WO2000060020A1 - Blackening inhibitors and antifreeze fluid/cooling fluid compositions with the use thereof - Google Patents
Blackening inhibitors and antifreeze fluid/cooling fluid compositions with the use thereof Download PDFInfo
- Publication number
- WO2000060020A1 WO2000060020A1 PCT/JP1999/001780 JP9901780W WO0060020A1 WO 2000060020 A1 WO2000060020 A1 WO 2000060020A1 JP 9901780 W JP9901780 W JP 9901780W WO 0060020 A1 WO0060020 A1 WO 0060020A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antifreeze
- acid
- aluminum
- blackening
- coolant
- 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.)
- Ceased
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
Definitions
- the present invention relates to a method for cooling aluminum or aluminum alloy used in a cooling system of an internal combustion engine such as an engine in an antifreeze coolant.
- the present invention relates to a black discoloration inhibitor for preventing discoloration to black and an antifreeze coolant composition using the same.
- Metals such as aluminum, aluminum alloys, iron, steel, brass, solder, and copper are used in the cooling system of internal combustion engines such as'. These metals can corrode on contact with water or air.
- antifreeze compositions and coolant compositions containing corrosion inhibitors such as phosphates, silicates, amine salts or borates have been proposed.
- corrosion inhibitors such as phosphates, silicates, amine salts or borates.
- these corrosion inhibitors have the following disadvantages. That is, when phosphates flow into rivers and the like, they cause eutrophication, and BOD and COD in water rise, causing algae to proliferate. As a result, there is a problem that red tide and slime are generated.
- phosphate reacts with the hard water component contained in the coolant to form precipitates, which reduces the function of the coolant to prevent corrosion, and deposits deposits to block the cooling system circulation path.
- Amine salts react with nitrites to produce the carcinogenic nitrosamine.
- silicates have poor stability in antifreeze Z coolant, and easily gel when heat or pH changes or when other salts coexist, and the corrosion prevention function deteriorates. There was a problem of doing.
- borate has a disadvantage that it easily corrodes aluminum aluminum alloy.
- an antifreeze Z coolant composition containing a carboxylic acid such as a hydrocarbon carboxylic acid as a corrosion inhibitor instead of a phosphate, an amine salt, a silicate or a borate having the above-mentioned problem has been proposed.
- carboxylic acids instead of phosphates, amine salts, silicates or borates blacken the surface of aluminum or aluminum alloy in the antifreeze / coolant. I was Some users believe that when blackening of aluminum and aluminum alloys occurs, the corrosion of those metals is also in progress or will soon begin.
- the blackening of the aluminum or aluminum alloy surface was caused by the formation of a passive aluminum oxide film on the aluminum or aluminum alloy surface in the antifreeze Z coolant by the carboxylic acids.
- the black aluminum oxide passivation film is preferred because it covers and protects the surface of aluminum and aluminum alloys and prevents the progress of corrosion.
- the antifreeze solution is unlikely to cause blackening on aluminum-aluminum alloys because of its poor appearance. / 7 Rejected liquid composition was judged as “good”. Under such circumstances, the present inventors have conducted intensive studies on the prevention of blackening of aluminum or aluminum alloys.
- the present invention provides a black discoloration inhibitor that prevents aluminum or an aluminum alloy from discoloring black in an antifreeze or a coolant, and an antifreeze composition and a coolant composition using the same. is there.
- the blackening inhibitor of the present invention is an antifreeze which does not contain phosphates, amine salts, silicates and borates in the solution, and which contains a carboxylic acid as a corrosion inhibitor and which creates a cooling solution. It is suitably used for a cooling liquid composition.
- the anti-blackening agent of the present invention may be used alone as an anti-freezing agent or directly in a cooling liquid instead of as a component of the antifreeze Z coolant composition.
- the blackening inhibitor comprises an aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof.
- Aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof are, as described above, free of phosphates, amine salts, silicates and borates, and antifreeze and cooling in the presence of carboxylic acids. Prevents the surface of aluminum or aluminum alloy from blackening in liquid. Although the mechanism is not clear, aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof are used as a corrosion inhibitor in antifreeze and cooling fluids. Before the passivation film of black aluminum oxide is formed on the surface, a film of fatty acid is quickly formed to cover the surface of the aluminum or aluminum alloy so as to protect it and prevent the formation of a film of black aluminum oxide. It is thought that it may be.
- Examples of the aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof having such an effect include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, stearic acid, and metal salts thereof. Preferred examples include ammonium salt and the like. Can be.
- the amount of the anti-freezing agent to be applied is arbitrary, but in order to obtain a sufficient anti-blackening effect, the range of 0.01 to 5.0% by weight is required. It is good.
- the antifreeze cooling liquid composition of the present invention is a composition containing a glycol as a main component and not containing a phosphate, a silicate, an amine salt, and a borate.
