ホスホン酸、
一般式
［式中、Ｒは水素原子又は低級アルキル基、Ｚは
前式と同義である］
で表わされるアルキルメタン−１−ヒドロキシ−
１，１−ジホスホン酸又はそれ等の塩から選ばれ
た１種又は２種以上の有機ホスホン酸（塩）との
反応により生成する亜リン酸リン酸亜鉛カリウム
系化合物を有効成分とすることを特徴とする防錆
顔料にかかるものである。
本発明にかかる防錆顔料において、有効成分と
して含有される亜リン酸リン酸亜鉛カリウム系化
合物の生成に使用できる原料のうち亜鉛化合物と
しては、例えば酸化亜鉛、水酸化亜鉛、炭酸亜
鉛、塩基性炭酸亜鉛、リン酸亜塩、リン酸水素亜
鉛、活性亜鉛華等の酸化亜鉛又はそれを生成させ
うる亜鉛化合物、カリウム化合物としては、酸化
カリウム、水酸化カリウム、リン酸カリウム、リ
ン酸水素カリウム、炭酸カリウム、炭酸水素カリ
ウム等の酸化カリウム又はそれを生成しうるカリ
ウム化合物、リン酸化合物としては、リン酸、リ
ン酸亜鉛、リン酸水素亜鉛、リン酸カリウム、リ
ン酸水素カリウム等のリン酸又はそれを生成しう
るリン酸化合物および亜リン酸化合物としては、
亜リン酸、亜リン酸カリウム等の亜リン酸又はそ
れを生成しうる亜リン酸カリウム化合物等が適当
である。
また、有機ホスホン酸（塩）としては一般式
RmN［（CH2）nP（Ｏ）（OZ）2］3-o………（）
［式中Ｒは低級アルキル基、ｍは０〜３、ｎ＝１
〜２、Ｚは水素、アルカリ金属又はアンモニウム
基を表わす］
で表わされるアミノアルキレンホスホン酸又はそ
の塩、一般式
［式中ｎは１〜３の整数、Ｚは前式と同義であ
る］
で表わされるエチレンジアミンテトラアルキレン
ホスホン酸又はその塩、および一般式
［式中、Ｒは水素原子又は低級アルキル基、Ｚは
前式と同義である］
で表わされるアルキルメタン−１−ヒドロキシ−
１，１−ジホスホン酸又はその塩である。
上記一般式（）、（）、（）で表わされる化
合物のうち、（）式の化合物としては例えばニ
トリロトリスメチレンホスホン酸、ニトリロトリ
スエチレンホスホン酸、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
等であり、（）式の化合物として例えばエチレ
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、（）式の
化合物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−ジホスホン酸及びそれ等の塩とし
ては、上記化合物のナトリウム、カリウム又はア
ンモニウム基で一部又は全部中和されたものがあ
げられ、それらは１種又は２種以上であつてもよ
い。
本発明にかかる防錆顔料は、上記の５種の化合
物を原料として湿式混合による反応によつて生成
する白色不溶性物質の亜リン酸リン酸亜鉛カリウ
ム系化合物を有効成分とするものであるが反応を
行うに当り原料の種類や、反応装置の如何によつ
て種々の混合反応が採用されるので所望の方式を
適宜設定することができる。例えば代表的には亜
鉛化合物例えば酸化亜鉛を分散させたカリウム化
合物例えば水酸化カリウム水溶液（Ａ液）にリン
酸化合物例えばリン酸、亜リン酸化合物例えば亜
リン酸および有機ホスホン酸（塩）からなる水溶
液（Ｂ液）を滴下する方法あるいはＡ液とＢ液と
を同時に接触混合させる方法、酸化亜鉛水性スラ
リーに亜リン酸、リン酸、有機ホスホン酸（塩）
および水酸化カリウム水溶液を個別かつ同時又は
個別経時的に添加する方法、又は亜リン酸、リン
酸および有機ホスホン酸（塩）混合水溶液に水酸
化カリウムを添加して中和しておき、これと亜鉛
化合物と混合する方法などがあげられるが必ずし
も上記に提案されるものではない。また、この反
応はバツチ式、連続式のいずれも可能であり、反
応装置によつては通常の撹拌混合、スタテイクミ
キサーでの混合、剪断混合あるいはそれらの組合
せにより均一な混合反応を行わせる。
上記反応において、有機ホスホン酸（塩）は、
亜リン酸の代替原料として用いられるもので亜リ
ン酸に対して少なくとも２重量％以上が必要であ
る。この理由は、２重量％未満の場合はその添加
に基づく防錆性の向上が認められないからで、そ
の添加量の上限は特に限定はないが、30重量％、
好ましくは20重量％までである。
本反応の機構は反応系が複雑で明らかではない
が有機ホスホン酸（塩）を除いて考えた場合、原
理的には、次式の反応式
aK2O＋bZnO＋cH2PHO3＋dH3PO4
→（１−ｘ）K2O・xZnO・ｙ［（１−ｚ）H2P
HO3・２／３zH3PO4］・nH2O………（）
によつて示され、有機ホスホン酸（塩）は反応し
て母液には実質的に存在しないところから、上記
亜リン酸の一部が上記割合において代替し存在し
ているものと推定される。
従つて、本発明に係る亜リン酸リン酸亜鉛カリ
ウム系化合物は、上記原料による反応生成物であ
るが、好ましくは上記式において0.67≦ｘ＜
0.98、0.2＜ｙ＜１、０＜ｚ＜1.3、３（１−ｘ）≦
ｙおよび０≦ｎ≦1.3で表わされ、かつ亜リン酸
に対し、有機ホスホン酸（塩）が少なくとも２重
量％以上存在しているものからなる化合物であ
る。
従つて、本反応における各原料の反応割合は、
上記のｘ、ｙ、ｚの限定によりこれに相当する割
合に、ａ、ｂ、ｃ及びｄが自ずと限定される。
反応は、通常は常圧下で行なわれ、特に加圧す
る必要はない。反応温度は通常、常温から約100
℃の範囲で行なわれ、特に冷却する必要はない。
しかし反応速度は温度に比例するので反応の完結
までに室温では約10時間、100℃では約１時間を
要する。
反応系原液の滴下速度は反応温度が低いときに
はゆつくりと、反応温度が高いときには早くてよ
い。但し、早急に調合すると粗い粒子が出来、湿
式ボールミル等で粉砕する必要が生ずる。
反応系原液は分散液又は水溶液であるが、その
濃度は如何なる濃度でもよいけれども、極度に低
濃度の場合には濾液が多量になり、又、高濃度の
場合には反応液の充分な撹拌が困難になるので通
常の沈澱反応における常識的濃度を選定すること
が望ましい。
反応は充分に撹拌をしながら行なわれるので、
それに適する撹拌機と反応容器を用いるのがよ
い。
このような適宜の反応条件下で、必要に応じて
