JP4492873B2 - antifreeze - Google Patents

Description

  The present invention relates to an antifreeze, and more particularly to an antifreeze used as a coolant.

  An internal combustion engine applied for propulsion of an automobile or the like is cooled by a coolant. As the coolant, antifreeze is used to prevent freezing in the cold season. As the antifreeze, generally, a rust inhibitor is added to glycols used as a freezing point depressant and diluted with water is used.

  The internal combustion engine includes a cooling system that circulates the coolant. The cooling system includes rubber parts formed from rubber. Examples of such rubber parts include connector packing, water pump mechanical seals, radiator hoses, and thermostat covers. Such rubber parts are cured by prolonged contact with the coolant. Curing of the rubber part contributes to leakage of coolant from the cooling system. For this reason, the internal combustion engine is regularly inspected, and the rubber parts are replaced with new ones before they are cured to the extent that the coolant leaks. It is desired to extend the maintenance interval of the apparatus by suppressing the curing of the rubber in contact with the coolant.

  Materials such as aluminum, cast iron, steel, brass, solder, and copper exist in the coolant path of the internal combustion engine. For this reason, the coolant is required to have a corrosion inhibiting effect on these materials, and various corrosion inhibitors are used. In particular, the amount of aluminum used is increasing from the viewpoint of reducing the weight of automobiles, and in particular, a corrosion inhibiting effect on aluminum is required. For this reason, an antifreeze that uses propylene glycol, which has a low environmental load, as a freezing point depressant and is resistant to metal corrosion is further desired.

  International Publication No. WO99 / 57218 discloses a diluted cooling liquid that improves the corrosion resistance of metal and suppresses the formation of scale to improve the lubricity of the mechanical seal of the water pump. The diluted cooling liquid is based on either deionized water from which corrosive ions and scale-forming ions have been separated and removed, an ethylene glycol aqueous solution using the deionized water, or a propylene glycol aqueous solution using the deionized water. In addition to improving the corrosion resistance of the metal, it suppresses the formation of scale and improves the lubricity of the mechanical seal of the water pump.

  Japanese Patent Application Laid-Open No. 2003-27047 discloses a coolant composition that prevents a water leakage phenomenon from a mechanical seal and enables a stable operation of a cooling device for a long period of time. The coolant composition contains at least water and a polyoxyalkylene glycol derivative.

International Publication No. WO99 / 57218 JP 2003-27047 A

It is an object of the present invention to provide an antifreeze liquid that extends the maintenance interval of an applied apparatus.
Another object of the present invention is to provide an antifreeze liquid that extends the maintenance interval of the applied apparatus, has a smaller environmental load, and is less likely to corrode metals.

The antifreeze liquid according to the present invention preferably contains a first component and a second component. The first component is formed from glycol. The second component is formed from a compound in which some or all of the six hydrogen atoms of the benzene molecule are substituted with substituents. The first group of at least one of the substituents is any one of the second group and the third group. The second group uses the first hydrocarbon group -R- and has the following chemical formula:
-R-OH
The third group is represented by the following chemical formula using the second hydrocarbon group -R'-:
-O-R'-OH
It is expressed by Of the substituents, the group other than the first group is a group selected from a hydroxyl group, a third hydrocarbon group, and an alkoxyl group. Moreover, the compound of the second component does not have a hydroxyl group, a hydrocarbon group, or an alkoxyl group when all of the substituents are the first group. That is, the compound does not necessarily have any of a hydroxyl group, a hydrocarbon group, and an alkoxyl group. Such an antifreeze liquid is hard to harden the rubber which contacts, and can extend the maintenance interval of the apparatus to which the antifreeze liquid is applied.

  The first hydrocarbon group has 1 to 8 carbon atoms, the second hydrocarbon group has 1 to 8 carbon atoms, the third hydrocarbon group has 1 to 8 carbon atoms, and The alkoxyl group preferably has 1 to 8 carbon atoms.

  The first component is preferably a substance selected from the group consisting of a mixture of ethylene glycol and propylene glycol. The mixture is a mixture of ethylene glycol and propylene glycol.

  It is preferable that a 2nd component is contained in the ratio of 0.001 mass part-10 mass parts with respect to 100 mass parts of 1st components.

により表現される第１化合物と、
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により表現される第２２化合物と、
他の混合物とから形成される集合から選択される物質である。このとき、その混合物は、第１化合物と第２化合物と第３化合物と第４化合物と第５化合物と第６化合物と第７化合物と第８化合物と第９化合物と第１０化合物と第１１化合物と第１２化合物と第１３化合物と第１４化合物と第１５化合物と第１６化合物と第１７化合物と第１８化合物と第１９化合物と第２０化合物と第２１化合物と第２２化合物とから形成される集合から選択される複数の化合物が混合された物質であることが好ましい。 Its second component is
The following chemical formula:

A first compound represented by:
The following chemical formula:

A second compound represented by:
The following chemical formula:

A third compound represented by:
The following chemical formula:

A fourth compound represented by:
The following chemical formula:

A fifth compound represented by:
The following chemical formula:

A sixth compound represented by:
The following chemical formula:

A seventh compound represented by:
The following chemical formula:

An eighth compound represented by:
The following chemical formula:

A ninth compound represented by:
The following chemical formula:

A tenth compound represented by:
The following chemical formula:

An eleventh compound represented by:
The following chemical formula:

A twelfth compound represented by:
The following chemical formula:

A thirteenth compound represented by:
The following chemical formula:

A fourteenth compound represented by:
The following chemical formula:

A fifteenth compound represented by:
The following chemical formula:

A sixteenth compound represented by:
The following chemical formula:

A seventeenth compound represented by:
The following chemical formula:

An eighteenth compound represented by:
The following chemical formula:

A nineteenth compound represented by:
The following chemical formula:

A twentieth compound represented by:
The following chemical formula:

A twenty-first compound represented by:
The following chemical formula:

A twenty-second compound represented by:
It is a substance selected from the assembly formed from other mixtures. At this time, the mixture includes the first compound, the second compound, the third compound, the fourth compound, the fifth compound, the sixth compound, the seventh compound, the eighth compound, the ninth compound, the tenth compound, and the eleventh compound. , The 12th compound, the 13th compound, the 14th compound, the 15th compound, the 16th compound, the 17th compound, the 18th compound, the 19th compound, the 20th compound, the 21st compound and the 22nd compound. It is preferable that the substance is a mixture of a plurality of compounds selected from:

  The antifreeze liquid according to the present invention further contains water. At this time, it is preferable that the density | concentration of a 1st component is 30-60 mass%.