- the antifreeze coolant composition contains a blackening inhibitor comprising an aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof. Aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof, as described above, can be used in the absence of phosphates, amine salts, silicates and borates, and in antifreeze or cooling in the presence of carboxylic acids. Prevents the surface of aluminum or aluminum alloy from blackening in liquid.
- aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof, carboxylic acids present as anticorrosion agents in antifreeze and cooling fluids are not suitable for aluminum or aluminum alloys.
- carboxylic acids present as anticorrosion agents in antifreeze and cooling fluids are not suitable for aluminum or aluminum alloys.
- a black aluminum oxide passivation film on the surface Before forming a black aluminum oxide passivation film on the surface, immediately form a fatty acid film to cover the aluminum or aluminum alloy surface and protect it to form a black aluminum oxide passivation film. It is thought that it will not be done.
- Examples of the aliphatic monobasic acid having 17 to 24 carbon atoms having such an effect or its salts include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, stearic acid, and metal salts thereof.
- Preferable examples include ammonium salts.
- the content of the blackening inhibitor in the antifreeze coolant composition is 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, a sufficient blackening prevention effect, that is, it becomes difficult to form a fatty acid film on the surface of aluminum or aluminum alloy, and if it exceeds 5.0% by weight, the content is 5%.
- An aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof in an amount exceeding 0% by weight has no meaning, and the amount is wasted and uneconomical.
- This antifreeze cooling liquid composition contains hydrocarbon carboxylic acids other than the above-mentioned aliphatic monobasic acids having 17 to 24 carbon atoms as corrosion inhibitors instead of phosphates, amine salts, silicates or borates.
- hydrocarbon carboxylic acids include butyric acid, 1-naphthylene acetic acid, 2-ethylbutyric acid, cyclohexylcarboxylic acid, and caproic acid.
- Aliphatic carboxylic acids such as 2-ethylhexanoic acid, caprylic acid, capric acid, and lauric acid, benzoic acid, 2-mercaptobenzoic acid, 4-tert-butylbenzoic acid, isopropylbenzoic acid, 2-cloth Benzoic acid, 3-chlorobenzoic acid, 4-monobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-methoxybenzoic acid, 4-methoxybenzoic acid, 2, 6-dimethoxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-hydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid Acid, 4 12 Toro Repose Acid, 3, 5-dinitro-benzoic acid, 3- menu Toxic-2-nitrobenzoic acid, toluic acid, salicylic acid, aromatic acids such as cinnamic
- hydrocarbon dicarboxylic acids examples include aliphatic dicarboxylic acids such as sebacic acid, sorbic acid, daltaric acid, adipic acid, azelaic acid, malonic acid, succinic acid, maleic acid, fumaric acid, and malic acid, and aromatics such as phthalic acid. Group dicarboxylic acids and the like.
- salts of hydrocarbon carboxylic acids or hydrocarbon dicarboxylic acids include alkali metal salts and ammonium salts.
- the content of hydrocarbon carboxylic acids excluding aliphatic monobasic acids having 17 to 24 carbon atoms, hydrocarbon dicarboxylic acids, or salts thereof is in the range of 0.1 to 10% by weight. Is preferred.
- the content thereof When the content thereof is less than the above range, it becomes impossible to obtain a sufficient effect of preventing corrosion of metals, especially iron and aluminum. If the content is larger than the above range, the effect beyond the range cannot be obtained, and it is uneconomical, and furthermore, it promotes the oxidative deterioration of the antifreeze coolant, which is preferable.
- the antifreeze cooling liquid composition may contain a triazole or magnesium compound.
- Triazoles such as tolyltriazole and benzotriazole, have an excellent corrosion protection function against metals, particularly copper.
- the triazoles are desirably contained in the range of 0.05 to 1.0% by weight in order to maintain an excellent corrosion prevention function.
- the magnesium compound include magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, magnesium benzoate, magnesium glutamate, magnesium succinate, magnesium phthalate, magnesium salicylate, magnesium maleate, magnesium chloride, and the like.
- Can be This magnesium compound has an excellent corrosion protection function, and even when mixed with other antifreeze coolant compositions containing silicate or phosphate in the antifreeze / coolant, It has a function to prevent corrosion of aluminum or its alloy in the cooling system.
- the content of the magnesium compound is preferably in the range of 0.001 to 0.5% by weight. If the content is less than 0.001% by weight, a sufficient corrosion preventing function cannot be obtained. On the other hand, if the content exceeds 0.5% by weight, the corrosion prevention function corresponding to the increased content cannot be obtained, which is uneconomical.
- the antifreeze / cooling liquid composition may further contain an antifoaming agent, a coloring agent, and the like in addition to the above-described components, and other conventionally known corrosion inhibitors such as molybdate and tungstate. , Sulfates, nitrates, mercaptobenzothiazole, alkali metal salts and the like may be used.
