WO2013129467A1 - 水系冷却剤 - Google Patents

水系冷却剤 Download PDF

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Publication number
WO2013129467A1
WO2013129467A1 PCT/JP2013/055111 JP2013055111W WO2013129467A1 WO 2013129467 A1 WO2013129467 A1 WO 2013129467A1 JP 2013055111 W JP2013055111 W JP 2013055111W WO 2013129467 A1 WO2013129467 A1 WO 2013129467A1
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Prior art keywords
salt
aqueous coolant
inorganic acid
water
coolant
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PCT/JP2013/055111
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English (en)
French (fr)
Inventor
真由 長谷川
雅久 後藤
克実 市谷
賢郎 野口
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出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to US14/380,806 priority Critical patent/US20150000710A1/en
Priority to CN201380011943.8A priority patent/CN104136634A/zh
Priority to KR1020147024254A priority patent/KR20140131941A/ko
Priority to JP2014502307A priority patent/JP6235997B2/ja
Priority to EP13754559.6A priority patent/EP2821510A4/en
Publication of WO2013129467A1 publication Critical patent/WO2013129467A1/ja

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    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
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    • C10M125/22—Compounds containing sulfur, selenium or tellurium
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24—Compounds containing phosphorus, arsenic or antimony
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/60—Aqueous agents
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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    • C10M2201/08—Inorganic acids or salts thereof
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
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    • C10N2010/00—Metal present as such or in compounds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

  • the present invention relates to an aqueous coolant, and more particularly to an aqueous coolant used for quenching metal parts.
  • Coolants (heat treatment liquids) used for quenching metal parts are roughly classified into oil-based and water-based (aqueous solutions), and oil-based heat treatment liquids are widely used. This is because the oil-based heat treatment liquid has an appropriate cooling performance, has a small quenching distortion, and does not have to worry about the occurrence of quenching cracks.
  • an oil-based heat treatment liquid uses a water-based heat treatment liquid because the cooling rate is slow and the cooling performance is insufficient.
  • the water-based heat treatment liquid has higher cooling performance than the oil-based heat treatment liquid, uneven cooling tends to occur and there is a risk of burning cracks.
  • a composition in which a water-soluble polymer is added to an aqueous heat treatment liquid is known to prevent burning cracks.
  • the water-soluble polymer adheres to the surface of the metal part, inhibits heat transfer, and suppresses cooling performance.
  • the aqueous heat treatment liquid composition to which a water-soluble polymer is added is widely used industrially, and polyalkylene glycol (PAG) is the mainstream as the water-soluble polymer.
  • PAG polyalkylene glycol
  • such a water-based heat treatment liquid composition has a drawback that the vapor film stage is long, and therefore cooling unevenness easily occurs.
  • an aqueous heat treatment liquid composition has been proposed in which a low-molecular-weight glycol is added to a high-molecular-weight polyalkylene glycol, thereby shortening the vapor film stage and improving the cooling unevenness performance (see Patent Document 1). .
  • an aqueous heat treatment liquid in which a water-soluble polyoxyalkylene derivative contains an alkali metal salt of carboxylic acid or sulfonic acid has also been proposed (see Patent Document 2).
  • quenching with a saline solution has been known for a long time as a technique for improving the uneven cooling performance. Since the salt solution does not have a vapor film stage, it has a high cooling performance and a high cooling nonuniformity performance, and has few burning cracks (see Non-Patent Document 1).
  • the cooling rate is not sufficient in the aqueous heat treatment liquids of Patent Documents 1 and 2. This seems to be due to the purpose of approaching the characteristics of oil-based quenching oil, in which the hot cracking risk area is cooled slowly.
  • the salt solution of Non-Patent Document 1 can hardly be used industrially because rust is generated in an extremely short time within 1 hour after the heat treatment and corrosion to equipment such as an oil tank is remarkable.
  • An object of the present invention is to provide an aqueous coolant that has high cooling performance and is unlikely to cause corrosion of a metal material to be cooled.