  The antifreeze liquid according to the present invention further includes a third component and a fourth component. At this time, the first component is propylene glycol. The third component includes a linear aliphatic dicarboxylic acid having 10 to 12 carbon atoms, a linear aliphatic dicarboxylic acid salt that is a salt of the linear aliphatic dicarboxylic acid, a linear aliphatic dicarboxylic acid, and a linear It is a substance selected from the group consisting of mixtures with aliphatic dicarboxylates. The fourth component has a benzimidazole skeleton compound having a benzimidazole skeleton, a benzimidazole skeleton compound salt that is a salt of the benzimidazole skeleton compound, and a triazine skeleton. Plural compounds selected from the group consisting of a triazine skeleton compound having a mercapto group, a triazine skeleton compound salt that is a salt of the triazine skeleton compound, a benzimidazole skeleton compound, a benzimidazole skeleton compound salt, a triazine skeleton compound, and a triazine skeleton compound salt A substance selected from the group consisting of a mixture of these substances.

  The method for producing antifreeze liquid according to the present invention preferably includes the steps of producing the antifreeze liquid according to the present invention and mixing water with the antifreeze liquid so that the concentration of the first component is 30 to 60% by mass. .

  The internal combustion engine according to the present invention is cooled using such antifreeze. That is, the internal combustion engine includes a cooling system for circulating the antifreeze liquid according to the present invention and an internal combustion engine body cooled by the cooling system. The cooling system includes rubber parts that are made of rubber and that come into contact with the antifreeze. At this time, the rubber part is hard to be cured, and the maintenance interval of the internal combustion engine can be extended. Such an internal combustion engine is suitable for generating power for propelling an automobile.

The antifreeze additive according to the present invention is a substance containing a compound in which some or all of the six hydrogen atoms of the benzene molecule are substituted with substituents. At this time, at least one first group of the substituents is any one of the second group and the third group. The second group uses the first hydrocarbon group -R- and has the following chemical formula:
-R-OH
The third group is represented by the following chemical formula using the second hydrocarbon group -R'-:
-O-R'-OH
It is expressed by Of the substituents, the group other than the first group is preferably a group selected from a hydroxyl group, a third hydrocarbon group, and an alkoxyl group.

  The antifreeze liquid according to the present invention can extend the maintenance interval of the applied apparatus.

  Hereinafter, embodiments of the antifreeze liquid according to the present invention will be described. The antifreeze contains a first component, a second component, a third component, a fourth component, a fifth component, a sixth component, and water.

  The first component is ethylene glycol, propylene glycol (1,2-propanediol), or a mixture of ethylene glycol and propylene glycol. The first component is added to lower the freezing point of the antifreeze liquid according to the present invention. When the concentration of the first component is extremely low, the antifreeze liquid has an insufficient effect for preventing freezing. The lower limit of the concentration of the first component depends on the environmental temperature at which the antifreeze is used. For this reason, the lower limit concentration is appropriately set. When the antifreeze according to the present invention is used as an engine coolant for automobiles, the concentration of the first component is preferably 30% by mass or more.

  Propylene glycol is a substance having a smaller environmental impact than ethylene glycol, and is also used as a food additive. For this reason, the antifreeze according to the present invention can contain only propylene glycol as the first component without containing ethylene glycol. Such an antifreeze is preferable in terms of reducing the environmental load. At this time, as the propylene glycol to be added, one obtained by an arbitrary production method can be used. For example, commercially available propylene glycol can also be used. In addition, the 1st component can also apply glycol different from ethylene glycol and propylene glycol.

The second component is an aromatic alcohol, that is, formed from a compound in which some or all of the six hydrogen atoms of the benzene molecule are substituted with substituents other than hydrogen atoms. The substituent is represented by the following chemical formula using a hydrocarbon group -R-:
-R-OH
Or a group represented by the following chemical formula:
-O-R'-OH
Is a group represented by Here, the hydrocarbon group -R- and the hydrocarbon group -R'- are groups obtained by removing two hydrogen atoms from a hydrocarbon molecule. The hydrocarbon is an alkane, alkene or alkyne, and the hydrocarbon skeleton is linear or branched. The hydrocarbon has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

  In addition, 1 to 6 of the substituents are bonded to the benzene molecule. At this time, the number of groups —R—OH bonded to the benzene molecule is 0 to 6, more preferably 0 to 2. The groups -R-OH may be different from each other when a plurality of the groups -R-OH are bonded to the benzene molecule. For example, the groups -R-OH may have different carbon numbers. The number of groups —O—R′—OH bonded to the benzene molecule is 0 to 6, more preferably 0 to 2. The groups —O—R′—OH may be different from each other when a plurality of the groups —O—R′—OH are bonded to the benzene molecule, for example, the groups —O—R′—OH may have different carbon numbers. May be.

  The compound of the second component may be a compound in which some or all of the remaining hydrogen atoms of the benzene molecule are substituted with groups other than hydrogen atoms. The group is a hydroxyl group, a hydrocarbon group, or an alkoxyl group.

  The hydrocarbon group is a group obtained by removing one hydrogen atom from a saturated hydrocarbon molecule having 1 to 3 carbon atoms. The hydrocarbon group is a group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon molecule having 1 to 8 carbon atoms, or a linear chain having 1 to 8 carbon atoms. Alternatively, it may be a group obtained by removing one hydrogen atom from a branched chain unsaturated hydrocarbon molecule.

  The alkoxyl group is a group in which one oxygen atom is bonded to one hydrogen atom of a saturated hydrocarbon molecule having 1 to 3 carbon atoms. In addition, the alkoxyl group is a group in which one oxygen atom is bonded to one hydrogen atom of a saturated hydrocarbon molecule having 1 to 8 carbon atoms, or an unsaturated hydrocarbon having 1 to 8 carbon atoms. It may be a group in which one oxygen atom is bonded to one hydrogen atom of the molecule.

