WO2005054397A1 - Composition de fluide de refroidissement - Google Patents

Composition de fluide de refroidissement Download PDF

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Publication number
WO2005054397A1
WO2005054397A1 PCT/JP2003/015330 JP0315330W WO2005054397A1 WO 2005054397 A1 WO2005054397 A1 WO 2005054397A1 JP 0315330 W JP0315330 W JP 0315330W WO 2005054397 A1 WO2005054397 A1 WO 2005054397A1
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WO
WIPO (PCT)
Prior art keywords
acid
salt
carbon atoms
salts
coolant
Prior art date
Application number
PCT/JP2003/015330
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English (en)
Japanese (ja)
Inventor
Hiroshi Egawa
Hidemi Kado
Original Assignee
Shishiai-Kabushikigaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shishiai-Kabushikigaisha filed Critical Shishiai-Kabushikigaisha
Priority to JP2005511254A priority Critical patent/JPWO2005054397A1/ja
Priority to PCT/JP2003/015330 priority patent/WO2005054397A1/fr
Priority to AU2003304592A priority patent/AU2003304592A1/en
Publication of WO2005054397A1 publication Critical patent/WO2005054397A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids

Definitions

  • the present invention relates to a coolant composition mainly used for a coolant of an internal combustion engine (more particularly, relates to a coolant composition for an internal combustion engine).
  • a coolant composition for an internal combustion engine.
  • Field of the Invention The present invention relates to a cooling liquid composition that is effective in reducing a reduction in face opening in a mechanical seal portion.
  • the coolant composition used in the cooling system of internal combustion engines mainly contains glycols and alcohols that lower the freezing point to prevent freezing during the cold season.
  • Metal corrosion inhibitor is added to prevent corrosion of steel.
  • metals such as aluminum or aluminum alloys, iron, steel, brass, solder, and copper have been used in the cooling system of internal combustion engines.
  • aluminum or aluminum alloys have been diversified as cooling system components for the purpose of reducing the weight of automobile bodies. These metals corrode on contact with water or air.
  • coolants used in the cooling system of internal combustion engines such as engines are used for phosphates, amine salts, borates, nitrates, nitrites, silicates, and organic acids. And other metal corrosion inhibitors.
  • phosphates have been used in many coolant compositions because of their excellent corrosion protection of aluminum or aluminum alloys.
  • the hard water component in the coolant is A large amount of precipitate was formed when diluted with hard water, since a precipitate was formed by reacting with water. The formation of sediment not only deteriorated the function of the coolant to prevent corrosion, but also caused the generated sediment to accumulate in the circulation path of the cooling system and block the cooling system.
  • the non-phosphorus-based cooling liquid composition contains, for example, daricols as a main component and contains p-tert-butylbenzoic acid, 2-ethylhexanoic acid, and benzoate and / or nitrate. (See Japanese Unexamined Patent Publication No. 2000-109980). Since this cooling liquid composition does not contain a phosphate, it does not form a precipitate even when diluted with hard water. However, this cooling liquid composition has a problem that the function of preventing corrosion of aluminum under running water is low, and aluminum is corroded.
  • the conventional coolant composition was added with a metal corrosion inhibitor of usually about 4% in order to obtain a predetermined protective effect, and had a considerably high concentration.
  • a metal corrosion inhibitor of usually about 4% in order to obtain a predetermined protective effect, and had a considerably high concentration.
  • daricols which is a main component of the coolant composition, are vaporized in the mechanical seal portion of the water pump, and the metal corrosion inhibitor in the coolant composition is partially evaporated. In this case, it was deposited as a solid and deposited.
  • the metal corrosion inhibitor precipitates and accumulates in this manner, the close contact state of the mechanical seal portion cannot be ensured, and the so-called “face opening” phenomenon may occur.