加熱、撹拌を行ない完全に反応が終了した後、常
法により濾過して沈澱を分離し、乾燥、粉砕して
製品とする。製品は特に水洗の必要は無く、又、
乾燥温度は一般に100〜250℃で行なうのがよい。
このようにして得られた亜リン酸リン酸亜鉛カ
リウム系化合物は白色の製品で、適切な反応条件
を選ぶことによつて、特別に粒度の調節をしなく
とも顔料として使用可能な適宜の粒度の製品が得
られる利点がある。
又、本発明にかかる防錆顔料は原料のカリウム
化合物、亜鉛化合物及びリン酸化合物、亜リン酸
化合物および有機ホスホン酸（塩）を適宜に選定
することにより、亜リン酸リン酸亜鉛カリウムを
必ず含有した白色の製品を得ることが出来る。な
お防錆顔料としては、いずれの組成又はいずれの
方法によつても同様の効果を示すことから、主と
して塩基性亜リン酸リン酸亜鉛カリウムに起因す
る作用と考えられる。従つて、本発明において亜
リン酸リン酸亜鉛カリウム系化合物を有効成分と
する防錆顔料というのは化学物質としては、有機
ホスホン酸（塩）含有の塩基性亜リン酸リン酸亜
鉛カリウム［Ａ］単独か、［Ａ］と例えば亜リン
酸カリウム、亜リン酸亜鉛、リン酸カリウム、有
機ホスホン酸カリウム、有機ホスホン酸亜鉛、リ
ン酸亜鉛、リン酸亜鉛、亜リン酸カリウム亜鉛、
有機ホスホン酸カリウム亜鉛、リン酸カリウム亜
鉛、及び未反応亜鉛化合物等の少なくとも１種と
の混合物又は複塩として存在するものをいい、多
くの場合、実質的にはＸ線回析上ピークが認めら
れない非晶質の白色微細粒子物質である。有機ホ
スホン酸（塩）の使用量が少ない場合、生成物中
に例えば未反応亜鉛華などのＸ線回析線が反応に
よつては認められることがある。
従つて、如何なる組成又は製法の態様を選択す
るかは、原料の種類や製品の具体的用途に応じて
適宜決定すればよい。
本発明にかかる防錆顔料において、有機ホスホ
ン酸（塩）含有の塩基性亜リン酸リン酸亜鉛カリ
ウム系化合物が防錆性に優れている理由は詳細に
は不明ではあるが、恐らく原料の有機ホスホン酸
（塩）がいずれも金属キレート作用に優れている
ので、亜鉛イオンとキレート化していることが推
定され、このことが、単なる無機リン酸よりも防
錆性に優れた作用を発揮させるものと思われる。
次に、本発明の効果を列挙すると下記の通りで
ある。
(1) 本発明の防錆顔料は無公害、低毒性の白色の
防錆顔料として有利な利用価値を有し、白色で
あるために自由に調色が出来るので防錆効果の
ある調合ペイントの製造が可能である。
(2) 本発明の防錆顔料を構造物用塗料である乾性
油を用いたJIS塗料として使用する場合、従来
の鉛系の防錆顔料配合品に比べて防錆力は同等
であり、特にクロム酸系の防錆顔料より優れた
防錆力を有する。
(3) 本発明の製品は無公害、低毒性であるため
に、特に食品分野において有用であり、食品関
係の工場又は冷蔵庫、冷凍庫、電子レンジ、食
品用ケースその他厨房用品等の食品関係機器の
防錆顔料として、或いは子供用の玩具用防錆塗
料用として利用できる。
(4) 合成樹脂の添加剤、触媒及び環元剤としての
利用も可能である。
以下に実施例及び比較例により本発明を具体的
に説明する。
実施例 １〜８
表１に示す量の水酸化カリウムを70mlの水に溶
解し、次いで、酸化亜鉛13.8ｇを加え10分間撹拌
する。これをＡ液とする。一方亜リン酸12.7ｇを
75mlの水に溶解し、正リン酸（75％）0.7ｇ及び
表１に示す量の有機ホスホン酸（塩）を加えた後
全量を80mlとする。これをＢ液とする。
液温が50℃以下で撹拌下にあるＢ液にＡ液を約
90分間で滴下し、終了後更に10分間撹拌し液温を
70℃に上げて１時間加熱熟成した。
反応後、常法に従つて固液を分離し、約120℃
で１時間乾燥、粉砕して白色無定形の防錆顔料を
得た。
The present invention relates to an anticorrosion pigment containing an improved potassium phosphite zinc phosphate compound as an active ingredient. Hitherto, red lead or zinc chromate has been widely used as the most typical rust-preventing pigment. These anti-rust pigments exhibit extremely excellent anti-rust properties, but their toxicity has recently become an issue because they contain toxic metals such as lead and chromium. Alternatively, there was a demand for the development of non-polluting rust-preventing pigments. In response to this demand, many proposals have been made as non-polluting rust-preventing pigments. So far, non-polluting rust-preventing pigments have been used as (a) metal condensed phosphates, such as condensed aluminum phosphate, (b) metal phosphates, such as silicon phosphate, titanium phosphate, and (C) metal phosphites. (d) metal hypophosphites such as calcium hypophosphite or iron hypophosphite; and (e) metal molybdates such as zinc salts, calcium salts. Although many proposals have been made, these non-polluting