により表現される化合物１と、
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により表現される化合物２０と、
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により表現される化合物２１と、
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により表現される化合物２２とが例示される。ここで、化合物１１と化合物１２とは、二重結合に関してｃｉｓ−、ｔｒａｎｓ−の２種類の幾何異性体が存在するが、両方の幾何異性体を適用することができる。 As the second component compound,
The following chemical formula:

Compound 1 represented by:
The following chemical formula:

Compound 2 represented by:
The following chemical formula:

Compound 3 represented by:
The following chemical formula:

Compound 4 represented by:
The following chemical formula:

Compound 5 represented by:
The following chemical formula:

Compound 6 represented by:
The following chemical formula:

Compound 7 represented by:
The following chemical formula:

Compound 8 represented by:
The following chemical formula:

Compound 9 represented by:
The following chemical formula:

Compound 10 represented by:
The following chemical formula:

Compound 11 represented by:
The following chemical formula:

Compound 12 represented by:
The following chemical formula:

Compound 13 represented by:
The following chemical formula:

Compound 14 represented by:
The following chemical formula:

Compound 15 represented by:
The following chemical formula:

Compound 16 represented by:
The following chemical formula:

Compound 17 represented by:
The following chemical formula:

Compound 18 represented by:
The following chemical formula:

Compound 19 represented by:
The following chemical formula:

Compound 20 represented by:
The following chemical formula:

Compound 21 represented by:
The following chemical formula:

And the compound 22 represented by: Here, compound 11 and compound 12 have two types of geometric isomers of cis- and trans- with respect to the double bond, but both geometric isomers can be applied.

  That is, the antifreeze liquid according to the present invention includes Compound 1, Compound 2, Compound 3, Compound 4, Compound 5, Compound 6, Compound 7, Compound 8, Compound 9, Compound 10, Compound 11, Compound 12, and Compound as the second component. One compound selected from the group formed from 13, 13, 14, 15, 16, 18, 19, 20, 21, and 22 or selected from the group A mixture in which a plurality of compounds are mixed is contained.

  The antifreeze liquid according to the present invention comprises, as the second component, Compound 1, Compound 2, Compound 3, Compound 4, Compound 5, Compound 6, Compound 7, Compound 8, Compound 9, Compound 10, Compound 11, Compound 12, Compound 13, and the like. It is further preferable that one compound selected from the group formed of the compound 14, the compound 15 and the compound 16 or a mixture in which a plurality of compounds selected from the group are mixed is contained.

  The third component is a straight-chain aliphatic dicarboxylic acid having 10 to 12 carbon atoms or a salt of the straight-chain aliphatic dicarboxylic acid, and is added to improve the corrosion inhibition effect of the antifreeze solution on the metal. Examples of such linear aliphatic dicarboxylic acids include sebacic acid, undecanedioic acid, and dodecanedioic acid. Examples of the salt of the linear aliphatic dicarboxylic acid include alkali metal salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal include lithium, sodium, and potassium. Examples of organic ammonium salts include alkyl ammonium salts and alkanol ammonium salts. The salt of the linear aliphatic dicarboxylic acid may be an acidic salt in which hydrogen remains in one of the two carboxyl groups of the linear aliphatic dicarboxylic acid, and the two carboxyl groups May be a salt that is ionically bonded to two different cations.

  The third component may be one of the exemplified compounds or a mixture of a plurality of compounds selected from the plurality of compounds. When the third component is a mixture thereof, it can also contain three or more cations.

  Furthermore, when the antifreeze liquid according to the present invention contains 0.1 to 5.0 parts by mass of the third component with respect to 100 parts by mass of the first component, the corrosion inhibiting effect is sufficient, and turbidity and precipitates are generated. It is preferable in that it becomes difficult. The antifreeze liquid according to the present invention preferably contains 0.3 to 3.0 parts by mass of the third component with respect to 100 parts by mass of the first component.

  The fourth component is a mixture of a benzimidazole skeleton compound, a benzimidazole skeleton compound salt, a triazine skeleton compound, a triazine skeleton compound salt, and a plurality of compounds selected from these compounds. The 4th component is added in order to improve the corrosion inhibitory effect with respect to the metal of antifreeze.

により表現される化合物が例示される。このようなベンゾイミダゾール骨格化合物は、環境負荷をより小さくし、かつ、腐食抑制効果を向上させる点で好ましい。 The benzimidazole skeleton compound is a compound having a benzimidazole skeleton. The benzimidazole skeleton compound has the following chemical formula:

The compound represented by is illustrated. Such a benzimidazole skeleton compound is preferable in that the environmental load is further reduced and the corrosion inhibition effect is improved.

At this time, the first group R ¹ is a hydrogen atom, a hydroxyl group, a carboxyl group, or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. In the hydrocarbon group, a hydrogen atom may be substituted with a carboxyl group or a hydroxyl group. That is, the first group R ¹ is a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a hydroxyl group, a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a carboxyl group, or a hydrocarbon group A group in which some hydrogen atoms are substituted with hydroxyl groups and other some hydrogen atoms are substituted with carboxyl groups may be used.

The second group R ² is designed in the same manner as the first group R ¹ . That is, the second group R ² is a hydrogen atom, a hydroxyl group, a carboxyl group, or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. In the hydrocarbon group, a hydrogen atom may be substituted with a carboxyl group or a hydroxyl group. That is, the second group R ² is a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a hydroxyl group, a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a carboxyl group, or a hydrocarbon group A group in which some hydrogen atoms are substituted with hydroxyl groups and other some hydrogen atoms are substituted with carboxyl groups may be used.

The third group R ³ is designed in the same manner as the first group R ¹ . That is, the third group R ³ is a hydrogen atom, a hydroxyl group, a carboxyl group, or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. In the hydrocarbon group, a hydrogen atom may be substituted with a carboxyl group or a hydroxyl group. That is, the third group R ³ is a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a hydroxyl group, a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a carboxyl group, or a hydrocarbon group A group in which some hydrogen atoms are substituted with hydroxyl groups and other some hydrogen atoms are substituted with carboxyl groups may be used.

The first group R ¹ and the second group R ² and the third group R ^3, may be different be coincident with each other.

The fourth group R ⁴ is a hydrogen atom, a hydrocarbon group, a group containing sulfur, a group containing nitrogen, or a group containing sulfur and nitrogen. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. The sulfur-containing group has the following chemical formula:
-SR ¹⁰
The group represented by is illustrated. At this time, the tenth group R ¹⁰ is a hydrogen atom or a linear, branched or cyclic alkyl group. The nitrogen-containing group has the following chemical formula:
-NR ¹¹ R ¹²
The group represented by is illustrated. At this time, the eleventh group R ¹¹ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The twelfth group R ¹² is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The eleventh group R ¹¹ and the twelfth group R ¹² may be the same as or different from each other.

