WO2005054396A1 - Composition de fluide de refroidissement - Google Patents

Composition de fluide de refroidissement Download PDF

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Publication number
WO2005054396A1
WO2005054396A1 PCT/JP2003/015329 JP0315329W WO2005054396A1 WO 2005054396 A1 WO2005054396 A1 WO 2005054396A1 JP 0315329 W JP0315329 W JP 0315329W WO 2005054396 A1 WO2005054396 A1 WO 2005054396A1
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WO
WIPO (PCT)
Prior art keywords
acid
strontium
salt
aluminum
carbon atoms
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PCT/JP2003/015329
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English (en)
Japanese (ja)
Inventor
Hiroshi Egawa
Nobuyuki Kaga
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 AU2003304581A priority Critical patent/AU2003304581A1/en
Priority to PCT/JP2003/015329 priority patent/WO2005054396A1/fr
Priority to JP2005511253A priority patent/JPWO2005054396A1/ja
Publication of WO2005054396A1 publication Critical patent/WO2005054396A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials

Definitions

  • the present invention mainly has an excellent effect of preventing corrosion of aluminum or aluminum alloy, iron, steel, etc. used for a long term in a cooling system of an internal combustion engine.
  • the present invention relates to a cooling liquid composition having excellent hard water stability even when a phosphate is contained.
  • metals such as aluminum or aluminum alloy, iron, steel, brass, solder, and copper have been used for cooling systems of internal combustion engines such as engines.
  • aluminum or aluminum alloy has been widely used for cooling system components for the purpose of reducing the weight of automobile bodies. These metals corrode on contact with water or air.
  • the coolant composition used in the cooling system of internal combustion engines includes phosphates, amine salts, borates, nitrates, nitrites, silicates, and organic acid salts. Contained a corrosion inhibitor.
  • phosphates have been used in many cooling compositions because of their superior corrosion of aluminum or aluminum alloys. For example, some were characterized by containing a melting point depressant selected from alcohols or glycols, phosphate, 2-phosphonobutane-1,2,4 tricarboxylic acid, and a calcium compound ( Japanese Patent Application Laid-Open No. 2002-3222467).
  • a non-phosphorus-based coolant composition containing no phosphate has been proposed.
  • a glycol as a main component at least one of sebacic acid or an alkali metal salt thereof is 0.5 to 4. Owt%, and at least one of p-tert-butylbenzoic acid or an alkali metal salt thereof is 0.5. 3.
  • An antifreeze (coolant composition) that contains Owt% and triazoles in the range of 0.05 to 1. Owt% and does not contain phosphate in its components has been proposed. I have. In the case of this cooling liquid composition, even when diluted with hard water, no precipitate is formed due to the absence of phosphate (see, for example, JP-A-4-1117481). However, this cooling liquid composition had a poor function of preventing corrosion of aluminum under running water, and had a problem that aluminum was corroded. On the other hand, a cooling liquid composition to which a scale inhibitor has been added has been proposed in order to suppress the formation of a precipitate when diluted with hard water.
  • the coolant composition (a) Monoe ethylenic unsaturated C 3 ⁇ C 6 _ homo- and copolymers of mono- force Rupon acid and salts thereof; (b) monoethylenically unsaturated C 3 -C 6 - Monokarupon acid and A homopolymer of the salt (the polymer is modified with a secondary alcohol); (c) a monomeric unit consisting of a monoethylenically unsaturated C4-C6-dicarboxylic acid and its salts and at least one other (D) monoethylenically unsaturated C 4 containing a monoethylenically unsaturated substituted monomer of formula (I) wherein the substituents are selected from the group consisting of alkyl vinyl ethers, olefins and vinyl esters and amides of carboxylic acids; At least one polycarbonate having a molecular weight range of from about 1200 to about 250,000 selected from the group consisting of -C6 monodicarbox
  • Containing over bets it is characterized in.
  • this cooling liquid composition a small amount selected from the group consisting of (a) to (d) is used.
  • At least one polycarboxylate is intended to reduce or eliminate hard water precipitation.
  • a coolant composition is effective in suppressing or preventing the formation of precipitates, it has a low aluminum corrosion prevention function.
  • JP-A-5-247433 DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been made in view of such circumstances, and is excellent in the function of preventing corrosion of aluminum or aluminum alloy, iron, steel, and the like, and in the presence of phosphate.
  • Means for Solving the Problems In order to achieve the above-mentioned object, in a coolant composition containing glycols as a main component, (a) 0.1 to 10% by weight of an alkylbenzoic acid or a salt thereof. At least one of
  • the coolant composition of the present invention contains glycols as a main component.
  • the glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, glycerin and the like.
  • ethylene glycol or propylene glycol is preferable in terms of chemical stability, handleability, price, availability, and the like.
  • the coolant composition of the present invention contains the above four components (a) to (d) in daricols, which are the main components, and aluminum or an aluminum alloy, iron, and iron due to a synergistic effect of these components. It has the effect of preventing corrosion of steel and the like.
  • alkylbenzoic acid that is a component of the coolant composition of the present invention include p-toluic acid, p-ethylbenzoic acid, p-propylbenzoic acid, p-butylbenzoic acid, p-isopropylbenzoic acid, p- Examples include tert-butyl benzoic acid, or an alkali metal salt, an ammonium salt, or an amine salt thereof.
