KR101106126B1 - Compositions of Antifreezing Liquid/Cooling Liquid with Improvements in Blackening Prevention and Long Term10 yr/0.2 million km Anti-corrosion - Google Patents

Compositions of Antifreezing Liquid/Cooling Liquid with Improvements in Blackening Prevention and Long Term10 yr/0.2 million km Anti-corrosion Download PDF

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KR101106126B1
KR101106126B1 KR1020080077407A KR20080077407A KR101106126B1 KR 101106126 B1 KR101106126 B1 KR 101106126B1 KR 1020080077407 A KR1020080077407 A KR 1020080077407A KR 20080077407 A KR20080077407 A KR 20080077407A KR 101106126 B1 KR101106126 B1 KR 101106126B1
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acid
barium
aluminum
weight
antifreeze
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KR20100018754A (en
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하영주
조창열
최동렬
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극동제연공업 주식회사
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    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
    • 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
    • C23F11/10—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 using organic inhibitors
    • 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
    • C23F11/10—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 using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01P—COOLING OF MACHINES OR ENGINES IN GENERAL; COOLING OF INTERNAL-COMBUSTION ENGINES
    • F01P11/00—Component parts, details, or accessories not provided for in, or of interest apart from, groups F01P1/00 - F01P9/00
    • F01P11/06—Cleaning; Combating corrosion

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

Abstract

본 발명은 글리콜계 동결방지제, C4-C18인 유기카르복실산 또는 그 알칼리염, 인산 또는 인산염, 아졸유도체, 바륨 또는 바륨화합물, 및 알칼리 금속 수산화물을 포함하는 부동액 조성물을 제공한다. 일반적으로 유기카르복실산 부식억제제를 사용시 산화알루미늄의 부동액 피막을 형성하여 흑색의 두꺼운 피막형성으로 전열을 방해하여 냉각효과를 떨어뜨릴 수 있으나, 본 발명의 바륨화합물을 함유한 조성물은 알루미늄과 알루미늄 합금표면의 두꺼운 산화피막 형성을 억제시켜 냉각효과를 저하시키지 않고, 바륨화합물의 방식피막으로 인한 알루미늄 재질의 고온 방식력도 향상시키는 효과를 가진다. 또한, 본 발명의 부동액 조성물은 알루미늄 또는 알루미늄 합금재질에 대한 장기간(10년/20만 ㎞)의 부식방지와 알루미늄 재질표면의 흑변을 방지 효과를 가져 장수명 부동액 조성물로 이용할 수 있다.The present invention provides an antifreeze composition comprising a glycol-based cryoprotectant, an organic carboxylic acid of C 4 -C 18 or an alkali salt thereof, phosphoric acid or phosphate, an azole derivative, a barium or barium compound, and an alkali metal hydroxide. In general, when an organic carboxylic acid corrosion inhibitor is used, an antifreeze film of aluminum oxide may be formed, and a black thick film may be formed to hinder the heat transfer to reduce the cooling effect. However, the composition containing the barium compound of the present invention may be aluminum and an aluminum alloy. By suppressing the formation of a thick oxide film on the surface, it does not lower the cooling effect, and also has the effect of improving the high temperature corrosion resistance of the aluminum material due to the anti-corrosion coating of the barium compound. In addition, the antifreeze composition of the present invention can be used as a long-life antifreeze composition having a long-term (10 years / 200,000 km) to prevent corrosion of the aluminum or aluminum alloy material and the black side of the aluminum surface.

부동액, 글리콜, 바륨, 아졸유도체, 방식성, 흑변 Antifreeze, glycol, barium, azole derivatives, anticorrosive, black stools

Description

흑변방지 및 장기간(10년/20만 ｋｍ) 내식성이 우수한 부동액/냉각액 조성물{Compositions of Antifreezing Liquid/Cooling Liquid with Improvements in Blackening Prevention and Long Term(10 yr/0.2 million km) Anti-corrosion}Compositions of Antifreezing Liquid / Cooling Liquid with Improvements in Blackening Prevention and Long Term (10 yr / 0.2 million km) Anti-corrosion}

본 발명은 글리콜계 동결방지제, C4-C18인 유기카르복실산 또는 그 알칼리염, 인산 또는 인산염, 아졸유도체, 바륨 또는 바륨화합물, 및 알칼리 금속 수산화물을 포함하는 부동액 조성물에 관한 것이다.The present invention relates to an antifreeze composition comprising a glycol-based cryoprotectant, an organic carboxylic acid of C 4 -C 18 or an alkali salt thereof, phosphoric acid or phosphate, an azole derivative, a barium or barium compound, and an alkali metal hydroxide.

알루미늄과 철계 부품의 부식을 방지하기 위하여 일반적으로 카르복실산 계열의 유기산 첨가제를 사용한다. 이 유기산 첨가제가 알루미늄과 알루미늄 합금 표면에 흑색을 나타내는 산화 알루미늄의 부동태 피막을 형성하면서 그 표면을 보호하여 부식의 진행을 방해하는 기능도 가지고 있으나, 오히려 부품의 외관을 심하게 변화시켜 부품의 상품성을 떨어뜨리기도 한다. 또한, 흑색의 피막형성 과정에서 알루미늄 이온 용출 반응이 활발하게 이루어져 알루미늄 무게변화량이 커지고 두꺼운 흑색의 산화 피막형성으로 열전달을 방해하는 현상을 일으키기도 한다.In order to prevent corrosion of aluminum and iron components, carboxylic acid-based organic acid additives are generally used. Although this organic acid additive forms a passivation film of black aluminum oxide on the surface of aluminum and aluminum alloy, it also has the function of protecting the surface and preventing the progress of corrosion. It can also be thrown. In addition, the aluminum ion elution reaction is actively performed during the black film formation process, causing a large amount of aluminum weight change and causing a phenomenon that hinders heat transfer due to the formation of a thick black oxide film.

이러한 알루미늄과 알루미늄 합금표면에 대한 흑변방지제로 지방족 다염기산 형 계면활성제(일본공개특허 제2002-38137호), C10-C20의 알킬기를 가진 디카르복실산 또는 트리카르복실산(일본공개특허 제2000-219981호), 플라본 유도체(일본공개특허 제2001-98258호), 폴리말레인산, 폴리아크릴산 또는 그 단위체의 공중합체(일본공개특허 제2001-279235호) 또는 리튬화합물(일본공개특허 평 제9-263976호) 등이 보고되고 있다.As a blackening agent for such aluminum and aluminum alloy surfaces, aliphatic polybasic acid type surfactants (Japanese Patent Laid-Open No. 2002-38137), dicarboxylic acids or tricarboxylic acids having an alkyl group of C 10 -C 20 (Japanese Laid-Open Patent Publication No. 2000-219981), flavone derivatives (JP-A-2001-98258), copolymers of polymaleic acid, polyacrylic acid, or units thereof (JP-A-2001-279235) or lithium compounds (JP-A-9) -263976) have been reported.

부동액의 장수명화가 요구되면서 많은 새로운 첨가제가 연구 개발되어 발표되고 있으며 유기산계 첨가제가 주류를 이루고 있다. 이러한 유기산 첨가제의 이용으로 알루미늄과 알루미늄합금 재질이 쉽게 흑변할 수 있는 조성물로 구성되고 있다.As the long life of the antifreeze is required, many new additives have been researched and published, and organic acid additives have become mainstream. By the use of such organic acid additives, aluminum and aluminum alloy material is composed of a composition that can easily turn black.

일본공개특허 제2002-38137호에는 지방족 다염기산형 계면활성제가 알루미늄과 알루미늄합금의 흑변을 효과적으로 억제하는 첨가제로 개시하고 있으나 이 지방족 다염기산형 계면활성제는 분자량이 커서 알루미늄과 알루미늄 합금 부품의 흑변 방지 여부를 떠나 장시간 사용 시 냉각수의 소포성이 나빠질 우려를 가지고 있다. 일본공개특허 제2001-98258호에는 플라본 유도체를 사용하는 냉각액 조성물이 개시되어 있다. 이 플라본 유도체는 고온 전열상태에서 흑변 방지 효과가 떨어지고 가격이 고가이며, 공업용 제품으로의 이용이 용이하지 않아 상업적 측면에서 고려할 때 적합하지 않을 수 있다.Japanese Laid-Open Patent Publication No. 2002-38137 discloses an aliphatic polybasic acid type surfactant as an additive that effectively inhibits black side of aluminum and aluminum alloy. However, the aliphatic polybasic acid type surfactant has a large molecular weight, and thus it is possible to prevent black side of aluminum and aluminum alloy parts. If you leave for a long time, there is a risk of deterioration of the defoaming of the cooling water. Japanese Patent Laid-Open No. 2001-98258 discloses a coolant composition using a flavone derivative. This flavone derivative may not be suitable in consideration of commercial aspects because it is inferior in blacking prevention effect at high temperature heat transfer state, is expensive, and is not easy to use as an industrial product.

