KR100299326B1 - Organic acid-based antifreeze composition - Google Patents

Organic acid-based antifreeze composition Download PDF

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KR100299326B1
KR100299326B1 KR1019970067036A KR19970067036A KR100299326B1 KR 100299326 B1 KR100299326 B1 KR 100299326B1 KR 1019970067036 A KR1019970067036 A KR 1019970067036A KR 19970067036 A KR19970067036 A KR 19970067036A KR 100299326 B1 KR100299326 B1 KR 100299326B1
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composition
acid
antifreeze
corrosion
antifreeze composition
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KR19990048372A (en
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최경욱
박기만
한순종
조창묵
김진호
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조민호
에스케이케미칼주식회사
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    • 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
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

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

Abstract

PURPOSE: Provided is an organic acid-based antifreeze composition which has a good compatibility with a hard water and does not form scale owing to the production of sparsely soluble salt, and which shows an excellent anticorrosion function against metal and can be used for a long time at a high temperature. CONSTITUTION: The antifreeze composition comprises 0.5-10.0 wt.% of 2-ethyl hexanoic acid(% is based on the total weight of the composition), 0.5-10.0 wt.% of benzoic acid, 0.1-5.0 wt.% of sebacic acid, 0.05-1.0 wt.% of triazoles, and the rest of glycols. The composition has a pH of 7.0-11.0. The pH is adjusted using alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The glycols is ethylene glycol or propylene glycol. The composition has a good compatibility with a hard water and does not form scale owing to production of sparsely soluble salt, as well as shows an excellent anticorrosion function against metal and can be used for a long time at a high temperature.

Description

유기산계 부동액 조성물Organic Acid Antifreeze Composition

[산업상 이용분야][Industrial use]

본 발명은 부동액 조성물에 관한 것으로서, 더욱 상세하게는 유기산계 부식 방지제만으로 이루어진 조성물로서 냉각계 내부의 스케일 발생 및 부식을 방지하기 위한 자동차 엔진 냉각수용 부동액 조성물에 관한 것이다.The present invention relates to an antifreeze composition, and more particularly, to an antifreeze composition for automobile engine coolant for preventing scale generation and corrosion in a cooling system as a composition consisting of only an organic acid-based corrosion inhibitor.

[종래 기술][Prior art]

자동차용 부동액은 에틸렌 글리콜 또는 프로필렌 글리콜, 부식 방지제 및 소포제로 이루어져 있고, 부식 방지제로는 대부분 아민, 보락스, 질산염, 아질산염, 인산염 및 규산염 등의 무기염이 사용된다. 그러나 부동액에 사용되는 무기염 방식제는 장시간 사용할 경우 냉각계 내부에 스케일을 형성하여 온도 조절 장치(thermostat)의 작동 불량을 초래하거나 워터 펌프(water pump)의 누수현상을 일으키고 라디에이터(radiator) 코아를 막히게 할 수 있다. 이러한 이유로 부동액 교환 주기를 연장하는 것이 어렵고, 부동액을 교환할 때에도 냉각계 전체를 세척하여 스케일 성분을 제거할 필요가 있다. 노후한 라디에이터의 내부를 관찰하면 하얀 스케일 성분을 발견할 수 있는데, 이러한 침전물들은 대부분 부동액 조성물로 사용된 무기물과 냉각계를 이루고 있는 금속 재료의 부식 생성물 또는 희석수 내의 이온과의 결합에 의해 생성된 것이다.Automotive antifreezes consist of ethylene glycol or propylene glycol, corrosion inhibitors and antifoams, and most of the corrosion inhibitors include inorganic salts such as amines, borax, nitrates, nitrites, phosphates and silicates. However, the inorganic salt anticorrosive used in the antifreeze forms a scale inside the cooling system when used for a long time, which may cause a malfunction of the thermostat or cause a water pump to leak and You can get stuck. For this reason, it is difficult to extend the antifreeze exchange cycle, and even when the antifreeze is changed, it is necessary to wash the entire cooling system to remove scale components. Observing the interior of the aging radiator reveals a white scale component, most of which is formed by the combination of ions in the dilution water or corrosion products of the metal materials in the cooling system with the minerals used in the antifreeze composition. will be.