- corrosion inhibitors such as molybdate and tungstate. , Sulfates, nitrates, mercaptobenzothiazole, alkali metal salts and the like may be used.
- Table 1 below preferred examples 1 to 4 of the antifreeze Z coolant composition of the present invention and aliphatics having 17 to 24 carbon atoms which are essential components in the antifreeze coolant composition of the present invention Metal corrosion tests were performed on Comparative Examples 1 and 2, which did not contain a monobasic acid or a salt thereof.
- Example 14 Necessary to neutralize the pH of antifreeze Z coolant composition to 8.1
- the metal corrosion tests for the above Example 14 and Comparative Examples 1 and 2 were performed based on JISK 2234-1987 two types of regulations.
- Antifreeze liquid to be used for the test ⁇ The coolant composition should be diluted to 30 V ⁇ 1% with the prepared water, and the metal to be used for the test should be aluminum, iron, steel, steel, brass, solder, copper Each test piece was used. Table 2 shows the results. Table 2
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
糸田 β 黒変防止剤、 およびそれを用いた不凍液/冷却液組成物 技術分野 本発明は、 エンジン等の内燃機関の冷却系統に使用されているアルミニウムま たはアルミニウム合金が、 不凍液ノ冷却液中において黒く変色するのを防止する 黒変防止剤及びそれを用いた不凍液 冷却液組成物に関する。 景技術 Itoda β Black discoloration inhibitor, and antifreeze / coolant composition using the same Technical field The present invention relates to a method for cooling aluminum or aluminum alloy used in a cooling system of an internal combustion engine such as an engine in an antifreeze coolant. The present invention relates to a black discoloration inhibitor for preventing discoloration to black and an antifreeze coolant composition using the same. Landscape technology
'等の内燃機関の冷却系統には、 アルミニウム、 アルミニウム合金、 铸 鉄、 鋼、 黄銅、 はんだ、 銅などの金属が使用されている。 これらの金属は、 水あ るいは空気との接触により腐食を生じる。 これら冷却系統における金属の腐食を 防止するため、 リン酸塩、 ケィ酸塩、 アミン塩、 あるいはホウ酸塩といった腐食 防止剤を含む不凍液組成物や冷却液組成物が提案されている。 ところが、 これらの腐食防止剤にあっては、 以下の如き欠点を有していた。 す なわちリン酸塩は、 これが河川等に流入すると、 富栄養化を引き起こし、 水中の B O D、 C O Dが上昇して藻類が繁殖し、 この結果、 赤潮やスライムが発生する という問題があった。 またリン酸塩は、 冷却液中に含まれる硬水成分と反応して沈殿を生じ、 これに より冷却液の腐食防止機能が低下し、 さらには沈殿物が堆積して冷却系統の循環 路が閉塞してしまうという事態を引き起こしていた。 アミン塩は、 亜硝酸塩と反応して発ガン性物質であるニトロソァミンを生成し 易いという欠点がある。 またケィ酸塩は、 不凍液 Z冷却液中での安定性に劣り、 熱や p Hが変化した場合や他の塩類が共存する場合には、 容易にゲル化してしま い、 腐食防止機能が低下するという不具合があった。 またホウ酸塩は、 アルミ二 ゥムゃアルミニウム合金を腐食させ易いという欠点があった。 そこで、 上記不具合を有するリン酸塩、 アミン塩、 ケィ酸塩あるいはホウ酸塩 に代わる腐食防止剤として炭化水素カルボン酸などのカルボン酸類を含ませた不 凍液 Z冷却液組成物が提案されていた。 ところが、 この不凍液 /令却液組成物にあっては、 リン酸塩、 アミン塩、 ケィ 酸塩あるいはホウ酸塩に代わるカルボン酸類が不凍液/冷却液中においてアルミ ニゥムまたはアルミニウム合金表面を黒変させていた。 ユーザ一間では、 アルミニウムやアルミニウム合金に黒変が生じたとき、 それ らの金属の腐食も進行している、 あるいはまもなく腐食が始まると信じられてい る。 ところが実際には、 アルミニウムまたはアルミニウム合金表面の黒変は、 力 ルボン酸類が不凍液 Z冷却液中において、 アルミニウムやアルミニウム合金表面 に黒色を呈する酸化アルミの不動態皮膜を形成することにより生じていた。 黒色を呈する酸化アルミの不動態皮膜は、 アルミニウムやアルミニウム合金の 表面を覆ってこれを保護し、 腐食の進行を妨げる働きがあり、 むしろ好ましいも のである。 しかしながらユーザ一間においては、 黒変と腐食との間には密接な関 係があるとの考えが根強く、 しかも見栄えも悪いことなどの点から、 アルミニゥ ムゃアルミニウム合金に黒変が生じにくい不凍液 /7令却液組成物が 「良」 とされ ていた。 本発明者は、 このような事情から、 アルミニウムまたはアルミニウム合金の黒 変防止について鋭意研究を重ねた結果、 黒変を引き起こす原因物質とされていた カルボン酸類の中で、 炭素数 1 7〜2 4の脂肪族一塩基酸またはその塩について は、 反対にアルミニウムまたはアルミニウム合金の黒変防止にきわめて有効であ ることを見い出し、 この知見に基づいて本発明を完成させたのである。 発明の開示 本発明は、 アルミニウムまたはアルミニウム合金が、 不凍液や冷却液中におい て黒く変色するのを防止する黒変防止剤、 及びそれを用いた不凍液組成物並びに 冷却液組成物を提供するものである。 本発明の黒変防止剤は、 液中にリン酸塩、 アミン塩、 ケィ酸塩及びホウ酸塩が 存在せず、 .しかも腐食防止剤としてのカルボン酸類が存在する不凍液や冷却液を 創り出す不凍液 冷却液組成物に好適に用いられる。 尚、 本発明の黒変防止剤は、 不凍液 Z冷却液組成物の一成分としてではなく、 不凍液や冷却液中に直接黒変防 止剤として単独で入れても良い。 この黒変防止剤は炭素数 1 7〜2 4の脂肪族一塩基酸またはその塩よりなる。 炭素数 1 7〜 2 4の脂肪族一塩基酸、 またはその塩は、 上記の如くリン酸塩、 ァ ミン塩、 ケィ酸塩及びホウ酸塩の不存在、 カルボン酸類の存在下の不凍液や冷却 液中において、 アルミニウムまたはアルミニウム合金の表面が黒変するのを防止 する。 そのメカニズムは明らかではないが、 炭素数 1 7〜2 4の脂肪族一塩基酸 またはその塩が、 不凍液や冷却液中において、 腐食防止剤として存在するカルボ ン酸類が、 アルミニウムまたはアルミニウム合金の表面に黒色の酸化アルミの不 動態皮膜を形成する前に、 いち早く脂肪酸の皮膜を形成して、 アルミニウムまた はアルミニウム合金表面を覆い、 これを保護して黒色の酸化アルミの皮膜を形成 させないようにするのではないかと考えられる。 