KR102548607B1 - Base oil comprising polyol ester and refrigerating machine oil composition comprising the same - Google Patents

Base oil comprising polyol ester and refrigerating machine oil composition comprising the same Download PDF

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KR102548607B1
KR102548607B1 KR1020220131570A KR20220131570A KR102548607B1 KR 102548607 B1 KR102548607 B1 KR 102548607B1 KR 1020220131570 A KR1020220131570 A KR 1020220131570A KR 20220131570 A KR20220131570 A KR 20220131570A KR 102548607 B1 KR102548607 B1 KR 102548607B1
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fatty acid
oil composition
refrigeration oil
polyol ester
tan
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KR1020220131570A
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Korean (ko)
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백주영
윤의중
송재욱
오성호
서지환
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지에스칼텍스 주식회사
애경케미칼 주식회사
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Priority to KR1020220131570A priority Critical patent/KR102548607B1/en
Priority to EP22210049.7A priority patent/EP4353803A1/en
Priority to CN202211509871.7A priority patent/CN116554952A/en
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008Lubricant compositions compatible with refrigerants
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/42Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40Replacement mixtures
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/30Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64Environmental friendly compositions
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/30Refrigerators lubricants or compressors lubricants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

본 발명에 따르면, 하이드록실기를 5개 이상 포함하는 다가 알코올; 탄소수 4 내지 6의 직쇄형 지방산인 제1지방산; 탄소수 4 내지 6의 분지형 지방산인 제2지방산; 및 탄소수 7 내지 10의 직쇄형 또는 분지형 지방산인 제3지방산;으로 합성되고, 40℃에서의 동점도(KV40)가 95~105 cSt이며, 지구 온난화 지수(GWP)가 0 내지 2,500인 냉매와 사용될 수 있는 폴리올 에스테르(polyol ester)를 함유하는 베이스 오일(base oil) 및 이를 포함하는 냉동기유 조성물을 제공할 수 있다.According to the present invention, a polyhydric alcohol containing 5 or more hydroxyl groups; A first fatty acid that is a straight chain fatty acid having 4 to 6 carbon atoms; A second fatty acid that is a branched fatty acid having 4 to 6 carbon atoms; And a third fatty acid, which is a linear or branched fatty acid having 7 to 10 carbon atoms; is synthesized and has a kinematic viscosity (KV40) at 40 ° C of 95 to 105 cSt and a global warming potential (GWP) of 0 to 2,500. It is possible to provide a base oil containing a polyol ester that can be used, and a refrigeration oil composition including the base oil.

Description

폴리올 에스테르를 포함하는 베이스 오일 및 이를 포함하는 냉동기유 조성물{BASE OIL COMPRISING POLYOL ESTER AND REFRIGERATING MACHINE OIL COMPOSITION COMPRISING THE SAME}Base oil containing polyol ester and refrigeration oil composition containing same

본 발명은 폴리올 에스테르(polyol ester, POE)를 포함하는 냉동기유(refrigerating machine oil) 조성물에 관한 것으로, 냉동기용 냉매 중 극성인 냉매와 혼화성이 우수한 폴리올 에스테르를 베이스 오일(base oil)로서 포함하고, 화학적 안정성이 뛰어난 냉동기유 조성물에 관한 것이다.The present invention relates to a refrigerating machine oil composition comprising a polyol ester (POE), comprising, as a base oil, a polyol ester having excellent miscibility with a polar refrigerant among refrigerants for a refrigerator, , It relates to a refrigeration oil composition with excellent chemical stability.

압축형 냉동기는 적어도 압축기, 응축기, 팽창 기구(팽창 밸브 등), 증발기 등이 구비된 냉동 시스템이다. 냉매와 냉동기유 조성물은 밀폐된 상기 냉동 시스템 내에 혼합되고 순환되어 작동하도록 구성되어 있다. 또한, 압축형 냉동기는 세부적인 장치의 종류에 따라 다르지만, 일반적으로 압축비 및 상(phase) 변화에 따라 고온과 저온의 환경이 조성되기 때문에, 냉매와 냉동기유 조성물의 혼합물은 저온에서부터 고온까지 폭 넓은 온도 범위 내에서도 상 분리가 일어나지 않고 냉동 시스템 내에서 순환되는 것이 요구된다. A compression type refrigerator is a refrigeration system equipped with at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), an evaporator, and the like. The refrigerant and refrigerant oil composition are mixed and circulated within the closed refrigeration system to operate. In addition, compression type refrigerators vary depending on the type of detailed device, but since high and low temperature environments are generally created according to compression ratio and phase change, the mixture of refrigerant and refrigeration oil composition can be used in a wide range from low to high temperatures. It is required to circulate in the refrigeration system without phase separation occurring even within the temperature range.