따라서 이러한 무기염 방식제를 대체하기 위한 많은 대체 첨가제들이 제안되어 왔는데 특히 유기산 계통의 부식 방지제가 많이 보고되었다. 유기산계 방식제는 1955년 미국 특허 제2,726,215호에서 세바신산(sebacic acid)이나 아젤라인산(azelaic acid)의 사용이 처음 제안된 후 여러 종류의 화합물이 소개되었다. 미국 특허 제4,324,675호에서는 벤조산 유도체를 이용한 부식 방지제가 소개되었고, 미국 특허 제4,390,439호, 제4,759,864호 및 제4,851,145호 등에서는 모노-카르복실산을 단독 혹은 혼용하는 기술이 보고되었다. 또한 미국 특허 제4,647,392호에서는 모노-카르복실산과 디-카르복실산을 적절한 비율로 첨가하여 방식 상승 효과를 얻을 수 있다고 보고하였다. 하지만 이들 기술들은 극히 한정된 조건에서만 방식성을 가지며 경수 조건 등에서는 좋은 방식효과를 얻을 수 없다.Therefore, many alternative additives have been proposed to replace these inorganic salt anticorrosive agents. In particular, many organic acid corrosion inhibitors have been reported. Organic acid-based anticorrosives were introduced in 1955 in US Pat. No. 2,726,215 after the use of sebacic acid or azelaic acid for the first time. In US Pat. No. 4,324,675, corrosion inhibitors using benzoic acid derivatives have been introduced, and US Pat. Nos. 4,390,439, 4,759,864, and 4,851,145 and the like have reported the use of mono-carboxylic acids alone or in combination. In addition, US Pat. No. 4,647,392 reports that anticorrosive effect can be obtained by adding mono-carboxylic acid and di-carboxylic acid in an appropriate ratio. However, these techniques are anticorrosive only under extremely limited conditions and do not achieve good anticorrosive effects in hard water conditions.

유기산계 방지제 중 모노-카르복실산인 2-에틸-헥산산(2-ethyl-hexanoic acid)은 저온 환경에서 철계 금속에 대한 방식성을 나타내지만, 고온 환경에서는 방식성이 감소하고 부동액이 사용되는 실제조건인 88℃ 이상에서는 단독으로는 아무런 효과도 얻을 수 없으며 오히려 첨가량의 증가에 따라 주철, 강 및 땜납 등에 심한 부식을 일으킬 수 있다.Among the organic acid inhibitors, 2-ethyl-hexanoic acid, which is a mono-carboxylic acid, exhibits anticorrosive properties to iron-based metals in a low temperature environment. Above 88 ℃, which is a condition, no effect can be obtained by itself. Rather, it can cause severe corrosion on cast iron, steel, and solder as the amount of the additive is increased.

다른 모노-카르복실산인 벤조산은 부동액에 일반적으로 사용되는 첨가제이지만, 함유량이 3% 이상이 되어도 더 이상의 방식 효과를 얻기 어렵고 부식성 경수 조건에서는 그 방식 효과가 더욱 작게 나타난다.Another mono-carboxylic acid, benzoic acid, is an additive commonly used in antifreezes, but even if the content is 3% or more, no further anticorrosive effect is obtained, and the corrosive hard water condition shows smaller anticorrosive effect.

한편 디-카르복실산인 세바신산은 일반 연수에서는 철이나 알루미늄 등에 방식성을 줄 수 있지만, 칼슘 이온과 염소 이온이 다량 함유되어 있는 부식성 경수 조건에서는 그 기능을 나타내지 못한다.On the other hand, sebacic acid, a di-carboxylic acid, can give corrosion resistance to iron, aluminum, etc. in general soft water, but it does not show its function in corrosive hard water conditions containing a large amount of calcium ions and chlorine ions.

본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 무기염 방식제를 사용할 때 나타나는 불용성 스케일을 발생시키지 않아 자동차 냉각계통의 고장 원인 중 스케일에 의하여 발생하는 라디에이터 코아의 막힘 또는 워터 펌프 등에서 기계적 손상을 유발하지 않으며 온도 조절 장치의 작동불량 등의 문제점을 해결하고, 부동액의 저장, 유통 기간에 생길 수 있는 침전물 발생 및 경수, 연수와의 혼용시 발생 가능한 난용성 침전물 문제를 해결하여 고부식성 경수에서도 부식 방지 기능을 나타낼 수 있는 부동액 조성물을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, the object of the present invention does not generate an insoluble scale that appears when using an inorganic salt anticorrosive agent of the radiator core caused by the scale of the failure cause of the cooling system of the automobile It does not cause mechanical damage in clogging or water pumps, and solves problems such as malfunction of the temperature control device, and precipitates that may occur during storage and distribution of the antifreeze, and poorly soluble precipitates that may occur when mixed with hard water or soft water. To solve the problem is to provide an antifreeze composition that can exhibit a corrosion protection even in high corrosive hard water.