또한, 일본공개특허 제2001-279235호에는 폴리말레인산, 폴리아크릴산 또는 말레인산 아크릴산 공중합체가 알루미늄 또는 알루미늄 합금에 대해 흑변방지 효과 가 있다고 기재되어 있다. 이 폴리말레인산과 폴리아크릴산 또는 그 단위체 공중합체는 알루미늄 또는 그 합금의 표면을 유기산계 부식방지제와 병용하여 사용 시 오히려 흑변을 촉진시키므로 유기산계 첨가제와 함께 사용 시에는 흑변 방지 효과가 현저히 감소하게 된다. 또한, 일본공개특허 평 제9-263976호는 리튬 화합물이 알루미늄과 알루미늄 합금재질의 흑변을 방지한다고 개시하고 있으나 방향족 카르복실산과 병용 사용 시 어느 정도의 효과를 볼 수도 있으나 지방족 카르복실산과 함께 사용 시 흑변 방지 효과는 현저히 떨어져 흑변 방지제로서의 역할을 할 수 없게 된다. 또한 글리콜에 대한 용해성이 낮아 사용량을 증가시킬 때 다량의 물을 이용해야 하는 문제점이 있다.In addition, Japanese Patent Laid-Open No. 2001-279235 discloses that polymaleic acid, polyacrylic acid, or maleic acid acrylic acid copolymer has an anti-blacking effect on aluminum or aluminum alloy. The polymaleic acid and polyacrylic acid or a copolymer of the monomers thereof promote the black stools when using the surface of aluminum or its alloy in combination with the organic acid-based corrosion inhibitor, so that the black stool-preventing effect is remarkably reduced when used with the organic acid-based additive. In addition, Japanese Patent Application Laid-open No. Hei 9-263976 discloses that lithium compounds prevent blackening of aluminum and aluminum alloy materials, but when used in combination with aromatic carboxylic acids, some effects may be obtained. The blackening prevention effect is remarkably dropped, and it cannot become a blackening agent. In addition, there is a problem in that the use of a large amount of water when increasing the amount of low solubility in glycol.

본 명세서 전체에 걸쳐 다수의 특허문헌이 참조되고 그 인용이 표시되어 있다. 인용된 특허문헌의 개시 내용은 그 전체로서 본 명세서에 참조로 삽입되어 본 발명이 속하는 기술 분야의 수준 및 본 발명의 내용이 보다 명확하게 설명된다.Throughout this specification many patent documents are referenced and their citations are indicated. The disclosures of the cited patent documents are incorporated by reference herein in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly described.

본 발명자들은 내연기관의 냉각장치에 이용되는 알루미늄 및 알루미늄 합금재질의 두꺼운 흑색의 산화피막(흑변)과 10년/20만 km의 장기간 부식을 억제하는 부동액 조성물을 개발하고자 노력하였다. 그 결과, 종래 부동액 조성물에 포함되는 동결방지제, 부식방지제 및 흑변방지제에 바륨 또는 바륨 화합물을 포함하여 제조하면, 고온에서 알루미늄 주물 전열면에 대한 부식방지 능력 향상, 알루미늄 주물 표면의 흑변을 방지하여 열전달 방해현상 방지 및 흑변을 형성하는 과정에서 발생하는 알루미늄 이온용출 반응을 억제시켜 알루미늄 재질에 대한장기간(10년/20만 km) 방식성을 유지하는 효과를 가짐을 확인함으로써, 본 발명을 완성하게 되었다.The present inventors endeavored to develop a thick black oxide film (black side) made of aluminum and aluminum alloy material used in a cooling device of an internal combustion engine and an antifreeze composition that inhibits corrosion for a long time of 10 years / 200,000 km. As a result, when barium or barium compounds are included in the cryoprotectant, corrosion inhibitor, and blackening agent included in the conventional antifreeze composition, the corrosion resistance of the aluminum casting heat transfer surface is improved at high temperatures, and the black side of the aluminum casting surface is prevented from being transferred. The present invention was completed by confirming that it has an effect of maintaining anticorrosion and preventing long-term (10 years / 200,000 km) corrosion resistance of aluminum materials by suppressing aluminum ion elution reaction occurring in the process of forming black stools. .

따라서, 본 발명의 목적은 부동액 조성물을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide an antifreeze composition.

본 발명의 다른 목적 및 이점은 하기의 발명의 상세한 설명 및 청구범위에 의해 보다 명확하게 된다.Other objects and advantages of the present invention will become apparent from the following detailed description and claims.

본 발명의 일 양태에 따르면, 본 발명은 글리콜계 동결방지제, C4-C18인 유기카르복실산 또는 그 알칼리염, 인산 또는 인산염, 아졸유도체, 바륨 또는 바륨화합물, 및 알칼리 금속 수산화물을 포함하는 부동액 조성물을 제공한다.In accordance with one aspect of the present invention, the present invention is glycol-based cryoprotectant, C 4 -C 18 organic acid or its alkali salt, a phosphoric acid or a phosphate, an azole derivative, a barium or a barium compound, and containing an alkali metal hydroxide An antifreeze composition is provided.

본 발명자들은 내연기관의 냉각장치에 이용되는 알루미늄 및 알루미늄 합금재질의 두꺼운 흑색의 산화피막(흑변)과 10년/20만 km의 장기간 부식을 억제하는 부동액 조성물을 개발하고자 노력하였다. 그 결과, 종래 부동액 조성물에 포함되는 동결방지제, 부식방지제 및 흑변방지제에 바륨 또는 바륨 화합물을 포함하여 제조하면, 고온에서 알루미늄 주물 전열면에 대한 부식방지 능력 향상, 알루미늄 주물 표면의 흑변을 방지하여 열전달 방해현상 방지 및 흑변을 형성하는 과정에서 발생하는 알루미늄 이온용출 반응을 억제시켜 알루미늄 재질에 대한 장기간(10년/20만 km) 방식성을 유지하는 효과를 가짐을 확인하였다.The present inventors endeavored to develop a thick black oxide film (black side) made of aluminum and aluminum alloy material used in a cooling device of an internal combustion engine and an antifreeze composition that inhibits corrosion for a long time of 10 years / 200,000 km. As a result, when barium or barium compounds are included in the cryoprotectant, corrosion inhibitor, and blackening agent included in the conventional antifreeze composition, the corrosion resistance of the aluminum casting heat transfer surface is improved at high temperatures, and the black side of the aluminum casting surface is prevented from being transferred. It was confirmed that it has the effect of maintaining the long-term (10 years / 200,000 km) corrosion resistance for aluminum material by preventing the interference phenomenon and suppress the aluminum ion elution reaction generated in the process of forming black stools.

본 발명의 바람직한 구현예에 따르면, 본 발명의 조성물은 조성물 전체 중량에 대하여 글리콜계 동결방지제 90-98 중량%, C4-C18인 유기카르복실산 또는 그 알칼리염 1-5 중량%, 인산 또는 인산염 0.05-1 중량%, 아졸유도체 0.01-1 중량%, 바륨 또는 바륨화합물 0.0005-1 중량%, 및 알칼리 금속 수산화물 0.5-2 중량%를 포함하고, 보다 바람직하게는 글리콜계 동결방지제 92-97.8492 중량%, C4-C18인 유기카르복실산 또는 그 알칼리염 1.5-4 중량%, 인산 또는 인산염 0.05-0.5 중량%, 아졸유도체 0.1-0.8 중량%, 바륨 또는 바륨화합물 0.0008-0.9 중량%, 및 알칼리 금속 수산화물 0.5-1.8 중량%이며, 가장 바람직하게는 글리콜계 동결방지제 93.5-97.119 중량%, C4-C18인 유기카르복실산 또는 그 알칼리염 2-3.5 중량%, 인산 또는 인산염 0.08-0.3 중량%, 아졸유도체 0.1-0.4 중량%, 바륨 또는 바륨화합물 0.001-0.8 중량%, 및 알칼리 금속 수산화물 0.7-1.5 중량%이다.According to a preferred embodiment of the present invention, the composition of the present invention is 90-98% by weight glycol-based cryoprotectant, organic carboxylic acid of C 4 -C 18 or 1-5% by weight of its alkali salt, phosphoric acid based on the total weight of the composition Or 0.05-1% by weight of phosphate, 0.01-1% by weight of azole derivative, 0.0005-1% by weight of barium or barium compound, and 0.5-2% by weight of alkali metal hydroxide, more preferably glycol-based cryoprotectant 92-97.8492 % By weight, 1.5 to 4 % by weight of an organic carboxylic acid or an alkali salt thereof, C 4 -C 18 , 0.05 to 0.5% by weight of phosphoric acid or phosphate, 0.1 to 0.8% by weight of an azole derivative, 0.0008 to 0.9% by weight of a barium or barium compound, And 0.5-1.8% by weight of alkali metal hydroxide, most preferably 93.5-97.119% by weight of glycol-based cryoprotectant, organic carboxylic acid having C 4 -C 18 or 2-3.5% by weight of its alkali salt, phosphoric acid or phosphate 0.08- 0.3 wt%, 0.1-0.4 wt% azole derivatives, barium or bariumation 0.001-0.8% by weight is water, and 0.7-1.5% by weight alkali metal hydroxide.

본 발명의 다른 바람직한 구현예에 따르면, 본 발명의 조성물에 이용되는 글리콜계 동결방지제는 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜, 디프로필렌글리콜, 글리세린, 트리에틸렌글리콜 또는 트리프로필렌글리콜이고, 보다 바람직하게는 에틸렌글리콜 또는 프로필렌글리콜이며, 가장 바람직하게는 에틸렌글리콜이다.According to another preferred embodiment of the present invention, the glycol-based cryoprotectant used in the composition of the present invention is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, triethylene glycol or tripropylene glycol, more preferably Is ethylene glycol or propylene glycol, most preferably ethylene glycol.