  • the present invention provides the following aqueous coolant.
  • One or more inorganic acids selected from phosphates, phosphites, sulfates, sulfites, borates, molybdates, tungstates, carbonates, bicarbonates, and sesquicarbonates
  • An aqueous coolant comprising a salt.
  • the aqueous coolant, wherein the inorganic acid salt is a metal salt of an inorganic acid.
  • the aqueous coolant, wherein the inorganic acid salt is at least one of a sodium salt, a potassium salt, a calcium salt, and a magnesium salt.
  • the amount of the inorganic acid salt is 1% by mass or more and 20% by mass or less based on the total amount of the coolant.
  • the phosphate is at least one of orthophosphate, hydrogen phosphate, dihydrogen phosphate, polyphosphate, and metaphosphate.
  • Aqueous coolant is a quenching oil or a cutting oil.
  • aqueous coolant that has a very high cooling performance and is unlikely to cause corrosion of a metal material to be cooled.
  • the aqueous coolant of the present invention (hereinafter sometimes abbreviated as “the present coolant”) is an aqueous solution obtained by blending a predetermined inorganic acid salt. Details will be described below.
  • Inorganic acid salts used in this coolant include phosphate, phosphite, sulfate, sulfite, borate, molybdate, tungstate, carbonate (excluding calcium carbonate), hydrogen carbonate Salt, sesquicarbonate, etc. are mentioned. These may be used alone or in combination.
  • phosphate is preferable from the viewpoint of cooling effect.
  • the phosphate may be any of orthophosphate, hydrogen phosphate, dihydrogen phosphate, polyphosphate, and metaphosphate.
  • the polyphosphate include diphosphate (pyrophosphate) and tripolyphosphate. Among these, pyrophosphate is preferable from the viewpoint of the cooling effect.
  • a metal salt is preferable, and specific examples thereof include a sodium salt, a potassium salt, a calcium salt, and a magnesium salt.
  • a sodium salt and potassium salt are preferable from a viewpoint of cooling property.
  • pH in this cooling agent it is preferable that it is 7 or more from a viewpoint of decay prevention.
  • the preferable blending amount of the inorganic acid salt in the present cooling agent is 1% by mass or more and 20% by mass or less, and the more preferable blending amount is 3% by mass or more and 15% by mass. If the blending amount of the inorganic acid salt is less than 1% by mass, the cooling effect may not be sufficient. On the other hand, even if the compounding amount of the inorganic acid salt exceeds 20% by mass, the improvement of the cooling effect cannot be expected so much.
  • the blending amount of the water-soluble rust preventive agent is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.00% by mass based on the total amount of the present coolant from the viewpoint of improving the rust preventive performance and economical balance. It is 03 mass% or more and 1 mass% or less.
  • water-soluble rust preventives include aliphatic monocarboxylates such as octanoate and aliphatic dicarboxylates such as octanedioic acid (suberic acid) salt and decanedioic acid (sebacic acid) salt.
  • potassium sebacate is preferably used.
  • aromatic carboxylate may be sufficient.
  • piperazine derivatives such as monohydroxymonoethylpiperazine can be suitably used as the water-soluble rust preventive.
  • benzotriazole compounds As the metal corrosion inhibitor, benzotriazole compounds, benzimidazole compounds, benzothiazole compounds, benzothiadiazole compounds, and the like can be suitably used. These may be used alone or in combination.
  • the benzotriazole compound means benzotriazole itself or a derivative thereof.
  • benzimidazole compounds, benzothiazole compounds, and benzothiadiazole compounds examples include alkylbenzotriazole in which an alkyl group is substituted on the benzene ring, and (alkyl) aminoalkylbenzotriazole in which an amino group hydrogen is substituted with an alkyl group.
