JP2776552B2 - Metal corrosion prevention method and inhibitor - Google Patents
Metal corrosion prevention method and inhibitorInfo
- Publication number
- JP2776552B2 JP2776552B2 JP1106446A JP10644689A JP2776552B2 JP 2776552 B2 JP2776552 B2 JP 2776552B2 JP 1106446 A JP1106446 A JP 1106446A JP 10644689 A JP10644689 A JP 10644689A JP 2776552 B2 JP2776552 B2 JP 2776552B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- tetrakis
- hydroxymethyl
- corrosion
- phosphonium salt
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は、金属腐食防止方法及び防止剤に関する。
さらに詳しくは、水系中における鉄系金属の腐食を効率
良く抑制することができる方法及び薬剤に関する。The present invention relates to a method and an inhibitor for preventing metal corrosion.
More specifically, the present invention relates to a method and an agent capable of efficiently suppressing corrosion of an iron-based metal in an aqueous system.
（ロ）従来の技術 軟鋼、鋳鉄等の鉄系金属は古くから各種工業用の構造
材例えば、パイプ、支柱、壁材等として広く用いられて
いるが、これらは水や湿分との接触によって腐食してそ
の構造材としての強度を低下させたり、腐食生成物を発
生させて各種の障害をもたらす。そこで、これらの障害
を防止又は抑制するために従来からいわゆる防食剤や防
錆剤を用いる方法が提案されている。(B) Conventional technology Iron-based metals such as mild steel and cast iron have been widely used as structural materials for various industries, for example, pipes, supports, wall materials, and the like. It corrodes to lower its strength as a structural material and generates corrosion products to cause various obstacles. Therefore, a method using a so-called anticorrosive or rust inhibitor has been conventionally proposed in order to prevent or suppress these obstacles.
そして、ことに工業要冷却水系、プロセス水系、水貯
留槽等の鉄系金属が水と直接接触する系においては、こ
の水系中に種々の化学物質、例えばリン酸、ホスホン酸
類、重金属塩等を添加して腐食の抑制又は防止を行う方
法が汎用されている。In particular, in systems where iron-based metals such as industrial cooling water systems, process water systems, and water storage tanks come into direct contact with water, various chemical substances such as phosphoric acid, phosphonic acids, and heavy metal salts are added to the water system. A method of suppressing or preventing corrosion by addition is widely used.
（ハ）発明が解決しようとする課題 この発明は、上記のごとく水系中に化学物質を添加し
て鉄系金属の腐食の防止又は抑制を行う一つの新しい方
法及び薬剤を提供しようとするものである。(C) Problems to be Solved by the Invention The present invention aims to provide a new method and a new agent for preventing or suppressing the corrosion of iron-based metals by adding a chemical substance to an aqueous system as described above. is there.
この発明に用いる一方の有効成分のテトラキス（ヒド
ロキシメチル）ホスホニウム塩は、従来から、難燃剤、
染色助剤、皮なめし剤等として知られており、さらに水
系中における殺菌処理剤として有効であることも知られ
ている（特開昭60−72807号、同62−42908号公報）。し
かしながら鉄系金属の腐食抑制成分として使用すること
は全く知られていない。One active ingredient of the present invention, a tetrakis (hydroxymethyl) phosphonium salt, has been conventionally used as a flame retardant,
It is known as a dyeing aid, a tanning agent, etc., and is also known to be effective as a disinfectant in aqueous systems (Japanese Patent Application Laid-Open Nos. 60-72807 and 62-42908). However, it is not known at all to use it as a corrosion inhibiting component for iron-based metals.