[과제를 해결하기 위한 수단][Means for solving the problem]

상기한 목적을 달성하기 위하여 본 발명은 글리콜류, 2-에틸-헥산산, 벤조산, 세바신산 및 트리아졸류를 포함하는 부동액 조성물을 제공한다.The present invention to achieve the above object is glycols, An antifreeze composition comprising 2-ethyl-hexanoic acid, benzoic acid, sebacic acid and triazoles is provided.

모노-카르복실산인 2-에틸-헥산산 및 벤조산은 조성물 총량에 대하여 0.5 내지 10.0중량%를 사용하는 것이 바람직하다. 0.5중량% 미만일 경우에는 주철과 같은 철계 금속의 부식이 유발되고, 10.0중량%를 초과하여 사용하면 용해성 문제로 인한 저장 안정성에 문제가 생겨 용액의 층 분리 현상이 일어날 수 있다.2-ethyl-hexanoic acid and benzoic acid which are mono-carboxylic acids are preferably used in an amount of 0.5 to 10.0% by weight based on the total amount of the composition. If the amount is less than 0.5% by weight, corrosion of iron-based metals such as cast iron is caused, and when used in excess of 10.0% by weight, there may be a problem in storage stability due to solubility problems, resulting in layer separation of the solution.

디-카르복실산인 세바신산은 조성물의 총량에 대하여 0.1 내지 5.0중량%를 사용하는 것이 바람직하다. 0.1중량% 미만일 경우에는 주철과 같은 철계 금속의 부식이 유발되고, 5.0중량%를 초과하면 용해성 문제로 인한 저장 안정성에 문제가 생겨 용액의 층 분리 현상이 일어날 수 있고 고가인 관계로 경제성에 문제가 있다.Sebacic acid, which is a di-carboxylic acid, is preferably used in an amount of 0.1 to 5.0% by weight based on the total amount of the composition. If it is less than 0.1 wt%, corrosion of iron-based metals such as cast iron is caused, and if it is more than 5.0 wt%, there is a problem of storage stability due to solubility problems, which may cause layer separation of the solution, and it is expensive, and thus economical problems are caused. have.

유기산계 화합물은 물 또는 글리콜류에 대하여 용해도가 좋지 않으므로 용해도를 증가시키기 위해 알칼리 금속 수산화물을 적당량 사용하여 부식 환경을 최소화할 수 있는 pH 7.0 내지 11.0의 약 알칼리성 용액으로 조절한다. 이때 사용할 수 있는 알칼리 금속 수산화물은 수산화 나트륨 또는 수산화 칼륨이며, 부동액 조성물의 pH가 강 알칼리화 되었을 경우에는 초산을 이용하여 산도를 조절한다.Since the organic acid compound is poorly soluble in water or glycols, an appropriate amount of alkali metal hydroxide is used to increase the solubility, so that the organic acid compound is adjusted to a weak alkaline solution having a pH of 7.0 to 11.0 to minimize the corrosive environment. At this time, the alkali metal hydroxide that can be used is sodium hydroxide or potassium hydroxide, and when the pH of the antifreeze composition is strongly alkalinized, the acidity is adjusted using acetic acid.

동계 금속의 부식 방지제인 트리아졸류는 벤조 트리아졸, 톨리 트리아졸, 메르캅토 벤조 티아졸 및 이들의 혼합물로 이루어진 군에서 선택되고 0.05 내지 1.0중량%를 사용한다. 0.05중량% 미만일 경우에는 동계 금속의 부식을 방지하지 못하고, 1.0중량%를 초과하여 사용하면 용액의 강알칼리화에 의한 영향으로 알루미늄 금속의 부식을 유발할 수 있다.Triazoles, which are corrosion inhibitors of copper-based metals, are selected from the group consisting of benzo triazole, toly triazole, mercapto benzo thiazole and mixtures thereof and use 0.05 to 1.0% by weight. If less than 0.05% by weight does not prevent corrosion of the copper metal, when used in excess of 1.0% by weight may cause corrosion of the aluminum metal due to the strong alkalinization of the solution.