  • the blending amount of such a metal corrosion inhibitor is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.1% by mass or more and 0.7% by mass or less based on the total amount of the present coolant. If the amount of the metal corrosion inhibitor is less than 0.01% by mass, the metal corrosion prevention effect may not be sufficient. On the other hand, even if the amount of the metal corrosion inhibitor exceeds 1% by mass, the improvement of the metal corrosion prevention effect cannot be expected so much.
  • the coolant may further contain general-purpose additives such as an antioxidant and a detergent / dispersant.
  • the coolant of the present invention has high cooling performance, and the metal material to be cooled is less likely to corrode, so it is suitable as a quenching oil or cutting oil for the metal material.
  • Examples 1 to 13, Comparative Examples 1 to 8 As shown in Table 1, various additives (inorganic acid salts and the like) were dissolved in ion-exchanged water to prepare an aqueous coolant and used as a sample solution. The concentration of the additive was 10% by mass based on the sample solution unless otherwise specified. In Examples 12 and 13, sodium bicarbonate was added by the amount shown in Table 1. Each sample solution was kept at 50 ° C., a cooling test was performed in accordance with JIS K2242B method, and the characteristic seconds were measured. Specifically, the time (seconds) required to reach the temperature (characteristic temperature) at which the vapor film stage ends in the cooling curve was measured. The results are shown in Table 1. In addition, the pH of various aqueous solutions is also listed in Table 1.
  • the additive concentration was 5% by mass. 2) No additive. 3) 30% by mass of an amine salt of a carboxylic acid having 9 carbon atoms (a salt of a carboxylic acid having an alkyl group having 8 carbon atoms and triethanolamine) was added.