このような作用効果を有する炭素数 1 7〜 2 4の脂肪族一塩基酸またはその塩 としては、 ォレイン酸、 リノール酸、 リノレン酸、 リシノール酸、 ステアリン酸、 及びそれらのアル力リ金属塩、 ァンモニゥム塩等を好ましい例として挙げること ができる。 この黒変防止剤を不凍液ノ冷却液組成物に適用する場合、 その適用量は任意で あるが、 十分な黒変防止効果を得るためには 0 . 0 1〜5 . 0重量％の範囲が好 ましい。 その量が 0 . 0 1重量％を下回る場合、 十分な黒変防止効果、 すなわち アルミニウムまたはアルミニウム合金表面に脂肪酸の皮膜が形成され難くなり、 5 . 0重量％を越える場合には、 5 . 0重量％を越えた分だけの炭素数 1 7〜2 4の脂肪族一塩基酸またはその塩は何の意味もなさず、 その分が無駄になり、 不 経済となる。 次に、 本発明の不凍液組成物並びに冷却液組成物 （以下、 不凍液/冷却液組成 物という） について説明する。 本発明の不凍液 冷却液組成物は、 グリコール類 を主成分とし、 リン酸塩、 ケィ酸塩、 アミン塩及びホウ酸塩を含まない組成物で ある。 グリコール類としては、 エチレングリコール、 プロピレングリコール、 1， 3ブチレングリコール、 へキシレングリコール、 ジエチレングリコール、 グリセ リン等が挙げられるが、 その中でも特にエチレングリコール、 或いはプロピレン グリコールが望ましい。 この不凍液 冷却液組成物中には、 炭素数 1 7〜2 4の脂肪族一塩基酸または その塩よりなる黒変防止剤を含んでいる。 炭素数 1 7〜2 4の脂肪族一塩基酸ま たはその塩は、 上記の如くリン酸塩、 アミン塩、 ケィ酸塩及びホウ酸塩の不存在、 カルボン酸類の存在下の不凍液や冷却液中において、 アルミニウムまたはアルミ ニゥム合金の表面が黒変するのを防止する。 そのメカニズムは明らかではないが、 炭素数 1 7〜2 4の脂肪族一塩基酸また はその塩が、 不凍液や冷却液中において、 腐食防止剤として存在するカルボン酸 類が、 アルミニウムまたはアルミニウム合金の表面に黒色の酸化アルミの不動態 皮膜を形成する前に、 いち早く脂肪酸の皮膜を形成して、 アルミニウムまたはァ ルミニゥム合金表面を覆い、 これを保護して黒色の酸化アルミの不動態皮膜を形 成させないようにするのではないかと考えられる。 このような作用効果を有する炭素数 1 7〜2 4の脂肪族一塩基酸またはその塩 としては、 ォレイン酸、 リノール酸、 リノレン酸、 リシノール酸、 ステアリン酸、 及びそれらのアル力リ金属塩、 ァンモニゥム塩等を好ましい例として挙げること ができる。 この黒変防止剤の不凍液 冷却液組成物における含有量は 0 . 0 1〜5 . 0重 量％である。 その含有量が 0 . 0 1重量％を下回る場合、 十分な黒変防止効果、 すなわちアルミニウムまたはアルミニウム合金表面に脂肪酸の皮膜が形成され難 くなり、 5 . 0重量％を越える場合には、 5 . 0重量％を越えた分だけの炭素数 1 7〜2 4の脂肪族一塩基酸またはその塩は何の意味もなさず、 その分が無駄に なり、 不経済となる。 この不凍液 冷却液組成物中には、 リン酸塩、 アミン塩、 ケィ酸塩あるいはホ ゥ酸塩に代わる腐食防止剤として上記炭素数 1 7〜2 4の脂肪族一塩基酸を除く 炭化水素カルボン酸、 炭化水素ジカルボン酸、 あるいはそれらの塩のいずれか 1 種もしくは 2種以上をさらに含ませることができる。 炭化水素カルボン酸のうち炭素数 1 7〜2 4の脂肪族一塩基酸を除いたものと しては、 酪酸、 1—ナフ夕レン酢酸、 2—ェチル酪酸、 シクロへキシルカルボン 酸、 カプロン酸、 2—ェチルへキサン酸、 力プリル酸、 力プリン酸、 ラウリン酸 などの脂肪族カルボン酸、 安息香酸、 2—メルカプト安息香酸、 4一 t e r t— ブチル安息香酸、 イソプロピル安息香酸、 2—クロ口安息香酸、 3—クロ口安息 香酸、 4一クロ口安息香酸、 2—ァミノ安息香酸、 3—ァミノ安息香酸、 4ーァ ミノ安息香酸、 2—メトキシ安息香酸、 4ーメトキシ安息香酸、 2 , 6—ジメト キシ安息香酸、 3—ヒドロキシ安息香酸、 4—ヒドロキシ安息香酸、 2， 6—ヒ ドロキシ安息香酸、 3， 4 , 5—トリヒドロキシ安息香酸、 2 _ニトロ安息香酸、 3—二トロ安息香酸、 4一二トロ安息香酸、 3 , 5—ジニトロ安息香酸、 3—メ トキシー 2—二トロ安息香酸、 トルィル酸、 サリチル酸、 桂皮酸などの芳香族力 ルボン酸等を挙げることができる。 また炭化水素ジカルボン酸としては、 セバシン酸、 ソルビン酸、 ダルタル酸、 アジピン酸、 ァゼライン酸、 マロン酸、 コハク酸、 マレイン酸、 フマル酸、 リン ゴ酸などの脂肪族ジカルボン酸、 フタル酸などの芳香族ジカルボン酸等を挙げる ことができる。 また炭化水素カルボン酸または炭化水素ジカルボン酸の塩としては、 アルカリ 金属塩、 アンモニゥム塩等を挙げることができる。 炭化水素カルボン酸のうち炭素数 1 7〜2 4の脂肪族一塩基酸を除いたもの、 炭化水素ジカルボン酸、 あるいはそれらの塩の含有量としては、 0 . 1〜 1 0重 量％の範囲が好ましい。 それらの含有量が前記範囲よりも少ないとき、 金属、 特 には鉄、 アルミニウムの十分な腐食防止効果を得ることができなくなる。 上記範 囲よりも含有量を多くしたときには、 範囲を超えて分だけの効果が得られず、 不 経済となり、 さらには不凍液 冷却液の酸化劣化を促進することになるので好ま Metals such as aluminum, aluminum alloys, iron, steel, brass, solder, and copper are used in the cooling system of internal combustion engines such as'. These metals can corrode on contact with water or air. In order to prevent metal corrosion in these cooling systems, antifreeze compositions and coolant compositions containing corrosion inhibitors such as phosphates, silicates, amine salts or borates have been proposed. However, these corrosion inhibitors have the following disadvantages. That is, when phosphates flow into rivers and the like, they cause eutrophication, and BOD and COD in water rise, causing algae to proliferate. As a result, there is a problem that red tide and slime are generated. In addition, phosphate reacts with the hard water component contained in the coolant to form precipitates, which reduces the function of the coolant to prevent corrosion, and deposits deposits to block the cooling system circulation path. Was causing the situation. Amine salts react with nitrites to produce the carcinogenic nitrosamine. There is a disadvantage that it is easy. In addition, silicates have poor stability in antifreeze Z coolant, and easily gel when heat or pH changes or when other