JP6118588B2 - Rust conversion agent for anticorrosion - Google Patents
Rust conversion agent for anticorrosion Download PDFInfo
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- JP6118588B2 JP6118588B2 JP2013042387A JP2013042387A JP6118588B2 JP 6118588 B2 JP6118588 B2 JP 6118588B2 JP 2013042387 A JP2013042387 A JP 2013042387A JP 2013042387 A JP2013042387 A JP 2013042387A JP 6118588 B2 JP6118588 B2 JP 6118588B2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 68
- 238000006243 chemical reaction Methods 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229940074391 gallic acid Drugs 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- -1 silicate compound Chemical class 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 7
- 239000001263 FEMA 3042 Substances 0.000 description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 7
- 235000015523 tannic acid Nutrition 0.000 description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 7
- 229940033123 tannic acid Drugs 0.000 description 7
- 229920002258 tannic acid Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- YISKQXFNIWWETM-UHFFFAOYSA-N magnesium;dinitrate;hydrate Chemical compound O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YISKQXFNIWWETM-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- 230000000007 visual effect Effects 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Description
本発明は防食用錆転換剤に関する。 The present invention relates to an anticorrosive rust conversion agent.
建造物の鉄骨部分は、その建造物の構造部分として、特に強度面が重要である。近年、鉄骨部分の老朽化が進んでおり、メンテナンスの時期を迎えている。前記鉄骨部分の老朽化は、鉄部に赤錆が発生することにより、強度等の低下が起こる。
従来、前記赤錆を除去する方法として、機械的方法としては、サンドブラスト、ショットブラスト等を行っていが、騒音、環境、コスト面等で問題となっている。
また、騒音、環境、コスト面等の問題を解決するために、前記赤錆を除去する方法として、化学的方法が用いられている。前記化学的方法としては、塩酸、硫酸、佛酸等の強酸を用い、赤錆を溶かし、除去する方法が一般的に行われている。
The strength of the steel frame portion of the building is particularly important as the structural portion of the building. In recent years, the aging of the steel frame has progressed, and it is time for maintenance. In the aging of the steel frame part, red rust is generated in the iron part, resulting in a decrease in strength and the like.
Conventionally, as a method for removing the red rust, sand blasting, shot blasting, and the like are performed as mechanical methods, but there are problems in terms of noise, environment, cost, and the like.
Further, in order to solve problems such as noise, environment, and cost, a chemical method is used as a method for removing the red rust. As the chemical method, a method of dissolving and removing red rust using a strong acid such as hydrochloric acid, sulfuric acid, and oxalic acid is generally performed.
しかし、塩酸、硫酸、佛酸等の強酸で赤錆を溶かして除去する前記化学的方法は、建造物の構造部分である鉄骨部分への影響が問題となっている。
また、それ以外の化学的方法としては、特許文献１には、硝酸マグネシウムの水和物に酸性フッ化アンモニウムを溶解し、界面活性剤としてポリエチレングリコールを添加した赤錆の除去剤が提唱されているが、広範囲において、赤錆が除去されているかは、十分に開示されていない。
また、特許文献２には、ボイラー等の容器の腐食防止を目的にボイラー水の中にアルカリ側でグルコン酸、キシリトール等を混ぜることにより防食防止が開示されているが、気化性錆止め剤の一種であり、長期の防食機能ではない。
また、特許文献３には、マグネタイトは磁性をもつことから磁石により赤錆を黒錆化することが提案されている。しかし、黒錆化するのに長時間必要であることや設備が必要なことから現場等の一般的な施工はできない。
また、特許文献４には、現場施工の手法として水性コーティングが開示されているが、リン酸系の防食用錆転換剤であるため、反応が遅く、かつ浸透力に乏しいため長期の防食は期待できない。
一方、特許文献５には、タンニン酸を用いて赤錆を黒錆に転換する防食用錆転換剤が提唱されているが、タンニン酸の含有量が多いため、防食用転換剤にて処理（下塗り）した後、下塗りに重ねて一般的な塗料を塗布した場合、防食用錆転換剤からタンニン酸が遊離し、塗布する塗料（塗膜）と下塗り層との密着性を低下させる問題がある。
However, hydrochloric acid, the chemical method of removing by dissolving rust sulfate, a strong acid such as Buddha acid, influence on the steel part is a structural part of the denominated creation has become a problem.