종래로부터 냉동기용 냉매로서 클로로플루오로카본(CFC), 하이드로클로로플루오로카본(HCFC) 등이 주로 사용되어 왔지만, 환경 문제(오존층 파괴)의 원인이 되는 염소를 포함하는 화합물이었기 때문에, 하이드로플루오로카본(HFC) 등의 염소를 함유하지 않는 대체 냉매가 검토되기에 이르렀다.Conventionally, chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been mainly used as refrigerants for refrigerators, but since they are compounds containing chlorine that cause environmental problems (depletion of the ozone layer), hydrofluorocarbons Alternative refrigerants containing no chlorine, such as carbon (HFC), have been studied.

이러한 하이드로플루오로카본으로서는, 예를 들면 1,1,1,2-테트라플루오로에탄, 1,1,1,2-테트라플루오로에탄과 펜타플루오로에탄의 5 : 5 혼합물, 펜타플루오로에탄, 트리플루오로메탄(이하, 각각 R134a, R410A, R125, R23라고 지칭함)으로 대표되는 하이드로플루오로카본이 주목받게 되고, 예를 들어 냉장고 시스템에는 R134a, 공기조화기술 시스템에는 R410A가 사용되어 왔다.Examples of such hydrofluorocarbon include 1,1,1,2-tetrafluoroethane, a 5:5 mixture of 1,1,1,2-tetrafluoroethane and pentafluoroethane, and pentafluoroethane. , Hydrofluorocarbons represented by trifluoromethane (hereinafter referred to as R134a, R410A, R125, and R23, respectively) have attracted attention, and for example, R134a has been used in refrigerator systems and R410A in air conditioning systems.

그러나, 이와 같은 HFC 계열 냉매도 지구 온난화에 미치는 악영향이 존재할 수 있다는 우려가 있었다. 따라서, 오존층 파괴에 미치는 영향이 낮아 더욱 환경 보호에 적합한 이른바 친환경 냉매, 즉, 지구 온난화 지수(GWP)가 상대적으로 낮은 냉매가 주목받고 있다. 이러한 친환경 냉매로는, 예를 들어, HFC 계열의 냉매로서 디플루오로메탄(이하 R32), 올레핀 결합이 포함된 HFO 계열의 냉매로 2,3,3,3-테트라플루오로-1-프로펜(이하 R1234yf) 및 HFC, HFO의 혼합 냉매로 R32과 R1234yf의 68.9 : 31.1의 혼합물, R1234yf와 R134a의 56 : 44의 혼합물(이하, 각각 R454B, R513A로 지칭함), 탄화수소체로 이루어진 HC 계열의 냉매로 이소부탄, 프로판(이하, 각각 R600a, R290로 지칭함)과 같은 냉매 등이 있다.However, there have been concerns that such HFC-based refrigerants may also have adverse effects on global warming. Therefore, so-called eco-friendly refrigerants that are more suitable for environmental protection because of their low impact on the ozone layer depletion, that is, refrigerants with relatively low global warming potential (GWP) are drawing attention. Such eco-friendly refrigerants include, for example, difluoromethane (hereinafter R32) as an HFC-based refrigerant, and 2,3,3,3-tetrafluoro-1-propene as an HFO-based refrigerant containing an olefin bond. (hereinafter R1234yf) and a mixed refrigerant of HFC and HFO, a mixture of 68.9: 31.1 of R32 and R1234yf, a 56: 44 mixture of R1234yf and R134a (hereinafter referred to as R454B and R513A, respectively), and an HC-type refrigerant made of hydrocarbons. and refrigerants such as isobutane and propane (hereinafter referred to as R600a and R290, respectively).