salts coexist, and the corrosion prevention function deteriorates. There was a problem of doing. Further, borate has a disadvantage that it easily corrodes aluminum aluminum alloy. Therefore, an antifreeze Z coolant composition containing a carboxylic acid such as a hydrocarbon carboxylic acid as a corrosion inhibitor instead of a phosphate, an amine salt, a silicate or a borate having the above-mentioned problem has been proposed. Was. However, in this antifreeze / repellent liquid composition, carboxylic acids instead of phosphates, amine salts, silicates or borates blacken the surface of aluminum or aluminum alloy in the antifreeze / coolant. I was Some users believe that when blackening of aluminum and aluminum alloys occurs, the corrosion of those metals is also in progress or will soon begin. In practice, however, the blackening of the aluminum or aluminum alloy surface was caused by the formation of a passive aluminum oxide film on the aluminum or aluminum alloy surface in the antifreeze Z coolant by the carboxylic acids. The black aluminum oxide passivation film is preferred because it covers and protects the surface of aluminum and aluminum alloys and prevents the progress of corrosion. However, among users, there is a strong belief that there is a close relationship between blackening and corrosion, and the antifreeze solution is unlikely to cause blackening on aluminum-aluminum alloys because of its poor appearance. / 7 Rejected liquid composition was judged as “good”. Under such circumstances, the present inventors have conducted intensive studies on the prevention of blackening of aluminum or aluminum alloys. As a result, among the carboxylic acids which were considered to be the causative substances of blackening, the number of carbon atoms was 17 to 24. The aliphatic monobasic acid or its salt On the contrary, they found that they were extremely effective in preventing blackening of aluminum or aluminum alloys, and completed the present invention based on this finding. DISCLOSURE OF THE INVENTION The present invention provides a black discoloration inhibitor that prevents aluminum or an aluminum alloy from discoloring black in an antifreeze or a coolant, and an antifreeze composition and a coolant composition using the same. is there. The blackening inhibitor of the present invention is an antifreeze which does not contain phosphates, amine salts, silicates and borates in the solution, and which contains a carboxylic acid as a corrosion inhibitor and which creates a cooling solution. It is suitably used for a cooling liquid composition. The anti-blackening agent of the present invention may be used alone as an anti-freezing agent or directly in a cooling liquid instead of as a component of the antifreeze Z coolant composition. The blackening inhibitor comprises an aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof. Aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof are, as described above, free of phosphates, amine salts, silicates and borates, and antifreeze and cooling in the presence of carboxylic acids. Prevents the surface of aluminum or aluminum alloy from blackening in liquid. Although the mechanism is not clear, aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof are used as a corrosion inhibitor in antifreeze and cooling fluids. Before the passivation film of black aluminum oxide is formed on the surface, a film of fatty acid is quickly formed to cover the surface of the aluminum or aluminum alloy so as to protect it and prevent the formation of a film of black aluminum oxide. It is thought that it may be. Examples of the aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof having such an effect include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, stearic acid, and metal salts thereof. Preferred examples include ammonium salt and the like. Can be. When this anti-blackening agent is applied to the antifreeze coolant composition, the amount of the anti-freezing agent to be applied is arbitrary, but in order to obtain a sufficient anti-blackening effect, the range of 0.01 to 5.0% by weight is required. It is good. When the amount is less than 0.01% by weight, a sufficient blackening preventing effect, that is, it becomes difficult to form a fatty acid film on aluminum or aluminum alloy surface, and when it exceeds 5.0% by weight, 5.0. Aliphatic monobasic acids having 17 to 24 carbon atoms or their salts in excess of% by weight have no meaning and are wasted and uneconomical. Next, the antifreeze composition and the coolant composition (hereinafter, referred to as antifreeze / coolant composition) of the present invention will be described. The antifreeze cooling liquid composition of the present invention is a composition containing a glycol as a main component and not containing a phosphate, a silicate, an amine salt, and a borate. Examples of the glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, and glycerin. Of these, ethylene glycol and propylene glycol are particularly desirable. The antifreeze coolant composition contains a blackening inhibitor comprising an aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof. Aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof, as described above, can be used in the absence of phosphates, amine salts, silicates and borates, and in antifreeze or cooling in the presence of carboxylic acids. Prevents the surface of aluminum or aluminum alloy from blackening in liquid. Although the mechanism is not clear, aliphatic monobasic acids having 17 to 24 carbon atoms or salts thereof, carboxylic acids present as anticorrosion agents in antifreeze and cooling fluids are not suitable for aluminum or aluminum alloys. Before forming a black aluminum oxide passivation film on the surface, immediately form a fatty acid film to cover the aluminum or aluminum alloy surface and protect it to form a black aluminum oxide passivation film. It is thought that it will not be done. Examples of the aliphatic monobasic acid having 17 to 24 carbon atoms having such an effect or its salts include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, stearic acid, and metal salts thereof. Preferable examples include ammonium salts. The content of the blackening inhibitor in the antifreeze coolant composition is 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, a sufficient blackening prevention effect, that is, it becomes difficult to form a fatty acid film on the surface of aluminum or aluminum alloy, and if it exceeds 5.0% by weight, the content is 5%. An aliphatic monobasic acid having 17 to 24 carbon atoms or a salt thereof in an amount exceeding 0% by weight has no meaning, and the amount is wasted and uneconomical. This antifreeze cooling liquid composition contains hydrocarbon carboxylic acids other than the above-mentioned aliphatic monobasic acids having 17 to 24 carbon atoms as corrosion inhibitors instead of phosphates, amine salts, silicates or borates. One or more of acids, hydrocarbon dicarboxylic acids, or salts thereof can be further included. Among the hydrocarbon carboxylic acids, those excluding aliphatic monobasic acids having 17 to 24 carbon atoms include butyric acid, 1-naphthylene acetic acid, 2-ethylbutyric acid, cyclohexylcarboxylic acid, and caproic acid. Aliphatic carboxylic acids such as 2-ethylhexanoic acid, caprylic acid, capric acid, and