As another chemical method, Patent Document 1 proposes a red rust remover obtained by dissolving acidic ammonium fluoride in magnesium nitrate hydrate and adding polyethylene glycol as a surfactant. However, it is not fully disclosed whether red rust has been removed in a wide range.
Patent Document 2 discloses anticorrosion prevention by mixing gluconic acid, xylitol, etc. in the boiler water on the alkali side for the purpose of preventing corrosion of containers such as boilers, but is a kind of vaporizable rust inhibitor. It is not a long-term anticorrosion function.
Patent Document 3 proposes that magnetite has magnetism, so that red rust is converted to black rust with a magnet. However, since it takes a long time for black rusting and facilities are required, general construction at the site or the like is not possible.
In addition, Patent Document 4 discloses an aqueous coating as a technique for on-site construction, but since it is a phosphoric acid-based anticorrosive rust conversion agent, the reaction is slow and the penetration is poor, so long-term anticorrosion is expected. Can not.
On the other hand, Patent Document 5, although anticorrosion rust conversion agent that converts red rust black rust using tannic acid have been proposed, since high content of tannic acid, treated with anti edible conversion agent (undercoat ) And then applying a common paint overlying the undercoat , tannic acid is liberated from the anticorrosive rust conversion agent , and there is a problem of reducing the adhesion between the applied paint (coating film) and the undercoat layer .
特許文献１〜５には、赤錆を除去する赤錆の除去剤または赤錆を黒錆に転換する防食用錆転換剤を用いた化学的方法が開示されている。しかし、特許文献１〜４に開示の赤錆除去剤または防食用錆転換剤は、赤錆の除去が十分は無く、長期の防食機能が期待できないといった問題がある。また、特許文献５に開示されている防食用錆転換剤は、タンニン酸の含有量が多いため、防食用錆転換剤を用いて下塗り層を形成した場合、下塗り層に重ねて形成される塗膜と下塗り層との界面において、防食用錆転換剤からタンニン酸が遊離し、界面の密着性を低下させる問題がある。
本発明は上記事情に鑑みられたものであって、建造物の構造部分である鉄骨部分等、鉄を使用しているあらゆるものの構造部分への影響が少なく、長期の防食機能が期待できる防食用錆転換剤を提供することを目的とする。
Patent Documents 1 to 5 disclose a chemical method using a red rust remover for removing red rust or an anticorrosive rust converter for converting red rust to black rust. However, the red rust remover or anticorrosive rust converter disclosed in Patent Documents 1 to 4 has a problem that red rust is not sufficiently removed and a long-term anticorrosive function cannot be expected. Moreover, since the anticorrosion rust conversion agent disclosed in Patent Document 5 has a large amount of tannic acid, when the undercoat layer is formed using the anticorrosion rust conversion agent, the coating formed on the undercoat layer is overlaid. at the interface between the film and the subbing layer, tannic acid released from the sacrificial rust conversion agent, there is a problem of lowering the adhesion at the interface.
The present invention was obtained in view of the above circumstances, steel part is a structural part of the construction creation such as less impact on the structural part of everything using iron, it can be expected anticorrosion function of the long-life It aims at providing the rust conversion agent for anticorrosion.
本発明者は、上記課題に鑑み、鋭意研究をした結果、フェノール性水酸基を有する化合物と、フッ素化合物と、カルボキシル基含有化合物と、多価アルコール及び水を含む溶媒とを含む防食用錆転換剤を用いることにより、該防食用錆転換剤が建造物の構造部分である鉄骨部分等、鉄を使用しているあらゆるものの構造部分への影響が少なく、長期の防食機能が期待できる防食用錆転換剤を提供できることを見出し、本発明に至った。 The present inventors, in view of the above problems, intensive result of research, the compound having a phenolic hydroxyl group, a fluorine compound, rust anti-corrosive comprising a carboxyl group-containing compounds, polyhydric alcohols and the including Solvent Water by using the conversion agent, steel parts such as-proof edible rust conversion agent is a structural part of the denominated creation, less impact on the structural part of everything using iron, can be expected anticorrosion function of the long-life The present inventors have found that an anticorrosive rust conversion agent can be provided, and have reached the present invention.