により表現される基、次化学式：

により表現される基が例示される。 The group containing sulfur and nitrogen has the following chemical formula:
-S-N = R ¹³
, That is, a group having a 5- or 6-membered heterocyclic ring having sulfur and nitrogen on the ring. At this time, the thirteenth group R ¹³ is a nitrogen-containing heterocyclic part, has 3 to 6 carbon atoms, and may have oxygen or nitrogen in the main chain. That is, the following chemical formula:
-S-N = R ¹³
The group represented by the following chemical formula:

The group represented by the following chemical formula:

The group represented by is illustrated.

The fourth group R ⁴ may be a hydrogen atom, a methyl group, an ethyl group, a mercapto group, a dibutylamino group, a phenylamino group, a thiazolyl group, a group represented by Chemical Formula 46, or a group represented by Chemical Formula 47. preferable.

  The benzimidazole skeleton compound is particularly preferably thiabendazole. Thiabendazole is a compound represented by CAS Registry Number 148-79-8.

  The benzimidazole skeleton compound salt is a salt of the benzimidazole skeleton compound described above. Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal include lithium, sodium, and potassium. Examples of organic ammonium salts include alkyl ammonium salts and alkanol ammonium salts. The benzimidazole skeleton compound salt is preferably an alkali metal salt of a benzimidazole skeleton compound, and particularly preferably a sodium salt of a benzimidazole skeleton compound or a potassium salt of a benzimidazole skeleton compound.

As the fourth component, benzotriazole in which the fourth group R ⁴ of the benzimidazole skeleton compound represented by Chemical Formula 45 and the carbon atom bonded to the fourth group R ⁴ are substituted with a nitrogen atom is applied. You can also

により表現される化合物が例示される。このようなトリアジン骨格化合物は、環境負荷をより小さくし、かつ、腐食抑制効果を向上させる点で好ましい。このとき、第５基Ｒ^５は、第４基Ｒ^４と同様に設計される。すなわち、第５基Ｒ^５は、水素原子、炭化水素基、硫黄を含む基、窒素を含む基、または、硫黄と窒素とを含む基である。その炭化水素基としては、直鎖もしくは分岐のアルキル基、アルケニル基、シクロアルキル基、シクロアルケニル基、アリール基が例示される。その炭化水素基は、炭素原子数が１〜２０であることが好ましく、炭素原子数が１〜８であることがより好ましい。その硫黄もしくは窒素を含有する基は、直鎖、分岐鎖または環状の基である。その硫黄を含む基としては、次化学式：
−ＳＲ^１０
により表現される基が例示される。このとき、第１０基Ｒ^１０は、水素原子、または、直鎖、分岐鎖もしくは環状のアルキル基である。その窒素を含む基としては、次化学式：
−ＮＲ^１１Ｒ^１２
により表現される基が例示される。このとき、第１１基Ｒ^１１は、水素原子または炭化水素基である。その炭化水素基としては、直鎖もしくは分岐のアルキル基、アルケニル基、シクロアルキル基、シクロアルケニル基、アリール基が例示される。第１２基Ｒ^１２は、水素原子または炭化水素基である。その炭化水素基としては、直鎖もしくは分岐のアルキル基、アルケニル基、シクロアルキル基、シクロアルケニル基、アリール基が例示される。第１１基Ｒ^１１と第１２基Ｒ^１２とは、互いに一致していても異なっていてもよい。 The triazine skeleton compound has a mercapto group. Such triazine skeleton compounds have the following chemical formula:

The compound represented by is illustrated. Such a triazine skeleton compound is preferable in that the environmental load is further reduced and the corrosion inhibition effect is improved. At this time, the fifth group R ⁵ is designed in the same manner as the fourth group R ⁴ . That is, the fifth group R ⁵ is a hydrogen atom, a hydrocarbon group, a group containing sulfur, a group containing nitrogen, or a group containing sulfur and nitrogen. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. The sulfur or nitrogen containing group is a linear, branched or cyclic group. The sulfur-containing group has the following chemical formula:
-SR ¹⁰
The group represented by is illustrated. At this time, the tenth group R ¹⁰ is a hydrogen atom or a linear, branched or cyclic alkyl group. The nitrogen-containing group has the following chemical formula:
-NR ¹¹ R ¹²
The group represented by is illustrated. At this time, the eleventh group R ¹¹ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The twelfth group R ¹² is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The eleventh group R ¹¹ and the twelfth group R ¹² may be the same as or different from each other.

The group containing sulfur and nitrogen has the following chemical formula:
-S-N = R ¹³
And a group having a 5- or 6-membered heterocyclic ring having sulfur and nitrogen on the ring. At this time, the thirteenth group R ¹³ is a nitrogen-containing heterocyclic part, has 3 to 6 carbon atoms, and may have oxygen or nitrogen in the main chain.

により表現される基、次化学式：

により表現される基がより好ましい。 As the fifth group R ⁵ , a hydrogen atom, a methyl group, an ethyl group, a mercapto group, a dibutylamino group, a phenylamino group, a thiazolyl group, the following chemical formula:

The group represented by the following chemical formula:

The group represented by is more preferable.

The sixth group R ⁶ is designed in the same manner as the fifth group R ⁵ . That is, the sixth group R ⁶ is a hydrogen atom, a hydrocarbon group, a group containing sulfur, a group containing nitrogen, or a group containing sulfur and nitrogen. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. The sulfur or nitrogen containing group is a linear, branched or cyclic group. The sulfur-containing group has the following chemical formula:
-SR ¹⁰
The group represented by is illustrated. At this time, the tenth group R ¹⁰ is a hydrogen atom or a linear, branched or cyclic alkyl group. The nitrogen-containing group has the following chemical formula:
-NR ¹¹ R ¹²
The group represented by is illustrated. At this time, the eleventh group R ¹¹ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The twelfth group R ¹² is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups. The eleventh group R ¹¹ and the twelfth group R ¹² may be the same as or different from each other.

The group containing sulfur and nitrogen has the following chemical formula:
-S-N = R ¹³
And a group having a 5- or 6-membered heterocyclic ring having sulfur and nitrogen on the ring. At this time, the thirteenth group R ¹³ is a nitrogen-containing heterocyclic part, has 3 to 6 carbon atoms, and may have oxygen or nitrogen in the main chain.

The sixth group R ⁶ is more preferably a hydrogen atom, a methyl group, an ethyl group, a mercapto group, a dibutylamino group, a phenylamino group, a thiazolyl group, a group represented by Chemical formula 49, or a group represented by Chemical formula 50.

