WO2006021980A1

WO2006021980A1 - Heating medium composition

Info

Publication number: WO2006021980A1
Application number: PCT/JP2004/012050
Authority: WO
Inventors: Naoshi Ito; Kouhei Yoshimura
Original assignee: Shishiai-Kabushikigaisha
Priority date: 2004-08-23
Filing date: 2004-08-23
Publication date: 2006-03-02

Abstract

A heating medium composition suitably used in the cooling system of an internal combustion engine such as an engine, the cooling system of a fuel cell, a solar system, a floor heating system, an air conditioning facility and the like. Since the heating medium composition employs one selected from water, alcohols, glycols and glycol ethers or a mixture of two or more selected therefrom as a base material and the base material contains 0.01-10 mass% of a germanium compound, blackening of aluminum or an aluminum alloy constituting the cooling system can be suppressed effectively.

Description

Specification

Heat medium composition

Technical field

[0001] 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.

Background art

[0002] 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.

[0003] However, these corrosion inhibitors have the following drawbacks. In other words, when phosphate flows into rivers, etc., it causes eutrophication, raising BOD and COD in the water and causing algae to grow, resulting in red tide and slime.

[0004] Phosphate reacts with hard water components contained in the cooling liquid to cause precipitation, thereby reducing the corrosion prevention function of the cooling liquid and further depositing the precipitate to circulate the cooling system. When the road was closed, I waked up the bow I.

[0005] On the other hand, 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.

[0006] Therefore, an antifreeze / cooling liquid composition containing a carboxylic acid such as a hydrocarbon carboxylic acid as a corrosion inhibitor in place of the above-mentioned disadvantageous phosphate, kayate, or borate has been proposed. (See Patent Document 1) However, when an antifreeze / cooling liquid composition containing carboxylic acids is used, the surface of aluminum or aluminum alloy constituting the cooling system in the antifreeze / cooling liquid will turn black, leading to a situation of inconvenience. Les

[0008] 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.

[0009] Conventionally, although 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. However, 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.

[0010] Therefore, there has been a demand for a coolant / antifreeze composition having excellent corrosion resistance for metals, particularly aluminum or aluminum alloys.

[0011] 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).

[0012] Patent Document 1: Japanese Patent Publication No. 4-42477

Patent Document 2: WOO00 / 60019

Disclosure of the invention

Problems to be solved by the invention

[0013] As a result of further diligent research on the prevention of blackening of aluminum or aluminum alloys, the present inventors have found that germanium compounds are extremely effective in preventing blackening of aluminum or aluminum alloys. Based on the knowledge, the present invention relating to a novel heat medium composition has been completed.

That is, 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.

Means for solving the problem

[0015] In order to achieve the above object, 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.

[0016] 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. Examples of 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.

[0017] Examples of 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.

[0018] The glycol ethers include, for example, ethylene glycol monomethyl ethereol, diethyleneglycolole monomethinoatenore, triethyleneglycolenomonomonotenoleate, tetraethyleneglycolenomonomethinoreatenore, ethyleneglycolenole. Monoethinore-tenole, diethyleneglycolenomonotenoleetenore, triethyleneglycolenoremonoetinore etenore, tetraethyleneglycolenomonotinoreethenore, ethyleneglycolenoremonobu chinoreetenore, diethyleneglycolenoremonobutinore Name one or a mixture of two or more selected from etherol, triethyleneglycol monobutyl ether, and tetraethylenedaricol monobutyl ether. Can.

[0019] 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. As 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 Examples thereof include germanium, tenorenol germanium, germanium ethylcarboxylate, tetra-n-butoxygermanium, magnesium germanate, sodium germanate, potassium germanate, lithium germanate, and the like.

[0020] Among the germanium compounds, germanium oxide such as germanium dioxide (tetragonal), germanium dioxide (hexagonal), germanium dioxide (amorphous), magnesium germanate, sodium germanate, potassium germanate, One or a mixture of two or more selected from germanates such as lithium germanate is more preferable because it has an excellent function of suppressing blackening of aluminum or an aluminum alloy.

[0021] The germanium compound is contained in the heat medium composition in a proportion of 0.01 to 10% by mass. When 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. On the other hand, when 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.

[0022] Further, the heat medium composition of the present invention may further contain one or a mixture of two or more selected from triazoles and thiazoles. Specific examples of the triazoles include benzotriazole, tolyltriazole, 4-phenyl-1,2,3-triazole, 2_naphthotriazole and 4_nitrobenzotriazole. Of these, benzotriazole and tolyltriazole are particularly desirable. Examples of thiazoles include benzothiazole and mercaptobenzothiazole.

[0023] 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.

[0024] 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.

[0025] 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 (R¾C

6 4 1 1 Alkyl benzoate represented by a C alkyl group)

Five

Acid, general formula R_C H— CH = C〇OH (R is C

6 4 1 1 C alkyl group or alkoxy group)

Five

And can be exemplified by a cinnamate, an alkyl cinnamate, an alkoxy cinnamate, and alkali metal salts, ammonium salts, and amine salts thereof. Among these, 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.

