WO2006021980A1 - Composition de support de chauffage - Google Patents

Composition de support de chauffage Download PDF

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Publication number
WO2006021980A1
WO2006021980A1 PCT/JP2004/012050 JP2004012050W WO2006021980A1 WO 2006021980 A1 WO2006021980 A1 WO 2006021980A1 JP 2004012050 W JP2004012050 W JP 2004012050W WO 2006021980 A1 WO2006021980 A1 WO 2006021980A1
Authority
WO
WIPO (PCT)
Prior art keywords
medium composition
mixture
compounds
heat medium
strontium
Prior art date
Application number
PCT/JP2004/012050
Other languages
English (en)
Japanese (ja)
Inventor
Naoshi Ito
Kouhei Yoshimura
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 PCT/JP2004/012050 priority Critical patent/WO2006021980A1/fr
Publication of WO2006021980A1 publication Critical patent/WO2006021980A1/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
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • 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
    • C23F11/18—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 using inorganic inhibitors

Definitions

  • the present invention relates to a heat transfer medium composition applied to a cooling system of an internal combustion engine such as an engine, a cooling system of a fuel cell, a solar system, a floor heating system, an air conditioner, and the like.
  • the present invention relates to a heat medium composition that can effectively suppress the blackening of the aluminum or aluminum alloy constituting it.
  • Metals such as aluminum, aluminum alloys, pig iron steel, brass, solder, and copper are used for cooling systems of internal combustion engines such as engines. These metals corrode on contact with water or air. In order to prevent the corrosion of these metals, antifreeze compositions and coolant compositions containing phosphates, kayates, borates, and corrosion inhibitors have been proposed.
  • silicates are inferior in stability in antifreeze / cooling liquid, and when heat and pH change or when other salts coexist, they easily gel and prevent corrosion. There was a problem that the function deteriorated. Further, the borate has a problem that it is corrosive to aluminum or aluminum alloy.
  • the blackening of the aluminum or aluminum alloy surface is caused by the formation of a black coating on the aluminum or aluminum alloy surface when the carboxylic acids are in the coolant Z antifreeze.
  • this blackened coating has a poor appearance, it has been considered to have a function of covering and protecting the surface of aluminum or an aluminum alloy and preventing the progress of corrosion.
  • recent research has revealed that there is a close relationship between corrosion and the black coating formed on the surface of aluminum or aluminum alloys. It was confirmed that the alloy exhibited corrosion.
  • the main component is beguglycol that meets these requirements, and it does not contain phosphates, kayates, and borates, and is a hydrocarbon dicarboxyl / reich compound.
  • An antifreeze / coolant composition characterized in that it is contained in a proportion by weight (see Patent Document 2).
  • Patent Document 1 Japanese Patent Publication No. 4-42477
  • Patent Document 2 WOO00 / 60019
  • an object of the present invention is to provide a heat medium composition capable of effectively suppressing the blackening of aluminum or aluminum alloy constituting the cooling system. Is.
  • the present invention is based on one or a mixture of two or more selected from water, alcohols, glycols, and glycol ethers.
  • the gist of the present invention is a heat medium composition characterized by containing 10% by mass of a germanium compound.
  • the heat medium composition of the present invention has a function of effectively suppressing blackening of aluminum or aluminum alloy constituting the cooling system, and the base in the composition includes water, It consists of one or a mixture of two or more selected from among alcohols, glyconoles, and darlicol ethers.
  • the alcohols include those composed of one or a mixture of two or more selected from methanol, ethanol, propanol, butanol, pentanole, hexanol, heptanol, and octanol.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, and hexylene glycol. Examples thereof include one selected or a mixture of two or more.
  • glycol ethers include, for example, ethylene glycol monomethyl ethereol, diethyleneglycolole monomethinoatenore, triethyleneglycolenomonomonotenoleate, tetraethyleneglycolenomonomethinoreatenore, ethyleneglycolenole.
  • the base contains a germanium compound.
  • the germanium compound is a component that effectively suppresses blackening of aluminum or aluminum alloy constituting the cooling system.
  • This germanium compound for example, germanium dioxide (tetragonal form), Germanium dioxide (hexagonal), germanium dioxide (amorphous), tetrasalt, germanium tetrabromide, germanium tetrabromide, germanium tetraiodide, germanium nitride, germanium oxalate, germanium monosulfide, germanium disulfide, selenization