rust-preventing pigments are not definitive as rust-preventing pigments whose rust-preventing power is comparable to lead-based and chromate-based pigments. Therefore, at present, two or three of these proposed pigments are used in combination in order to obtain the necessary rust prevention properties. By the way, the present applicant has developed a white potassium zinc phosphite pigment that is non-polluting and has excellent rust prevention properties, unlike the conventional rust prevention pigments, and has already filed a patent application (Japanese Patent Application No. 80090). The present invention was completed as a result of research to further improve the rust prevention properties of the above pigments, and it was discovered that the effect is remarkable when a portion of phosphorous acid is used as an organic phosphonic acid (salt). be. That is, the present invention provides a zinc compound, a potassium compound, a phosphorous acid compound, a phosphoric acid compound, and at least 2% by weight or more of the general formula RmN[(CH 2 )nP(O)(OZ) 2 based on the phosphorous acid. ] 3-o [In the formula, R is a lower alkyl group, m is 0 to 3, n = 1
~2, Z represents hydrogen, alkali metal or ammonium group] Aminoalkylenephosphonic acid represented by the general formula [In the formula, n is an integer of 1 to 3, Z has the same meaning as in the previous formula] Ethylenediaminetetraalkylenephosphonic acid represented by the general formula [In the formula, R is a hydrogen atom or a lower alkyl group, and Z has the same meaning as the previous formula] Alkylmethane-1-hydroxy-
The active ingredient is a phosphorous acid zinc phosphate potassium compound produced by a reaction with one or more organic phosphonic acids (salts) selected from 1,1-diphosphonic acid or salts thereof. This relates to the characteristic rust-preventing pigment. In the rust preventive pigment according to the present invention, among the raw materials that can be used to produce the potassium phosphite zinc phosphate compound contained as an active ingredient, zinc compounds include, for example, zinc oxide, zinc hydroxide, zinc carbonate, basic Zinc oxide such as zinc carbonate, subsalt phosphate, zinc hydrogen phosphate, activated zinc white, etc., or zinc compounds and potassium compounds that can produce it, include potassium oxide, potassium hydroxide, potassium phosphate, potassium hydrogen phosphate, Potassium oxides such as potassium carbonate and potassium hydrogen carbonate, or potassium compounds and phosphoric acid compounds that can produce them, include phosphoric acids such as phosphoric acid, zinc phosphate, zinc hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, etc. The phosphoric acid compounds and phosphorous acid compounds that can produce it are:
Phosphorous acid, potassium phosphite, and other potassium phosphite compounds that can produce phosphorous acid are suitable. In addition, as an organic phosphonic acid (salt), the general formula RmN[( CH2 )nP(O)(OZ) 2 ] 3-o ......() [wherein R is a lower alkyl group, m is 0 to 3, n=1
~2, Z represents hydrogen, alkali metal or ammonium group] Aminoalkylenephosphonic acid or its salt represented by the general formula [In the formula, n is an integer of 1 to 3, Z has the same meaning as in the previous formula] Ethylenediaminetetraalkylenephosphonic acid or a salt thereof represented by the following, and the general formula [In the formula, R is a hydrogen atom or a lower alkyl group, and Z has the same meaning as the previous formula] Alkylmethane-1-hydroxy-
1,1-diphosphonic acid or a salt thereof. Among the compounds represented by the above general formulas (), (), and (), examples of the compounds of formula () include nitrilotrismethylenephosphonic acid, nitrilotrisethylenephosphonic acid, nitrilotrispropylenephosphonic acid, nitrilodiethylmethylenephosphonic acid, Nitrilopropyl bismethylene phosphonic acid, etc. Compounds of formula () include ethylenediaminetetramethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, ethylenediaminetetrapropylenephosphonic acid, and compounds of formula () include, for example, methane-1-hydroxy-
1,1-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid and salts thereof include sodium, potassium or ammonium groups of the above compounds. Examples include those that are partially or completely neutralized, and one or more of them may be used. The anticorrosion pigment according to the present invention has as an active ingredient a potassium phosphite zinc phosphite compound, which is a white insoluble substance produced by a wet mixing reaction using the five types of compounds listed above as raw materials. In carrying out this process, various mixed reactions can be adopted depending on the type of raw materials and the type of reaction apparatus, so a desired method can be set as appropriate. For example, it typically consists of a potassium compound such as a potassium hydroxide aqueous solution (liquid A) in which a zinc compound such as zinc oxide is dispersed, a phosphoric acid compound such as phosphoric acid, a phosphorous acid compound such as phosphorous acid, and an organic phosphonic acid (salt). A method of dropping an aqueous solution (liquid B) or a method of contacting and mixing liquids A and B at the same time, adding phosphorous acid, phosphoric acid, and organic phosphonic acid (salt) to zinc oxide aqueous slurry.