  • alkylbenzoic acid among carboxylic acids, it is possible to ensure the function of preventing corrosion of aluminum, aluminum alloy, iron and steel for a long period of time. Above all, p-toluic acid and p-tert-butyl benzoic acid are excellent in the corrosion inhibiting performance of aluminum or aluminum alloy, and it is desirable that at least one of them is contained. Alkyl benzoic acid also has a function of suppressing precipitation due to reaction with hard water components in the liquid. The content of the alkyl benzoic acid or a salt thereof was set to 0.1 to 10% by weight. If the content is less than 1% by weight, a sufficient corrosion-preventing function cannot be exhibited.
  • the 2-phosphonobutane-1,1,2,4-tricarboxylic acid or a salt thereof can provide an effect of preventing corrosion of aluminum or aluminum alloys, iron and steel, etc., and particularly, an effect of improving corrosion prevention in a high temperature range.
  • Examples of the salt of 2-phosphonobutane-11,2,4 tricarboxylic acid include its sodium salt and potassium salt.
  • 2-Phosphonobtan-1,2,4 tricarboxylic acid is contained in the range of 0.01 to 0.5% by weight. If the content is outside this range, the above effects cannot be achieved or the economy becomes uneconomical.
  • the strontium compound By containing the strontium compound, the function of preventing corrosion of aluminum or aluminum alloy is improved, particularly the function of preventing corrosion of aluminum or aluminum alloy at high temperatures is enhanced, and more effective corrosion prevention is achieved. become.
  • the strontium compound is contained in the range of 0.001 to 0.1% by weight. If the content is out of the above range, sufficient effect of preventing corrosion of aluminum or an aluminum alloy, particularly, an effect of improving corrosion prevention in a high temperature range may not be obtained, or it may be uneconomical.
  • the strontium compound has a function of preventing blackening of aluminum or an aluminum alloy and suppressing corrosion in cooperation with 2-phosphonobutane-1,2,4-tricarboxylic acid.
  • a calcium compound can be used instead of the strontium compound or in addition to the stonium compound.
  • Calcium compounds include formic acid, calcium formate, calcium acetate, calcium propionate, calcium butyrate, calcium valerate, calcium laurate, calcium stearate, calcium oleate, calcium glutamate, calcium lactate, calcium succinate, calcium phosphate, tartaric acid Calcium, calcium maleate, calcium citrate, calcium oxalate, calcium malonate, calcium sebacate, calcium benzoate, calcium phthalate, calcium salicylate, calcium mandelate, calcium oxide, calcium hydroxide, permanganate Calcium, calcium chromate, calcium fluoride, calcium iodide, calcium carbonate, calcium nitrate, calcium sulfate, titanate Calcium, calcium tungstate, calcium borate, calcium phosphate, Ru can be exemplified dihydrogen phosphate calcium.
  • this calcium compound By containing this calcium compound, it has a function of preventing corrosion of aluminum or aluminum alloy, and particularly has a function of preventing corrosion of aluminum or aluminum alloy at high temperatures.
  • the total amount of the calcium compound or the strontium compound is in the range of 0.001 to 0.1% by weight for the same reason as that of the strontium.
  • polycarboxylic acid (d) examples include monoethylene dicarboxylic acids such as maleic acid and fumaric acid, and alkali metal salts and ammonium salts thereof.
  • a polymer or copolymer of monoethylene monocarboxylic acids such as methacrylic acid or their alkali metal salts and ammonium salts, or the above monoethylene dicarboxylic acids and monoethylene monocarboxylic acid It comprises at least one selected from copolymers composed of acids. Specific examples include polymers or copolymers of polymaleic acid, polyacrylic acid, maleic acid / acrylic acid, and the like.
  • polycarboxylic acids together with the 2-phosphonobutane-1,2-, 4-tricarboxylic acid, have an excellent corrosion-inhibiting function against aluminum or aluminum alloys, and particularly, the heat transfer surface of aluminum at high temperatures. It works very effectively to control corrosion.
  • the coexistence of the above-mentioned polycarboxylic acids and the above-mentioned 2-phosphonobutane-1,1,2,4 tricarbonates exerts a function with excellent hard water stability even in the presence of phosphate. In other words, it has a function to effectively prevent the hard water component contained in the cooling liquid from reacting with the phosphate to form a precipitate, and functions as a dispersant having excellent stability upon dilution with hard water. .
  • polymaleic acid, or its sodium salt, potassium salt, or ammonium salt has excellent stability when diluted with hard water.
  • these polycarboxylic acids have a protective property against aluminum or an aluminum alloy under a high temperature for a long time due to the coexistence of the 2-phosphonobutane-1,2,4 tricarboxylic acid and a strontium compound or a Z and calcium compound. Can be improved.
  • 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, a sufficient corrosion-inhibiting function cannot be obtained, and if the molecular weight is more than 2000, it becomes difficult to dissolve in the composition.
  • the polymer is in a polymerization form such as random polymerization or block polymerization.
  • the content of the polycarboxylic acids and the like is preferably 0.01 to 0.5% by weight, More preferably, it is 0.05 to 0.3% by weight.
  • the content of the polycarboxylic acid is less than 0.01% by weight, the function of preventing corrosion of aluminum or aluminum alloy and the function of suppressing the formation of precipitates under flowing water or at a high temperature are not sufficiently exhibited. If it exceeds, there is no effect as much as it exceeds, and it becomes uneconomical.
  • the content ratio of 2-phosphonobutane-1,2,4 tricarboxylic acid to polycarboxylic acids is not particularly limited, but is preferably 3: 1 to 1: 3. With this content ratio, even if phosphate is present, the reaction between the hard water component in the coolant and the phosphate is suppressed, and corrosion to aluminum or aluminum alloy under flowing water or at high temperatures is prevented. The prevention function will be exhibited reliably.