상술한 글리콜계 동결방지제는 부동액 조성물 전체 중량에 대하여 90-98 중량%로 포함되는 주성분이고, 보다 바람직하게는 92-97.8492 중량%, 가장 바람직하게는 93.5-97.119 중량%이다. 글리콜계 동결방지제가 98 중량%를 초과하는 경우에는 첨가제를 사용할 수 있는 가용범위가 줄어들어 부식억제력이 감소하며, 90 중량% 미만인 경우에는 글리콜 함량 부족으로 인한 냉각시스템 부품의 동결현상이나 끓는점 저하로 인한 끓어 넘치는 현상을 일으킬 수 있다. The above-described glycol-based cryoprotectant is a main component contained in 90-98% by weight relative to the total weight of the antifreeze composition, more preferably 92-97.8492% by weight, most preferably 93.5-97.119% by weight. If the glycol-based cryoprotectant exceeds 98% by weight, the available range of the additive can be reduced, and the corrosion inhibitory power is reduced.When the glycol freeze-protecting agent is lower than 90% by weight, the freezing phenomenon of the cooling system parts due to the lack of glycol content or the lowering of the boiling point Boiling may occur.

본 발명의 또 다른 바람직한 구현예에 따르면, 본 발명의 조성물에서 알루미늄과 철계재질에 대한 부식방지제로 이용되는 C4-C18인 유기카르복실산 또는 그 알칼리염은 아디픽산, 수베르산, 세바식산, 글루타릭산, 네오데칸산, 네오옥타논산, 숙신산, 계피산, 아젤라익산, 메틸계피산, 하이드록시계피산, 에틸계피산, 프로필계피산, 부틸계피산, 에톡시계피산, 에틸벤조산, 프로필벤조산, 피멜릭산, 디시클 로펜타디엔 디카르복실산, 운데칸산, 벤조산, 노난산, 프탈산, 데칸산, 테레프탈산, 도테칸산, 메틸벤조산, 헥산산, 시클로헥세논산, 2-에틸헥산산, 부틸벤조산, 옥탄산 및 헵탄산으로 구성된 군으로부터 최소 1 종의 성분이 선택되고, 보다 바람직하게는 세바식산, 숙신산, 계피산, 벤조산, 2-에틸헥산산 및 부틸벤조산으로 구성된 군으로부터 최소 1 종의 성분이 선택되며, 가장 바람직하게는 계피산, 2-에틸헥산산 및 부틸벤조산으로 구성된 군으로부터 최소 1 종의 성분이 선택된다.According to another preferred embodiment of the present invention, C 4 -C 18 organic carboxylic acid or an alkali salt thereof used as a corrosion inhibitor for aluminum and iron materials in the composition of the present invention is adipic acid, subic acid, seba Food acid, glutaric acid, neodecanoic acid, neooctanoic acid, succinic acid, cinnamic acid, azelaic acid, methyl cinnamic acid, hydroxy cinnamic acid, ethyl cinnamic acid, propyl cinnamic acid, butyl cinnamic acid, ethoxy cinnamic acid, ethylbenzoic acid, propylbenzoic acid, pimelic acid, Dicyclopentadiene dicarboxylic acid, undecanoic acid, benzoic acid, nonanoic acid, phthalic acid, decanoic acid, terephthalic acid, dotecanoic acid, methylbenzoic acid, hexanoic acid, cyclohexenoic acid, 2-ethylhexanoic acid, butylbenzoic acid, octanoic acid and At least one component is selected from the group consisting of heptanoic acid, more preferably at least one from the group consisting of sebacic acid, succinic acid, cinnamic acid, benzoic acid, 2-ethylhexanoic acid and butylbenzoic acid The selection of the components and, the component of at least one kinds selected from Most preferably, the group consisting of 2-ethylhexanoic acid and butyl benzoic acid cinnamic acid.

상술한 C4-C18인 유기카르복실산 또는 그 알칼리염은 부동액 조성물 전체 중량에 대하여 1-5 중량%로 포함되고, 보다 바람직하게는 1.5-4 중량%, 가장 바람직하게는 2-3.5 중량%이다. C4-C18인 유기카르복실산 또는 그 알칼리염이 5 중량%를 초과하는 경우에는 첨가제의 용해성과 경제성이 떨어지게 되고 부동액의 안정성도 나빠지는 문제점이 있으며, 1 중량% 미만인 경우에는 냉각시스템의 대부분을 차지하고 있는 알루미늄 및 주철계열의 부품의 부식을 방지할 수 없는 문제점이 있다.The aforementioned organic carboxylic acid of C 4 -C 18 or an alkali salt thereof is included in an amount of 1-5% by weight, more preferably 1.5-4% by weight, most preferably 2-3.5% by weight, based on the total weight of the antifreeze composition. %to be. When C 4 -C 18 organic carboxylic acid or its alkali salt is more than 5% by weight, the solubility and economical efficiency of the additives are deteriorated, and the stability of the antifreeze is also deteriorated. There is a problem that can not prevent corrosion of the parts of the aluminum and cast iron series that occupy most.

본 발명의 바람직한 구현예에 따르면, 본 발명의 조성물에 이용되는 인산 또는 인산염은 인산, 오르토인산, 인산나트륨, 인산칼륨, 인산1수소나트륨, 인산1수소칼륨, 인산2수소나트륨 또는 인산2수소칼륨이고, 보다 바람직하게는 인산, 인산나트륨 또는 인산칼륨, 가장 바람직하게는 인산이다.According to a preferred embodiment of the present invention, the phosphoric acid or phosphate used in the composition of the present invention is phosphoric acid, orthophosphoric acid, sodium phosphate, potassium phosphate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate More preferably phosphoric acid, sodium phosphate or potassium phosphate, most preferably phosphoric acid.

바람직하게는 상술한 인산 또는 인산염은 부동액 조성물 전체 중량에 대하여 0.05-1 중량%로 포함되고, 보다 바람직하게는 0.05-0.5 중량%, 가장 바람직하게는 0.08-0.3 중량%이다. 0.05 중량% 미만인 경우에는 알루미늄과 철계재질에 대한 초기 방식량이 적어 방식효과를 기대할 수 없고, 각 부품의 변색을 일으킬 수 있으며, 2 중량%를 초과한 경우에는 경도성분인 칼슘 및 마그네슘 이온 등과 반응하여 불용성 침전으로 소모되어 방식능력이 감소할 수 있으며 불용성 침전의 생성으로 인한 워터펌프의 누액과 각종 트러블을 일으키는 문제점이 있다.Preferably the above-mentioned phosphoric acid or phosphate salt is included at 0.05-1% by weight relative to the total weight of the antifreeze composition, more preferably 0.05-0.5% by weight, most preferably 0.08-0.3% by weight. If it is less than 0.05 wt%, the initial anticorrosive amount for aluminum and iron materials is small and anticorrosive effect cannot be expected, and it may cause discoloration of each component. If it exceeds 2 wt%, it reacts with calcium and magnesium ions, which are hardness components. The insoluble sediment may be consumed and the anticorrosive ability may be reduced, causing leakage of the water pump and various problems due to the generation of insoluble sediment.

본 명세서에서 용어“아졸 유도체”는 통상 헤테로 원자로서 2개의 N 원자 및 0개의 S 원자, 3개의 N 원자 및 0개의 S 원자 또는 1개의 N 원자 및 1개의 S 원자를 포함하는 5-원 헤테로 고리 화합물을 의미한다.As used herein, the term “azole derivative” is usually a hetero-membered five-membered hetero ring comprising two N atoms and zero S atoms, three N atoms and zero S atoms or one N atom and one S atom. Means a compound.

본 발명의 다른 바람직한 구현예에 따르면, 본 발명의 조성물에 이용되는 아졸유도체는 이미다졸, 트리아졸 또는 티아졸이고, 보다 바람직하게는 벤즈이미다졸, 벤조트리아졸, 토릴트리아졸, 메르캅토벤조티아졸 또는 그 유도체화합물과 그것의 알카리금속염이고, 가장 바람직하게는 벤조트리아졸, 토릴트리아졸 또는 메르캅토벤조티아졸이다. 상술한 아졸유도체는 부동액 조성물 전체 중량에 대하여 0.01-1 중량%, 보다 바람직하게는 0.1-0.8 중량%, 가장 바람직하게는 0.1-0.4 중량%이다. 0.01 중량% 미만인 경우에는 동과 황동재질에 대해 부식을 일으킬 수 있고, 동 이온 용출에 의해 오히려 알루미늄과 철계 재질에 대해 부식을 촉진시킬 수 있는 문제점이 있으며, 1 중량%를 초과한 경우에는 철계 재질의 부식을 일으킬 수 있으며 경제성도 떨어진다.According to another preferred embodiment of the invention, the azole derivatives used in the composition of the invention are imidazole, triazole or thiazole, more preferably benzimidazole, benzotriazole, toryltriazole, mercaptobenzothiazole Or derivative compounds thereof and alkali metal salts thereof, most preferably benzotriazole, tolyltriazole or mercaptobenzothiazole. The azole derivative described above is 0.01-1% by weight, more preferably 0.1-0.8% by weight and most preferably 0.1-0.4% by weight relative to the total weight of the antifreeze composition. If less than 0.01% by weight can cause corrosion of copper and brass, and the copper ion dissolution, rather than to promote the corrosion of aluminum and iron-based material, if exceeding 1% by weight of iron-based material May cause corrosion and economic efficiency.