  The triazine skeleton compound is particularly preferably dimercapto-s-triazine or trimercapto-s-triazine. Trimercapto-s-triazine is a compound represented by CAS Registry Number 638-16-4.

  The triazine skeleton compound salt is a salt of the aforementioned triazine skeleton compound. Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal include lithium, sodium, and potassium. Examples of organic ammonium salts include alkyl ammonium salts and alkanol ammonium salts. The triazine skeleton compound salt is preferably an alkali metal salt of the triazine skeleton compound, particularly preferably a sodium salt of the triazine skeleton compound or a potassium salt of the triazine skeleton compound.

  The fourth component may be one compound among a plurality of substances exemplified as the fourth component, or a mixture of a plurality of compounds selected from the plurality of compounds. When the fourth component is a mixture thereof, it can also contain three or more cations.

Furthermore, it is preferable that the antifreeze liquid according to the present invention contains 0.01 to 5.0 parts by mass of the fourth component with respect to 100 parts by mass of the first component in terms of sufficient corrosion inhibition effect. Here, using the mass T of the benzimidazole skeleton compound and the benzimidazole skeleton compound salt with respect to the mass 100 of the first component, and the mass S of the triazine skeleton compound and the triazine skeleton compound salt with respect to the mass 100 of the first component, The value X is given by the following formula:
X = T + S × 3
Defined by The antifreeze liquid according to the present invention preferably has a value X of 0.06 to 1.2, more preferably 0.08 to 0.9. At this time, either the mass S or the mass T may be zero.

により表現される。このとき、第７基Ｒ^７は、水素原子、水酸基、アミノ基、または、炭素原子数１〜６の炭化水素基である。第８基Ｒ^８は、水素原子、水酸基、アミノ基、または、炭素原子数１〜６の炭化水素基である。第９基Ｒ^９は、水素原子、水酸基、アミノ基、または、炭素原子数１〜６の炭化水素基である。第７基Ｒ^７と第８基Ｒ^８と第９基Ｒ^９とは、互いに一致していても異なっていてもよい。 The fifth component is an aromatic carboxylic acid, a salt of the aromatic carboxylic acid, or a mixture of these compounds, and is added to improve the anti-corrosion effect of the antifreeze solution on the metal. The aromatic carboxylic acid has the following chemical formula:

It is expressed by At this time, the seventh group R ⁷ is a hydrogen atom, a hydroxyl group, an amino group, or a hydrocarbon group having 1 to 6 carbon atoms. The eighth group R ⁸ is a hydrogen atom, a hydroxyl group, an amino group, or a hydrocarbon group having 1 to 6 carbon atoms. The ninth group R ⁹ is a hydrogen atom, a hydroxyl group, an amino group, or a hydrocarbon group having 1 to 6 carbon atoms. The seventh group R ⁷ , the eighth group R ⁸ and the ninth group R ⁹ may be the same as or different from each other.

  Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, p-tertiarybutylbenzoic acid, p-hydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, p-aminobenzoic acid, and anthranilic acid. The The aromatic carboxylic acid is p-tertiarybutylbenzoic acid, p-hydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, p-aminobenzoic acid, and anthranilic acid. And it is preferable at the point which improves a corrosion inhibitory effect. The aromatic carboxylic acid is more preferably p-hydroxybenzoic acid or p-aminobenzoic acid.

  As the aromatic carboxylic acid salt, a salt which can be dissolved in the antifreeze solution according to the present invention is applied. Examples of such salts include alkali metal salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal salt include lithium salt, sodium salt, and potassium salt. Examples of the organic ammonium salt include alkyl ammonium salts and alkanol ammonium salts.

  The fifth component may be one of a plurality of substances exemplified as the fifth component or a mixture of a plurality of substances selected from the plurality of substances. When the fifth component is a mixture thereof, it can also contain three or more cations.

  Furthermore, it is more preferable that the antifreeze liquid according to the present invention contains 0.02 to 4.0 parts by mass of the fifth component with respect to 100 parts by mass of the first component in terms of improving the corrosion inhibition effect. More preferably, the antifreeze liquid according to the present invention contains 0.07 to 2.0 parts by mass of the fifth component with respect to 100 parts by mass of the first component.

  The sixth component is nitric acid or nitrate, and is added to improve the anti-corrosion effect of the antifreeze on the metal. As the nitric acid, one obtained by an arbitrary production method can be used, and commercially available nitric acid can also be used. As the nitrate, a salt soluble in the antifreeze according to the present invention is applied. Examples of such salts include alkali metal salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal salt include lithium salt, sodium salt, and potassium salt. Examples of the organic ammonium salt include alkyl ammonium salts and alkanol ammonium salts.

  The sixth component may be one of the plurality of substances exemplified as the sixth component, or may be a mixture of a plurality of substances selected from the plurality of substances. For this reason, when the sixth component is a mixture thereof, it can also contain three or more kinds of cations.

  Furthermore, it is preferable that the antifreeze liquid according to the present invention contains 0.02 to 1.0 part by mass of the sixth component with respect to 100 parts by mass of the first component in terms of further improving the corrosion inhibition effect. The antifreeze liquid according to the present invention more preferably contains 0.07 to 0.8 parts by mass of the sixth component with respect to 100 parts by mass of the first component.

  The antifreeze according to the invention is added with water for economic reasons, i.e. to reduce the price per mass. As the water, water having few suspended particles and few dissolved ions is applied. Examples of such water include ion exchange water. The antifreeze liquid according to the present invention can be used as it is without adding water. The antifreeze according to the present invention may be further added with a hydroxide when diluted with water. Hydroxide is added to adjust the pH of the antifreeze. Examples of the hydroxide include sodium hydroxide and potassium hydroxide. The antifreeze is preferably 7.0 to 9.0 in terms of surely exhibiting a corrosion inhibiting effect, and more preferably has a pH of 7.4 to 8.4. When the antifreeze solution according to the present invention is used after being diluted with water, it is preferable from the viewpoint of economy that the antifreeze solution is further diluted so that the concentration of the first component is 60% by mass or less.

  The antifreeze liquid according to the present invention is applied to, for example, an internal combustion engine that converts heat into mechanical power and is applied for propulsion of an automobile or the like. The internal combustion engine includes a radiator that circulates coolant and cools the main body of the internal combustion engine. The radiator includes a rubber part formed from rubber. Examples of such rubber parts include connector packing, water pump mechanical seals, radiator hoses, and thermostat covers. Examples of the rubber include NBR, SBR, and EPDM. Such rubber parts are generally cured by prolonged contact with the coolant. Curing of the rubber part contributes to leakage of coolant from the cooling system. For this reason, the internal combustion engine is regularly inspected, and the rubber parts are replaced with new ones before they are cured to the extent that the coolant leaks.