  • the composition of the present invention can take a form containing a phosphate in addition to the above components (a) to (d).
  • the phosphate examples include orthophosphoric acid, pyrophosphoric acid, trimetaphosphoric acid, and tetrametaphosphoric acid, and corrosion of aluminum or an aluminum alloy by containing one or two or more thereof is included. The prevention will be further improved.
  • the content of the phosphate is preferably in the range of 0.01 to 2.0% by weight. Even in the presence of such a phosphate, the cooling composition of the present invention exhibits stability upon dilution with hard water due to a synergistic effect of the four components (a) to (d) in the glycols as the main components. Can be secured.
  • the coolant composition of the present invention can contain triazoles such as tolyltriazole and benzotriazole, which have an excellent corrosion inhibiting function for metals, particularly copper.
  • the content of triazoles is preferably 0.05 to 1.0% by weight.
  • the coolant composition of the present invention may contain an antifoaming agent, a coloring agent, and the like in addition to the above components.Also, conventionally known corrosion inhibitors such as molybdate, tungstate, nitrate, Sulfates, thiazoles and the like can also be used. Effects of the Invention In the coolant composition of the present invention, (a) 0 :!
  • the components (a) to (d) are (a) toluic acid, (b) 2-phosphonobutane-1,2,4 tricarboxylic acid, (c) strontium nitrate, and (d) polymalein, respectively.
  • Experiments were carried out using the compositions of the following Examples and Comparative Examples using an acid.
  • Example 2 Composition containing all components (a) to (cl) and phosphoric acid (Comparative Example 1) ... Composition containing only component (a) and components (b) to (d) Composition with no components and no phosphoric acid
  • Examples 1 and 2 and Comparative Examples 1 to 6 were subjected to a metal corrosion test using hard water dilution water to confirm the change in mass (mg / cm 2 ) of each metal and the presence or absence of abnormalities in appearance. It was confirmed. Table 2 shows the results.
  • the metal corrosion test was performed in accordance with JIS K2234 Metal Corrosion Rules, and aluminum metal, iron, steel, brass, solder, and copper test pieces were used as the metals for this test. .
  • As the dilution water prepared water prepared by adding calcium chloride to ion-exchanged water to adjust the total hardness to 80 Omg.
  • Table 2 shows that the samples according to Examples 1 and 2 both have excellent corrosion prevention properties against metals, and particularly have excellent corrosion protection properties against aluminum-based metals as compared with Comparative Examples. It was confirmed that there was little change in appearance. On the other hand, it was confirmed that all of Comparative Examples 1 to 6 had poor corrosion prevention properties.
  • a long-term metal corrosion test was performed on each of the samples of Examples 1 and 2 and Comparative Examples 1 to 6 to confirm the change in mass (mg / cm 2 ) of each metal, and to determine whether there was any abnormality in appearance. confirmed.
  • the long-term metal corrosion test was performed based on the JISK2324 metal corrosion test, and the test time was 100 hours. Less than margin
  • Example 1 and Example 2 showed little change in mass and no change in appearance for all metals as compared with the comparative example. In particular, it was confirmed that there was almost no change in mass with respect to aluminum-based metal and that it had excellent corrosion protection. On the other hand, in Comparative Examples, except for Comparative Examples 3 and 6, skin roughness and local corrosion were caused, and it was confirmed that long-term corrosion prevention was poor. Next, a hard water stability test was performed on Example 2 and Comparative Examples 3, 4, and 6 containing a phosphate. Phosphate reacts with hard water components to form a precipitate, and when diluted with hard water, a large amount of precipitate is generated.
  • Example 2 The formation of sediment not only degrades the coolant's ability to prevent corrosion, but can also cause the sediment to accumulate in the cooling circuit circuit and block the cooling system.
  • This test confirms the magnitude of the function of inhibiting the reaction with hard water components (hard water stability), including sodium sulfate 48 mg, sodium chloride 165 mg, sodium hydrogencarbonate 138 mg, and calcium chloride.
  • hard water stability including sodium sulfate 48 mg, sodium chloride 165 mg, sodium hydrogencarbonate 138 mg, and calcium chloride.
  • the sample of Example 2 and Comparative Examples 3, 4 and 6 was used as a test solution having a concentration of 50% using synthetic hard water prepared by dissolving 275 mg of the compound in 11 distilled water. The appearance of the test solution (presence or absence of precipitation) at 24 hours at 88 ° C was confirmed. Table 4 shows the results.
  • Example 12 Replacement paper (Rule 26) Table 4 As is evident from Table 4, no precipitate was observed in Comparative Example 4, but in Comparative Examples 3 and 6, precipitation was observed, whereas in Example 2 there was no precipitate and the hard water stability was excellent. It was confirmed that.
  • a high-temperature aluminum heat transfer surface test was performed to confirm the amount of corrosion (mg Z cm 2 ) of each metal and to determine whether there was any abnormal appearance. confirmed.
  • the high-temperature aluminum heat transfer surface test was performed in accordance with the JISK2234 aluminum aluminum heat transfer surface corrosion test. The test temperature was set at 160 ° C, and the heat-resistant glass cell used as the test container was made of stainless steel. The one made of steel was used. Table 5 shows the test results.