本発明者らは、上記ホスホニウム塩の有する殺菌作用
を前提としてこれをさらに腐食抑制成分として作用させ
る可能性について鋭意研究を行った。その結果、上記ホ
スホニウム塩自体はほとんど腐食抑制効果を示さない
が、この化合物と亜鉛化合物とを各々特定量併用添加す
ることにより、各々の単独使用時には見られない優れた
腐食抑制効果が奏される事実を見出した。The present inventors have conducted intensive studies on the possibility of further acting as a corrosion inhibiting component on the premise of the bactericidal action of the above phosphonium salt. As a result, the phosphonium salt itself hardly exhibits a corrosion inhibitory effect, but by adding a specific amount of this compound and a zinc compound in combination, an excellent corrosion inhibitory effect not seen when each is used alone is exhibited. Found the fact.
（ニ）課題を解決するための手段 かくしてこの発明によれば、鉄系金属と接触する水系
中に、テトラキス（ヒドロキシメチル）ホスホニウム塩
と水中で亜鉛イオンを容易に放出しうる亜鉛化合物と
を、前者の濃度が4mg/以上、後者の濃度が亜鉛量とし
て1mg/以上となるように併用添加して、上記鉄系金属
の腐食を抑制することを特徴とする金属腐食防止方法が
提供される。(D) Means for Solving the Problems According to the present invention, a tetrakis (hydroxymethyl) phosphonium salt and a zinc compound capable of easily releasing zinc ions in water are provided in an aqueous system in contact with an iron-based metal, A method for preventing metal corrosion is provided, in which the former is added together so that the concentration of the former is 4 mg / or more and the latter is 1 mg / or more as the amount of zinc to suppress the corrosion of the iron-based metal.
この発明に用いるテトラキス（ヒドロキシメチル）ホ
スホニウム塩は、下式（Ｉ）： （式中、Ｘは対陰イオンを意味する）で表わされる化合
物であり、通常、吸湿性の大きい白色の粉末状結晶とし
て入手でき、水とは任意の割合で溶解するが、低級アル
コール以外の有機溶剤にはほとんど溶解しない性質を有
する。また、かかるホスホニウム塩は、例えば特開昭60
−72807号公報に記載の方法により、製造することがで
きる。The tetrakis (hydroxymethyl) phosphonium salt used in the present invention has the following formula (I): (Wherein, X represents a counter anion), which is usually available as white powdery crystals having high hygroscopicity and dissolves in water at an arbitrary ratio. It has the property that it hardly dissolves in organic solvents. Further, such phosphonium salts are described in, for example,
It can be produced by the method described in -72807.
これらのホスホニウム塩の中でもとくに、テトラキス
（ヒドロキシメチル）ホスホニウム塩酸塩（式（Ｉ）の
Ｘ がCl-）又はテトラキス（ヒドロキシメチル）ホス
ホニウム硫酸塩（式（Ｉ）中のＸ が1/2SO4 2-）を用い
るのが好ましい。 Among these phosphonium salts, particularly, tetrakis
(Hydroxymethyl) phosphonium hydrochloride (of formula (I)
X Is Cl-) Or tetrakis (hydroxymethyl) phos
Honium sulfate (X in formula (I) Is 1 / 2SOFour 2-)
Preferably.
一方、この発明に用いる亜鉛化合物は、亜鉛イオンを
水中に効率良く供給する亜鉛源として用いられ、従って
水中での解離度が高い亜鉛塩が適しており、ことに、塩
化亜鉛、硫酸亜鉛、硝酸亜鉛又はスルファミン酸亜鉛を
用いるのが好ましい。On the other hand, the zinc compound used in the present invention is used as a zinc source for efficiently supplying zinc ions to water, and therefore a zinc salt having a high degree of dissociation in water is suitable. Particularly, zinc chloride, zinc sulfate, and nitric acid It is preferred to use zinc or zinc sulfamate.
もちろん、これらは各々組合わせて用いられてもよ
い。Of course, each of these may be used in combination.