and potassium hydroxide aqueous solution individually and simultaneously or separately over time, or by adding potassium hydroxide to a mixed aqueous solution of phosphorous acid, phosphoric acid, and organic phosphonic acid (salt) to neutralize it. Examples include a method of mixing with a zinc compound, but this is not necessarily the method proposed above. Further, this reaction can be carried out either batchwise or continuously, and depending on the reactor, a uniform mixing reaction can be carried out by ordinary stirring mixing, mixing in a static mixer, shearing mixing, or a combination thereof. In the above reaction, the organic phosphonic acid (salt) is
It is used as a substitute raw material for phosphorous acid, and must be used in an amount of at least 2% by weight based on the phosphorous acid. The reason for this is that if the amount is less than 2% by weight, no improvement in rust prevention is observed due to its addition.There is no particular upper limit to the amount added, but 30% by weight,
Preferably up to 20% by weight. The mechanism of this reaction is not clear due to the complexity of the reaction system, but if we exclude the organic phosphonic acid (salt), in principle the reaction formula is as follows: aK 2 O + bZnO + cH 2 PHO 3 + dH 3 PO 4 → (1 −x)K 2 O・xZnO・y[(1−z)H 2 P
HO 3・2/3zH 3 PO 4 ]・nH 2 O……() Since the organic phosphonic acid (salt) reacts and is not substantially present in the mother liquor, the above phosphorous acid It is estimated that a part of the above exists in place of the above ratio. Therefore, the potassium zinc phosphite phosphite compound according to the present invention is a reaction product of the above-mentioned raw materials, and preferably satisfies 0.67≦x< in the above formula.
0.98, 0.2<y<1, 0<z<1.3, 3(1-x)≦
It is a compound represented by y and 0≦n≦1.3, and in which organic phosphonic acid (salt) is present in an amount of at least 2% by weight based on phosphorous acid. Therefore, the reaction ratio of each raw material in this reaction is
Due to the above limitations on x, y, and z, a, b, c, and d are naturally limited to corresponding proportions. The reaction is usually carried out under normal pressure, and there is no need to apply particular pressure. The reaction temperature is usually about 100℃ from room temperature.
It is carried out in the range of °C, and there is no need for particular cooling.
However, since the reaction rate is proportional to temperature, it takes about 10 hours to complete the reaction at room temperature and about 1 hour at 100°C. The dropping rate of the reaction stock solution may be slow when the reaction temperature is low, or fast when the reaction temperature is high. However, if the mixture is prepared too quickly, coarse particles will be formed, which will require pulverization using a wet ball mill or the like. The reaction stock solution is a dispersion or an aqueous solution, and its concentration may be any concentration, but if the concentration is extremely low, a large amount of filtrate will be produced, and if the concentration is high, sufficient stirring of the reaction solution may be required. Since this may be difficult, it is desirable to select a concentration that is common sense in ordinary precipitation reactions. The reaction takes place with sufficient stirring, so
It is advisable to use a suitable stirrer and reaction vessel. Under such appropriate reaction conditions, heating and stirring are performed as necessary to complete the reaction, and then the precipitate is separated by filtration by a conventional method, dried and pulverized to obtain a product. The product does not need to be washed with water, and
The drying temperature is generally preferably 100 to 250°C. The potassium zinc phosphite compound obtained in this way is a white product, and by selecting appropriate reaction conditions, it can be used as a pigment without any special particle size adjustment. This product has the advantage of being obtained. In addition, the anticorrosive pigment of the present invention can be produced by appropriately selecting the raw materials potassium compound, zinc compound, phosphoric acid compound, phosphorous acid compound, and organic phosphonic acid (salt) to ensure that potassium phosphite and zinc phosphate are not contained. A white product can be obtained. As a rust-preventing pigment, the effect is thought to be mainly due to the basic phosphorous acid zinc potassium phosphate, since the same effect is exhibited regardless of the composition or method. Therefore, in the present invention, the anticorrosion pigment containing a potassium phosphite zinc phosphate compound as an active ingredient is a basic potassium phosphite zinc phosphate [A ] Alone or with [A], for example, potassium phosphite, zinc phosphite, potassium phosphate, potassium organic phosphonate, zinc organic phosphonate, zinc phosphate, zinc phosphate, potassium zinc phosphite,