即ち、本発明は、フェノール性水酸基を有する化合物０．５質量％〜１０．０質量％と、フッ素化合物（ただし、前記フェノール性水酸基を有する化合物である物を除く。）０．２質量％〜５．０質量％と、カルボキシル基含有化合物（ただし、前記特徴フェノール性水酸基を有する化合物又は前記フッ素化合物である物を除く。）０．５質量％〜１０．０質量％と、多価アルコール及び水を含む溶媒とを含有する防食用錆転換剤である。
前記フェノール性水酸基を有する化合物の少なくとも１つのベンゼン環にフェノール性水酸基を２個以上有することが好ましい。
前記フェノール性水酸基を有する化合物がタンニン酸、没食子酸またはピロガロールであることが好ましい。
前記フッ素化合物がフッ酸、フッ化アンモニウム、酸性フッ化アンモニウム、フッ素カリウム、またはフッ化ナトリウムであることが好ましい。
前記カルボキシル基含有化合物がクエン酸、酒石酸、グリコール酸及びその誘導体またはＥＤＴＡ及びその誘導体であることが好ましい。
前記溶媒のｐＨは、６．０以下であることが好ましい。
前記溶媒中において、水以外の成分に対する水の割合が１０：１〜１：１０であることが好ましい。
That is, in the present invention, 0.5% by mass to 10.0% by mass of a compound having a phenolic hydroxyl group, and 0.2% by mass of a fluorine compound (excluding a compound having a phenolic hydroxyl group). 5.0% by mass, a carboxyl group-containing compound (except the compound having the characteristic phenolic hydroxyl group or the fluorine compound) 0.5% by mass to 10.0% by mass, a polyhydric alcohol, and water is a preventive edible rust conversion agent you containing a including solvent.
It is preferable that at least one benzene ring of the compound having a phenolic hydroxyl group has two or more phenolic hydroxyl groups.
The compound having a phenolic hydroxyl group is preferably tannic acid, gallic acid or pyrogallol.
It is preferable that the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium acid fluoride, potassium fluoride, or sodium fluoride.
The carboxyl group-containing compound is preferably citric acid, tartaric acid, glycolic acid and derivatives thereof, or EDTA and derivatives thereof.
The pH of the pre Ki溶 medium is preferably 6.0 or less.
Prior Ki溶 medium in the proportion of water against the components other than water 10: 1 to 1: preferably from 10.
本発明によれば、建造物の構造部分である鉄骨部分等、鉄を使用しているあらゆるものの構造部分への影響が少なく、長期の防食機能が期待できる防食用錆転換剤を提供することができる。 According to the present invention, such as steel part is a structural part of the denominated creation, less impact on the structural part of everything using iron, corrosion function of long-term to provide an anti edible rust conversion agent that can be expected be able to.
以下、本発明の防食用錆転換剤について詳細に説明する。 Hereinafter, the anticorrosion rust conversion agent of the present invention will be described in detail.
本発明の防食用錆転換剤は、フェノール性水酸基を有する化合物０．５質量％〜１０．０質量％と、フッ素化合物（ただし、前記フェノール性水酸基を有する化合物である物を除く。）０．２質量％〜５．０質量％と、カルボキシル基含有化合物（ただし、前記フェノール性水酸基を有する化合物又は前記フッ素化合物である物を除く。）０．５質量％〜１０．０質量％と、多価アルコール及び水を含む溶媒とを含むことを特徴とする。 The anticorrosive rust converting agent of the present invention comprises 0.5% by mass to 10.0% by mass of a compound having a phenolic hydroxyl group, and a fluorine compound (excluding a compound having a phenolic hydroxyl group). 2% by mass to 5.0% by mass, a carboxyl group-containing compound (excluding the compound having the phenolic hydroxyl group or the compound that is the fluorine compound) 0.5% by mass to 10.0% by mass, and many the polyhydric alcohols and water, characterized in that it comprises a including solvent.
前記フェノ−ル性化合物として、前記フェノ−ル性水酸基を有する化合物の少なくとも１つのベンゼン環にフェノ−ル性水酸基を２個以上有することが好ましく、タンニン酸、没食子酸またはピロガロ−ルであることが最も好ましい。 The phenolic compound preferably has at least one phenolic hydroxyl group in at least one benzene ring of the compound having a phenolic hydroxyl group, and is tannic acid, gallic acid or pyrogallol. Is most preferred.