상기의 글리콜류는 에틸렌 글리콜 또는 프로필렌 글리콜을 사용할 수 있다.Ethylene glycol or propylene glycol can be used for said glycols.

[실시예]EXAMPLE

다음은 본 발명의 이해를 돕기 위하여 바람직한 실시예 및 비교예를 제시한다. 그러나 하기의 실시예들은 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다.The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

유기산계 화합물의 농도에 따른 방식성 시험Anticorrosive test according to the concentration of organic acid compound

모노-카르복실산인 2-에틸-헥산산 및 벤조산과 디-카르복실산인 세바신산을 각각 표 1에 나타낸 것처럼 다양하게 혼합비를 변화시키면서 부식 방지에 대한 상승 효과를 실험하였다. 유기산계 화합물의 함유량은 원액 기준이고 부식 테스트는 KS M 2142 방법을 기준으로 하였으며, 부식 조합수는 칼슘 이온 농도가 약 400ppm 함유되어 있는 인공 합성 경수를 이용하여 25부피%로 희석한 후 88±2℃에서 168시간 동안 시험하였다. 시험에 사용한 성분비와 시험 결과를 표 1에 나타내었다.The synergistic effect on the corrosion protection was tested with varying mixing ratios of 2-ethyl-hexanoic acid, mono-carboxylic acid and sebacic acid, benzoic acid and di-carboxylic acid, respectively, as shown in Table 1. The content of organic acid compounds is based on the undiluted solution and the corrosion test is based on the KS M 2142 method.The corrosion combination water is diluted to 88% by volume using artificial synthetic hard water containing about 400ppm calcium ion concentration. It was tested at 168 hours. The component ratio used for the test and the test result are shown in Table 1.

유기산계 화합물의 농도에 따른 방식성 시험Anticorrosive test according to the concentration of organic acid compound 성분(중량%)Ingredient (% by weight) 금속 부식성1 Corrosive to metals 1 2-에틸-헥산산2-ethyl-hexanoic acid 세바신산Sebacic acid 벤조산Benzoic acid 알루미늄aluminum 주철cast iron 강River 땜납pewter 1One 22 ×× △△ △△ △△ 22 44 ×× ×× ×× ×× 33 66 ×× ×× ×× ×× 44 22 ○○ ×× ×× △△ 55 44 ○○ △△ △△ △△ 66 66 △△ ×× ×× △△ 77 22 ×× ○○ ○○ △△ 88 44 ×× ○○ ○○ ○○ 99 66 ×× ○○ ○○ ○○ 1010 22 22 ×× △△ △△ ×× 1111 33 33 ×× △△ △△ ×× 1212 22 22 ×× ×× ×× ×× 1313 33 33 ×× ×× ×× ×× 1414 22 22 ×× △△ ×× ×× 1515 33 33 ×× △△ ×× ×× 1616 22 22 22 ○○ ○○ ○○ ○○ 1717 22 1One 33 ◎◎ ◎◎ ◎◎ ◎◎

1◎: 우수한 방식성, ○: 약간의 방식성, △: 변화 없음, ×:부식성 1 ◎: excellent anticorrosive, ○: slight anticorrosive, Δ: no change, ×: corrosion resistance

상기의 표 1의 결과로부터 유기산계 화합물의 단독 또는 두 가지의 조합으로는 그 양과 조성의 변화에도 불구하고 오히려 부식성을 초래할 수도 있으며, 세 가지 물질을 적절히 배합함으로써 단독 또는 두 가지 물질을 사용할 때보다 금속에 대한 부식 방지 기능이 크게 상승하는 효과를 얻을 수 있으며 특히 고부식성 경수에서 매우 우수한 방식 기능을 발휘할 수 있음을 알 수 있었다.From the results of Table 1 above, the organic acid compound alone or in combination of the two may cause corrosiveness in spite of the change in the amount and composition, and by appropriate combination of the three materials, It can be seen that the corrosion protection function for the metal can be greatly increased, and in particular, it can exhibit a very good corrosion protection function in high corrosive hard water.

실시예 1∼2Examples 1-2

다음 표 2의 함량으로 각 성분을 혼합하였다.Next, the ingredients were mixed in the amounts shown in Table 2.