Refers to a substance that exists as a mixture or double salt with at least one of potassium zinc organic phosphonate, potassium zinc phosphate, and an unreacted zinc compound, and in many cases, substantially a peak is observed in X-ray diffraction. It is a non-crystalline white fine particle substance. When the amount of organic phosphonic acid (salt) used is small, X-ray diffraction lines such as unreacted zinc white may be observed in the product depending on the reaction. Therefore, the composition or manufacturing method to be selected may be appropriately determined depending on the type of raw materials and the specific use of the product. The reason why the basic phosphorous acid zinc potassium phosphate compound containing organic phosphonic acid (salt) has excellent rust preventive properties in the rust preventive pigment of the present invention is not clear in detail, but it is probably due to the organic Since all phosphonic acids (salts) have excellent metal chelating effects, it is presumed that they chelate with zinc ions, and this is what allows them to exhibit superior rust prevention properties compared to simple inorganic phosphoric acid. I think that the. Next, the effects of the present invention are listed below. (1) The anti-corrosion pigment of the present invention has advantageous utility as a non-polluting, low-toxic white anti-corrosion pigment, and since it is white, the color can be adjusted freely, so it can be used as a compound paint with anti-rust effect. Manufacture is possible. (2) When the rust-preventive pigment of the present invention is used as a JIS paint using drying oil, which is a paint for structures, the rust-preventive power is equivalent to that of conventional lead-based rust-preventive pigment formulations; It has better anti-corrosion properties than chromic acid-based anti-rust pigments. (3) Since the product of the present invention is non-polluting and has low toxicity, it is particularly useful in the food field, and is used in food-related factories or food-related equipment such as refrigerators, freezers, microwave ovens, food cases, and other kitchen utensils. It can be used as a rust-preventing pigment or as a rust-preventing paint for children's toys. (4) It can also be used as an additive, catalyst, and ring agent for synthetic resins. The present invention will be specifically explained below using Examples and Comparative Examples. Examples 1-8 Potassium hydroxide in the amount shown in Table 1 is dissolved in 70 ml of water, then 13.8 g of zinc oxide is added and stirred for 10 minutes. This is called liquid A. Meanwhile, 12.7g of phosphorous acid
Dissolve in 75 ml of water, add 0.7 g of orthophosphoric acid (75%) and the amount of organic phosphonic acid (salt) shown in Table 1, and make the total volume 80 ml. This is called liquid B. Add liquid A to liquid B under stirring at a liquid temperature of 50°C or below.
Drop the mixture over 90 minutes, then stir for another 10 minutes to bring the temperature down.
The temperature was raised to 70°C and the mixture was heated and aged for 1 hour. After the reaction, separate the solid and liquid according to a conventional method and heat at approximately 120℃.
The mixture was dried for 1 hour and ground to obtain a white amorphous antirust pigment.
【表】【table】
【表】
比較例 １〜３
実施例１と同様の操作によつて比較試料を得
た。但し有機ホスホン酸（塩）の替わりに表２に
示す量の有機ホスホン酸（塩）無添加、代表的キ
レート剤であるEDTAを使用した。[Table] Comparative Examples 1 to 3 Comparative samples were obtained in the same manner as in Example 1. However, instead of the organic phosphonic acid (salt), EDTA, which is a typical chelating agent, was used without the addition of organic phosphonic acid (salt) in the amount shown in Table 2.
【表】
試験例 １
次に、実施例１〜８及び比較例１〜３の防錆顔
料の防錆試験結果を示す。
◎塗料化方法
下記の配合組成で塗料化を行つた。
防錆顔料 3.0重量部
二酸化チタン（ルチル型） 12.0重量部
沈降性硫酸バリウム 32.0重量部
ビヒクル（注１） 40.0重量部
ミネラルスピリツト 12.0重量部
ドライヤー（注２） 1.0重量部
但し
注１ ベツコゾール1334［大日本インキ化学(株)］
不揮発分50％、中油アルキツド樹脂
注２ 液状ドライヤー（JIS Ｋ−5691、１種
Ａ）
上記の配合原料とガラスビーズ［東芝硝子(株)
製GB603］100ｇを200mlのマヨネーズビンに
入れ、ペイントシエーカーを用いて１時間分散
させて塗料化した。
◎防錆試験
上記の方法で製造した塗料を冷間圧延鋼板
［日本テストパネル工業(株)製JIS G3141、SPCC
−SB、1.0×70×150mm］にバーコーターを用
いて１回塗りし、乾燥後の膜厚が15μｍになる
ようにする。この後、上塗りをすることなく、
５％食塩水によるJIS K5400の塩水噴霧試験
［スガ試験機(株)製、塩水噴霧試験機ST−ISO−
２を使用］を行うことにより防錆能力の性能評
価をした。
防錆試験の結果は表３の通りである。[Table] Test Example 1 Next, the rust prevention test results of the rust prevention pigments of Examples 1 to 8 and Comparative Examples 1 to 3 are shown. ◎Painting method Painting was carried out using the following composition. Rust preventive pigment 3.0 parts by weight Titanium dioxide (rutile type) 12.0 parts by weight Precipitated barium sulfate 32.0 parts by weight Vehicle (Note 1) 40.0 parts by weight Mineral spirits 12.0 parts by weight Dryer (Note 2) 1.0 parts by weight However, Note 1 Betucosol 1334 [ Dainippon Ink Chemical Co., Ltd.]