  The antifreeze liquid according to the present invention can suppress the hardening of the rubber in contact with the antifreeze liquid not containing the second component. For this reason, the internal combustion engine to which the antifreeze liquid according to the present invention is applied as a coolant can use the rubber part for a longer period of time compared to the antifreeze liquid not containing the second component. That is, the antifreeze according to the present invention can extend the interval for checking the rubber parts of the applied internal combustion engine.

  The antifreeze liquid according to the present invention can further prevent the metal in contact from being corroded by containing the third component, the fourth component, the fifth component, and the sixth component. The third component, the fourth component, the fifth component, and the sixth component are not essential components of the antifreeze liquid according to the present invention, and the antifreeze liquid according to the present invention includes the third component, the fourth component, the fifth component, and the second component. Some or all of the six components may not be contained. The antifreeze liquid according to the present invention may further contain a pH adjuster, an antifoaming agent, and a colorant to such an extent that the suppression of rubber curing is not hindered.

  The method for producing an antifreeze liquid according to the present invention includes a step of preparing a first intermediate product, a step of preparing a second intermediate product, and a step of preparing an antifreeze solution. In the step of preparing the first intermediate product, the first component, the second component, the third component, the fourth component, the fifth component, and the sixth component are mixed to prepare the first intermediate product. . At this time, an aqueous solution in which each of the first component, the second component, the third component, the fourth component, the fifth component, and the sixth component is dissolved in water can be used. Further, at this time, a hydroxide can be mixed. Furthermore, the first component may be mixed with an amount of water in which the concentration of the first component does not become 25% by mass or less. In the step of preparing the second intermediate product, a second intermediate product is prepared by adding a hydroxide to the first intermediate product so that the pH is 7.0 to 9.0. . In the step of preparing the antifreeze solution, ion-exchanged water is added so that the concentration of the first component is 30% by mass or more and 60% by mass or less to prepare the antifreeze solution.

  The antifreeze additive according to the present invention is formed from the second component contained in the antifreeze according to the present invention. At this time, in the antifreeze manufacturing method according to the present invention, first, an antifreeze containing no second component is manufactured. Next, the antifreeze additive according to the present invention is added to the antifreeze and mixed to produce the antifreeze according to the present invention. According to such an antifreeze additive, the antifreeze according to the present invention can be easily manufactured by adding the antifreeze additive to the antifreeze sold on the market.

The antifreeze can be evaluated for the degree to which the rubber is cured by an immersion test defined in JIS K6253. In the immersion test, the hardness of a plurality of rubber test pieces is measured, the rubber test pieces are immersed in an antifreeze solution at 60 ° C. for one month, and the hardness of the rubber test pieces after immersion is measured. The hardness change is calculated from The plurality of rubber test pieces are formed of NBR, SBR, and EPDM, respectively. The hardness indicates the ratio of the strain of the rubber test piece to the stress applied to the rubber test piece. The hardness change V is expressed by the following formula using the hardness Ha after immersion and the hardness Hb before immersion:
V = (Ha−Hb) ÷ Hb × 100
Is calculated by That is, the hardness change V indicates that the smaller the value, the more preferable it is that the antifreeze liquid hardens the rubber.

  With reference to the drawings, an example of antifreeze according to the present invention will be described. FIG. 1 shows the composition of Comparative Examples 1 to 5 and the hardness change that is the result of the immersion test of Comparative Examples 1 to 5.

  The antifreeze in Comparative Example 1 has a propylene glycol concentration of 45 mass% and a water concentration of 55 mass%.

  According to the immersion test, the antifreeze solution in Comparative Example 1 has a hardness change of 0.5% for the rubber test piece formed from NBR and a hardness change of 8.3% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 11.1%.

  The antifreeze in Comparative Example 2 has an ethylene glycol concentration of 45 mass% and a water concentration of 55 mass%.

In the antifreeze solution in Comparative Example 2, the hardness change of the rubber test piece formed from NBR is 0.2% and the hardness change of the rubber test piece formed from SBR is 7.8% according to the immersion test. The hardness change of the rubber test piece formed from EPDM is 12.0%.

  The antifreeze solution in Comparative Example 3 has a propylene glycol concentration of 45 mass%, a potassium sebacate concentration of 1.5 mass%, a benzotriazole concentration of 0.2 mass%, and a potassium phosphate concentration. Is 0.3 mass%, the concentration of sodium nitrate is 0.3 mass%, and the concentration of water is 52.7 mass%.

  According to the immersion test, the antifreeze in Comparative Example 3 has a hardness change of 3.0% for the rubber test piece formed from NBR and a hardness change of 9.7% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 11.1%.

  The antifreeze in Comparative Example 4 has a propylene glycol concentration of 45 mass%, a compound 1 concentration of 0.0005 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.6695% by mass.

  In the antifreeze solution in Comparative Example 4, the hardness change of the rubber test piece formed from NBR is 2.5% and the hardness change of the rubber test piece formed from SBR is 9.2% according to the immersion test. The hardness change of the rubber test piece formed from EPDM is 9.9%.

  The antifreeze in Comparative Example 5 has a propylene glycol concentration of 45 mass%, a compound 11 concentration of 0.0005 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.6695% by mass.

  According to the immersion test, the antifreeze in Comparative Example 5 has a change in hardness of the rubber test piece formed from NBR of 2.8% and a change in hardness of the rubber test piece formed from SBR is 9.2%. The hardness change of the rubber test piece formed from EPDM is 10.6%.

  FIG. 2 shows the compositions of Examples 1-7 and the results of the immersion tests of Examples 1-7. The antifreeze in Example 1 has a propylene glycol concentration of 45 mass%, a compound 1 concentration of 0.01 mass%, and a water concentration of 54.99 mass%.

  According to the immersion test, the antifreeze liquid in Example 1 has a hardness change of −3.3% for the rubber test piece formed from NBR and a hardness change of 6.8% for the rubber test piece formed from SBR. Yes, the hardness change of the rubber test piece formed from EPDM is 6.9%. That is, this test result shows that the antifreeze liquid according to Example 1 is harder to cure the rubber than the antifreeze liquids according to Comparative Examples 1 to 5.

  The antifreeze in Example 2 has a propylene glycol concentration of 45 mass%, a compound 1 concentration of 0.01 mass%, and a water concentration of 54.99 mass%.