この発明の方法において、上記ホスホニウム塩は、優
れた腐食防止効果の点で、腐食防止を意図する水系中に
4mg/以上となるように添加される。その上限は、とく
に限定されないが、50mg/程度が適している。50mg/
を越えても増量に見合う効果の向上が期待できず、経済
性の点で好ましくない。一方、併用する亜鉛化合物は、
優れた腐食防止効果の点で、亜鉛量として1mg/以上と
なるように添加され、その上限は前記と同様な理由で30
mg/程度が適している。かかる範囲の添加量において
も、ことにホスホニウム塩：亜鉛の重量比として19:1〜
1:4の範囲で添加するのが好ましい。In the method of the present invention, the above-mentioned phosphonium salt is used in an aqueous system intended for corrosion prevention in terms of an excellent corrosion prevention effect.
It is added so that it becomes 4 mg / or more. The upper limit is not particularly limited, but about 50 mg / about is suitable. 50mg /
Even if it exceeds, an improvement in the effect corresponding to the increase in the amount cannot be expected, which is not preferable in terms of economy. On the other hand, the zinc compound used in combination
In terms of an excellent corrosion inhibitory effect, zinc is added in an amount of 1 mg / or more, and the upper limit is 30% for the same reason as described above.
mg / degree is suitable. Even in such an addition amount, the weight ratio of phosphonium salt: zinc is preferably 19: 1 to
It is preferable to add in a range of 1: 4.
この発明の方法は、上記二種の有効成分を対象水系中
に同時又は別々に添加して実施することができる。その
際の形態は、粉状そのままあるいは適当な溶媒に溶解せ
しめた液剤として用いることができる。通常、これらの
両成分を混合してなる粉剤や両成分を水に溶解してなる
液剤として用いるのが適している。このような薬剤は、
腐食抑制剤としてそれ自体新規なものであり、従ってこ
の発明は、かかる両成分を少なくとも含有する鉄系金属
腐食抑制剤をも提供するものである。The method of the present invention can be carried out by simultaneously or separately adding the above two kinds of active ingredients to a target aqueous system. The form at that time can be used as a powder as it is or as a solution dissolved in an appropriate solvent. Usually, it is suitable to use as a powder prepared by mixing these two components or a liquid prepared by dissolving both components in water. Such drugs are
It is a novel corrosion inhibitor per se, and the present invention therefore also provides an iron-based metal corrosion inhibitor containing at least such both components.
このような両成分の併用により各々の単独使用時には
見られない顕著な腐食抑制効果が奏され、鉄系金属の腐
食による各種障害が防止又は抑制されることとなる。The combined use of these two components provides a remarkable effect of inhibiting corrosion that is not observed when each is used alone, and prevents or suppresses various obstacles due to corrosion of the iron-based metal.
なお、この発明の方法及び薬剤において、この発明の
効果が阻害されない他の成分、例えばモリブデン酸塩、
アゾール類、ホスホン酸類、ホスフィン酸類、アクリル
酸系低分子重合体、マレイン酸系低分子重合体のような
他の腐食又はスケール防止剤が併用又は含有されていて
もよい。In the method and the drug of the present invention, other components that do not inhibit the effects of the present invention, for example, molybdate,
Other corrosion or scale inhibitors such as azoles, phosphonic acids, phosphinic acids, acrylic acid-based low molecular weight polymers, and maleic acid-based low molecular weight polymers may be used in combination or contained.
（ホ）実施例 試験液として大阪市水道水５倍濃縮水を用いて、軟鋼
テストピースに対する防食効果確認試験を行った。(E) Example A test for confirming the anticorrosion effect on mild steel test pieces was performed using 5 times concentrated tap water in Osaka City as a test liquid.
まず、１の平底ビーカーに所定量の薬剤を加えた試
験液１を収容し、モーターと連動した撹拌棒の先端に
軟鋼のテストピース［市販品名SPCC、形状は30×50×1m
mの長方形板状である］を懸吊し、液中に浸漬した。次
いで、サーモスタットを付設してマントルヒータにて50
℃に液温を保ち、上記テストピースを100rpmの速度で回
転させつつ５日間テストした。First, a test liquid 1 containing a predetermined amount of a drug is contained in one flat-bottomed beaker, and a mild steel test piece [commercial product name: SPCC, shape is 30 × 50 × 1 m]
m in the shape of a rectangular plate] was suspended and immersed in the liquid. Next, attach a thermostat and use a mantle heater for 50
The temperature was maintained at ℃, and the test piece was tested for 5 days while rotating at a speed of 100 rpm.