Non-volatile content 50%, medium oil alkyd resin Note 2 Liquid dryer (JIS K-5691, Class 1A) The above compounded raw materials and glass beads [Toshiba Glass Corporation]
GB603] was placed in a 200ml mayonnaise bottle and dispersed for 1 hour using a paint shaker to form a paint. ◎Rust prevention test The paint produced by the above method was applied to a cold rolled steel plate [JIS G3141 manufactured by Japan Test Panel Industry Co., Ltd., SPCC
-SB, 1.0 x 70 x 150 mm] using a bar coater to coat once to a film thickness of 15 μm after drying. After this, without applying a topcoat,
JIS K5400 salt spray test using 5% saline solution [manufactured by Suga Test Instruments Co., Ltd., salt spray tester ST-ISO-
2] was used to evaluate the rust prevention ability. The results of the rust prevention test are shown in Table 3.
【表】【table】
【表】
試験例 ２
実施例１〜８および比較例１〜３で調製した防
錆顔料および市販の防錆顔料（２種）について、
それぞれ下記の通りに従つた簡易腐食試験によつ
て腐食度（mdd）の７日までの経時変化を測定し
たところ表４に示す結果が得られた。又、この結
果より、１日および２日後の腐食度と有機ホスホ
ン酸（塩）量との関係を調べたところ、第１図お
よび第２図に示すグラフが得られた。[Table] Test Example 2 Regarding the rust preventive pigments prepared in Examples 1 to 8 and Comparative Examples 1 to 3 and commercially available rust preventive pigments (2 types),
When the change in corrosion degree (mdd) over time was measured for up to 7 days by a simple corrosion test according to the following procedure, the results shown in Table 4 were obtained. Furthermore, based on these results, the relationship between the degree of corrosion after 1 day and 2 days and the amount of organic phosphonic acid (salt) was investigated, and the graphs shown in FIGS. 1 and 2 were obtained.
【表】【table】
【表】
＜簡易腐食試験法＞
(i) 試験液…３重量％の食塩水500ｇに試験試料
（防錆顔料）0.5ｇを加えたものを試験液とす
る。
(ii) テスト鋼板…30ｍ／ｍ×50ｍ／ｍ×３ｍ／ｍ
の冷間圧延鋼板（JIS−Ｇ−3141、SPCC−Ｂ）
を用い、表面を耐水研磨紙（JIS R6253、
CC320番）で磨き、アセトンおよびエタノール
で洗浄後乾燥し、常温で１時間以上デシケータ
ー中で放置後使用する。
(iii) 測定法…冷却還流器付の円筒形ガラス容器に
試験液を入れ、テスト鋼板をビニール糸にて容
器中央部に吊す。これを50±２℃に設定した恒
温水槽に入れ、液を50℃に保ちつつ0.5／
minの空気をガス分散管より吹込む。この状態
において、24時間毎にテスト鋼板を取り出し、
ナイロンブラシで付着物を除去して水洗、更に
黄銅ブラシで付着物を取除いた後水洗し、エタ
ノール洗浄した後乾燥したものを常温で１時間
以上デシケーター中にて放置後重量測定して変
化を0.1mgまで量る。これより試験前後の質量
差より腐食度（mdd＝mg／ｄm2／day）を算出
する。なお試験はくり返し２回行い、その平均
値を測定値とする。[Table] <Simple corrosion test method> (i) Test liquid: Add 0.5 g of the test sample (rust-preventing pigment) to 500 g of 3% by weight salt solution as the test liquid. (ii) Test steel plate…30m/m×50m/m×3m/m
Cold rolled steel plate (JIS-G-3141, SPCC-B)
using waterproof abrasive paper (JIS R6253,
CC320), wash with acetone and ethanol, dry, and leave in a desiccator for at least 1 hour at room temperature before use. (iii) Measurement method: Put the test liquid in a cylindrical glass container equipped with a cooling reflux device, and hang the test steel plate in the center of the container with a vinyl string. This was placed in a constant temperature water bath set at 50±2℃, and while keeping the liquid at 50℃,
Blow in min air from the gas dispersion tube. In this state, take out the test steel plate every 24 hours,
Remove the deposits with a nylon brush, wash with water, then remove the deposits with a brass brush, wash with water, wash with ethanol, dry, leave in a desiccator at room temperature for more than 1 hour, then weigh and check for changes. Weigh to 0.1 mg. From this, the degree of corrosion (mdd=mg/dm 2 /day) is calculated from the difference in mass before and after the test. The test is repeated twice, and the average value is taken as the measured value.