  • the aqueous coolant of the present invention is an aqueous solution of a predetermined inorganic acid salt, the characteristic seconds are very short and the cooling performance is extremely high. Moreover, since there is no corrosive factor such as halogen, there is no possibility of causing corrosion on the metal material. Therefore, it can be understood that it is extremely effective for quenching and cutting of metal materials. In general, when the temperature of water becomes 30 ° C. or higher, the cooling property is rapidly lowered and baking does not occur. The aqueous coolant of the present invention exhibits excellent cooling performance even at a liquid temperature of 50 ° C., and should be noted.
  • the ion-exchange water of Comparative Example 1 to which no predetermined inorganic acid salt of the present invention is added does not provide sufficient cooling performance. Further, even if an inorganic acid salt is different from the inorganic acid salt of the present invention or an organic acid salt is added, the cooling performance cannot be improved. Further, since the additives of Comparative Examples 7 and 8 have halogen, the cooling performance is high, but there is a problem in corrosivity.
  • the coolant of the present invention has high cooling performance and the metal material to be cooled is less likely to be corroded, so that it can be used as quenching oil or cutting oil for the metal material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Combustion & Propulsion (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract

　水系冷却剤は、リン酸塩、亜リン酸塩、硫酸塩、亜硫酸塩、ホウ酸塩、モリブデン酸塩、タングステン酸塩、炭酸塩、炭酸水素塩、およびセスキ炭酸塩のいずれか１種以上の無機酸塩を配合してなることを特徴とする。本発明の水系冷却剤によれば、高い冷却性能を備え、冷却対象となる金属材料が腐食を生じにくいので、金属材料の焼入れ油や切削油として好適である。

Description

水系冷却剤
　本発明は水系冷却剤に関し、詳しくは、金属部品の焼入れなどに使用される水系冷却剤に関する。
　金属部品の焼入れに使用される冷却剤（熱処理液）は、油系および水系（水溶液）に大別され、油系の熱処理液が広く用いられている。油系の熱処理液は適度な冷却性能があり、焼入れ歪が小さく、焼割れ発生の心配がないからである。
　一方、特に大きな金属部品や、焼入れ性の悪い金属部品の場合、油系の熱処理液では、冷却速度が遅く、冷却性能が不足するので、水系の熱処理液が用いられる。ところが、水系の熱処理液は、油系熱処理液よりも冷却性能が高いので、冷却むらが生じやすく焼割れのおそれがある。
　そこで、焼割れを防止するため、水溶性ポリマーを水系熱処理液に添加した組成物が知られている。このような水系熱処理液組成物は、水溶性ポリマーが金属部品の表面に付着して、熱伝達を阻害し、冷却性能を抑制する。水溶性ポリマーを添加した水系熱処理液組成物は、工業的には普及しており、水溶性ポリマーとしてポリアルキレングリコール（ＰＡＧ）が主流である。ただし、このような水系熱処理液組成物は、蒸気膜段階が長く、それ故に冷却むらが起き易いという欠点がある。
　そこで、高分子量のポリアルキレングリコールに低分子量のグリコールを添加することで、蒸気膜段階を短くし、耐冷却むら性能を向上させた水系熱処理液組成物が提案されている（特許文献１参照）。また、水溶性のポリオキシアルキレン誘導体にカルボン酸またはスルホン酸のアルカリ金属塩を含有させた水系熱処理液も提案されている（特許文献２参照）。