lauric acid, benzoic acid, 2-mercaptobenzoic acid, 4-tert-butylbenzoic acid, isopropylbenzoic acid, 2-cloth Benzoic acid, 3-chlorobenzoic acid, 4-monobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-methoxybenzoic acid, 4-methoxybenzoic acid, 2, 6-dimethoxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-hydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid Acid, 4 12 Toro Repose Acid, 3, 5-dinitro-benzoic acid, 3- menu Toxic-2-nitrobenzoic acid, toluic acid, salicylic acid, aromatic acids such as cinnamic acid, and the like. Examples of the hydrocarbon dicarboxylic acids include aliphatic dicarboxylic acids such as sebacic acid, sorbic acid, daltaric acid, adipic acid, azelaic acid, malonic acid, succinic acid, maleic acid, fumaric acid, and malic acid, and aromatics such as phthalic acid. Group dicarboxylic acids and the like. Examples of the salts of hydrocarbon carboxylic acids or hydrocarbon dicarboxylic acids include alkali metal salts and ammonium salts. The content of hydrocarbon carboxylic acids excluding aliphatic monobasic acids having 17 to 24 carbon atoms, hydrocarbon dicarboxylic acids, or salts thereof is in the range of 0.1 to 10% by weight. Is preferred. When the content thereof is less than the above range, it becomes impossible to obtain a sufficient effect of preventing corrosion of metals, especially iron and aluminum. If the content is larger than the above range, the effect beyond the range cannot be obtained, and it is uneconomical, and furthermore, it promotes the oxidative deterioration of the antifreeze coolant, which is preferable.
またこの不凍液ノ冷却液組成物中には、 上記成分の他に、 トリァゾール類ゃマ グネシゥム化合物を含ませることができる。 トリァゾ一ル類は、 トリルトリァゾ ールやべンゾトリアゾールなどであるが、 これらは金属、 特に銅に対して優れた 腐食防止機能を有している。 このトリァゾ一ル類は、 優れた腐食防止機能を維持 するため、 0 . 0 5〜 1 . 0重量％の範囲で含まれるのが望ましい。 マグネシウム化合物としては、 例えば水酸化マグネシウム、 酸化マグネシウム、 炭酸マグネシウム、 硫酸マグネシウム、 硝酸マグネシウム、 安息香酸マグネシゥ ム、 グルタミン酸マグネシウム、 琥珀酸マグネシウム、 フタル酸マグネシウム、 サリチル酸マグネシウム、 マレイン酸マグネシウム、 塩化マグネシウム等を挙げ ることができる。 このマグネシウム化合物は優れた腐食防止機能を有しており、 しかもケィ酸塩やリン酸塩を成分とする他の不凍液ノ冷却液組成物と不凍液/冷 却液中にて混合されても、 · 冷却系統のアルミニウムまたはその合金の腐食を防止 する機能を有している。 このマグネシウム化合物の含有量としては、 0 . 0 0 1 〜0 . 5重量％の範囲が好ましく、 その含有量が 0 . 0 0 1重量％よりも少ない 場合、 十分な腐食防止機能が得られず、 また 0 . 5重量％を越える場合には、 含 有量が増した分だけの腐食防止機能が得られず不経済となる。 なお、 この不凍液/冷却液組成物には、 前記の成分以外にさらに消泡剤、 着色 剤等を含有させても良いし、 他の従来公知の腐食防止剤であるモリブデン酸塩、 タングステン酸塩、 硫酸塩、 硝酸塩、 メルカプトべンゾチアゾール及びアルカリ 金属塩等を使用しても良い。 実施例 下記表 1に示す、 本発明の不凍液 Z冷却液組成物の好ましい実施例 1〜4並び に本発明の不凍液 冷却液組成物における必須成分である炭素数 1 7〜2 4の脂 肪族一塩基酸またはその塩を含まない比較例 1及び 2について、 金属腐食試験を 行った。 In addition, in addition to the above components, the antifreeze cooling liquid composition may contain a triazole or magnesium compound. Triazoles, such as tolyltriazole and benzotriazole, have an excellent corrosion protection function against metals, particularly copper. The triazoles are desirably contained in the range of 0.05 to 1.0% by weight in order to maintain an excellent corrosion prevention function. Examples of the magnesium compound include magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, magnesium benzoate, magnesium glutamate, magnesium succinate, magnesium phthalate, magnesium salicylate, magnesium maleate, magnesium chloride, and the like. Can be This magnesium compound has an excellent corrosion protection function, and even when mixed with other antifreeze coolant compositions containing silicate or phosphate in the antifreeze / coolant, It has a function to prevent corrosion of aluminum or its alloy in the cooling system. The content of the magnesium compound is preferably in the range of 0.001 to 0.5% by weight. If the content is less than 0.001% by weight, a sufficient corrosion preventing function cannot be obtained. On the other hand, if the content