JPH0119472B2 - - Google Patents
Info
- Publication number
- JPH0119472B2 JPH0119472B2 JP59278770A JP27877084A JPH0119472B2 JP H0119472 B2 JPH0119472 B2 JP H0119472B2 JP 59278770 A JP59278770 A JP 59278770A JP 27877084 A JP27877084 A JP 27877084A JP H0119472 B2 JPH0119472 B2 JP H0119472B2
- Authority
- JP
- Japan
- Prior art keywords
- rust preventive
- added
- rust
- cooling water
- internal combustion
- 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
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)
- Lubricants (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
＜技術分野＞
本発明は、内燃機関用冷却水に添加して冷却系
統の金属を防錆する防錆剤組成物に関する。
＜従来技術＞
一般に、冷却水が流通する内燃機関の冷却系統
は、金属材料としてアルミニウム鋳物、鋳鉄、
鋼、黄銅、はんだおよび銅で構成されており、一
方、内燃機関の構成材料は、主として鋳鉄とアル
ミニウム合金とである。したがつて、内燃機関の
冷却系統の防錆剤は、これらの多種の金属のすべ
てに対して充分な防錆効果を有することが必要と
される。従来、亜硝酸塩単独あるいは硝酸塩との
混合系にリン酸を加えた防錆剤があるが、この防
錆剤は、冷却水に添加した場合に激しくNOxが
発生して好ましくない。また、リン酸に代えてメ
ルカプトベンゾチアゾールのナトリウム塩を加え
た防錆剤もあるが、メルカプトベンゾチアゾール
のナトリウム塩は高価であり、工業的利用には好
ましくない。
さらに、前記のように内燃機関の主な構成材料
は、鋳鉄とアルミニウム合金とであり、冷却水に
よるそれらの腐食性が異なるために、それらに対
して同等の防錆効果を有する防錆剤でなければ、
内燃機関の主な構成材料によつて防錆剤を使い分
けなければならないという不都合が生じる。しか
しながら、現在そのような内燃機関を構成する多
種の金属材料の総てに対し同時に充分な防錆効果
を発揮するような防錆剤はほとんどない。
また、冷却系統、なかんづく、ラジエータ部分
においては熱伝導性の良い銅や黄銅の細い部品で
構成されており、その接続部分をはんだ熔接する
ことにより密閉構造を形成している。すなわち、
はんだはラジエータ部分にあつてはシール剤の役
目を果たしており、はんだが腐食されラジエータ
の密閉構造が崩れると、内燃機関の冷却機能が失
われることになる。
そこで、本件出願人は、特願昭59−19151号に
おいて、NOxを発生させることなく、安価に、
内燃機関の冷却系統および内燃機関を構成する各
種金属材料を効果的に防錆する防錆剤組成物を提
案した。
しかしながら、この先行出願の防錆剤組成物で
は、それを構成する防錆剤成分の種類が比較的多
くなるという難点がある。
＜目的＞
本発明は、上記先行出願の改良に係り、防錆剤
組成物を構成する各防錆剤成分の添加量を特定の
割合にすることにより、先行出願に比べて防錆剤
成分の種類を減らした防錆剤組成物を提供しよう
とするものである。
＜構成＞
本件発明者らは、上述の目的を達成するために
鋭意研究した結果、内燃機関の冷却水への添加量
が、0.03〜2.0重量％であるベンゾトリアゾール
と水溶性アミンとの付加塩、前記冷却水への添加
量が、0.03〜0.6重量％であるリン酸塩および前
記冷却水への添加量が、0.05〜4.0重量％である
tert−ブチル安息香酸と水溶性アミンとの付加塩
を含有する内燃機関の冷却水用防錆剤組成物を見
出し本発明を完成した。
すなわち、本発明の防錆剤組成物を前記所定の
添加量になるように内燃機関の冷却水に添加する
ことによつて、NOxを発生させることなく内燃
機関を構成する多種類の金属材料を十分効果的に
防錆できることを見出した。
本発明に用いられるBT・SAは、ベンゾトリ
アゾールと水溶性アミンとを60〜70℃で加熱し反
応させることにより得られ、たとえば、千代田化
学研究所製のＴ・228が用いられるが、ベンゾト
リアゾール、水溶性アミンをそれぞれ単独に用い
てもよい。しかしながら、付加塩として用いるこ
とによつて、ベンゾトリアゾールの溶解度が上昇
する。水溶性アミンとしては、モノエタノールア
ミン、ジエタノールアミン、トリエタノールアミ
ン、シクロヘキシルアミン、イソプロピルアミン
などがあげられる。BT・SAは、銅、黄銅に対
する防錆効果が優れており、その冷却水への好ま
しい添加量は、0.03〜2.0％（重量％以下同様）
であり、より好ましくは0.05〜1.0％である。添
加量が、0.03％未満であると、銅、黄銅に対する
防錆効果が劣り、逆に２％を超えて添加すると、
防錆効果が飽和し不経済であるとともに、過剰の
場合は冷却液相が暗褐色となり、商品価値を低下
させる結果となる。
本発明に用いられるリン酸塩としては、
NaH2PO4、KH2PO4などのリン酸二水素塩があ
げられ、その好ましい添加量は、0.03〜0.6％で
あり、より好ましく0.05〜0.5％である。リン酸
塩は、はんだ、アルミニウムに対して特に防錆効
果を有するが、鋳鉄、鋼に対しても防錆効果を有
する。このリン酸塩の添加量の0.03％未満では、
アルミニウム、はんだに対する防錆効果が劣り、
逆に、0.6％を超えて添加すると、BT・SAおよ
びTBA・SAを分解し、ベンゾトリアゾール、
tert−ブチル安息香酸の沈澱を生じ好ましくな
い。
本発明に用いられるTBA・SAは、たとえば、
tert−ブチル安息香酸と水溶性アミンとを水また
はイソプロピルアルコールに１：1.1のモル比で
添加し、60〜70℃で加熱することにより得られ
る。または溶媒を用いることなく、tert−ブチル
安息香酸と水溶性アミンとを直接混合してもよ
い。TBA・SAは、はんだ、鋳鉄、鋼に対する防
錆効果が優れており、冷却水への添加量は、0.05
〜4.0％であり、より好ましくは、0.2〜3.0％であ
る。この添加量が0.05％未満であると、はんだ、
鋳鉄、鋼に対する防錆効果が劣り、逆に4.0％を
超えて添加しても防錆効果の向上は見られない。
本発明に用いられる防錆剤組成物には、安息香
酸塩を含有させてもよく、この安息香酸塩として
は、安息香酸ナトリウム、安息香酸カリウムなど
があげられる。この安息香酸塩は、はんだ、鋳
鉄、鋼に対して優れた防錆効果を有し、その添加
量は0.05〜4.0％であり、より好ましくは0.2〜3.0
％である。安息香酸塩の添加量が、0.05％未満で
は、はんだ、鋳鉄、鋼に対する防錆効果が劣り、
逆に4.0％を超えて添加しても防錆効果の向上は、
見られない。
TBA・SAおよび安息香酸塩は、上述のように
はんだ、鋳鉄、鋼に対する防錆効果が優れてお
り、TBA・SAおよび安息香酸塩の少なくとも一
方とリン酸塩との混合系では、一層、防錆効果の
向上が見られる。
本発明に用いられる防錆剤組成物には、また、