  • Coolant compositions have been proposed by the applicant.
  • the cooling liquid composition contains one or more alkyl benzoic acids or an alkali metal salt, an ammonium salt or an amine salt thereof, a hydrocarbon triazole, and an alkali metal nitrate, and has an aliphatic monobasic acid in the components. Does not contain (See Japanese Patent Application Laid-Open No. Hei 8-109484).
  • the present invention has been made in view of the above circumstances, and has an excellent anti-corrosion property of aluminum and an aluminum alloy, and a reduction in face opening in a mechanical seal portion of a water pump. It is an object of the present invention to provide a cooling liquid composition that can perform the cooling.
  • the present invention provides a cooling liquid composition containing a glycol as a main component, comprising: (a) 0.1 to 10% by weight of At least one selected from aliphatic monobasic acids, alkylbenzoic acids or salts thereof, and (b) 0.01 to 2% by weight of 2-phosphonobutane-11,2,4 tricarboxylic acid; c) 0.01 to 2% by weight of a polymer or copolymer of an unsaturated monoethylene dicarboxylic acid having 4 to 6 carbon atoms or a salt thereof (hereinafter referred to as monoethylene dicarboxylic acids); Polymers and copolymers of a saturated monoethylene monocarboxylic acid or a salt thereof (hereinafter, referred to as monoethylene monocarboxylic acids), or the above-mentioned unsaturated monoethylene dicarboxylic acid having 4 to 6 carbon atoms or a salt thereof and the above-mentioned 4 to 6
  • a gist of the present invention is a coolant composition comprising at least one selected from the group consisting of copolymers of carboxylic acids and salts thereof (hereinafter, referred to as polycarboxylic acids).
  • Dalicols which are the main components of the coolant composition of the present invention (hereinafter simply referred to as composition), include ethylene glycol, propylene glycol, and 1,3-butylene glycol. Examples include coal, hexylene glycol, diethylene glycol, and glycerin. Among them, ethylene glycol and propylene glycol are preferable in terms of chemical stability, handling, price, and availability.
  • aliphatic monobasic acids or salts thereof include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid Oleic acid, linoleic acid, linolenic acid, ricinoleic acid, stearic acid and their alkali metal salts, ammonium salts and the like can be mentioned as preferred examples.
  • alkyl benzoic acid examples include P-toluic acid, P-ethyl benzoic acid, p-propyl benzoic acid, p-isopropyl benzoic acid, and p-butyl benzoic acid.
  • Salts, ammonium salts, amine salts and the like can be mentioned. Particularly preferred are alkali metal salts, and among them, sodium salts and potassium salts are most preferred.
  • the component, alkyl benzoic acid and aliphatic monobasic acid or their salts exhibit excellent anticorrosion performance, particularly against aluminum and iron-based metals, and prevent corrosion of metals in cooling systems, This suppresses the formation of precipitates due to the reaction between the hard water component contained in the coolant and the component contained in the coolant, and has a stabilizing effect on hard water.
  • Alkyl benzoic acid and aliphatic monobasic acid or their salts are 0.1 to 10 weight
  • alkylbenzoic acid and aliphatic monobasic acid or their salts are included in the range of%. If the content of alkylbenzoic acid and aliphatic monobasic acid or their salts is less than 0.1% by weight, the corrosion-inhibiting function is not sufficiently exhibited. Is not effective, and is uneconomical.
  • the component (b), 2-phosphonobutane-1,1,2,4 tricarboxylic acid, is a heterogeneous gold It exhibits excellent corrosion protection against intermetallic contact, especially between aluminum alloys, iron and solder and dissimilar metals, and also exhibits excellent corrosion resistance against aluminum heat transfer surface corrosion. It is. Furthermore, even in the presence of phosphoric acid, it has the function of suppressing the formation of precipitates due to the reaction between phosphate and hard water components in the solution.
  • 2-Phosphonobtan-1,2,4 tricarboxylic acid is contained in the range of 0.01 to 2% by weight. If the content of polycarboxylic acids and the like is less than 0.01% by weight, the corrosion-preventing function is not sufficiently exhibited. This is because