따라서, 상기와 같이 다양한 냉매, 특히 극성이 높은 냉매에 대한 우수한 혼화성(상용성)을 가짐과 동시에, 냉동기에서 사용될 때 높은 내화학성, 내마모성을 가져 뛰어난 화학적 안정성을 나타내는 베이스 오일(base oil) 및 이를 포함하는 냉동기유 조성물을 개발하는 것이 필요한 실정이다.Therefore, as described above, it has excellent miscibility (compatibility) for various refrigerants, especially refrigerants with high polarity, and at the same time has high chemical resistance and abrasion resistance when used in refrigerators, resulting in excellent chemical stability. Base oil and It is necessary to develop a refrigeration oil composition comprising the same.

본 발명의 목적은 극성이 높은 냉매, 특히, 극성이 높으면서 지구 온난화 지수(GWP)가 낮은 친환경 냉매와 혼화성이 우수하고, 높은 점도를 통해 내마모성을 가질 수 있는 폴리올 에스테르를 기반으로 한 베이스 오일(base oil)을 제공하는 것이다.An object of the present invention is to provide a base oil based on a polyol ester that is excellent in miscibility with a highly polar refrigerant, in particular, an eco-friendly refrigerant having a high polarity and a low global warming potential (GWP), and can have abrasion resistance through high viscosity ( base oil).

본 발명의 다른 목적은 폴리올 에스테르를 포함하는 베이스 오일(base oil)을 함유하면서, 화학적 안정성이 뛰어난 냉동기용 냉동기유 조성물을 제공하는 것이다.Another object of the present invention is to provide a refrigeration oil composition for a refrigerator containing a base oil containing a polyol ester and having excellent chemical stability.

본 발명의 목적들은 이상에서 언급한 목적으로 제한되지 않으며, 언급되지 않은 본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있고, 본 발명의 실시예에 의해 보다 분명하게 이해될 것이다. 또한, 본 발명의 목적 및 장점들은 특허 청구범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned above can be understood by the following description and will be more clearly understood by the examples of the present invention. It will also be readily apparent that the objects and advantages of the present invention may be realized by means of the instrumentalities and combinations thereof set forth in the claims.

상기 목적을 달성하기 위하여, 본 발명의 일 양태에 따르면, 하이드록실기를 5개 이상 포함하는 다가 알코올; 탄소수 4 내지 6의 직쇄형 지방산인 제1지방산; 탄소수 4 내지 6의 분지형 지방산인 제2지방산; 및 탄소수 7 내지 10의 직쇄형 또는 분지형 지방산인 제3지방산;으로 합성되는 폴리올 에스테르를 함유하고, 지구 온난화 지수(GWP)가 0 내지 2,500인 냉매와 사용되고, 40℃에서의 동점도(KV40)가 95~105 cSt인, 폴리올 에스테르를 포함하는 베이스 오일 및 이를 포함하는 냉동기유 조성물을 제공할 수 있다.In order to achieve the above object, according to one aspect of the present invention, a polyhydric alcohol containing 5 or more hydroxyl groups; A first fatty acid that is a straight chain fatty acid having 4 to 6 carbon atoms; A second fatty acid that is a branched fatty acid having 4 to 6 carbon atoms; And a third fatty acid that is a linear or branched fatty acid having 7 to 10 carbon atoms; contains a polyol ester synthesized with, is used with a refrigerant having a global warming potential (GWP) of 0 to 2,500, and has a kinematic viscosity (KV40) at 40 ° C. 95 ~ 105 cSt, it is possible to provide a base oil containing a polyol ester and a refrigeration oil composition containing the base oil.

상기 냉매는 R32, R134a, R410A, R1234yf, R454B 및 R513A로 구성되는 군에서 선택되는 1종 이상을 포함할 수 있다.The refrigerant may include one or more selected from the group consisting of R32, R134a, R410A, R1234yf, R454B and R513A.

상기 폴리올 에스테르는 하기 측정방법 (1)에 따라 측정한 플록 포인트(floc point)가 -30℃ 이하일 수 있다. The polyol ester may have a floc point of -30°C or less as measured according to the following measurement method (1).