テスト終了後テストピースを取り出し酸洗、水洗、乾
燥後重量を測定し、重量減少量からMDD（mg/dm2・da
y），即ち１日当たりの腐食減量を測定した。使用した
試験液の水質を第１表に示す。After the test is completed, remove the test piece, pickle it, wash it with water, dry it, measure the weight, and calculate the MDD (mg / dm 2
y), that is, the corrosion loss per day was measured. Table 1 shows the water quality of the test solutions used.
試験結果から第２表に示す。なお、表中、薬剤名中の
記号は、下記の薬剤名で表わす。 Table 2 shows the test results. In the table, the symbols in the drug names are represented by the following drug names.
＊1.THPS…テトラキス（ヒドロキシメチル）ホスホニ
ウム硫酸塩 ＊2.THPC…テトラキス（ヒドロキシメチル）ホスホニ
ウム塩酸塩 ＊3.PBS…２−ホスホノブタン−1,2,4−トリカルボン
酸 ＊4.P−１…トリブチルテトラデシルフォスフォニウ
ム塩酸塩 ＊5.P−２…ビス（ポリ−２−カルボキシエチル）ホ
スフィン酸 ＊6.K−１…塩化ベンザルコニウム 上記試験結果から明らかなように、テトラキス（ヒド
ロキシメチル）ホスホニウム塩単独使用時においてはMD
Dが150〜190であり、亜鉛化合物単独使用時においても1
75〜185であって腐食抑制効果はほとんど認められない
のに対し、各々4mg/以上及び1mg/以上併用すること
によりMDDが20以下に著しく低下し優れた腐食抑制効果
が奏されることが判る。* 1.THPS ... tetrakis (hydroxymethyl) phosphonium sulfate * 2.THPC ... tetrakis (hydroxymethyl) phosphonium hydrochloride * 3.PBS ... 2-phosphonobutane-1,2,4-tricarboxylic acid * 4.P-1 ... Tributyltetradecylphosphonium hydrochloride * 5.P-2 ... bis (poly-2-carboxyethyl) phosphinic acid * 6.K-1 ... benzalkonium chloride As is clear from the above test results, when tetrakis (hydroxymethyl) phosphonium salt was used alone, the MD
D is 150 to 190, even when using the zinc compound alone
Although the corrosion inhibition effect is hardly recognized at 75 to 185, the MDD is remarkably reduced to 20 or less by using 4 mg / or more and 1 mg / or more, respectively, and it is understood that an excellent corrosion inhibition effect is exhibited. .
また、この効果は、防食性化合物として公知のホスホ
ン酸類やホスフィン酸類あるいはベンザルコニウム塩を
亜鉛化合物として併用した場合に比して、極めて優れた
ものであることが判る。Further, it can be seen that this effect is extremely superior to the case where a phosphonic acid, a phosphinic acid or a benzalkonium salt known as an anticorrosive compound is used in combination as a zinc compound.
（ヘ）発明の効果 この発明によれば、殺菌剤の一種である特定のホスホ
ニウム塩を、亜鉛化合物の存在下において腐食抑制成分
として作用させることが可能となると共に、優れた鉄系
金属の腐食抑制効果を発現することができる。(F) Effect of the Invention According to the present invention, it is possible to cause a specific phosphonium salt, which is a kind of fungicide, to act as a corrosion inhibitor in the presence of a zinc compound, and to provide excellent corrosion of iron-based metals. An inhibitory effect can be exhibited.