  • germanium oxide such as germanium dioxide (tetragonal), germanium dioxide (hexagonal), germanium dioxide (amorphous), magnesium germanate, sodium germanate, potassium germanate,
  • germanium oxide such as germanium dioxide (tetragonal), germanium dioxide (hexagonal), germanium dioxide (amorphous), magnesium germanate, sodium germanate, potassium germanate,
  • germanates such as lithium germanate is more preferable because it has an excellent function of suppressing blackening of aluminum or an aluminum alloy.
  • the germanium compound is contained in the heat medium composition in a proportion of 0.01 to 10% by mass.
  • the content of the germanium compound is less than 0.01% by mass, it is not possible to expect a sufficient blackening-suppressing effect of the aluminum or aluminum alloy.
  • the content of the germanium compound exceeds 10% by mass, the effect of suppressing the blackening of aluminum or aluminum alloy is obtained, but the effect of exceeding 10% by mass cannot be obtained. It becomes uneconomical.
  • the heat medium composition of the present invention may further contain one or a mixture of two or more selected from triazoles and thiazoles.
  • the triazoles include benzotriazole, tolyltriazole, 4-phenyl-1,2,3-triazole, 2_naphthotriazole and 4_nitrobenzotriazole. Of these, benzotriazole and tolyltriazole are particularly desirable.
  • thiazoles include benzothiazole and mercaptobenzothiazole.
  • Addition of these triazoles or thiazoles can improve the anticorrosion effect of copper-based metals such as brass and copper.
  • the content of thiazoles is preferably in the range of 0.05-1.0% by mass.
  • the content of thiazoles is preferably in the range of 0.01-1.0.0% by mass. That's right.
  • the heat medium composition of the present invention includes one kind selected from an aromatic monobasic acid, an aromatic dibasic acid, an aliphatic monobasic acid, an aliphatic dibasic acid, and salts thereof. Alternatively, a mixture of two or more can be included.
  • Aromatic monobasic acids and salts thereof include benzoic acids such as benzoic acid, nitrobenzoic acid, and hydroxybenzoic acid, p-tolylic acid, p-ethylbenzoic acid, p-propylbenzoic acid, p —Isopropylbenzoic acid, alkylbenzoic acid such as p-tert-butylbenzoic acid, general formula RO—CH 2 —COOH (R3 ⁇ 4C
  • a cinnamate an alkyl cinnamate, an alkoxy cinnamate, and alkali metal salts, ammonium salts, and amine salts thereof.
  • benzoic acid, p-toluic acid, and p-tertbutylbenzoic acid are excellent in the corrosion prevention performance of aluminum or aluminum alloys, and it is desirable that at least one of these be included.
  • aromatic dibasic acid and salts thereof examples include phthalic acid, isophthalic acid, terephthalic acid, and alkali metal salts and ammonium salts thereof.
  • the content of the aromatic monobasic acid or aromatic dibasic acid is preferably in the range of 0.1 to 10% by mass.
  • the content of these aromatic monobasic acids or aromatic dibasic acids is less than 0.1% by mass, a sufficient corrosion prevention effect on aluminum or aluminum filings cannot be expected, and when the content is more than 10% by mass. Is uneconomical because an effect exceeding 10% by mass cannot be obtained.
  • Aliphatic monobasic acids and salts thereof include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, oleic acid, Examples thereof include linolenolic acid, linolenic acid, ricinoleic acid, stearic acid, and alkali metal salts and ammonium salts thereof.
  • Aliphatic dibasic acids and salts thereof include oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, piperic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, Examples include brassylic acid and taptic acid, or alkali metal salts, amine salts, and ammonium salts thereof. Among them, suberic acid, azelaic acid, Vacic acid, undecane diacid and dodecane diacid are more preferred because of their superior performance.
  • the aliphatic monobasic acid, the aliphatic dibasic acid, and salts thereof are desirably contained in the range of 0.1 to 10% by mass.
  • the content of aliphatic monobasic acid, aliphatic dibasic acid and salts thereof is less than 0.1% by mass, sufficient corrosion prevention effect for aluminum and iron-based metals is not exhibited, and exceeds 10% by mass. In some cases, it will be uneconomical because of the effect that exceeds that amount.
  • the heat medium composition of the present invention can further contain one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.
  • strontium compounds include strontium oxide, strontium hydroxide, strontium chloride, strontium fluoride, strontium iodide, strontium sulfate, strontium nitrate, strontium titanate, strontium borate, strontium tungstateate, strontium oxalate, Strontium dihydrogen oxalate, strontium oxalate, strontium acetate, strontium propionate, strontium butyrate, strontium valerate, strontium laurate, strontium stearate, strontium oleate, strontium glutamate, strontium lactate, strontium succinate Strontium phosphate, strontium tartrate, strontium maleate, strontium citrate, Strontium acid, strontium malonate, strontium