本発明の防食用錆転換剤において、前記フェノ−ル性水酸基を有する化合物は、防食用錆転換剤全質量に対して０．５質量％〜１０．０質量％であり、０．５質量％〜５．０質量％であることがより好ましく、１．０質量％〜３．０質量％であることが最も好ましい。 In the anticorrosive rust converting agent of the present invention, the compound having a phenolic hydroxyl group is 0.5% by mass to 10.0% by mass with respect to the total mass of the anticorrosive rust converting agent, and 0.5% by mass. More preferably, it is -5.0 mass%, and it is most preferable that it is 1.0 mass%-3.0 mass%.
前記フッ素化合物がフッ酸、中性フッ化アンモニウム、酸性フッ化アンモニウム、フッ素カリウム、またはフッ化ナトリウムであることが好ましい。 The fluorine compound is preferably hydrofluoric acid, neutral ammonium fluoride, acidic ammonium fluoride, potassium fluoride, or sodium fluoride.
本発明の防食用錆転換剤において、前記フッ素化合物は、防食用錆転換剤全質量に対して０．２質量％〜５．０質量％であり、０．２質量％〜３．０質量％であることがより好ましく、０．２質量％〜２．０質量％であることが最も好ましい。 In the anticorrosive rust converting agent of the present invention, the fluorine compound is 0.2% by mass to 5.0% by mass, and 0.2% by mass to 3.0% by mass with respect to the total mass of the anticorrosive rust converting agent. It is more preferable that it is 0.2 mass%-2.0 mass%.
前記カルボキシル基含有化合物がクエン酸、酒石酸、グリコ−ル酸及びその化合物またはＥＤＴＡ及びその化合物であることが好ましい。 The carboxyl group-containing compound is preferably citric acid, tartaric acid, glycolic acid and its compound or EDTA and its compound.
本発明の防食用錆転換剤において、前記カルボキシル基含有化合物は、防食用錆転換剤全質量に対して０．５質量％〜１０．０質量％であり、０．５質量％〜５．０質量％であることがより好ましく、１．０質量％〜４．０質量％であることが最も好ましい。 In the anticorrosive rust converting agent of the present invention, the carboxyl group-containing compound is 0.5% by mass to 10.0% by mass, and 0.5% by mass to 5.0% by mass with respect to the total mass of the anticorrosive rust converting agent. It is more preferable that it is mass%, and it is most preferable that it is 1.0 mass%-4.0 mass%.
前記多価アルコールとしては、特に限定されることはないが、エチレングリコール、グリセリンが挙げられ、グリセリンが最も好ましい。 Although it does not specifically limit as said polyhydric alcohol, Ethylene glycol and glycerol are mentioned, Glycerol is the most preferable.
前記多価アルコール及び水を含む溶媒としては、前記多価アルコールが含まれていれば特に限定されることはないが、前記多価アルコールと共にメタノール、イソプロピルアルコール（以下、「ＩＰＡ」と略称する。）、ブタノール、Ｎ-メチル-2-ピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）、二塩基酸エステル（ＤＢＥ）などの溶媒を含むことが好ましい。 Examples of the polyhydric alcohol and water including Solvent, the polyvalent although is not particularly limited if it contains alcohol, methanol together with the polyhydric alcohol, isopropyl alcohol (hereinafter abbreviated as "IPA" ), Butanol, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dibasic acid ester (DBE) and the like.
また、本発明の防食用錆転換剤において、シリカ成分を含有していても良く、前記シリカ成分は、アルコキシシラン化合物及びその加水分解物、シリケ−ト化合物及びその加水分解物、コロイダルシリカ、シリカ粉体及びその表面修飾物からなる群から選択される少なくとも一つである。 Further, the anticorrosive rust conversion agent of the present invention may contain a silica component, and the silica component is an alkoxysilane compound and a hydrolyzate thereof, a silicate compound and a hydrolyzate thereof, colloidal silica, silica. It is at least one selected from the group consisting of a powder and a surface modification product thereof.
前記シリカ成分を含有する場合には、防食用錆転換剤全質量に対して０．１質量％〜１０．０質量％が好ましく、０．５質量％〜５．０質量％であることが最も好ましい。 When the silica component is contained, the content is preferably 0.1% by mass to 10.0% by mass and most preferably 0.5% by mass to 5.0% by mass with respect to the total mass of the anticorrosive rust conversion agent. preferable.