  • Preferred examples of the monoethylene monocarboxylic acids in the polycarboxylic acids (c) as component (c) include, for example, acrylic acid, methacrylic acid, acrylic acid, vinyl acetic acid, and alkali metal salts and ammonium salts thereof. it can.
  • Monoethylene dicarboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali metal salts and ammonium salts thereof, and maleic acid is most preferred. It is.
  • polystyrene resin Preferable examples of the polymer and copolymer of monoethylene dicarboxylic acid, the polymer and copolymer of monoethylene monocarboxylic acid, and the copolymer of monoethylene dicarboxylic acid and monoethylene monocarboxylic acid include polymalein. Examples include acids, polyacrylic acid, and maleic / acrylic acid copolymer. These polycarboxylic acids and the like have a function of effectively suppressing the precipitation of the hard water component contained in the coolant and the metal corrosion inhibitor in the coexistence of a phosphate. Excellent stability at dilution. It also has the function of preventing corrosion of aluminum or aluminum alloy and the function of preventing blackening.
  • polymaleic acid or an alkali metal salt or an ammonium salt thereof has an excellent effect of preventing blackening.
  • the molecular weight of the polymer or copolymer in the above-mentioned polycarboxylic acids and the like is preferably 100 to 2000. If the molecular weight is less than 1000, sufficient hard water stability, corrosion prevention function and blackening prevention function will not be obtained, and if the molecular weight exceeds 2000, it will be difficult to dissolve in the composition. Become. Further, the copolymer is in a polymerization form such as random polymerization or block polymerization. Polycarboxylic acids and the like are contained in the range of 0.01 to 2% by weight. If the content of polycarbonates, etc.
  • the composition of the present invention comprises a metal such as aluminum, aluminum alloy, iron, steel, brass, solder, copper, etc., by coexistence of the three components (a) to (c) in the main component. It has the effect of being excellent in corrosion inhibition and hard water stability in the presence of phosphate.
  • the component (b) and the component (c) provide an excellent effect of preventing corrosion of aluminum and aluminum alloys at high temperatures, and have a high corrosion inhibitory property and hard water stability with a small content. Therefore, even under high temperature conditions, the precipitation and accumulation of metal corrosion inhibitor solids due to the vaporization of glycols, the main component, in the mechanical seal portion of the water pump are reduced. The occurrence of the "face opening" phenomenon is suppressed, and the sealing state of the seal portion is ensured.
  • the composition of the present invention can also contain a phosphate. By containing a phosphate, the corrosion prevention of aluminum and aluminum alloys in particular can be further improved.
  • the phosphate examples include orthophosphoric acid, pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, and the like, and one or more of these can be contained.
  • the content of the phosphate is not particularly limited, but is preferably contained in the range of 0.01 to 2.0% by weight.
  • a form not containing molybdate may be employed. In this case, there is an advantage that the adverse effect of promoting the oxidative deterioration of glycols by molybdate can be prevented.
  • the main component is selected from (a) 0.1 to 10% by weight of an aliphatic monobasic acid, an alkylbenzoic acid or a salt thereof. At least one kind; (b) 0.01 to 2% by weight of 2-phosphonobutane-1,2,4 tricarboxylic acid; and (c) 0.01 to 2% by weight of a polycarboxylic acid.
  • the coexistence of the three components (1) and (2) has the effect of providing excellent corrosion protection for metals such as aluminum, aluminum alloys, iron, steel, brass, solder, and copper, and excellent hard water stability in the presence of phosphate. You can do it.