  • magnesium compound examples include magnesium oxide, magnesium chloride, magnesium hydroxide, magnesium carbonate, magnesium nitrate, magnesium sulfate, magnesium titanate, magnesium tungstate, magnesium borate, magnesium phosphate, magnesium dihydrogen phosphate.
  • magnesium phosphate, magnesium chromate, magnesium permanganate, magnesium fluoride, magnesium iodide and other inorganic acids magnesium formate, magnesium acetate, magnesium propionate, magnesium butyrate, magnesium valerate, lauric acid
  • Magnesium acid, stearic acid Gnesium, magnesium oleate, magnesium glutamate, magnesium lactate, magnesium oxalate, magnesium malate, magnesium tartrate, magnesium hydrogen tartrate, magnesium maleate, magnesium citrate, magnesium oxalate, magnesium malonate, magnesium sebacate, magnesium benzoate
  • magnesium compounds of organic acids such as magnesium phthaloleate, magnesium salicylate, and magnesium mandelate.
  • calcium compounds include calcium formate, calcium acetate, potassium propionate, calcium butyrate, calcium valerate, calcium laurate, stearic acid power, calcium oleate, calcium glutamate, calcium lactate, calcium succinate, Calcium malate, calcium tartrate, calcium maleate, calcium citrate, calcium oxalate, calcium malonate, calcium sebacate, calcium benzoate, calcium phthalate, calcium salicylate, calcium mandelate, calcium oxide, calcium hydroxide, Calcium permanganate, calcium chromate, calcium fluoride, calcium iodide, calcium carbonate, calcium nitrate, calcium sulfate, calcium titanate Beam, calcium tungstate, calcium borate, phosphate force Honoré Shiumu, such as calcium dihydrogen phosphate and the like.
  • At least one or a mixture of two or more selected from the above strontium compounds, magnesium compounds, and calcium compounds is contained in the range of 0.0001 to 0.1% by mass. If the content of these compounds is less than 0.0001% by mass, a sufficient corrosion prevention effect of aluminum or an aluminum alloy cannot be expected. If the content exceeds 0.1% by mass, the effect of the excess is lost. It becomes uneconomical.
  • the heat medium composition of the present invention desirably takes a form that does not contain a phosphate, a kaate, a borate and a chromate.
  • phosphates cause eutrophication when they flow into rivers, etc., and also cause precipitation by reacting with hard water components contained in the cooling liquid. It is inferior in stability and has a problem that the corrosion prevention function is lowered due to easy gelation and separation when the temperature and pH change, or when other salts coexist.
  • borate has a problem of being corrosive to aluminum or aluminum alloy, and chromate has an adverse effect on the human body. This is because there is a problem.
  • the heat medium composition of the present invention contains a conventionally known corrosion inhibitor such as an antifoaming agent, a colorant, molybdate, tungstate, sulfate, and nitrate. It's a trick.
  • the heat medium composition of the present invention is based on one or a mixture of two or more selected from water, alcohols, glycols, and Daricol ethers. — Since 10% by mass of germanium compound is contained, it is possible to effectively suppress the blackening of aluminum or aluminum alloy constituting the cooling system.
  • Example 1 In each sample of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 shown in Table 1 below, a metal corrosion test was performed to confirm the change in mass of each metal and to confirm the presence or absence of abnormal appearance. . The test results are shown in Table 2. The metal corrosion test was conducted based on the JIS K 2234 metal corrosive regulations. For this test, metal specimens of aluminum, pig iron, steel, brass, solder and copper were used. .
  • the heat medium composition of the present invention is suitably used for, for example, a cooling system of an internal combustion engine such as an engine, a cooling system of a fuel cell, a solar system, a floor heating system, an air conditioner, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention a pour objet une composition de support de chauffage pouvant être appliquée à un système de refroidissement d'un moteur à combustion interne tel qu’un moteur, au système de refroidissement d'une pile à combustible, d’un système solaire, d’un système de chauffage par le sol, d’un système de climatisation ou d’autres éléments similaires. La composition du support de chauffage employant un élément sélectionné parmi l'eau, l'alcool, les glycols et les éthers de glycol ou un mélange d’au moins deux de ces éléments, comme matériau de base, et le matériau de base contenant entre 0,01 et 10% en masse d'un composé de germanium, le noircissement d'aluminium ou d'un alliage d'aluminium, constituant le système de refroidissement, peut être efficacement supprimé.
PCT/JP2004/012050 2004-08-23 2004-08-23 Composition de support de chauffage WO2006021980A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/012050 WO2006021980A1 (fr) 2004-08-23 2004-08-23 Composition de support de chauffage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/012050 WO2006021980A1 (fr) 2004-08-23 2004-08-23 Composition de support de chauffage