ホウ酸塩を含有させてもよい。このホウ酸塩は、
ナトリウム塩が好ましく、防錆剤溶液の緩衝作用
に預かり、PH変動を減少させる。このホウ酸塩の
添加量としては、好ましくは0.001〜0.7％であ
り、この添加量が0.001％未満であると、防錆剤
溶液の緩衝作用が劣り、逆に、0.7％を超えると、
特に鋳鉄に対する防錆効果が阻害されるととも
に、緩衝作用が飽和してしまう。
＜効果＞
以上説明したように本発明に用いられる防錆剤
組成物は、銅、黄銅に対して優れた防錆効果を有
するBT・SA、はんだ、アルミニウムに対して
優れた防錆効果を有するリン酸塩を含有し、か
つ、アルミニウム、鋳鉄、鋼、はんだに対して優
れた防錆効果を有するTBA・SAを含有してお
り、これによつて、はんだを始めとする多種類の
金属材料に優れた防錆効果を発揮する。したがつ
て、本発明の防錆剤組成物は、特に内燃機関およ
び内燃機関の冷却系統、なかんづくラジエータに
対して有効に適用しうる。さらに、本発明の防錆
剤組成物は、さらに、本発明の防錆剤組成物は、
エチレングリコール等の凍結防止剤がすでに混入
している冷却系統に対しても何等問題なく適用す
ることができる。
＜実施例＞
以下、実施例、参考例および比較例によつて本
発明をさらに詳細に説明するが、これらの実施例
はいかなる意味でも本発明を限定するものではな
い。
実施例１〜５、７、８、参考例６、比較例１〜３
11の蒸留水に硫酸ナトリウム148mg、塩化ナト
リウム165mgおよび炭酸水素ナトリウム138mgを溶
解し、ついで第１表に示す添加量（単位重量％）
に従つて防錆剤成分を添加することによつて
JISK2408に規定する試験液を作製した。
このようにして作製された試験液750mlをトー
ルビーカーに取り、試験片としてのアルミニウム
鋳物はJISH5202に規定するAC2A、鋳鉄は
JISG3141に規定するSPCC−Ｂ、黄銅は
JISH3100に規定するC2680P、はんだはJISZ3282
に規定するH30Aおよび銅はJISH3100に規定す
るC1100Pを用いてJISK2408（1981）に従つて本
発明の防錆剤組成物および比較例の組成物の防錆
効果を評価した。その結果を第２表に示す。な
お、第２表には、JISK2408（1981）の規定値を併
せて掲げている。
<Technical Field> The present invention relates to a rust preventive composition that is added to cooling water for an internal combustion engine to prevent metals in a cooling system from rusting. <Prior art> In general, the cooling system of an internal combustion engine through which cooling water flows is made of metal materials such as aluminum castings, cast iron,
It is composed of steel, brass, solder and copper, while the construction materials of internal combustion engines are mainly cast iron and aluminum alloys. Therefore, a rust preventive agent for the cooling system of an internal combustion engine is required to have a sufficient rust preventive effect on all of these various metals. Conventionally, there are rust preventive agents that include nitrite alone or a mixture with nitrate and phosphoric acid, but when added to cooling water, this rust preventive agent generates a large amount of NOx, which is undesirable. There is also a rust preventive agent in which a sodium salt of mercaptobenzothiazole is added in place of phosphoric acid, but the sodium salt of mercaptobenzothiazole is expensive and is not preferred for industrial use. Furthermore, as mentioned above, the main constituent materials of internal combustion engines are cast iron and aluminum alloy, and since they have different corrosive properties due to cooling water, there are no rust preventive agents that have the same rust prevention effect on them. If not,
This creates the inconvenience of having to use different rust inhibitors depending on the main constituent materials of the internal combustion engine. However, at present, there are almost no rust inhibitors that simultaneously exhibit sufficient rust prevention effects on all of the various metal materials that constitute such internal combustion engines. The cooling system, especially the radiator, is made of thin copper or brass parts with good thermal conductivity, and the connecting parts are soldered to form a sealed structure. That is,
Solder serves as a sealant in the radiator section, and if the solder corrodes and the radiator's sealing structure collapses, the cooling function of the internal combustion engine will be lost. Therefore, in Japanese Patent Application No. 59-19151, the applicant proposed that