본 발명의 또 다른 바람직한 구현예에 따르면, 본 발명의 조성물에 이용되는 바륨 또는 바륨화합물은 바륨, 염화바륨, 수산화바륨, 질산바륨, 탄산바륨, 초산바륨, 황산바륨, 브롬산바륨, 티오시안산바륨, 티탄산바륨, 불화바륨, 시안산바륨, 벤젠술폰산바륨, 브롬화바륨, 디티온산바륨, 옥살산바륨, 페로시안바륨, 포름산바륨, 헥산불화 규산바륨, 치아인산바륨, 아질산바륨, 산화바륨, 과염소산 바륨, 과망간산바륨, 제이인산바륨, 바륨시아노백금산, 아황산바륨, 티오시아산바륨, 티오황산바륨, 유기바륨 중합체 또는 카르복실산류의 바륨이고, 보다 바람직하게는 바륨, 염화바륨, 수산화바륨, 질산바륨, 탄산바륨, 황산바륨, 불화바륨, 벤젠술폰산바륨, 브롬화바륨, 아질산바륨, 산화바륨, 과염소산 바륨, 과망간산바륨, 제이인산바륨, 아황산바륨, 티오황산바륨, 가장 바람직하게는 바륨, 염화바륨 또는 황산바륨이다.According to another preferred embodiment of the present invention, the barium or barium compound used in the composition of the present invention is barium, barium chloride, barium hydroxide, barium nitrate, barium carbonate, barium acetate, barium sulfate, barium bromide, thiocyanate Barium, barium titanate, barium fluoride, barium cyanate, barium benzenesulfonate, barium bromide, barium dithionate, barium oxalate, barium ferrocyanide, barium formate, barium hexafluoride, barium phosphate, barium nitrite, barium oxide, barium perchlorate Barium permanganate, barium diphosphate, barium cyanoplatinic acid, barium sulfite, barium thiocyanate, barium thiosulfate, organic barium polymer or barium of carboxylic acids, more preferably barium, barium chloride, barium hydroxide, barium nitrate Barium carbonate, barium sulfate, barium fluoride, barium benzenesulfonate, barium bromide, barium nitrite, barium oxide, barium perchlorate, barium permanganate, barium phosphate, barium sulfite, thio Barium, and most preferably, barium, barium chloride or barium sulphate.

상술한 바륨 또는 바륨화합물을 조성물 전체 중량에 대하여 0.0005-1 중량%이고, 보다 바람직하게는 0.0008-0.9 중량%, 가장 바람직하게는 0.001-0.8 중량%이다. 0.0005 중량% 미만인 경우 알루미늄 재질에 대한 고온 및 장기간의 방식력이 미약하고 알루미늄 재질 표면의 흑변도 방지할 수 없는 문제점이 있으며, 1 중량% 초과한 경우 용해도가 감소하고, 액 중 침전 발생 또는 철계 재질에 대한 부식을 일으킬 수 있으며, 알루미늄 재질의 장기간의 부식방지에도 역효과를 줄 수 있다.The barium or barium compound described above is 0.0005-1% by weight, more preferably 0.0008-0.9% by weight, most preferably 0.001-0.8% by weight based on the total weight of the composition. If it is less than 0.0005% by weight, there is a problem that the high temperature and long-term corrosion resistance of the aluminum material is weak and the black surface of the aluminum material cannot be prevented, and when it exceeds 1% by weight, the solubility decreases and precipitation in the liquid occurs or iron-based material. It can cause corrosion and adversely affect the long-term corrosion protection of aluminum.

본 발명의 가장 큰 특징은 본 발명의 부동액 조성물에 포함된 바륨 또는 바륨화합물이 알루미늄 또는 알루미늄 합금재질에 대한 장기간(10년/20만㎞)의 부식 방지와 알루미늄 재질표면의 흑변을 방지하는 역할을 하며 특히, 고온 알루미늄 전열면에서 우수한 변색방지 효과를 나타낸다. 일반적으로 유기카르복실산 부식억제제를 사용시 산화알루미늄의 부동액 피막을 형성하여 흑색의 두꺼운 피막형성으로 전열을 방해하여 냉각효과를 떨어뜨릴 수 있으나, 본 발명의 바륨화합물을 함유한 조성물은 알루미늄과 알루미늄 합금표면의 두꺼운 산화 피막 형성을 억제시켜 냉각효과를 저하시키지 않고, 바륨화합물의 방식 피막으로 인한 알루미늄 재질의 고온 방식력도 향상시킨다.The biggest feature of the present invention is that the barium or barium compound contained in the antifreeze composition of the present invention serves to prevent corrosion of aluminum or aluminum alloy for a long time (10 years / 200,000 km) and blackening of the aluminum surface. In particular, it exhibits an excellent discoloration preventing effect on the high temperature aluminum heat transfer surface. In general, when an organic carboxylic acid corrosion inhibitor is used, an antifreeze film of aluminum oxide may be formed, and a black thick film may be formed to hinder the heat transfer to reduce the cooling effect. However, the composition containing the barium compound of the present invention may be aluminum and an aluminum alloy. By suppressing the formation of a thick oxide film on the surface, the cooling effect is not lowered, and the high temperature anticorrosion force of the aluminum material due to the anticorrosive coating of the barium compound is also improved.

본 발명의 바람직한 구현예에 따르면, 본 발명의 조성물에서 pH를 7-9의 범위로 조절하기 위하여 이용되는 알칼리 금속 수산화물은 수산화칼륨 또는 수산화나트륨이고, 보다 바람직하게는 수산화칼륨이다. 상술한 알칼리 금속 수산화물은 조성물 전체 중량에 대하여 0.5-2 중량%로 포함되고, 보다 바람직하게는 0.5-1.8 중량%, 가장 바람직하게는 0.7-1.5 중량%이다.According to a preferred embodiment of the present invention, the alkali metal hydroxide used to adjust the pH in the range of 7-9 in the composition of the present invention is potassium hydroxide or sodium hydroxide, more preferably potassium hydroxide. The above-mentioned alkali metal hydroxide is included in an amount of 0.5-2% by weight based on the total weight of the composition, more preferably 0.5-1.8% by weight, most preferably 0.7-1.5% by weight.

본 발명의 다른 바람직한 구현예에 따르면, 본 발명의 부동액 조성물은 폴리말레인산, 폴리아크릴산, 아크릴산-말레인산 공중합체, 폴리비닐피롤리돈, 폴리비닐이미다졸, 비닐피롤리돈-비닐이미다졸 공중합체, 불포화 카르복실산 및 올레핀의 공중합체, 포스피노 카르복실산 공중합체, 2-포스포노부탄-1,2,4-트리카르복실산, 1-하이드록시에틸리덴-1,1-디포스폰산, 소듐트리폴리포스페이트, 포스피노카르복실산, 폴리포스피노카르복실산, 설페이티드 포스포노카르복실산 폴리머 및 아미노트 리메틸렌포스폰산으로 이루어진 군으로부터 적어도 1종 또는 2종 이상의 성분을 추가적으로 포함한다.According to another preferred embodiment of the present invention, the antifreeze composition of the present invention comprises polymaleic acid, polyacrylic acid, acrylic acid-maleic acid copolymer, polyvinylpyrrolidone, polyvinylimidazole, vinylpyrrolidone-vinylimidazole air Copolymers of copolymers, unsaturated carboxylic acids and olefins, phosphino carboxylic acid copolymers, 2-phosphonobutane-1,2,4-tricarboxylic acids, 1-hydroxyethylidene-1,1-dipo At least one or two or more components may be additionally added from the group consisting of spongic acid, sodium tripolyphosphate, phosphinocarboxylic acid, polyphosphinocarboxylic acid, sulfated phosphonocarboxylic acid polymer and aminotrimethylenephosphonic acid Include.

본 발명의 특징 및 이점을 요약하면 다음과 같다:The features and advantages of the present invention are summarized as follows:

(ⅰ) 본 발명은 바륨 또는 바륨 화합물을 포함하는 부동액 조성물을 제공한다.(Iii) The present invention provides an antifreeze composition comprising a barium or barium compound.

(ⅱ) 일반적으로 유기카르복실산 부식억제제를 사용시 산화알루미늄의 부동액 피막을 형성하여 흑색의 두꺼운 피막형성으로 전열을 방해하여 냉각효과를 떨어뜨릴 수 있으나, 본 발명의 바륨화합물을 함유한 조성물은 알루미늄과 알루미늄 합금표면의 두꺼운 산화 피막 형성을 억제시켜 냉각효과를 저하시키지 않고, 바륨화합물의 방식 피막으로 인한 알루미늄 재질의 고온 방식력도 향상시키는 효과를 가진다.(Ii) In general, when an organic carboxylic acid corrosion inhibitor is used, an antifreeze film of aluminum oxide may be formed to hinder the heat transfer by forming a black thick film, thereby reducing the cooling effect, but the composition containing the barium compound of the present invention may be made of aluminum. It has the effect of suppressing the formation of a thick oxide film on the surface of the aluminum alloy and reducing the cooling effect, and also improving the high temperature corrosion resistance of the aluminum material due to the anticorrosive coating of the barium compound.