  According to the immersion test, the antifreeze in Example 2 has a hardness change of -2.9% for the rubber test piece formed from NBR and a hardness change of 7.5% for the rubber test piece formed from SBR. Yes, the hardness change of the rubber test piece formed from EPDM is 6.1%. That is, this test result shows that the antifreeze liquid according to Example 2 is harder to cure the rubber than the antifreeze liquids according to Comparative Examples 1 to 5.

  The antifreeze in Example 3 has a propylene glycol concentration of 45 mass%, a compound 1 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 3 has a hardness change of 0.4% for rubber test pieces formed from NBR and a hardness change of 6.5% for rubber test pieces formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.9%. That is, this test result shows that the antifreeze liquid according to Example 3 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 1, 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. It is shown that EPDM is harder to harden than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 4 has a propylene glycol concentration of 45 mass%, a compound 2 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 4 has a hardness change of 0.2% for the rubber test piece formed from NBR and a hardness change of 7.1% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.6%. That is, this test result shows that the antifreeze liquid according to Example 4 is harder to cure the rubber than the antifreeze liquids according to Comparative Examples 1 to 5.

  The antifreeze in Example 5 has a propylene glycol concentration of 45 mass%, a compound 3 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 5 has a hardness change of 0.8% for a rubber test piece formed from NBR and a hardness change of 7.8% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.5%. That is, this test result shows that the antifreeze liquid according to Example 5 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  In the antifreeze liquid in Example 6, the concentration of propylene glycol is 45 mass%, the concentration of compound 4 is 0.01 mass%, the concentration of potassium sebacate is 1.5 mass%, and the concentration of benzotriazole is It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 6 has a hardness change of 1.3% for the rubber test piece formed from NBR and a hardness change of 8.2% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 8.4%. That is, this test result indicates that the antifreeze liquid according to Example 6 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and the SBR is harder to harden than the antifreeze liquid according to Comparative Examples 1, 3, 4, and 5. It is shown that EPDM is harder to harden than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 7 has a propylene glycol concentration of 45 mass%, a compound 5 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 7 has a hardness change of 1.9% for a rubber test piece formed from NBR, and a hardness change of 6.5% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.7%. That is, this test result shows that the antifreeze liquid according to Example 7 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  FIG. 3 shows the compositions of Examples 8-14 and the results of the immersion tests of Examples 8-14. The antifreeze in Example 8 has a propylene glycol concentration of 45 mass%, a compound 6 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  In the antifreeze solution in Example 8, the hardness change of the rubber test piece formed from NBR is −0.3% according to the immersion test, and the hardness change of the rubber test piece formed from SBR is 7.3%. Yes, the hardness change of the rubber test piece formed from EPDM is 7.1%. That is, this test result shows that the antifreeze liquid according to Example 8 is harder to cure the rubber than the antifreeze liquids according to Comparative Examples 1 to 5.

  The antifreeze in Example 9 has a propylene glycol concentration of 45 mass%, a compound 7 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 9 has a hardness change of 1.5% for a rubber test piece formed from NBR and a hardness change of 7.7% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.3%. That is, this test result shows that the antifreeze liquid according to Example 9 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  In the antifreeze solution in Example 10, the concentration of propylene glycol is 45 mass%, the concentration of compound 8 is 0.01 mass%, the concentration of potassium sebacate is 1.5 mass%, and the concentration of benzotriazole is It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 10 has a hardness change of 0.8% for a rubber test piece formed from NBR and a hardness change of 6.9% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.3%. That is, this test result shows that the antifreeze liquid according to Example 10 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 11 has a propylene glycol concentration of 45 mass%, a compound 9 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 11 has a hardness change of 0.5% for a rubber test piece formed from NBR and a hardness change of 7.0% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.7%. That is, this test result indicates that the antifreeze liquid according to Example 11 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 12 has a propylene glycol concentration of 45 mass%, a compound 10 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 12 has a hardness change of 0.4% for a rubber test piece formed from NBR and a hardness change of 7.2% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.7%. That is, this test result shows that the antifreeze liquid according to Example 12 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 1, 3, 4, and 5, and the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. It is shown that EPDM is harder to harden than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 13 has a propylene glycol concentration of 45 mass%, a compound 11 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 13 has a hardness change of 1.3% for the rubber test piece formed from NBR and a hardness change of 7.8% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 8.1%. That is, this test result shows that the antifreeze liquid according to Example 13 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 14 has a propylene glycol concentration of 45 mass%, a compound 12 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 14 has a hardness change of 1.1% for a rubber test piece formed from NBR and a hardness change of 7.5% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 8.1%. That is, this test result shows that the antifreeze liquid according to Example 14 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  FIG. 4 shows the compositions of Examples 15-22 and the results of the immersion tests of Examples 15-22. In the antifreeze solution in Example 15, the concentration of propylene glycol is 45 mass%, the concentration of compound 13 is 0.01 mass%, the concentration of potassium sebacate is 1.5 mass%, and the concentration of benzotriazole is It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 15 has a hardness change of 0.5% for a rubber test piece formed from NBR and a hardness change of 7.3% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.9%. That is, this test result shows that the antifreeze liquid according to Example 15 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  In the antifreeze solution in Example 16, the concentration of propylene glycol is 45 mass%, the concentration of compound 14 is 0.01 mass%, the concentration of potassium sebacate is 1.5 mass%, and the concentration of benzotriazole is It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 16 has a hardness change of 0.3% for a rubber test piece formed from NBR and a hardness change of 7.3% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.9%. That is, this test result shows that the antifreeze liquid according to Example 16 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 17 has a propylene glycol concentration of 45 mass%, a compound 15 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 17 has a hardness change of 0.4% for a rubber test piece formed from NBR and a hardness change of 6.4% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.7%. That is, this test result indicates that the antifreeze liquid according to Example 17 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 18 has a propylene glycol concentration of 45 mass%, a concentration of compound 16 of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 18 has a hardness change of 0.4% for a rubber test piece formed from NBR and a hardness change of 6.5% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 6.6%. That is, this test result shows that the antifreeze liquid according to Example 18 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 19 has a propylene glycol concentration of 45 mass%, a compound 1 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 19 has a hardness change of 0.8% for the rubber test piece formed from NBR and a hardness change of 8.2% for the rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 8.3%. That is, this test result shows that the antifreeze liquid according to Example 19 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and the SBR is harder to harden than the antifreeze liquid according to Comparative Examples 1, 3, 4, and 5. It is shown that EPDM is harder to harden than the antifreeze liquids of Comparative Examples 1 to 5.