  • the component (b) and the component (c) provide an excellent effect of preventing corrosion of aluminum and aluminum alloys at high temperatures, and have a high corrosion inhibitory property and hard water stability with a small content. Therefore, even under high-temperature conditions, the precipitation and accumulation of metal corrosion inhibitor solids due to the vaporization of the main component, dalicols, are reduced in the mechanical seal of the water pump. The occurrence of the "face opening" phenomenon is suppressed, and the sealing state of the seal portion is ensured.
  • Fig. 1 is a schematic diagram showing a leak test device for checking the leakage of coolant from the mechanical seal.
  • Table 1 shows Examples 1 and 2 of the present invention and Comparative Examples 1 to 4. Example 1
  • Example 2 contains the components (a) to (c), and Example 2 further includes phosphoric acid in Example 1.
  • Comparative Example 1 contains the component (a) but does not contain the components (b) and (c)
  • Comparative Example 2 contains the components (a) and (c)
  • Comparative Example 3 contains the component (a).
  • Comparative Example 4 contains only component (a).
  • p-tert-butylbenzoic acid was contained as the component (a)
  • Comparative Example 4 contained toluic acid as the component (a).
  • Example 1 and 2 and Comparative Examples 1 to 4 were subjected to a metal corrosion test to confirm the change in mass of each metal and to confirm the presence or absence of abnormalities in appearance.
  • the results are shown in Table 2.
  • the metal corrosion test was carried out based on the JISK2 2 3 4 metal corrosion test, and aluminum metal, iron, steel, brass, solder, and copper test pieces were used as the metals for this test. .
  • test was carried out in accordance with the rules for corrosion resistance on aluminum heat transfer surfaces in 2 324. However, the test temperature was 160 ° C and the heat-resistant glass cell was made of stainless steel.
  • Example 1 Example 2, and Comparative Example 1 had a smaller amount of corrosion than Comparative Examples 2 and 3, and no abnormalities were observed in appearance. However, it was confirmed that the high-temperature aluminum heat transfer surface had excellent corrosion protection.
  • Example 2 Example 2 containing phosphoric acid in addition to components (a) to (c), and (a) containing no components (b) and (c).
  • a hard water stability test was performed on each sample of Comparative Example 3 containing p-tert-butylbenzoic acid and phosphoric acid as components.
  • each sample to be subjected to the test was prepared by dissolving 48 mg ZL of sodium sulfate, 165 mg ZL of sodium chloride, 38 mg / L of sodium hydrogen carbonate, and 275 mg / L of calcium chloride in distilled water using synthetic hard water. After dilution to 50% by weight, the diluted solution was left at 88 t for 24 hours, and the appearance of the test solution after the test was observed. The results are shown in Table 4.
  • a mechanical seal 3 is provided at the center of a chamber 2 filled with a coolant 1 obtained by diluting a coolant composition with water, and the mechanical seal 3 has a hollow mounting ⁇ 4. Disk-shaped holding member 6 that is connected to the rotating shaft 5 and rotates together And is held at a predetermined pressure.
  • the mechanical seal 3 is formed of a fixed ring 3 a attached to the mounting base 4 and a rotating ring 3 b that rotates the holding member 6 integrally, and the fixed ring 3 a and the rotating ring 3 b are brought into close contact with each other. This prevents the coolant 1 from entering the mechanical seal 3.
  • a heater 7 for heating the coolant 1 to a predetermined temperature is mounted inside the chamber 1, and further, the coolant 1 is externally pressurized at a predetermined pressure on the ceiling surface of the chamber 12. Pressurizing port 8 is formed. Then, in the test, when the coolant 1 leaks from the sliding surface between the fixed ring 3a and the rotating ring 3b into the inside of the mechanical seal 3, the leaked liquid 1a flows along the outer peripheral surface of the rotating shaft 5 to the atmosphere side. Leaks into the mounting table 4 and accumulates in the collection pipe 9. Therefore, the accumulated leaked liquid 1a was quantified.
  • Example 1 has a leakage amount of 9 m1 and Comparative Examples 1, 2 and 4 have 19 ml, 17 m1 and 3 lm1, respectively. It is judged that the leakage amount of 1 is small. From this, it is determined that the coexistence of the three components (a) to (c) in the coolant can suppress the so-called “plane opening” phenomenon.