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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, qui comprend: a) 0,1 à 10 % en poids d'au moins un acide alkylbenzoïque et de sels de celui-ci, b) 0,01 à 0,5 % en poids d'acide 2-phosphonobutane-1, 2, 4-tricarboxylique ou d'un sel de celui-ci, c) 0,0001 à 0,1 % en poids d'un composé de strontium et d) 0,01 à 0,5 % 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 des sels de ceux-ci, des polymères ou des copolymères d'acides monoéthylène dicarboxyliques 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 refroidissement possède une excellente capacité de prévention de corrosion de l'aluminium ou d'un alliage d'aluminium, du fer coulé, de l'acier et analogue, et une excellente stabilité à l'eau dure même en présence d'un phosphate.
PCT/JP2003/015329 2003-12-01 2003-12-01 Composition de fluide de refroidissement WO2005054396A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003304581A AU2003304581A1 (en) 2003-12-01 2003-12-01 Cooling fluid composition
PCT/JP2003/015329 WO2005054396A1 (fr) 2003-12-01 2003-12-01 Composition de fluide de refroidissement
JP2005511253A JPWO2005054396A1 (ja) 2003-12-01 2003-12-01 冷却液組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/015329 WO2005054396A1 (fr) 2003-12-01 2003-12-01 Composition de fluide de refroidissement