We have proposed a rust preventive composition that effectively protects the cooling system of an internal combustion engine and the various metal materials that make up the engine. However, the rust preventive composition of this prior application has a drawback in that the types of rust preventive components that constitute it are relatively large. <Purpose> The present invention relates to an improvement of the above-mentioned prior application, and by adjusting the amount of each rust preventive component added in the rust preventive composition to a specific ratio, the amount of the rust preventive component is reduced compared to the prior application. The present invention aims to provide a rust preventive composition with a reduced number of types. <Structure> As a result of intensive research to achieve the above-mentioned object, the inventors of the present invention found that an addition salt of benzotriazole and a water-soluble amine, which is added to cooling water of an internal combustion engine in an amount of 0.03 to 2.0% by weight, , the amount added to the cooling water is 0.03 to 0.6% by weight, and the amount added to the cooling water is 0.05 to 4.0% by weight.
The present invention was completed by discovering a rust preventive composition for internal combustion engine cooling water containing an addition salt of tert-butylbenzoic acid and a water-soluble amine. That is, by adding the rust preventive composition of the present invention to the cooling water of an internal combustion engine in the predetermined amount, it is possible to improve the quality of various metal materials that make up the internal combustion engine without generating NOx. It has been found that rust can be prevented effectively. BT/SA used in the present invention is obtained by heating and reacting benzotriazole and a water-soluble amine at 60 to 70°C. For example, T-228 manufactured by Chiyoda Chemical Research Institute is used, but benzotriazole , water-soluble amine may be used alone. However, by using it as an addition salt, the solubility of benzotriazole is increased. Examples of water-soluble amines include monoethanolamine, diethanolamine, triethanolamine, cyclohexylamine, and isopropylamine. BT/SA has an excellent rust prevention effect on copper and brass, and the preferable amount added to cooling water is 0.03 to 2.0% (same as below weight%)
and more preferably 0.05 to 1.0%. If the amount added is less than 0.03%, the rust prevention effect on copper and brass will be poor, and on the other hand, if it is added in excess of 2%,
The rust prevention effect becomes saturated, which is uneconomical, and if the amount is excessive, the cooling liquid phase becomes dark brown, resulting in a decrease in commercial value. As the phosphate used in the present invention,
Dihydrogen phosphate salts such as NaH 2 PO 4 and KH 2 PO 4 are mentioned, and the amount added is preferably 0.03 to 0.6%, more preferably 0.05 to 0.5%. Phosphates have a rust-preventing effect particularly on solder and aluminum, but also on cast iron and steel. At less than 0.03% of this phosphate addition,
It has poor rust prevention effect on aluminum and solder.