第１図および第２図は、本発明にかかる防錆顔
料において有機ホスホン酸（塩）添加量に対する
腐食度との関係を示すグラフである。
FIGS. 1 and 2 are graphs showing the relationship between the amount of organic phosphonic acid (salt) added and the degree of corrosion in the anticorrosion pigment according to the present invention.
Claims (1)
物、リン酸化合物および、亜リン酸に対して少な
くとも２重量％以上の 一般式 RmN［（CH2）nP（Ｏ）（OZ）2］3-o ［式中Ｒは低級アルキル基、ｍは０〜３、ｎ＝１
〜２、Ｚは水素、アルカリ金属又はアンモニウム
基を示す］ で表わされるアミノアルキレンホスホン酸、 一般式 ［式中ｎは１〜３の整数、Ｚは前式と同義であ
る］ で表わされるエチレンジアミンテトラアルキレン
ホスホン酸、 一般式 ［式中、Ｒは水素原子又は低級アルキル基、Ｚは
前式と同義である］ で表わされるアルキルメタン−１−ヒドロキシ−
１，１−ジホスホン酸又はそれ等の塩から選ばれ
た１種又は２種以上の有機ホスホン酸（塩）との
反応により生成する亜リン酸リン酸亜鉛カリウム
系化合物を有効成分とすることを特徴とする防錆
顔料。[Claims] 1. A zinc compound, a potassium compound, a phosphorous acid compound, a phosphoric acid compound, and at least 2% by weight or more of the general formula RmN[(CH 2 )nP(O)(OZ) based on the phosphorous acid. 2 ] 3-o [In the formula, R is a lower alkyl group, m is 0 to 3, n = 1
~2, Z represents hydrogen, alkali metal or ammonium group] Aminoalkylenephosphonic acid represented by the general formula [In the formula, n is an integer of 1 to 3, Z has the same meaning as in the previous formula] Ethylenediaminetetraalkylenephosphonic acid represented by the general formula [In the formula, R is a hydrogen atom or a lower alkyl group, and Z has the same meaning as the previous formula] Alkylmethane-1-hydroxy-
The active ingredient is a phosphorous acid zinc phosphate potassium compound produced by a reaction with one or more organic phosphonic acids (salts) selected from 1,1-diphosphonic acid or salts thereof. A characteristic anti-rust pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23267683A JPS60124660A (en) | 1983-12-12 | 1983-12-12 | Rust-resisting pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23267683A JPS60124660A (en) | 1983-12-12 | 1983-12-12 | Rust-resisting pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60124660A JPS60124660A (en) | 1985-07-03 |
| JPH0256377B2 true JPH0256377B2 (en) | 1990-11-30 |
Family
ID=16943043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23267683A Granted JPS60124660A (en) | 1983-12-12 | 1983-12-12 | Rust-resisting pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60124660A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69533671T8 (en) * | 1995-08-25 | 2006-06-08 | Grace Gmbh & Co. Kg | Anticorrosive pigments and compositions containing them |
-
1983
- 1983-12-12 JP JP23267683A patent/JPS60124660A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60124660A (en) | 1985-07-03 |
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