(단위: 중량%)(Unit: weight%) 성 분ingredient 실시예 1Example 1 실시예 2Example 2 벤조산Benzoic acid 3.63.6 3.03.0 2-에틸-헥산산2-ethyl-hexanoic acid 1.71.7 1.91.9 세바신산Sebacic acid 0.50.5 0.70.7 톨리 트리아졸Toly triazole 0.10.1 0.10.1 수산화 칼륨Potassium hydroxide 1.21.2 1.21.2 소포제Antifoam 0.010.01 0.010.01 에틸렌 글리콜Ethylene glycol 92.8992.89 93.0993.09

비교예 1Comparative Example 1

유기산 및 아졸계로 이루어진 미국 Texaco사의 Havoline 부동액을 사용하였다.Havoline antifreeze of Texaco, USA, consisting of organic acids and azoles, was used.

비교예 2Comparative Example 2

인산염 약 0.5중량%, 보레이트염 1.5중량%, 질산염 0.3중량%, 규산염 0.2중량%, 아졸류 0.3중량% 및 수분 3.0중량%를 함유하는 한국 유공(SK)의 KS형 부동액, SUPER-A를 사용하였다.KS-type antifreeze of Korea Yugong (SK) containing about 0.5% by weight of phosphate, 1.5% by weight of borate salt, 0.3% by weight of nitrate, 0.2% by weight of silicate, 0.3% by weight of azoles and 3.0% by weight of water is used It was.

실시예 1, 2에 따라 제조된 부동액 및 비교예 1, 2의 부동액을 KS M 2142법에 따라 부식시험을 시행하였다. 희석수는 증류수에 염화칼슘을 396㎎/ℓ로 첨가한 고부식성 경수를 사용하였고, 희석 비율은 25%였다. 이 조건은 KS M 2142법에 명시된 인공 부식 혼합수보다 매우 부식성이 강하고 희석비가 낮은 조건이었다. 시험 결과는 표 3에 나타내었다.The antifreeze prepared according to Examples 1 and 2 and the antifreeze of Comparative Examples 1 and 2 were subjected to a corrosion test according to the KS M 2142 method. Dilution water was used as a highly corrosive hard water with 396 mg / l of calcium chloride in distilled water, the dilution rate was 25%. This condition was much more corrosive and the dilution ratio was lower than the artificial corrosion mixed water specified in the KS M 2142 method. The test results are shown in Table 3.

KS M 2142법에 따른 부식성 시험 결과Corrosion test results according to KS M 2142 method 금 속metal 금속 시험편의 시험 후 무게감량 (㎎/㎠)Weight loss after the test of metal specimens (mg / cm 2) 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2 동copper -0.03-0.03 -0.03-0.03 -0.04-0.04 -0.33-0.33 땜납pewter -0.02-0.02 -0.02-0.02 -0.39-0.39 -0.43-0.43 황동Brass -0.03-0.03 -0.04-0.04 -0.05-0.05 -0.34-0.34 강River -0.01-0.01 -0.01-0.01 -0.15-0.15 -0.55-0.55 주철cast iron -0.05-0.05 -0.06-0.06 -0.35-0.35 -0.95-0.95 알루미늄aluminum +0.03+0.03 +0.01+0.01 +1.75+1.75 +1.92+1.92

비교예 1의 경우는 KS M 2142법에 따른 인공 부식 혼합수로 30% 희석하여 시험하였을 때에는 좋은 방식성을 나타내지만 표 3에 나타난 바와 같이 고부식성 경수에서는 그 기능을 발휘하지 못했다. 실시예 1 및 2에서는 이러한 고부식성 경수 조건에서도 그 방식성이 잘 유지되었다.Comparative Example 1 shows good corrosion resistance when tested by diluting with 30% of artificial corrosion mixed water according to KS M 2142 method, but it did not show its function in high corrosive hard water as shown in Table 3. In Examples 1 and 2, the corrosion resistance was well maintained even in such highly corrosive hard water conditions.

실시예 1, 2에 따라 제조된 부동액 및 비교예 1, 2의 부동액을 엔진 냉각계를 모사한 순환 부식 테스트의 한 방법인 오펠(OPEL)식 핫 핑거 시험(hot finger test)법에 따라 부식 시험을 시행하였다. 시험 시간은 총 168시간으로 하였고, 시험액은 고부식성 경수로 25% 희석하여 사용하였다. 시험 결과는 표 4에 나타내었다.The antifreeze prepared according to Examples 1 and 2 and the antifreeze of Comparative Examples 1 and 2 were subjected to the corrosion test according to the OPEL hot finger test method, which is a method of circulating corrosion test that simulates an engine cooling system. Was implemented. The test time was 168 hours in total, and the test solution was diluted 25% with highly corrosive hard water. The test results are shown in Table 4.