On the other hand, if it is added in excess of 0.6%, BT・SA and TBA・SA will be decomposed and benzotriazole,
Precipitation of tert-butylbenzoic acid occurs, which is undesirable. TBA/SA used in the present invention is, for example,
It is obtained by adding tert-butylbenzoic acid and a water-soluble amine to water or isopropyl alcohol in a molar ratio of 1:1.1, and heating at 60 to 70°C. Alternatively, tert-butylbenzoic acid and a water-soluble amine may be directly mixed without using a solvent. TBA/SA has an excellent rust prevention effect on solder, cast iron, and steel, and the amount added to cooling water is 0.05
~4.0%, more preferably 0.2~3.0%. If this addition amount is less than 0.05%, solder,
The rust preventive effect on cast iron and steel is poor, and on the contrary, no improvement in the rust preventive effect is seen even when added in excess of 4.0%. The rust preventive composition used in the present invention may contain a benzoate, and examples of the benzoate include sodium benzoate and potassium benzoate. This benzoate has an excellent antirust effect on solder, cast iron, and steel, and the amount added is 0.05 to 4.0%, more preferably 0.2 to 3.0%.
%. If the amount of benzoate added is less than 0.05%, the rust prevention effect on solder, cast iron, and steel will be poor.
On the other hand, even if it is added in excess of 4.0%, the rust prevention effect will not improve.
can not see. As mentioned above, TBA/SA and benzoate have excellent rust-preventing effects on solder, cast iron, and steel, and a mixed system of at least one of TBA/SA and benzoate with phosphate provides even greater protection. An improvement in the rust effect can be seen. The rust preventive composition used in the present invention also includes:
A borate may also be included. This borate is
Sodium salts are preferred and rely on the buffering action of the rust inhibitor solution to reduce PH fluctuations. The amount of borate added is preferably 0.001 to 0.7%; if the amount added is less than 0.001%, the buffering effect of the rust preventive solution will be poor; on the contrary, if it exceeds 0.7%,
In particular, the antirust effect on cast iron is inhibited, and the buffering effect is saturated. <Effect> As explained above, the rust preventive composition used in the present invention has an excellent rust preventive effect on copper and brass, and has an excellent rust preventive effect on BT/SA, solder, and aluminum. Contains TBA/SA, which contains phosphate and has an excellent rust prevention effect on aluminum, cast iron, steel, and solder. Demonstrates excellent rust prevention effect. Therefore, the rust preventive composition of the present invention can be particularly effectively applied to internal combustion engines and cooling systems of internal combustion engines, especially radiators. Furthermore, the rust preventive composition of the present invention further comprises:
It can be applied without any problems to cooling systems that are already mixed with antifreeze agents such as ethylene glycol. <Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, Reference Examples, and Comparative Examples, but these Examples are not intended to limit the present invention in any way. Examples 1 to 5, 7, 8, Reference Example 6, Comparative Examples 1 to 3 148 mg of sodium sulfate, 165 mg of sodium chloride, and 138 mg of sodium hydrogen carbonate were dissolved in the distilled water of 11, and then the amounts added (units) shown in Table 1 were dissolved. weight%)
By adding rust preventive ingredients according to
A test solution specified in JISK2408 was prepared. Take 750ml of the test solution prepared in this way into a tall beaker, and use AC2A as specified in JISH5202 for aluminum castings and AC2A for cast iron as specified in JISH5202.
SPCC-B specified in JISG3141, brass is
C2680P specified in JISH3100, solder is JISZ3282
The rust preventive effect of the rust preventive composition of the present invention and the composition of the comparative example was evaluated in accordance with JISK2408 (1981) using H30A specified in 1 and C1100P specified in JISH3100 for copper. The results are shown in Table 2. Table 2 also lists the specified values of JISK2408 (1981).