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012166A (ja) * 2009-07-01 2011-01-20 Sakamoto Yakuhin Kogyo Co Ltd 不凍液組成物
CN107629764A (zh) * 2017-09-04 2018-01-26 可附特汽车零部件制造(北京)有限公司 一种用于四季的防冻液组合物

Citations (5)

* 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
EP1081250A1 (fr) * 1999-09-02 2001-03-07 CCI Kabushiki Kaisha Composition de refroidissement à basse teneur en phosphore
JP2002294227A (ja) * 2001-03-29 2002-10-09 Komatsu Ltd 不凍液／冷却液組成物
JP2003213465A (ja) * 2002-01-16 2003-07-30 Toyota Motor Corp 自動車用冷却水の再生方法及び再生用添加剤

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2002332479A (ja) * 2001-05-11 2002-11-22 Ipposha Oil Ind Co Ltd 冷却液組成物

Patent Citations (5)

* 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
EP1081250A1 (fr) * 1999-09-02 2001-03-07 CCI Kabushiki Kaisha Composition de refroidissement à basse teneur en phosphore
JP2002294227A (ja) * 2001-03-29 2002-10-09 Komatsu Ltd 不凍液／冷却液組成物
JP2003213465A (ja) * 2002-01-16 2003-07-30 Toyota Motor Corp 自動車用冷却水の再生方法及び再生用添加剤

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012166A (ja) * 2009-07-01 2011-01-20 Sakamoto Yakuhin Kogyo Co Ltd 不凍液組成物
CN107629764A (zh) * 2017-09-04 2018-01-26 可附特汽车零部件制造(北京)有限公司 一种用于四季的防冻液组合物

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AU2003304581A1 (en) 2005-06-24

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