[0026] In addition, examples of the aromatic dibasic acid and salts thereof include phthalic acid, isophthalic acid, terephthalic acid, and alkali metal salts and ammonium salts thereof.

[0027] The content of the aromatic monobasic acid or aromatic dibasic acid is preferably in the range of 0.1 to 10% by mass. When 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.

[0028] 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.

[0029] 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.

[0030] The aliphatic monobasic acid, the aliphatic dibasic acid, and salts thereof are desirably contained in the range of 0.1 to 10% by mass. When 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.

[0031] Further, 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. Examples of 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 sebacate, strontium benzoate, strontium phthalate, strontium salicylate, strontium mandelate, etc. Among them, strontium nitrate, strontium sulfate, strontium phosphate it can.

[0032] Examples of the magnesium compound 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 And magnesium compounds of organic acids such as magnesium phthaloleate, magnesium salicylate, and magnesium mandelate.

[0033] In addition, 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.

[0034] It is desirable that 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.

[0035] In addition, 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. This is because 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. In addition, 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.

[0036] In addition to the above-mentioned components, 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 invention's effect

[0037] 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. BEST MODE FOR CARRYING OUT THE INVENTION

[0038] Examples

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. .

[0039] [Table 1]

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2

Oxidized germanium 0.3 0.3

p-tert-Futylbenzoic acid 4 2 4 2

Benzoic acid 2 ― 2 ―

Seha 'Shin-2-2

Tolyltriazole 0.3 0.3 0.3 0.3

Mercatoft 'Nsothiasol ― 0.3 ― 0.3

Sodium nitrate 0.1 0.3 0.1 0.3

Nitrate McNessium 0.01 ― 0.01 ―

Strontium nitrate ― 0.01 ― 0.01

Water 2 2 2 2 Hydroxide or Jum Suitable amount Suitable amount Suitable amount Mm.

Ethylene gericol remainder remainder remainder remainder remainder

S □ 1 100 100 100 100 pH value 7.4 7.4 7.4 7.4 m Item Example 1 Example 2 Comparative example 1 Comparative example 2 Appearance of aluminum flaws No black change Black change Black change Black amount Aluminum fouling substance change mgZcm ² —0. 03-0. 06 —0. 1 6 One 0. 1 5

[0041] From Table 2, in each sample of Comparative Example 1 and Comparative Example 2 that do not contain a germanium compound, blackening occurred and mass changes were also -0.16 mg / cm ² and _0.15 mg / cm ² . while showing a higher number value, for each Sanpunore according to example 1 and example 2, blackening is rather name also mass change - 0. 03MgZcm ² and - and 0. 06MgZcm ² and negligible numerical Thus, it was confirmed that the effect of preventing blackening was excellent.

Industrial applicability

[0042] 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.

Claims

The scope of the claims

[1] Water, alcohols, glycols, and darikol ethers are selected based on one or a mixture of two or more, and 0.01 to 10% by weight of a germanium compound is added to the base. A heat transfer medium composition characterized by comprising.

[2] The heat medium composition according to claim 1, wherein the germanium compound is one or a mixture of two or more selected from among germanium oxide and germanate.

[3] The heat medium composition according to claim 1, further comprising one or a mixture of two or more selected from triazoles and thiazoles.

[4] The heat medium composition according to claim 2, further comprising one or a mixture of two or more selected from triazoles and thiazoles.

[5] It further comprises one or a mixture of two or more selected from aromatic monobasic acids, aromatic dibasic acids, aliphatic monobasic acids, aliphatic dibasic acids and salts thereof. The heat medium composition according to claim 1.

[6] It further comprises one or a mixture of two or more selected from aromatic monobasic acids, aromatic dibasic acids, aliphatic monobasic acids, aliphatic dibasic acids and salts thereof. The heat medium composition according to claim 2.

[7] It further comprises one or a mixture of two or more selected from aromatic monobasic acids, aromatic dibasic acids, aliphatic monobasic acids, aliphatic dibasic acids and salts thereof. The heat medium composition according to claim 3.

[8] It further comprises one or a mixture of two or more selected from aromatic monobasic acids, aromatic dibasic acids, aliphatic monobasic acids, aliphatic dibasic acids and salts thereof. The heat medium composition according to claim 4.

9. The heat medium composition according to claim 1, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

10. The heat medium composition according to claim 2, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

11. The heat medium composition according to claim 3, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

12. The heat medium composition according to claim 4, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

[13] The heat medium composition according to claim 5, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

14. The heat medium composition according to claim 6, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

15. The heat medium composition according to claim 7, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

16. The heat medium composition according to claim 8, further comprising one or a mixture of two or more selected from strontium compounds, calcium compounds, and magnesium compounds.

[17] The heat transfer medium composition according to any one of claims 1 to 16, characterized in that it does not contain any of phosphate, cate, borate and chromate.