  In the antifreeze solution in Example 20, the concentration of propylene glycol is 45% by mass, the concentration of Compound 1 is 0.01% by mass, the concentration of potassium sebacate is 1.5% by mass, and the concentration of benzotriazole is It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  In the antifreeze solution in Example 20, according to the immersion test, the hardness change of the rubber test piece formed from NBR is 0.1%, and the hardness change of the rubber test piece formed from SBR is 6.0%. The hardness change of the rubber test piece formed from EPDM is 6.2%. That is, this test result shows that the antifreeze liquid according to Example 20 is harder to cure the rubber than the antifreeze liquids according to Comparative Examples 1 to 5.

  The antifreeze in Example 21 has a propylene glycol concentration of 45 mass%, a compound 11 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 21 has a hardness change of 1.7% of the rubber test piece formed from NBR and a hardness change of the rubber test piece formed of SBR of 8.1%. The hardness change of the rubber test piece formed from EPDM is 8.4%. That is, this test result shows that the antifreeze liquid according to Example 21 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4, and 5, and the SBR is harder to harden than the antifreeze liquid according to Comparative Examples 1, 3, 4, and 5. It is shown that EPDM is harder to harden than the antifreeze liquids of Comparative Examples 1 to 5.

  The antifreeze in Example 22 has a propylene glycol concentration of 45 mass%, a compound 11 concentration of 0.01 mass%, a potassium sebacate concentration of 1.5 mass%, and a benzotriazole concentration of It is 0.2% by mass, the concentration of potassium phosphate is 0.3% by mass, the concentration of sodium nitrate is 0.3% by mass, and the concentration of water is 52.69% by mass.

  According to the immersion test, the antifreeze in Example 22 has a hardness change of 0.7% for a rubber test piece formed from NBR and a hardness change of 7.0% for a rubber test piece formed from SBR. The hardness change of the rubber test piece formed from EPDM is 7.3%. That is, this test result shows that the antifreeze liquid according to Example 22 is harder to harden the NBR than the antifreeze liquids according to Comparative Examples 3, 4 and 5, and shows that the SBR is harder to harden than the antifreeze liquids according to Comparative Examples 1 to 5. This shows that EPDM is harder to cure than the antifreeze liquids of Comparative Examples 1 to 5.

FIG. 1 is a table showing the compositions of Comparative Examples 1 to 5 and the results of immersion tests of Comparative Examples 1 to 5. FIG. 2 is a table showing the compositions of Examples 1 to 7 and the results of immersion tests of Examples 1 to 7. FIG. 3 is a table showing the compositions of Examples 8 to 14 and the results of the immersion tests of Examples 8 to 14. FIG. 4 is a table showing the compositions of Examples 15-22 and the results of the immersion tests of Examples 15-22.

Claims (9)

A first component;
A second component,
The first component is formed from glycol ;
The second component is
The following chemical formula:

A first compound represented by:
The following chemical formula:

A second compound represented by:
The following chemical formula:

A third compound represented by :
The following chemical formula:

A fifth compound represented by:
The following chemical formula:

A sixth compound represented by:
The following chemical formula:

A seventh compound represented by:
The following chemical formula:

An eighth compound represented by:
The following chemical formula:

A ninth compound represented by:
The following chemical formula:

A tenth compound represented by:
The following chemical formula:

An eleventh compound represented by:
The following chemical formula:

A twelfth compound represented by:
The following chemical formula:

A thirteenth compound represented by:
The following chemical formula:

A fourteenth compound represented by:
The following chemical formula:

A fifteenth compound represented by:
The following chemical formula:

16 substance der Ru antifreeze selected from the group compounds Toka et formed represented by.   In claim 1,
  The first component is
  Ethylene glycol,
  Propylene glycol,
  A substance selected from the group consisting of a mixture of ethylene glycol and propylene glycol
  antifreeze.   In either claim 1 or claim 2,
  The second component is included in a proportion of 0.001 to 10 parts by mass with respect to 100 parts by mass of the first component.
  antifreeze. In any one of Claims 1-3 ,
Further including water,
The concentration of the first component is 30 to 60% by mass. In any one of Claims 1-4 ,
A third component;
A fourth component,
The first component is propylene glycol;
The third component is
A linear aliphatic dicarboxylic acid having 10 to 12 carbon atoms;
A linear aliphatic dicarboxylate which is a salt of the linear aliphatic dicarboxylic acid;
A substance selected from the group consisting of a mixture of the linear aliphatic dicarboxylic acid and the linear aliphatic dicarboxylic acid salt;
The fourth component is
A benzimidazole skeleton compound having a benzimidazole skeleton,
A benzimidazole skeleton compound salt that is a salt of the benzimidazole skeleton compound;
A triazine skeleton compound having a triazine skeleton and a mercapto group;
A triazine skeleton compound salt which is a salt of the triazine skeleton compound;
An antifreeze, which is a substance selected from the group consisting of a mixture of a plurality of substances selected from the group consisting of the benzimidazole skeleton compound, the benzimidazole skeleton compound salt, the triazine skeleton compound, and the triazine skeleton compound salt. Producing an antifreeze liquid according to any one of claims 1 to 3 ,
Mixing the water with the antifreeze so that the concentration of the first component is 30 to 60% by mass. A cooling system for circulating the antifreeze liquid according to any one of claims 1 to 5 ,
An internal combustion engine body cooled by the cooling system,
The internal combustion engine, wherein the cooling system includes a rubber component that is formed of rubber and that contacts the antifreeze. An automobile propelled by power generated by the internal combustion engine according to claim 7 . The following chemical formula:

A first compound represented by:
The following chemical formula:

A second compound represented by:
The following chemical formula:

A third compound represented by:
The following chemical formula:

A fifth compound represented by:
The following chemical formula:

A sixth compound represented by:
The following chemical formula:

A seventh compound represented by:
The following chemical formula:

An eighth compound represented by:
The following chemical formula:

A ninth compound represented by:
The following chemical formula:

A tenth compound represented by:
The following chemical formula:

An eleventh compound represented by:
The following chemical formula:

A twelfth compound represented by:
The following chemical formula:

A thirteenth compound represented by:
The following chemical formula:

A fourteenth compound represented by:
The following chemical formula:

A fifteenth compound represented by:
The following chemical formula:

An antifreeze additive which is a substance selected from the group formed from the sixteenth compound represented by

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