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

Abstract

L'invention concerne une composition de fluide de refroidissement contenant un glycol comme composant primaire, caractérisée en ce qu'elle comprend a) 0,1 à 10 % en poids d'au moins un acide sélectionné parmi les acides monobasiques aliphatiques, les acides alkylbenzoïques et des sels de ceux-ci, b) 0,01 à 2 % en poids d'un acide 2-phosphonobutane-1, 2, 4-tricarboxylique et c) 0,01 à 2 % en poids d'au moins l'un des polymères et copolymères d'acides monoéthylène dicarboxyliques insaturés sélectionné comprenant quatre à six atomes de carbone ou de sels de ceux-ci, des polymères ou des copolymères d'acides monoéthylène dixarboxyliques insaturés comprenant quatre à six atomes de carbone ou des sels de ceux-ci, et des copolymères de l'acide monoéthylène dicarboxylique insaturé précité comprenant quatre à six atomes de carbone ou un sel de celui-ci. Ladite composition de fluide de refroidissement possède une excellente capacité de prévention de corrosion de l'aluminium ou d'un alliage d'aluminium, et permet de limiter le phénomène de formation d'intervalle entre des faces dans une partie de scellement mécanique d'une pompe à eau de moteur à combustion interne.
PCT/JP2003/015330 2003-12-01 2003-12-01 Composition de fluide de refroidissement WO2005054397A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2005511254A JPWO2005054397A1 (ja) 2003-12-01 2003-12-01 冷却液組成物
PCT/JP2003/015330 WO2005054397A1 (fr) 2003-12-01 2003-12-01 Composition de fluide de refroidissement
AU2003304592A AU2003304592A1 (en) 2003-12-01 2003-12-01 Cooling fluid composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/015330 WO2005054397A1 (fr) 2003-12-01 2003-12-01 Composition de fluide de refroidissement

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WO2005054397A1 true WO2005054397A1 (fr) 2005-06-16

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AU (1) AU2003304592A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009133989A (ja) * 2007-11-29 2009-06-18 Seiko Epson Corp プロジェクタ
JP2011007875A (ja) * 2009-06-23 2011-01-13 Asahi Kasei E-Materials Corp ワイヤグリッド偏光板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5360834A (en) * 1976-11-12 1978-05-31 Sakai Chemical Industry Co Corrosion inhibitor
JPS53146279A (en) * 1977-05-26 1978-12-20 Kurita Water Ind Ltd Corrosion, scale, and stain inhibitor in aqueous system
JPH07173651A (ja) * 1993-12-21 1995-07-11 C C I Kk 冷却液組成物
JP2002332479A (ja) * 2001-05-11 2002-11-22 Ipposha Oil Ind Co Ltd 冷却液組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU601050B2 (en) * 1987-06-16 1990-08-30 Nippon Shokubai Kagaku Kogyo Co. Ltd. Antifreeze composition
DE69828205T2 (de) * 1998-05-06 2005-12-15 Shishiai-K.K., Seki Verdünntes kühlmittel
JP2001279235A (ja) * 2000-03-29 2001-10-10 Cci Corp 不凍液／冷却液組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5360834A (en) * 1976-11-12 1978-05-31 Sakai Chemical Industry Co Corrosion inhibitor
JPS53146279A (en) * 1977-05-26 1978-12-20 Kurita Water Ind Ltd Corrosion, scale, and stain inhibitor in aqueous system
JPH07173651A (ja) * 1993-12-21 1995-07-11 C C I Kk 冷却液組成物
JP2002332479A (ja) * 2001-05-11 2002-11-22 Ipposha Oil Ind Co Ltd 冷却液組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009133989A (ja) * 2007-11-29 2009-06-18 Seiko Epson Corp プロジェクタ
JP2011007875A (ja) * 2009-06-23 2011-01-13 Asahi Kasei E-Materials Corp ワイヤグリッド偏光板

Also Published As

Publication number Publication date
AU2003304592A1 (en) 2005-06-24
JPWO2005054397A1 (ja) 2007-06-28

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