(ⅲ) 또한, 본 발명의 부동액 조성물은 알루미늄 또는 알루미늄 합금재질에 대한 장기간(10년/20만 ㎞)의 부식방지와 알루미늄 재질표면의 흑변을 방지 효과를 가져 장수명 부동액 조성물로 이용할 수 있다.(Iii) In addition, the antifreeze composition of the present invention can be used as a long-life antifreeze composition because it has a long-term (10 years / 200,000 km) of corrosion protection against the aluminum or aluminum alloy material and prevents blackening of the aluminum surface.

이상에서 상세히 설명한 바와 같이, 본 발명은 글리콜계 동결방지제, C4-C18인 유기카르복실산 또는 그 알칼리염, 인산 또는 인산염, 아졸유도체, 바륨 또는 바륨화합물, 및 알칼리 금속 수산화물을 포함하는 부동액 조성물을 제공한다. 일반적으로 유기카르복실산 부식억제제를 사용시 산화알루미늄의 부동액 피막을 형성하여 흑색의 두꺼운 피막형성으로 전열을 방해하여 냉각효과를 떨어뜨릴 수 있으나, 본 발명의 바륨화합물을 함유한 조성물은 알루미늄과 알루미늄 합금표면의 두꺼운 산화피막 형성을 억제시켜 냉각효과를 저하시키지 않고, 바륨화합물의 방식피막으로 인한 알루미늄 재질의 고온 방식력도 향상시키는 효과를 가진다. 또한, 본 발명의 부동액 조성물은 알루미늄 또는 알루미늄 합금재질에 대한 장기간(10년/20만 ㎞)의 부식방지와 알루미늄 재질표면의 흑변을 방지 효과를 가져 장수명 부동액 조성물로 이용할 수 있다.As described in detail above, the present invention provides an antifreeze comprising a glycol-based cryoprotectant, an organic carboxylic acid having C 4 -C 18 or an alkali salt thereof, phosphoric acid or phosphate, an azole derivative, a barium or barium compound, and an alkali metal hydroxide. To provide a composition. In general, when an organic carboxylic acid corrosion inhibitor is used, an antifreeze film of aluminum oxide may be formed, and a black thick film may be formed to hinder the heat transfer to reduce the cooling effect. However, the composition containing the barium compound of the present invention may be aluminum and an aluminum alloy. By suppressing the formation of a thick oxide film on the surface, it does not lower the cooling effect, and also has the effect of improving the high temperature corrosion resistance of the aluminum material due to the anti-corrosion coating of the barium compound. In addition, the antifreeze composition of the present invention can be used as a long-life antifreeze composition having a long-term (10 years / 200,000 km) to prevent corrosion of the aluminum or aluminum alloy material and the black side of the aluminum surface.

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명 하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 요지 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어서 자명할 것이다. Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples in accordance with the gist of the present invention to those skilled in the art. Will be self explanatory.

실시예Example

실시예Example 1: 부동액 조성물의 제조 1: Preparation of Antifreeze Composition

부동액 조성물은 하기 표 1 및 2에 기재된 성분의 함량을 저울로 칭량하여 에틸렌글리콜에 투입하고 용액의 온도가 50℃가 되도록 가열하여 완전히 용해되어 잔류물이 없는 균일한 용액이 될 때까지 교반하여 제조하였다. 황산바륨 또는 염화바륨을 포함하지 않는 부동액 조성물을 대조군으로 이용하였다.The antifreeze composition is prepared by weighing the contents of the ingredients shown in Tables 1 and 2 below on a scale and adding them to ethylene glycol, heating them to a temperature of 50 ° C., and stirring them until they are completely dissolved to form a homogeneous solution with no residue. It was. An antifreeze composition containing no barium sulfate or barium chloride was used as a control.

본 발명 부동액 조성물의 조성Composition of the Invention Antifreeze Composition 조성성분 (중량 %)Ingredients (% by weight) 조성물 1Composition 1 조성물 2Composition 2 조성물 3Composition 3 조성물 4Composition 4 조성물 5Composition 5 조성물 6Composition 6 에틸렌글리콜Ethylene glycol 94.99994.999 95.19295.192 96.9096.90 94.3094.30 94.2094.20 94.0594.05 계피산Cinnamon 2.02.0 -- -- 1.01.0 -- 1.01.0 2-에틸헥산산2-ethylhexanoic acid -- 3.03.0 -- 2.52.5 2.42.4 2.42.4 부틸벤조산Butylbenzoic acid 1.01.0 -- 2.02.0 -- 1.01.0 -- 인산Phosphoric Acid 0.10.1 0.10.1 -- -- -- -- 토릴트리아졸Toryltriazole 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 황산바륨Barium sulfate 0.0010.001 -- 0.10.1 -- -- 0.80.8 염화바륨Barium chloride -- 0.0080.008 -- 0.30.3 0.60.6 -- 수산화칼륨Potassium hydroxide 1.61.6 1.41.4 0.70.7 1.61.6 1.51.5 1.451.45

대조군 부동액 조성물의 조성Composition of Control Antifreeze Composition 조성성분 (중량 %)Ingredients (% by weight) 대조군 1Control group 1 대조군 2Control 2 대조군 3Control group 3 대조군 4Control 4 대조군 5Control group 5 대조군 6Control group 6 에틸렌글리콜Ethylene glycol 95.095.0 95.1095.10 97.097.0 94.6094.60 94.8094.80 94.8594.85 계피산Cinnamon 2.02.0 -- -- 1.01.0 -- 1.01.0 2-에틸헥산산2-ethylhexanoic acid -- 3.03.0 -- 2.52.5 2.42.4 2.42.4 부틸벤조산Butylbenzoic acid 1.01.0 -- 2.02.0 -- 1.01.0 -- 인산Phosphoric Acid 0.10.1 0.10.1 -- -- -- -- 토릴트리아졸Toryltriazole 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 황산바륨Barium sulfate -- -- -- -- -- -- 염화바륨Barium chloride -- -- -- -- -- -- 수산화칼륨Potassium hydroxide 1.61.6 1.51.5 0.70.7 1.61.6 1.51.5 1.451.45

이하 금속 부식성 시험, 알루미늄주물 전열면 부식성 시험, pH 값 및 예비 알칼리도 측정의 시험 방법 및 규격은 한국 산업 규격 KS M2142에 따라 실시하였다.The test method and the specification of the metal corrosion test, the aluminum casting heat transfer surface corrosion test, the pH value and the preliminary alkalinity measurement were carried out according to the Korean Industrial Standard KS M2142.

실시예Example 2: 금속 부식성 시험 2: metal corrosive test

금속부식성 시험은 KS M2142 금속부식성 시험에 규정된 조합수(증류수 1L에 Na2SO4 148 mg, NaCl 165 mg 및 NaHCO3 138 mg을 용해시킨 용액)를 사용하여 본 발명 및 대조군 조성물의 농도를 30 부피%가 되도록 혼합한 용액 750 ㎖와 금속시험편 1세트를 톨비이커에 넣고 온도계, 통기관 및 냉각관을 가열장치 위에 부착시킨 다음 건조공기를 매분 100± 10 ㎖의 유량으로 액 중에 흘려보내면서 부동액의 온도를 88±2℃에서 336시간(14일) 유지시켜 금속부식성을 시험하였다. 시험 종료 후 시편을 산세정하여 무게변화를 0.1 ㎎ 단위까지 측정하여 그 결과를 표 3에 나타내었다. The metal corrosion test was performed using the combination water specified in the KS M2142 metal corrosion test (a solution in which 148 mg of Na 2 SO 4 , 165 mg of NaCl and 138 mg of NaHCO 3 was dissolved in 1 L of distilled water). Place 750 ml of the mixed solution to volume% and one set of metal test specimens in a tol beaker, attach thermometer, vent pipe and cooling tube on the heating device, and then dry air is flowed into the liquid at a flow rate of 100 ± 10 ml per minute. The metal corrosion was tested by maintaining the temperature at 88 ± 2 ° C. for 336 hours (14 days). After the test was finished, the specimen was pickled, and the weight change was measured to 0.1 mg. The results are shown in Table 3.