Publications (1)

Publication Number Publication Date
WO2006021980A1 true WO2006021980A1 (fr) 2006-03-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/012050 WO2006021980A1 (fr) 2004-08-23 2004-08-23 Composition de support de chauffage

Country Status (1)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783104A (en) * 1996-04-16 1998-07-21 Gas Research Institute Absorption refrigeration compositions having germanium based compounds
EP0902074A1 (fr) * 1996-03-29 1999-03-17 CCI Co. Limited Additif inhibant la noircissement d'alumine et composition de refroidissement le contenant
WO2000060019A1 (fr) * 1999-04-02 2000-10-12 Shishiai-Kabushikigaisha Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs
JP2003171655A (ja) * 2001-12-10 2003-06-20 Hokkaido Technology Licence Office Co Ltd 保温材
JP2004211056A (ja) * 2002-12-19 2004-07-29 Nippon Shokubai Co Ltd 蓄熱体及び蓄熱体を用いた蓄熱システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0902074A1 (fr) * 1996-03-29 1999-03-17 CCI Co. Limited Additif inhibant la noircissement d'alumine et composition de refroidissement le contenant
US5783104A (en) * 1996-04-16 1998-07-21 Gas Research Institute Absorption refrigeration compositions having germanium based compounds
WO2000060019A1 (fr) * 1999-04-02 2000-10-12 Shishiai-Kabushikigaisha Inhibiteurs de noircissement et compositions de fluides antigel/fluides de refroidissement utilisant lesdits inhibiteurs
JP2003171655A (ja) * 2001-12-10 2003-06-20 Hokkaido Technology Licence Office Co Ltd 保温材
JP2004211056A (ja) * 2002-12-19 2004-07-29 Nippon Shokubai Co Ltd 蓄熱体及び蓄熱体を用いた蓄熱システム

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