핫 핑거 부식성 시험Hot Finger Corrosion Test 금7 속7 gold 금속 시험편의 시험 후 무게감량 (㎎/㎠)Weight loss after the test of metal specimens (mg / cm 2) 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2 동copper -0.02-0.02 -0.03-0.03 -0.18-0.18 -0.23-0.23 땜납pewter -0.05-0.05 -0.04-0.04 -0.30-0.30 -0.55-0.55 황동Brass -0.03-0.03 -0.03-0.03 -0.15-0.15 -0.24-0.24 강River -0.02-0.02 -0.04-0.04 -0.20-0.20 -0.40-0.40 주철cast iron -0.07-0.07 -0.06-0.06 -0.45-0.45 -0.85-0.85 알루미늄aluminum +0.06+0.06 +0.05+0.05 +0.85+0.85 +1.25+1.25

자동차 냉각 시스템 조건에 가장 유사한 이 시험에서 실시예 1 및 2에 따라 제조된 부동액은 비교예 1 및 2의 부동액에 비해 좋은 방식성을 나타내었다.In this test, which is most similar to automotive cooling system conditions, the antifreezes prepared according to Examples 1 and 2 showed better anticorrosive properties than the antifreezes of Comparative Examples 1 and 2.

이상의 실시예 및 비교예에서 확인된 바와 같이 본 발명에 따르는 부동액 조성물은 칼슘 이온 농도가 약 400ppm 함유되어 있는 고부식성 희석수를 사용했을 때에도 기존의 부동액 조성물에 비해 높은 방식성을 나타냄을 알 수 있었다.As confirmed in the above examples and comparative examples, it was found that the antifreeze composition according to the present invention exhibited higher corrosion resistance than the conventional antifreeze composition even when a highly corrosive dilution water containing about 400 ppm of calcium ion was used. .

본 발명의 부동액 조성물은 기존의 무기계 방식제인 아민, 보락스, 질산염, 아질산염, 인산염 및 규산염 등이 함유되지 않고, 분해되기 힘든 유기산계 방식제 화합물의 조합을 사용함으로써 경수와의 혼용성이 우수하여 난용성 염의 생성에 의한 스케일 형성이 없고, 각각의 첨가제가 열 및 화학적 안정성이 뛰어나 고온에서 장기간 사용하여도 금속의 부식 방지기능을 나타낼 수 있다.The antifreeze composition of the present invention does not contain amine, borax, nitrate, nitrite, phosphate, and silicate, which are conventional inorganic anticorrosive, and has excellent compatibility with hard water by using a combination of organic acid anticorrosive compounds that are difficult to decompose. There is no scale formation due to the formation of poorly soluble salts, and each additive has excellent thermal and chemical stability, and can exhibit corrosion protection of the metal even when used at a high temperature for a long time.

Claims (4)

조성물 총 중량에 대하여 0.5 내지 10.0 중량%의 2-에틸-헥산산; 0.5 내지 10.0 중량%의 벤조산; 0.1 내지 5.0 중량%의 세바신산; 0.05 내지 1.0 중량%의 트리아졸류; 및 잔여의 글리콜류를 포함하는 부동액 조성물.0.5-10.0 wt.% 2-ethyl-hexanoic acid, based on the total weight of the composition; 0.5-10.0 weight percent benzoic acid; 0.1 to 5.0 weight percent sebacic acid; 0.05 to 1.0 wt% triazoles; And residual glycols. 제1항에 있어서, 상기 부동액 조성물은 pH가 7.0 내지 11.0인 부동액 조성물.The antifreeze composition of claim 1, wherein the antifreeze composition has a pH of 7.0 to 11.0. 제2항에 있어서, 상기 pH는 수산화 나트륨 또는 수산화 칼륨인 알칼리금속 수산화물을 사용하여 조절하는 부동액 조성물.The antifreeze composition of claim 2 wherein the pH is adjusted using an alkali metal hydroxide that is sodium hydroxide or potassium hydroxide. 제1항에 있어서, 상기 글리콜류는 에틸렌 글리콜 또는 프로필렌 글리콜인 유기산계 부동액 조성물.The organic acid antifreeze composition of claim 1, wherein the glycols are ethylene glycol or propylene glycol.
KR1019970067036A 1997-12-09 1997-12-09 Organic acid-based antifreeze composition KR100299326B1 (en)

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