금속부식성 시험결과Metal Corrosion Test Results 측정 항목Measurement item KS M2142
규격KS M2142
standard 본 발명 조성물Invention Composition 대조군Control group 1One 22 33 44 55 1One 22 33 44 55 시험편의
무게변화
(㎎/㎠)Test piece
Weight change
(Mg / cm 2) 알루미늄
주물aluminum
fetish ± 0.30± 0.30 -0.09-0.09 -0.07-0.07 -0.12-0.12 -0.18-0.18 -0.14-0.14 -0.38-0.38 -0.41-0.41 -0.62-0.62 -0.73-0.73 -1.2-1.2 주 철Cast iron ± 0.15± 0.15 -0.04-0.04 -0.03-0.03 -0.06-0.06 -0.05-0.05 -0.06-0.06 -0.12-0.12 -0.06-0.06 -0.09-0.09 -0.07-0.07 -0.08-0.08 강River ± 0.15± 0.15 -0.02-0.02 -0.04-0.04 -0.03-0.03 -0.06-0.06 -0.03-0.03 -0.09-0.09 -0.08-0.08 -0.05-0.05 -0.08-0.08 -0.07-0.07 황 동Brass ± 0.15± 0.15 +0.07+0.07 -0.05-0.05 -0.03-0.03 +0.08+0.08 +0.09+0.09 +0.09+0.09 +0.07+0.07 -0.12-0.12 +0.08+0.08 +0.05+0.05 땜 납Pewter ± 0.30± 0.30 -0.08-0.08 -0.09-0.09 -0.10-0.10 -0.07-0.07 -0.08-0.08 -0.14-0.14 -0.12-0.12 -0.48-0.48 -0.24-0.24 -0.16-0.16 구 리Copper ± 0.15± 0.15 -0.06-0.06 +0.07+0.07 +0.04+0.04 +0.08+0.08 -0.07-0.07 -0.09-0.09 -0.11-0.11 +0.08+0.08 +0.14+0.14 -0.12-0.12 알루미늄주물의 외관Exterior of aluminum casting 변화
없음change
none 변화
없음change
none 변화
없음change
none 변화
없음change
none 변화
없음change
none 엷음
흑변Thin
Black side 엷음
흑변Thin
Black side 흑변Black side 흑변Black side 흑변Black side

상기 표 3에서 확인할 수 있듯이, 대조군 조성물의 경우 알루미늄 주물의 무게변화율이 규격치를 벗어나 불안정한 방식성을 나타내었고, 알루미늄주물 시험편의 외관도 모두 흑변하였다. 본 발명 조성물의 경우 각 시험편의 무게 변화율이 금속부식성 시험규격치을 벗어나지 않고 안정된 부식방지 능력을 보였으며, 알루미늄주물 시험편의 외관도 흑변되는 현상 없이 모두 양호하였다.As can be seen in Table 3, in the case of the control composition, the weight change rate of the aluminum casting was unstable and showed an unstable anticorrosive property, and all of the appearance of the aluminum casting test piece was also blackened. In the case of the composition of the present invention, the weight change rate of each test piece showed stable corrosion preventing ability without departing from the metal corrosion test standard value, and the appearance of the aluminum casting test piece was also good without any phenomenon of blacking.

실시예Example 3: 알루미늄주물  3: aluminum casting 전열면Electric heat 부식성 시험 Corrosive Test

고온의 엔진헤드나 실린더 블록 부위에서 발생하기 쉬운 알루미늄 주물의 방식성과 알루미늄주물 재질의 변색 영향성을 비교하기 위해 전열면 부식성 시험을 실시하였다. 전열면 부식성 시험은 증류수 750 ㎖에 본 발명 및 대조군 조성물 250 ㎖를 넣고 염화나트륨 165 ㎎을 용해시킨 다음 균일하게 혼합시켜 500 ㎖를 분취하여 시험편과 상부 조립판 사이에 오링(O-ring)을 이용하여 내열성 유리셀을 조립한 장치에 주입하였다. 압축공기 150 Kpa 압력을 가한 상태에서 가열하여 시험온도가 135±2℃에 도달했을 때 최종 압력이 193 Kpa 되도록 하여 이 상태에서 168±2시간 동안 유지하였다. 시험 종료 후 시험편 처리를 하여 시험편의 무게를 0.1 ㎎단위까지 측정하여 그 결과를 표 4에 나타내었다.In order to compare the corrosion resistance of aluminum castings and the discoloration effects of aluminum castings, which were prone to occur at high temperatures in the engine head or cylinder block areas, the corrosion resistance test was conducted. Heat-resistant corrosion test is to put 250 ml of the present invention and the control composition in 750 ml of distilled water, dissolve 165 mg of sodium chloride, and then mix it uniformly to fractionate 500 ml using an O-ring between the test piece and the upper assembly plate. Heat-resistant glass cells were injected into the assembled device. Heated with 150 Kpa of compressed air, the final pressure was 193 Kpa when the test temperature reached 135 ± 2 ℃, and maintained at 168 ± 2 hours. After completion of the test, the test piece was treated and the weight of the test piece was measured up to 0.1 mg. The results are shown in Table 4.

알루미늄주물 전열면 부식성시험 결과Aluminum casting heat transfer surface corrosion test result 측정 항목Measurement item ASTM D 4340 규격ASTM D 4340 standard 본 발명 조성물Invention Composition 대조군Control group 1One 22 33 44 55 1One 22 33 44 55 무게변화
(㎎/㎠)Weight change
(Mg / cm 2) ± 1.0± 1.0 -0.03-0.03 -0.01-0.01 -0.03-0.03 -0.02-0.02 -0.03-0.03 -1.53-1.53 -1.28-1.28 -1.45-1.45 -1.12-1.12 -1.10-1.10 알루미늄주물
시편의 외관Aluminum casting
Appearance of the Psalms 변화
없음change
none 변화
없음change
none 변화
없음change
none 변화
없음change
none 변화
없음change
none 흑변Black side 흑변Black side 흑변Black side 흑변Black side 흑변Black side

상기 표 4에서 볼 수 있듯이, 본 발명 조성물의 경우 알루미늄 주물표면에 흑변현상이 없이 양호하였으며, 고온에서의 부식성도 모두 우수하였다. 대조군의 경우 알루미늄 주물 시험편 표면이 모두 흑변하였으며 무게 변화율도 많았음을 확인 할 수 있었다.As can be seen in Table 4, the composition of the present invention was good without blackening on the surface of the aluminum casting, it was also excellent in both corrosion at high temperatures. In the case of the control group, the aluminum casting specimens were all blackened and the weight change rate was also high.

실시예Example 4: 20만  4: 200,000 kmkm 실차주행Driving 시험 exam

부동액 실차시험 시, 본 발명의 부동액 조성물 1 및 수도수를 1:1 비율로 혼합하여 실제 차량의 사용농도에서 평가가 이루어질 수 있도록 하였으며, 실차 부동액의 물성변화를 비교하기 위해 외관, pH 및 예비 알칼리도 변화율(%) 등의 일반성상을 측정하였다. 부동액과 접촉하는 각종 냉각장치 부품과 물리 화학적으로 반응하여 부식반응이 이루어질 때 발생하는 Fe, Cu, Al 및 Zn 등의 금속이온의 농도변화를 측정하여 부동액의 부식이온 용출정도를 평가하여 장기내구성을 평가하였다.In the antifreeze vehicle test, the antifreeze composition 1 and tap water of the present invention were mixed at a ratio of 1: 1 so that evaluation can be made at the actual concentration of the vehicle, and the appearance, pH and preliminary alkalinity were compared to compare the physical property change of the antifreeze solution. General properties such as percent change were measured. Measure the concentration of metal ions such as Fe, Cu, Al, and Zn that occur when corrosion reaction occurs by physical and chemical reaction with various cooling device parts in contact with antifreeze, and evaluate the degree of dissolution of the anticorrosive ion in antifreeze Evaluated.

부동액 내의 부식방지제의 고갈정도를 평가하기 위해 실차종료 후 차량에서 부동액을 채취하여 금속부식성 시험과 알루미늄 전열면 부식성 시험을 실시하여 20만㎞ 실차주행 후에도 부동액이 부식방지 내구성을 유지하고 있는지 평가하기 위한 시험항목으로 설정하였다. 20만 ㎞ 이상 실차주행 후 실차시험 차량의 냉각장치를 분해하여 부품별 부식정도를 관찰하여 내구성을 평가하였다. 상기 시험 결과를 표 5 내지 7에 나타내었다.To evaluate the degree of depletion of corrosion inhibitor in antifreeze, antifreeze was taken from the vehicle after the end of the actual vehicle, and the metal corrosion test and the aluminum surface corrosion test were conducted to evaluate whether the antifreeze maintains the anti-corrosion durability even after 200,000 km. It was set as a test item. After driving more than 200,000 km, the cooling system of the test vehicle was disassembled, and the durability was evaluated by observing the corrosion degree of each part. The test results are shown in Tables 5 to 7.