exceeds 0.5% by weight, the corrosion prevention function corresponding to the increased content cannot be obtained, which is uneconomical. In addition, the antifreeze / cooling liquid composition may further contain an antifoaming agent, a coloring agent, and the like in addition to the above-described components, and other conventionally known corrosion inhibitors such as molybdate and tungstate. , Sulfates, nitrates, mercaptobenzothiazole, alkali metal salts and the like may be used. Examples As shown in Table 1 below, preferred examples 1 to 4 of the antifreeze Z coolant composition of the present invention and aliphatics having 17 to 24 carbon atoms which are essential components in the antifreeze coolant composition of the present invention Metal corrosion tests were performed on Comparative Examples 1 and 2, which did not contain a monobasic acid or a salt thereof.
(以下余白） (Hereinafter the margin)
表 1 table 1
( 1 ) ： 不凍液 Z冷却液組成物の p Hを 8 . 1まで中和するのに必要な 上記実施例 1 4並びに比較例 1及び 2についての金属腐食試験は、 J I S K 2234- 1987 2種の規定に基づいて行った。 試験に供する不凍液 Ζ 冷却液組成物は、 調合水にて 30 V ο 1 %に希釈したものを使用し、 試験に供す る金属には、 アルミニウム铸物、 铸鉄、 鋼、 黄銅、 はんだ、 銅の試験片をそれぞ れ使用した。 この結果を表 2に示した。 表 2 (1): Necessary to neutralize the pH of antifreeze Z coolant composition to 8.1 The metal corrosion tests for the above Example 14 and Comparative Examples 1 and 2 were performed based on JISK 2234-1987 two types of regulations. Antifreeze liquid to be used for the test 冷却 The coolant composition should be diluted to 30 V ο 1% with the prepared water, and the metal to be used for the test should be aluminum, iron, steel, steel, brass, solder, copper Each test piece was used. Table 2 shows the results. Table 2
Claims
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1999/001780 WO2000060020A1 (en) | 1999-04-02 | 1999-04-02 | Blackening inhibitors and antifreeze fluid/cooling fluid compositions with the use thereof |
| JP2000609515A JP4214302B2 (en) | 1999-04-02 | 1999-04-02 | Anti-blackening agent and antifreeze / coolant composition using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1999/001780 WO2000060020A1 (en) | 1999-04-02 | 1999-04-02 | Blackening inhibitors and antifreeze fluid/cooling fluid compositions with the use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006508230A (en) * | 2002-12-02 | 2006-03-09 | テキサコ ディベラップメント コーポレイション | Antifreeze coolant composition for high temperature applications |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152185A (en) * | 1979-05-09 | 1980-11-27 | Conner Alvin James Sen | Antiicorrosion agent composition |
| JPH09263976A (en) * | 1996-03-29 | 1997-10-07 | Cci Corp | Blackening preventive agent of aluminum or aluminum alloy in cooling liquid and cooling liquid composition containing the same |
-
1999
- 1999-04-02 WO PCT/JP1999/001780 patent/WO2000060020A1/en not_active Ceased
- 1999-04-02 JP JP2000609515A patent/JP4214302B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152185A (en) * | 1979-05-09 | 1980-11-27 | Conner Alvin James Sen | Antiicorrosion agent composition |
| JPH09263976A (en) * | 1996-03-29 | 1997-10-07 | Cci Corp | Blackening preventive agent of aluminum or aluminum alloy in cooling liquid and cooling liquid composition containing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006508230A (en) * | 2002-12-02 | 2006-03-09 | テキサコ ディベラップメント コーポレイション | Antifreeze coolant composition for high temperature applications |
| JP4860153B2 (en) * | 2002-12-02 | 2012-01-25 | テキサコ ディベラップメント コーポレイション | Antifreeze coolant composition for high temperature applications |
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| JP4214302B2 (en) | 2009-01-28 |
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