【表】【table】
【表】
実施例１〜５、７、８、参考例６は、本発明の
防錆剤組成物の防錆効果を示すとともに、各防錆
剤成分の添加量の違いによる影響を示している。
実施例２と比較例１とを比べることによつて、
BT・SAが銅および黄銅に対して防錆効果を有
することがわかる。実施例２、８と比較例２とを
比べることによつて、TBA・SAが、はんだ、鋳
鉄、鋼に対して防錆効果を有することがわかる。
また、実施例２と比較例３とを比べることによつ
て、リン酸塩がはんだ、アルミニウムに対して優
れた防錆効果を有することがわかる。
このように各種金属材料を効果的に防錆する本
発明の防錆剤組成物は、冷却水に上記特定の割合
で添加される防錆剤成分を配合することによつ
て、はじめて得られるものであつて、比較例の組
成物では到底得られるものではない。[Table] Examples 1 to 5, 7, 8, and Reference Example 6 show the rust preventive effect of the rust preventive composition of the present invention, and also show the influence of different amounts of each rust preventive component added. .
By comparing Example 2 and Comparative Example 1,
It can be seen that BT/SA has a rust-preventing effect on copper and brass. By comparing Examples 2 and 8 with Comparative Example 2, it can be seen that TBA/SA has a rust preventive effect on solder, cast iron, and steel.
Furthermore, by comparing Example 2 and Comparative Example 3, it can be seen that phosphate has an excellent antirust effect on solder and aluminum. The rust preventive composition of the present invention, which effectively prevents the rust of various metal materials, can only be obtained by blending the rust preventive components added in the above-mentioned specific proportions to cooling water. This cannot be achieved with the composition of the comparative example.
Claims (1)
であつて、 前記冷却水への添加量が、0.03〜2.0重量％で
あるベンゾトリアゾールと水溶性アミンとの付加
塩、 前記冷却水への添加量が、0.03〜0.6重量％で
あるリン酸塩および 前記冷却水への添加量が、0.05〜4.0重量％で
あるtert−ブチル安息香酸と水溶性アミンとの付
加塩を含有することを特徴とする内燃機関の冷却
水用防錆剤組成物。[Scope of Claims] 1. A rust preventive composition added to cooling water of an internal combustion engine, which comprises addition of benzotriazole and water-soluble amine in an amount of 0.03 to 2.0% by weight added to the cooling water. addition of a water-soluble amine with a salt, a phosphate salt added in an amount of 0.03 to 0.6% by weight to the cooling water, and tert-butylbenzoic acid added to the cooling water in an amount of 0.05 to 4.0% by weight; A rust preventive composition for cooling water of an internal combustion engine, characterized in that it contains a salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27877084A JPS61149489A (en) | 1984-12-25 | 1984-12-25 | Corrosion inhibitor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27877084A JPS61149489A (en) | 1984-12-25 | 1984-12-25 | Corrosion inhibitor composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61149489A JPS61149489A (en) | 1986-07-08 |
| JPH0119472B2 true JPH0119472B2 (en) | 1989-04-11 |
Family
ID=17601940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27877084A Granted JPS61149489A (en) | 1984-12-25 | 1984-12-25 | Corrosion inhibitor composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61149489A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000046637A (en) * | 1998-12-31 | 2000-07-25 | 성재갑 | Anti-corrosion composition for aerosol product container |
| US6982062B2 (en) * | 2003-07-22 | 2006-01-03 | Ashland Inc. | Corrosion inhibiting composition |
| ES2592158T3 (en) * | 2009-06-02 | 2016-11-28 | Nippon Steel & Sumitomo Metal Corporation | Photocurable composition suitable for the prevention of rust from a threaded joint for steel pipes |
| CN108485779B (en) * | 2018-04-28 | 2020-10-30 | 九江职业技术学院 | Antirust cutting fluid and preparation method thereof |
| CN108913316B (en) * | 2018-07-10 | 2021-11-16 | 富地润滑科技股份有限公司 | Environment-friendly water-based antirust cutting fluid and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456040A (en) * | 1977-09-20 | 1979-05-04 | Otsuka Chem Co Ltd | Metal corrosion preventing composition |
| JPS60162785A (en) * | 1984-02-03 | 1985-08-24 | Tatsuta Electric Wire & Cable Co Ltd | Rust inhibitor composition for internal combustion engine cooling water |
-
1984
- 1984-12-25 JP JP27877084A patent/JPS61149489A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61149489A (en) | 1986-07-08 |
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