WO2000060020A1 - Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs - Google Patents

Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs Download PDF

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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
Application number
PCT/JP1999/001780
Other languages
English (en)
Japanese (ja)
Inventor
Yuhji Miyake
Hiroshi Egawa
Original Assignee
Shishiai-Kabushikigaisha
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shishiai-Kabushikigaisha filed Critical Shishiai-Kabushikigaisha
Priority to JP2000609515A priority Critical patent/JP4214302B2/ja
Priority to PCT/JP1999/001780 priority patent/WO2000060020A1/fr
Publication of WO2000060020A1 publication Critical patent/WO2000060020A1/fr

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Classifications

    • 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
    • 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)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne des inhibiteurs de noircissement destinés à empêcher le noircissement de l'aluminium ou de ses alliages dans des liquides antigel ou des liquides de refroidissement ; ainsi que des compositions de liquide antigel/liquide de refroidissement utilisant lesdits inhibiteurs. Ces inhibiteurs, qui comprennent des acides monobasiques C17-24 aliphatiques, ou leurs sels, empêchent efficacement le noircissement en surface de l'aluminium ou de ses alliages dans des liquides antigel ou des liquides de refroidissement exempts de phosphates, de silicates, de sels aminés ou de borates. Les compositions précitées sont des compositions qui renferment comme composant principal des glycols, et qui sont exemptes de phosphates, de silicates ou de sels aminés, caractérisées en ce qu'elles contiennent de 0,01 à 5,0 % en poids d'inhibiteurs susmentionnés.
PCT/JP1999/001780 1999-04-02 1999-04-02 Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs WO2000060020A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2000609515A JP4214302B2 (ja) 1999-04-02 1999-04-02 黒変防止剤、およびそれを用いた不凍液／冷却液組成物
PCT/JP1999/001780 WO2000060020A1 (fr) 1999-04-02 1999-04-02 Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1999/001780 WO2000060020A1 (fr) 1999-04-02 1999-04-02 Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs

Publications (1)

Publication Number Publication Date
WO2000060020A1 true WO2000060020A1 (fr) 2000-10-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006508230A (ja) * 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 高温用途のための不凍冷却液組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55152185A (en) * 1979-05-09 1980-11-27 Conner Alvin James Sen Antiicorrosion agent composition
JPH09263976A (ja) * 1996-03-29 1997-10-07 Cci Corp 冷却液中におけるアルミニウムまたはアルミニウム合金の黒変防止剤、及びそれを含む冷却液組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55152185A (en) * 1979-05-09 1980-11-27 Conner Alvin James Sen Antiicorrosion agent composition
JPH09263976A (ja) * 1996-03-29 1997-10-07 Cci Corp 冷却液中におけるアルミニウムまたはアルミニウム合金の黒変防止剤、及びそれを含む冷却液組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006508230A (ja) * 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 高温用途のための不凍冷却液組成物
JP4860153B2 (ja) * 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 高温用途のための不凍冷却液組成物

Also Published As

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