従って、各種水系例えば工業用冷却水系、プロセス水
系、水貯留槽等における腐食に基づく障害を防止するこ
とができ、微生物が原因となる腐食も抑制又は防止する
ことが可能となる。Therefore, it is possible to prevent corrosion-based obstacles in various water systems such as industrial cooling water systems, process water systems, water storage tanks, and the like, and it is also possible to suppress or prevent corrosion caused by microorganisms.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C23F 11/00,11/167 C09K 15/32──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C23F 11 / 00,11 / 167 C09K 15/32
Claims (7)
（ヒドロキシメチル）ホスホニウム塩と水中で亜鉛イオ
ンを容易に放出しうる亜鉛化合物とを、前者の濃度が4m
g/以上、後者の濃度が亜鉛量として1mg/以上となる
ように併用添加して、上記鉄系金属の腐食を抑制するこ
とを特徴とする金属腐食防止方法。1. An aqueous system which comes into contact with an iron-based metal, a tetrakis (hydroxymethyl) phosphonium salt and a zinc compound capable of easily releasing zinc ions in water, the former having a concentration of 4 m
A method for preventing metal corrosion, which comprises adding together g / g or more and the latter having a zinc content of 1 mg / g or more to suppress corrosion of the iron-based metal.
ウム塩が４〜50mg/、亜鉛化合物が亜鉛量として１〜3
0mg/添加される請求項１記載の腐食防止方法。2. The tetrakis (hydroxymethyl) phosphonium salt has a content of 4 to 50 mg / zinc compound, and the zinc compound has a zinc content of 1 to 3 mg / l.
The method for preventing corrosion according to claim 1, wherein 0 mg / addition is provided.
ウム塩が、テトラキス（ヒドロキシメチル）ホスホニウ
ムの塩酸塩又は硫酸塩である請求項１記載の腐食防止方
法。3. The method according to claim 1, wherein the tetrakis (hydroxymethyl) phosphonium salt is a hydrochloride or a sulfate of tetrakis (hydroxymethyl) phosphonium.
亜鉛又はスルファミン酸亜鉛である請求項１記載の腐食
防止方法。4. The method according to claim 1, wherein the zinc compound is zinc chloride, zinc sulfate, zinc nitrate or zinc sulfamate.
ウム塩と、水中で亜鉛イオンを容易に放出しうる亜鉛化
合物とを有効成分として含有してなる金属腐食防止剤。5. A metal corrosion inhibitor comprising a tetrakis (hydroxymethyl) phosphonium salt and a zinc compound capable of easily releasing zinc ions in water as active ingredients.
ウム塩が、テトラキス（ヒドロキシメチル）ホスホニウ
ムの塩酸塩又は硫酸塩である請求項５記載の腐食防止
剤。6. The corrosion inhibitor according to claim 5, wherein the tetrakis (hydroxymethyl) phosphonium salt is tetrakis (hydroxymethyl) phosphonium hydrochloride or sulfate.
亜鉛又はスルファミン酸亜鉛である請求項５記載の腐食
防止剤。7. The corrosion inhibitor according to claim 5, wherein the zinc compound is zinc chloride, zinc sulfate, zinc nitrate or zinc sulfamate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1106446A JP2776552B2 (en) | 1989-04-25 | 1989-04-25 | Metal corrosion prevention method and inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1106446A JP2776552B2 (en) | 1989-04-25 | 1989-04-25 | Metal corrosion prevention method and inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02285082A JPH02285082A (en) | 1990-11-22 |
| JP2776552B2 true JP2776552B2 (en) | 1998-07-16 |
Family
ID=14433847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1106446A Expired - Lifetime JP2776552B2 (en) | 1989-04-25 | 1989-04-25 | Metal corrosion prevention method and inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2776552B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0010161D0 (en) * | 2000-04-27 | 2000-06-14 | Rhodia Cons Spec Ltd | Novel phosphine compounds |
-
1989
- 1989-04-25 JP JP1106446A patent/JP2776552B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02285082A (en) | 1990-11-22 |
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