また、本発明の防食用錆転換剤は、界面活性剤や湿潤剤を併用していても良い。界面活性剤や湿潤剤は特に限定されることはなく、公知のものであればよいが、例えば、界面活性剤としてはイオン性（ノニオン、アニオン）であるものや、非イオン性（ＨＬＢ;１５以上）が挙げられる。 Moreover, the anticorrosive rust conversion agent of this invention may use surfactant and a wetting agent together. The surfactant and the wetting agent are not particularly limited and may be any known one. For example, the surfactant may be ionic (nonionic, anionic) or nonionic (HLB; 15 Above).
前記溶媒のｐＨは、６．０以下であることが好ましく、３．０〜５．０であることが最も好ましい。 PH before Ki溶 medium is preferably 6.0 or less, and most preferably 3.0 to 5.0.
前記溶媒における、水以外の成分に対する水の割合が１０：１〜１：１０であることが好ましく、１０：５〜５：１０がより好ましく、１０：８〜８：１０であることが最も好ましい。 In the solvent, the ratio of water to the components other than water 10: 1 to 1: is preferably 10, 10: 5 to 5: 10, more preferably, 10: 8 to 8: and most preferably 10 .
以下、実施例により本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
試験用基板は、鋼板ＳＵＳ３４０の黒皮を除去し、２年以上自然放置し、錆が鋼板全面に発生している鋼板の浮き錆を３種ケレンで処理し、キシレンで洗浄し、錆板を作製した。 The test substrate removes the black skin of the steel plate SUS340, is left to stand for more than 2 years, the floating rust of the steel plate where rust is generated on the entire surface of the steel plate is treated with three types of keren, washed with xylene, and the rust plate is removed. Produced.
実施例において、使用した防食用錆転換剤の使用材料（化学薬品）を以下に示す。
・没食子酸：関東化学(株)製１級
・クエン酸：昭和化工(株)製
・EDTA;キレスト(株)製
・ピロガロ−ル：純正化学(株)製特級
・酸性フッ化アンモニウム：ステラケミファ(株)製
・中性フッ化アンモニウム：純正化学(株)製特級
・フッ化ナトリウム：純正化学(株)製特級
・フッ化カリウム：純正化学(株)製特級
・フッ酸：森田化学(株)製 ５５％溶液
・リン酸：ラサ工業(株) ７５％溶液
・メタノ−ル：ニッコウケミカル(株)製
・ＩＰＡ：デルタ(株)製
・グリセリン：純正化学(株)製１級
・テトラエトキシシラン（ＴＥＯＳ）；信越シリコ−ン(株)製；ＫＢＥ−０４
・シランカップリング；信越シリコ−ン(株)製；ＫＢＭ−４０３；エポキシ基含有シラン（３−グリシドキシプロピルトリエトキシシラン）
In the examples, the materials (chemicals) used for the anticorrosive rust converter used are shown below.
・ Gallic acid: 1st grade manufactured by Kanto Chemical Co., Ltd. ・ Citric acid: Showa Kako Co., Ltd. ・ EDTA; Kirest Co., Ltd. ・ Pyrogalol: Pure Chemical Co., Ltd. special grade ・ Ammonium acid fluoride: Stellachemifa・ Neutral ammonium fluoride manufactured by: Pure Chemical Co., Ltd. ・ Sodium fluoride: special grade manufactured by Junsei Chemical Co., Ltd. ・ Potassium fluoride: manufactured by Junsei Chemical Co., Ltd. ・ Hydrofluoric acid: Morita Chemical Co., Ltd. ) 55% solution ・ Phosphoric acid: Rasa Kogyo Co., Ltd. 75% solution ・ Methanol: Nikko Chemical Co., Ltd. ・ IPA: Delta Co., Ltd. ・ Glycerin: Pure Chemical Co., Ltd. Class 1 ・ Tetraethoxy Silane (TEOS); Shin-Etsu Silicon Co., Ltd .; KBE-04
Silane coupling; Shin-Etsu Silicon Co., Ltd .; KBM-403; epoxy group-containing silane (3-glycidoxypropyltriethoxysilane)
以下の表１〜４に示す配合にて、防食用錆転換剤を塗布し、さび板に塗布し、塗布後1時間放置した後８０℃、１０分間の乾燥を行ったものを評価基板とし、外観観察を目視により防評価を行った。試験１〜３、５〜６、８〜９、１１〜１３、１５〜２０は実施例であり、試験４、７、１０、１４は比較例である。
・変化なし：黒色しない（赤錆のまま）。
・やや黒色：若干黒色になる（やや赤錆が黒錆に転換されたと考えられる）。
・黒色：全面黒色になる（完全に赤錆が黒錆に転換されたと考えられる）。
In the composition shown in Tables 1 to 4 below, an anticorrosive rust conversion agent was applied, applied to a rust plate, left for 1 hour after application, and then dried at 80 ° C. for 10 minutes as an evaluation substrate. Appearance observation was evaluated by visual observation. Tests 1-3, 5-6, 8-9, 11-13, 15-20 are examples, and tests 4, 7, 10, 14 are comparative examples.