20만 km 실차주행 시험 결과200,000 km real car driving test result 차량번호the car's number 1One 22 33 44 55 66 77 88 주행사항Driving matters 주행기간(月)Driving period (月) 1111 1111 1111 1111 1111 1111 1111 2121 주행거리(㎞)Mileage (km) 258,188258,188 270,750270,750 261,472261,472 249,380249,380 263,392263,392 265,139265,139 250,433250,433 310,603310,603 농도(부피%)Concentration (% by volume) 46.646.6 45.145.1 43.643.6 41.941.9 43.543.5 43.443.4 46.246.2 60.160.1 일반성상General characteristics 외관Exterior 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good pHpH 7.057.05 7.337.33 7.187.18 7.497.49 7.527.52 7.357.35 7.217.21 7.057.05 예비 알칼리도
변화율(%)Preliminary alkalinity
% Change 21.6521.65 18.4218.42 20.1820.18 17.5617.56 18.2618.26 20.0620.06 20.8620.86 23.4623.46 침전량
(부피%)Sedimentation
(volume%) 0.140.14 0.120.12 0.100.10 0.110.11 0.090.09 0.080.08 0.130.13 0.070.07 금속이온농도 (ppm)Metal ion concentration (ppm) FeFe 19.019.0 15.415.4 32.432.4 34.234.2 7.37.3 8.28.2 31.531.5 3.13.1 CuCu 16.516.5 6.66.6 5.45.4 4.44.4 1.71.7 9.49.4 7.67.6 24.724.7 AlAl 2.32.3 0.90.9 1.11.1 1.51.5 1.11.1 1.21.2 1.61.6 1.21.2 ZnZn 12.112.1 11.211.2 9.89.8 9.59.5 6.76.7 7.87.8 9.99.9 12.412.4 금속
부식성
(㎎/㎠)metal
causticity
(Mg / cm 2) 알루미늄
주물aluminum
fetish ± 0.30± 0.30 -0.01-0.01 +0.01+0.01 -0.02-0.02 +0.03+0.03 -0.01-0.01 -0.02-0.02 +0.02+0.02 +0.03+0.03 주철cast iron ± 0.15± 0.15 +0.04+0.04 +0.02+0.02 +0.03+0.03 +0.02+0.02 -0.06-0.06 +0.02+0.02 +0.04+0.04 +0.03+0.03 강River ± 0.15± 0.15 +0.04+0.04 +0.02+0.02 +0.01+0.01 +0.02+0.02 -0.01-0.01 -0.02-0.02 +0.02+0.02 +0.01+0.01 황동Brass ± 0.15± 0.15 -0.04-0.04 -0.03-0.03 -0.06-0.06 -0.05-0.05 -0.01-0.01 -0.04-0.04 -0.04-0.04 -0.07-0.07 땜납pewter ± 0.30± 0.30 -0.22-0.22 -0.27-0.27 -0.21-0.21 -0.19-0.19 -0.16-0.16 -0.20-0.20 -0.21-0.21 -0.24-0.24 구리Copper ± 0.15± 0.15 -0.01-0.01 -0.02-0.02 -0.04-0.04 -0.03-0.03 -0.04-0.04 -0.07-0.07 -0.03-0.03 -0.06-0.06 알루미늄 주물
전열면
부식성
(㎎/㎤)Aluminum casting
Electric heat
causticity
(Mg / cm 3) 알루미늄주물Aluminum casting ± 1.0± 1.0 -0.76-0.76 -0.44-0.44 -0.25-0.25 -0.51-0.51 -0.33-0.33 -0.49-0.49 -0.07-0.07 -0.68-0.68

20만 km 실차주행 시험 결과200,000 km real car driving test result 차량번호the car's number 99 1010 1111 1212 1313 1414 1515 1616 주행사항Driving matters 주행기간(月)Driving period (月) 2424 2424 2525 1717 2424 2020 2121 2020 주행거리(㎞)Mileage (km) 223,140223,140 219,121219,121 249,699249,699 211,328211,328 205,353205,353 202,469202,469 220,491220,491 206,860206,860 농도(부피%)Concentration (% by volume) 59.459.4 46.646.6 56.356.3 57.657.6 45.945.9 51.551.5 63.863.8 44.644.6 일반성상General characteristics 외관Exterior 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good pHpH 7.087.08 7.017.01 7.047.04 7.007.00 7.287.28 7.087.08 7.167.16 7.167.16 예비 알칼리도
변화율(%)Preliminary alkalinity
% Change 21.7621.76 24.8524.85 23.6623.66 24.2424.24 19.4619.46 21.8521.85 19.8419.84 19.2419.24 침전량
(부피%)Sedimentation
(volume%) 0.090.09 0.120.12 0.050.05 0.080.08 0.070.07 0.040.04 0.060.06 0.040.04 금속이온농도 (ppm)Metal ion concentration (ppm) FeFe 1.81.8 1.61.6 0.80.8 0.50.5 1.51.5 0.80.8 0.90.9 0.60.6 CuCu 6.26.2 7.27.2 3.93.9 10.810.8 0.70.7 5.65.6 31.131.1 4.74.7 AlAl 0.90.9 3.33.3 0.60.6 1.11.1 3.83.8 1.21.2 3.33.3 0.60.6 ZnZn 7.67.6 10.910.9 9.09.0 6.26.2 5.35.3 7.27.2 11.511.5 8.18.1 금속
부식성
(㎎/㎠)metal
causticity
(Mg / cm 2) 알루미늄주물Aluminum casting ± 0.30± 0.30 +0.04+0.04 -0.03-0.03 +0.02+0.02 +0.04+0.04 -0.02-0.02 +0.02+0.02 -0.02-0.02 -0.02-0.02 주철cast iron ± 0.15± 0.15 -0.04-0.04 -0.02-0.02 +0.05+0.05 +0.03+0.03 +0.02+0.02 +0.01+0.01 +0.02+0.02 -0.07-0.07 강River ± 0.15± 0.15 -0.02-0.02 -0.04-0.04 +0.01+0.01 +0.2+0.2 -0.01-0.01 +0.01+0.01 -0.03-0.03 +0.01+0.01 황동Brass ± 0.15± 0.15 -0.07-0.07 -0.04-0.04 -0.06-0.06 -0.05-0.05 -0.09-0.09 -0.04-0.04 -0.04-0.04 -0.08-0.08 땜납pewter ± 0.30± 0.30 -0.15-0.15 -0.17-0.17 -0.14-0.14 -0.19-0.19 -0.21-0.21 -0.12-0.12 -0.21-0.21 -0.23-0.23 구리Copper ± 0.15± 0.15 -0.02-0.02 -0.08-0.08 -0.04-0.04 -0.07-0.07 -0.08-0.08 -0.03-0.03 -0.05-0.05 -0.07-0.07 알루미늄 주물
전열면
부식성
(㎎/㎤)Aluminum casting
Electric heat
causticity
(Mg / cm 3) 알루미늄주물Aluminum casting ± 1.0± 1.0 -0.62-0.62 -0.21-0.21 -0.18-0.18 -0.42-0.42 -0.57-0.57 -0.32-0.32 -0.12-0.12 -0.28-0.28

20만 km 실차주행 시험 결과200,000 km real car driving test result 차량번호the car's number 1717 1818 1919 2020 2121 2222 2323 2424 주행사항Driving matters 주행기간(月)Driving period (月) 2121 2525 2525 2121 2020 2525 1919 2121 주행거리(㎞)Mileage (km) 201,523201,523 226,840226,840 270,872270,872 203,389203,389 211,622211,622 202,018202,018 212,004212,004 204,471204,471 농도(부피%)Concentration (% by volume) 58.658.6 57.857.8 45.945.9 50.350.3 45.845.8 59.359.3 53.2153.21 51.151.1 일반성상General characteristics 외관Exterior 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good pHpH 7.087.08 7.197.19 7.097.09 7.147.14 7.067.06 7.137.13 7.247.24 7.177.17 예비 알칼리도 변화율(%)Preliminary alkalinity change rate (%) 21.4621.46 19.6619.66 22.4422.44 21.3621.36 23.4223.42 22.4822.48 19.9619.96 21.1221.12 침전량
(부피%)Sedimentation
(volume%) 0.110.11 0.090.09 0.120.12 0.070.07 0.090.09 0.080.08 0.070.07 0.070.07 금속이온농도 (ppm)Metal ion concentration (ppm) FeFe 0.60.6 4.04.0 0.80.8 0.80.8 1.61.6 1.71.7 1.21.2 1.51.5 CuCu 21.021.0 16.716.7 10.510.5 14.814.8 14.414.4 29.729.7 12.112.1 14.214.2 AlAl 1.41.4 6.16.1 4.54.5 3.53.5 1.61.6 3.83.8 2.32.3 2.12.1 ZnZn 8.08.0 12.812.8 6.26.2 7.97.9 8.28.2 7.87.8 6.76.7 8.48.4 금속
부식성
(㎎/㎠)metal
causticity
(Mg / cm 2) 알루미늄주물Aluminum casting ± 0.30± 0.30 -0.02-0.02 -0.01-0.01 -0.01-0.01 +0.01+0.01 +0.02+0.02 -0.03-0.03 -0.02-0.02 +0.01+0.01 주철cast iron ± 0.15± 0.15 -0.03-0.03 -0.01-0.01 -0.02-0.02 -0.02-0.02 -0.01-0.01 -0.02-0.02 +0.01+0.01 +0.01+0.01 강River ± 0.15± 0.15 -0.02-0.02 -0.01-0.01 -0.01-0.01 +0.01+0.01 +0.03+0.03 -0.02-0.02 -0.02-0.02 -0.02-0.02 황동Brass ± 0.15± 0.15 -0.09-0.09 -0.05-0.05 -0.09-0.09 -0.07-0.07 -0.07-0.07 -0.03-0.03 -0.07-0.07 -0.08-0.08 땜납pewter ± 0.30± 0.30 -0.20-0.20 -0.14-0.14 -0.18-0.18 -0.21-0.21 -0.15-0.15 -0.24-0.24 -0.18-0.18 -0.19-0.19 구리Copper ± 0.15± 0.15 -0.08-0.08 -0.04-0.04 -0.06-0.06 -0.03-0.03 -0.05-0.05 -0.02-0.02 -0.04-0.04 -0.06-0.06 알루미늄 주물
전열면
부식성
(㎎/㎤)Aluminum casting
Electric heat
causticity
(Mg / cm 3) 알루미늄주물Aluminum casting ± 1.0± 1.0 -0.27-0.27 -0.10-0.10 +0.24+0.24 +0.05+0.05 -0.29-0.29 -0.01-0.01 -0.12-0.12 -0.27-0.27

상기 표 5 내지 7에서 확인할 수 있듯이, 실차시험 결과에서 20만 ㎞ 실차주행 중에도 급격한 외관변화나 pH와 예비 알칼리도의 저하는 없었으며 부식반응 생성물인 Fe, Cu, Al 및 Zn 등의 금속이온 농도의 증가도 양호하였다. 실차 주행 후 부동액의 부식성 평가에서도 우수한 방식성을 유지하고 있어서 20만 ㎞ 이상의 방식내구성을 유지하고 있음을 확인할 수 있었다. As can be seen from Tables 5 to 7, there was no sudden appearance change or pH and preliminary alkalinity decrease during the 200,000 km actual vehicle test, and the concentration of metal ions such as Fe, Cu, Al and Zn, which are corrosion reaction products, The increase was also good. It was confirmed that the corrosion resistance of the antifreeze was maintained even after the actual vehicle running, and thus the corrosion resistance was maintained more than 200,000 km.