　一方、耐冷却むら性能を高くする技術として、古くから食塩水による焼入れが知られている。食塩水は、蒸気膜段階が無いので、高い冷却性能を有しながら耐冷却むら性能が高く焼割れが少ない（非特許文献１参照）。
特開平９－２２７９３２号公報 特開平６－３３６６０７号公報
大和久重雄、「焼割れを考える」、熱処理、昭和４２年６月、第７巻、第３号、ｐ．１４０～１４４
　しかしながら、特許文献１、２の水系熱処理液では冷却速度が十分ではない。これは、焼割れ危険領域はゆっくり冷やす、という油系焼入れ油の特長に近づける目的があるためと思われる。一方、非特許文献１の食塩水では、熱処理後１時間以内という極めて短時間で錆が発生し、油槽等の設備への腐食も著しいことから工業的にはほとんど使用できない。
　本発明の目的は、高い冷却性能を有しながら、冷却対象となる金属材料が腐食を生じにくい水系冷却剤を提供することにある。
　前記課題を解決すべく、本発明は、以下のような水系冷却剤を提供するものである。
（１）リン酸塩、亜リン酸塩、硫酸塩、亜硫酸塩、ホウ酸塩、モリブデン酸塩、タングステン酸塩、炭酸塩、炭酸水素塩、およびセスキ炭酸塩のいずれか１種以上の無機酸塩を配合してなることを特徴とする水系冷却剤。
（２）上述の水系冷却剤において、前記無機酸塩が無機酸の金属塩であることを特徴とする水系冷却剤。
（３）上述の水系冷却剤において、前記無機酸塩がナトリウム塩、カリウム塩、カルシウム塩、およびマグネシウム塩の少なくともいずれかであることを特徴とする水系冷却剤。
（４）上述の水系冷却剤において、前記無機酸塩の配合量が当該冷却剤全量基準で１質量％以上２０質量％以下であることを特徴とする水系冷却剤。
（５）上述の水系冷却剤において、前記リン酸塩が、オルトリン酸塩、リン酸水素塩、リン酸二水素塩、ポリリン酸塩、およびメタリン酸塩の少なくともいずれかであることを特徴とする水系冷却剤。
（６）上述の水系冷却剤が焼入れ油または切削油であることを特徴とする水系冷却剤。
　本発明によれば、極めて高い冷却性能を有しながら、冷却対象となる金属材料が腐食を生じにくい水系冷却剤を提供することができる。
　本発明の水系冷却剤（以下、「本冷却剤」と略記する場合がある。）は、所定の無機酸塩を配合してなる水溶液である。以下、詳細に説明する。
　本冷却剤に用いられる無機酸塩としては、リン酸塩、亜リン酸塩、硫酸塩、亜硫酸塩、ホウ酸塩、モリブデン酸塩、タングステン酸塩、炭酸塩（炭酸カルシウムを除く）、炭酸水素塩、およびセスキ炭酸塩などが挙げられる。これらは単独で用いてもよいし、混合して用いてもよい。
　上述の無機酸塩の中では、冷却効果の観点よりリン酸塩が好ましい。リン酸塩としては、オルトリン酸塩、リン酸水素塩、リン酸二水素塩、ポリリン酸塩、およびメタリン酸塩のいずれでもよい。ポリリン酸塩としては、二リン酸塩（ピロリン酸塩）やトリポリリン酸塩などが挙げられる。これらの中では、冷却効果の観点より、ピロリン酸塩が好ましい。
　このような無機酸塩としては、金属塩が好ましく具体的には、ナトリウム塩、カリウム塩、カルシウム塩、およびマグネシウム塩などが挙げられる。これらの中では、冷却性の観点よりナトリウム塩やカリウム塩が好ましい。
　また、本冷却剤におけるｐＨとしては、腐敗防止の観点より、７以上であることが好ましい。
　本冷却剤における無機酸塩の好ましい配合量は、１質量％以上２０質量％以下であり、より好ましい配合量は、３質量％以上１５質量％である。無機酸塩の配合量が１質量％未満では冷却効果が十分ではなくなるおそれがある。一方、無機酸塩の配合量が２０質量％を超えても冷却効果の向上はそれほど期待できない。
　本冷却剤には、必要に応じてさらに水溶性防錆剤や金属腐食防止剤を配合してもよい。
　水溶性防錆剤の配合量は、防錆性能の向上および経済性のバランスなどの面から、本冷却剤全量基準で好ましくは０．０１質量％以上、５質量％以下、より好ましくは０．０３質量％以上、１質量％以下である。このような水溶性防錆剤としては、オクタン酸塩等の脂肪族モノカルボン酸塩や、オクタン二酸（スベリン酸）塩、デカン二酸（セバシン酸）塩等の脂肪族ジカルボン酸塩が挙げられ、例えばセバシン酸カリウム等が好適に用いられる。なお、水溶性防錆剤としては、芳香族カルボン酸塩でもよい。また、水溶性防錆剤としては、モノヒドロキシモノエチルピペラジン等のピペラジン誘導体等も好適に用いることができる。
　金属腐食防止剤としては、ベンゾトリアゾール系化合物、ベンゾイミダゾール系化合物、ベンゾチアゾール系化合物、およびベンゾチアジアゾール系化合物などを好適に用いることができる。これらは単独で用いてもよいし、混合して用いてもよい。