-No change: No black (red rust).
・ Slightly black: Slightly black (slightly red rust converted to black rust).
Black: The entire surface becomes black (it is considered that red rust has been completely converted to black rust).
表１〜４の結果から、本発明の防食用錆転換剤用いることにより、赤錆が黒錆に転換されたと考えられる。また、試験１〜２においては、赤錆が黒錆に転換されたと考えられるものの、フェノール性水酸基を有する化合物である没食子酸の量が多いため、白色の粉末が残存した。 From the results of Tables 1 to 4, it is considered that red rust was converted to black rust by using the anticorrosive rust conversion agent of the present invention. In Tests 1 and 2, although it was considered that red rust was converted to black rust, a large amount of gallic acid, which is a compound having a phenolic hydroxyl group, left a white powder.
試験１８及び２０の配合を塗布量１０ｍ２／ｋｇでさび板に塗布し、塗布後１時間放置した後８０℃、１０分の乾燥し、下塗剤；溶剤系ジンクリッチペイント、中塗剤；溶剤系エポキシ樹脂と上塗剤；水性アクリルウレタン樹脂を全塗膜約１００μｍで塗布後、１日放置した後８０℃、１０分の乾燥し、その後３日放置した試料の塩水噴霧ＪＩＳＺ２３７１で防食性評価を行った。その結果を以下表５に示す。 The composition of Tests 18 and 20 was applied to a rust plate at an application amount of 10 m 2 / kg, left for 1 hour after application, then dried at 80 ° C. for 10 minutes, undercoat; solvent-based zinc rich paint, intermediate coating; Epoxy resin and topcoat; water-based acrylic urethane resin was applied at a total coating thickness of about 100 μm, left to stand for 1 day, dried at 80 ° C. for 10 minutes, and then evaluated for corrosion resistance with salt spray JISZ2371 for 3 days. It was. The results are shown in Table 5 below.
表５の結果より、未処理（赤さびの状態）に比べて極端に防食能が向上していることが判る。 From the results in Table 5, it can be seen that the anticorrosion ability is extremely improved as compared with the untreated (red rust state).
本発明の防食用錆転換剤は、橋、船舶、プラント、建造物の鉄骨部分等、鉄を使用しているあらゆるものの構造部分に対して有用である。 Anticorrosion rust conversion agent of the present invention, a bridge, a ship, plant, steel frame portion of the building or the like, useful for structural parts of everything using iron.
Claims (4)
フッ素化合物（ただし、前記フェノ−ル性水酸基を有する化合物である物を除く。）０．２質量％〜５．０質量％と、
カルボキシル基含有化合物（ただし、前記フェノ−ル性水酸基を有する化合物又は前記フッ素化合物である物を除く。）０．５質量％〜１０．０質量％と、
多価アルコール及び水を含む溶媒と、を含有し、
前記フェノ−ル性水酸基を有する化合物は、没食子酸又はピロガロールであり、
前記フッ素化合物は、フッ酸、中性フッ化アンモニウム又は酸性フッ化アンモニウムであり、
前記カルボキシル基含有化合物は、クエン酸又はＥＤＴＡであり、
前記多価アルコールは、グリセリンであることを特徴とする防食用錆転換剤。 0.5% by mass to 10.0% by mass of a compound having a phenolic hydroxyl group;
Fluorine compound (excluding a compound having a phenolic hydroxyl group) 0.2% by mass to 5.0% by mass;
Carboxyl group-containing compound (however, excluding the compound having the phenolic hydroxyl group or the fluorine compound) 0.5% by mass to 10.0% by mass;
A solvent containing a polyhydric alcohol and water ,
The compound having a phenolic hydroxyl group is gallic acid or pyrogallol,
The fluorine compound is hydrofluoric acid, neutral ammonium fluoride or acidic ammonium fluoride,
The carboxyl group-containing compound is citric acid or EDTA,
The anticorrosive rust conversion agent , wherein the polyhydric alcohol is glycerin .
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