따라서, 고온에서의 알루미늄 방식과 흑변방지를 위해 바륨화합물을 사용한 본 발명의 조성물이 고온에서 알루미늄 주물 전열면에 대한 부식방지 능력을 향상시키고, 알루미늄 주물표면의 두꺼운 흑색의 산화 피막형성을 방지시켜 열전달 방해현상을 방지하고, 알루미늄 또는 알루미늄 주물 표면에 흑색 피막을 형성시키는 과정에서 발생하는 알루미늄 이온용출 반응을 억제시켜 알루미늄 재질 등에 대한 장기간(10년/20만 ㎞) 방식성을 유지하는 것을 알 수 있었다.Therefore, the composition of the present invention using a barium compound to prevent the aluminum method and blackening at high temperature improves the corrosion protection ability of the aluminum casting heat transfer surface at high temperatures, and prevents the formation of a thick black oxide film on the aluminum casting surface heat transfer It can be seen that it prevents the interference phenomenon and suppresses the elution of aluminum ions generated during the process of forming a black film on the surface of aluminum or aluminum casting to maintain the long-term corrosion resistance for aluminum materials (10 years / 200,000 km). .

이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (9)

글리콜계 동결방지제 90-98중량%, C4-C18인 유기카르복실산 또는 그 알칼리염 1-5중량%, 인산 또는 인산염 0.05-1중량%, 아졸유도체 0.01-1중량%, 바륨 또는 바륨화합물 0.0005-1중량%, 및 알칼리 금속 수산화물 0.5-2중량%를 포함하는 부동액 조성물.90-98% by weight glycol cryoprotectant, 1-5% by weight of organic carboxylic acid or C 4 -C 18 or an alkali salt thereof, 0.05-1% by weight of phosphoric acid or phosphate, 0.01-1% by weight of azole derivative, barium or barium An antifreeze composition comprising 0.0005-1% by weight of a compound, and 0.5-2% by weight of an alkali metal hydroxide. 삭제delete 제 1 항에 있어서, 상기 글리콜계 동결방지제는 에틸렌글리콜, 플로필렌글리콜, 디에틸렌글리콜, 디프로필렌글리콜, 글리세린, 트리에틸렌글리콜 및 트리프로필렌글리콜으로 구성된 군으로부터 선택되는 것을 특징으로 하는 부동액 조성물.The antifreeze composition according to claim 1, wherein the glycol-based cryoprotectant is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, triethylene glycol and tripropylene glycol. 제 1 항에 있어서, 상기 C4-C18인 유기카르복실산 또는 그 알칼리염은 아디픽산, 수베르산, 세바식산, 글루타릭산, 네오데칸산, 네오옥타논산, 숙신산, 계피산, 아젤라익산, 메틸계피산, 하이드록시계피산, 에틸계피산, 프로필계피산, 부틸계피산, 에톡시계피산, 에틸벤조산, 프로필벤조산, 피멜릭산, 디시클로펜타디엔 디카르복실산, 운데칸산, 벤조산, 노난산, 프탈산, 데칸산, 테레프탈산, 도테칸산, 메틸벤조산, 헥산산, 시클로헥세논산, 2-에틸헥산산, 부틸벤조산, 옥탄산 및 헵탄산으로 구성된 군으로부터 최소 1 종의 성분이 선택되는 것을 특징으로 하는 부동액 조성물According to claim 1, wherein the C 4 -C 18 organic carboxylic acid or an alkali salt thereof is adipic acid, subic acid, sebacic acid, glutaric acid, neodecanoic acid, neooctanoic acid, succinic acid, cinnamic acid, azelaic acid , Methyl cinnamic acid, hydroxy cinnamic acid, ethyl cinnamic acid, propyl cinnamic acid, butyl cinnamic acid, ethoxy cinnamic acid, ethyl benzoic acid, propylbenzoic acid, pimelic acid, dicyclopentadiene dicarboxylic acid, undecanoic acid, benzoic acid, nonanoic acid, phthalic acid, decane Antifreeze composition characterized in that at least one component is selected from the group consisting of acid, terephthalic acid, dotecanoic acid, methylbenzoic acid, hexanoic acid, cyclohexenoic acid, 2-ethylhexanoic acid, butylbenzoic acid, octanoic acid and heptanoic acid 제 1 항에 있어서, 상기 인산 또는 인산염은 오르토인산, 인산나트륨, 인산칼륨, 인산1수소나트륨, 인산1수소칼륨, 인산2수소나트륨 또는 인산2수소칼륨인 것을 특징으로 하는 부동액 조성물.The antifreeze composition of claim 1, wherein the phosphoric acid or phosphate salt is orthophosphoric acid, sodium phosphate, potassium phosphate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate. 제 1 항에 있어서, 상기 아졸유도체는 벤조트리아졸, 토릴트리아졸 , 메르캅토벤조티아졸 또는 그 유도체 화합물인 것을 특징으로 하는 부동액 조성물.The antifreeze composition according to claim 1, wherein the azole derivative is benzotriazole, toryltriazole, mercaptobenzothiazole or a derivative compound thereof. 제 1 항에 있어서, 상기 바륨화합물은 염화바륨, 수산화바륨, 질산바륨, 탄산바륨, 초산바륨, 브롬산바륨, 티오시안산바륨, 티탄산바륨, 불화바륨, 시안산바륨, 벤젠술폰산바륨, 브롬화바륨, 디티온산바륨, 옥살산바륨, 페로시안바륨, 포름산바륨, 헥산불화 규산바륨, 치아인산바륨, 아질산바륨, 산화바륨, 과염소산 바륨, 과망간산바륨, 제이인산바륨, 바륨시아노백금산, 아황산바륨, 티오시아산바륨, 티오황산바륨, 유기바륨 중합체 및 카르복실산류의 바륨으로 구성된 군으로부터 선택되는 것을 특징으로 하는 부동액 조성물.The barium compound of claim 1, wherein the barium compound is barium chloride, barium hydroxide, barium nitrate, barium carbonate, barium acetate, barium bromide, barium thiocyanate, barium titanate, barium fluoride, barium cyanide, barium sulfonate, barium bromide Barium dithionate, barium oxalate, barium ferrocyanide, barium formate, barium hexane fluoride, barium phosphate, barium nitrite, barium oxide, barium perchlorate, barium permanganate, barium phosphate, barium cyanoplatinum, barium sulfite, thiocylate An antifreeze composition selected from the group consisting of barium arsenite, barium thiosulfate, organic barium polymers, and barium of carboxylic acids. 제 1 항에 있어서, 상기 알칼리 금속 수산화물은 수산화칼륨 또는 수산화나트륨인 것을 특징으로 하는 부동액 조성물.The antifreeze composition of claim 1, wherein the alkali metal hydroxide is potassium hydroxide or sodium hydroxide. 제 1 항에 있어서, 상기 부동액 조성물은 폴리말레인산, 폴리아크릴산, 아크릴산-말레인산 공중합체, 폴리비닐피롤리돈, 폴리비닐이미다졸, 비닐피롤리돈-비닐이미다졸 공중합체, 불포화 카르복실산 및 올레핀의 공중합체, 포스피노 카르복실산 공중합체, 2-포스포노부탄-1,2,4-트리카르복실산, 1-하이드록시에틸리덴-1,1-디포스폰산, 소듐트리폴리포스페이트, 포스피노카르복실산, 폴리포스피노카르복실산, 설페이티드 포스포노카르복실산 폴리머 및 아미노트리메틸렌포스폰산으로 이루어진 군으로부터 최소 1종 또는 2종 이상의 성분을 추가적으로 포함하는 것을 특징으로 하는 부동액 조성물.The antifreeze composition of claim 1, wherein the antifreeze composition comprises polymaleic acid, polyacrylic acid, acrylic acid-maleic acid copolymer, polyvinylpyrrolidone, polyvinylimidazole, vinylpyrrolidone-vinylimidazole copolymer, unsaturated carboxylic acid. And copolymers of olefins, phosphino carboxylic acid copolymers, 2-phosphonobutane-1,2,4-tricarboxylic acids, 1-hydroxyethylidene-1,1-diphosphonic acid, sodium tripolyphosphate Antifreeze further comprising at least one or two or more components from the group consisting of phosphinocarboxylic acid, polyphosphinocarboxylic acid, sulfated phosphonocarboxylic acid polymer and aminotrimethylenephosphonic acid Composition.
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