　ここで、ベンゾトリアゾール系化合物とは、ベンゾトリアゾール自身やその誘導体を意味する。ベンゾイミダゾール系化合物、ベンゾチアゾール系化合物、およびベンゾチアジアゾール系化合物についても同様である。例えば、ベンゾトリアゾール系化合物としては、ベンゼン環にアルキル基が置換したアルキルベンゾトリアゾールや、さらにアミノ基水素がアルキル基で置換された（アルキル）アミノアルキルベンゾトリアゾールなどが挙げられる。このような金属腐食防止剤の配合量としては、本冷却剤全量基準で０．０１質量％以上１質量％以下が好ましく、０．１質量％以上０．７質量％以下がより好ましい。金属腐食防止剤の配合量が０．０１質量％未満では金属腐食防止効果が十分ではなくなるおそれがある。一方、金属腐食防止剤の配合量が１質量％を超えても金属腐食防止効果の向上はそれほど期待できない。
　本冷却剤には、さらに、汎用される添加剤、例えば酸化防止剤、および清浄分散剤などが配合されていてもよい。
　本発明の冷却剤は、高い冷却性能を備え、冷却対象となる金属材料が腐食を生じにくいので、金属材料の焼入れ油や切削油として好適である。
　次に実施例、比較例により本発明をさらに詳しく説明するが、本発明はこれらの例によって何ら制限されるものではない。
［実施例１～１３、比較例１～８］
　表１に示すように各種の添加剤（無機酸塩等）をイオン交換水に溶解して水系冷却剤を調製し、試料液とした。添加剤の濃度は、特に記載のないかぎりいずれも試料液基準で１０質量％とした。実施例１２、１３は、表１に記載した量だけ炭酸水素ナトリウムを追加した。
　各試料液を５０℃に保ち、ＪＩＳ Ｋ２２４２Ｂ法に準拠して冷却試験を行い、特性秒
数を測定した。具体的には、冷却曲線において蒸気膜段階が終了する温度（特性温度）に到達するまでの時間（秒数）を測定した。結果を表１に示す。なお、併せて、各種水溶液のｐＨも表１に記載した。
Figure JPOXMLDOC01-appb-T000001
１）添加剤濃度は５質量％とした。
２）添加剤なし。
３）炭素数９のカルボン酸のアミン塩（炭素数８のアルキル基を有するカルボン酸とトリエタノールアミンとの塩）を３０質量％添加した。
［評価結果］
　表１の結果より、本発明の水系冷却剤は所定の無機酸塩の水溶液であるため、いずれも特性秒数が非常に短く、極めて冷却性能が高いことがわかる。しかも、ハロゲンのような腐食性因子を有さないので金属材料に対して腐食を生じるおそれがない。それ故、金属材料の焼入れや切削に極めて有効であることが理解できる。
　一般に、水は液温が３０℃以上になると、急激に冷却性が低下し、焼きが入らなくなる。本発明の水系冷却剤は、５０℃の液温でも優れた冷却性能を発揮しており、特筆すべきである。
　これに対して、本発明所定の無機酸塩を全く添加していない比較例１のイオン交換水では、冷却性能が十分に出ない。また、無機酸の塩でも本発明の無機酸塩とは異なる塩や、有機酸の塩を添加しても冷却性能を上げることはできない。また、比較例７、８の添加剤は、ハロゲンを有するため、冷却性能は高いが腐食性に問題がある。
　本発明の冷却剤は、高い冷却性能を備え、冷却対象となる金属材料が腐食を生じにくいので、金属材料の焼入れ油や切削油として利用できる。

Claims (6)

  1. 　リン酸塩、亜リン酸塩、硫酸塩、亜硫酸塩、ホウ酸塩、モリブデン酸塩、タングステン酸塩、炭酸塩、炭酸水素塩、およびセスキ炭酸塩のいずれか１種以上の無機酸塩を配合してなる
    　ことを特徴とする水系冷却剤。
  2. 　請求項１に記載の水系冷却剤において、
    　前記無機酸塩が無機酸の金属塩である
    　ことを特徴とする水系冷却剤。
  3. 　請求項２に記載の水系冷却剤において、
    　前記無機酸塩がナトリウム塩、カリウム塩、カルシウム塩、およびマグネシウム塩の少なくともいずれかである
    　ことを特徴とする水系冷却剤。
  4. 　請求項１から請求項３までのいずれか１項に記載の水系冷却剤において、
    　前記無機酸塩の配合量が当該冷却剤全量基準で１質量％以上２０質量％以下である
    　ことを特徴とする水系冷却剤。
  5. 　請求項１から請求項４までのいずれか１項に記載の水系冷却剤において、
    　前記リン酸塩が、オルトリン酸塩、リン酸水素塩、リン酸二水素塩、ポリリン酸塩、およびメタリン酸塩の少なくともいずれかである
    　ことを特徴とする水系冷却剤。
  6. 　請求項１から請求項５までのいずれか１項に記載の水系冷却剤が焼入れ油または切削油である
    　ことを特徴とする水系冷却剤。
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EP2821510A1 (en) 2015-01-07
EP2821510A4 (en) 2015-11-11
TW201343923A (zh) 2013-11-01
US20150000710A1 (en) 2015-01-01
KR20140131941A (ko) 2014-11-14
CN104136634A (zh) 2014-11-05

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