[측정방법 (1)] 폴리올 에스테르 및 냉매와의 총 중량 100vol%를 기준으로 할 때, 상기 냉매를 80vol% 혼합하는 것을 기준으로 하여, ASHRAE STANDARD 86에 의거하여 플록 포인트(Floc point)를 측정함.[Measurement method (1)] Floc point is measured in accordance with ASHRAE STANDARD 86, based on mixing 80 vol% of the refrigerant based on 100 vol% of the total weight of the polyol ester and the refrigerant .

상기 냉동기유 조성물은 부식 방지제 및 산포착제로 구성되는 군에서 선택되는 1종 이상의 첨가제를 더 포함할 수 있고, 40℃에서의 동점도(kinematic viscosity 40℃; KV40)가 70~90 cSt일 수 있고, 전산가(total acid number; TAN)는 0.010~0.100 mgKOH/g일 수 있다.The refrigeration oil composition may further include at least one additive selected from the group consisting of a corrosion inhibitor and a scattering agent, and may have a kinematic viscosity of 40° C. (KV40) of 70 to 90 cSt at 40° C., The total acid number (TAN) may be 0.010 to 0.100 mgKOH/g.

본 발명에 따른 폴리올 에스테르를 포함하는 베이스 오일은 지구 온난화 지수(GWP)가 낮은 친환경 극성 냉매와 혼화성이 우수하고, 높은 점도를 가질 수 있다. The base oil containing the polyol ester according to the present invention may have excellent miscibility with an eco-friendly polar refrigerant having a low global warming potential (GWP) and may have a high viscosity.

본 발명에 따른 폴리올 에스테르를 포함하는 베이스 오일을 함유하는 냉동기유 조성물은 화학적 안정성이 현저히 향상될 수 있다. The chemical stability of the refrigeration oil composition containing the base oil containing the polyol ester according to the present invention can be remarkably improved.

상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 사항을 설명하면서 함께 기술한다.In addition to the effects described above, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.

전술한 목적, 특징 및 이점은 이하에서 상세하게 설명되며, 이에 따라 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 것이다. 본 발명을 설명함에 있어서 본 발명과 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 상세한 설명을 생략한다. 후술되는 용어들은 본 발명에서의 기능 및 작용을 고려하여 기재된 용어들로서, 각 용어의 의미는 본 명세서 전반에 걸친 내용을 토대로 해석되어야 할 것이다.The above objects, features, and advantages will be described in detail below, and accordingly, those skilled in the art will be able to easily implement the technical spirit of the present invention. In describing the present invention, if it is determined that the detailed description of the known technology related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. Terms to be described later are terms described in consideration of functions and operations in the present invention, and the meaning of each term should be interpreted based on the contents throughout the present specification.

본 명세서에서 사용되는 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "구성된다", "포함한다", "함유한다" 등의 용어는 명세서 상에 기재된 여러 구성 요소들을 반드시 모두 포함하는 것으로 해석되지 않아야 하며, 그 중 일부 구성 요소들은 포함되지 않을 수도 있고, 또는 추가적인 구성 요소들을 더 포함할 수 있는 것으로 해석되어야 한다.Singular expressions used herein include plural expressions unless the context clearly dictates otherwise. In this application, terms such as "comprises," "includes," and "includes" should not be construed as necessarily including all of the various elements described in the specification, and some of them may not be included. It should be construed that there is, or may further include additional components.

이하에서는, 본 발명의 폴리올 에스테르를 포함하는 베이스 오일 및 이를 포함하는 냉동기유 조성물에 대하여 상세하게 설명한다.Hereinafter, the base oil containing the polyol ester of the present invention and the refrigeration oil composition containing the base oil will be described in detail.

폴리올 에스테르(POE)를 포함하는 베이스 오일(base oil)Base oils containing polyol esters (POEs)

본 발명에 따른 냉동기유 조성물용 베이스 오일은 폴리올 에스테르를 포함하는 것을 특징으로 하고, 상기 폴리올 에스테르는 냉동기용 냉매 중 지구 온난화 지수(GWP)가 낮고 극성이 높은 냉매와 혼화성이 매우 우수하고, 냉동기에서의 내마모성을 높이기 위해 높은 점도를 가질 수 있다.The base oil for a refrigeration oil composition according to the present invention is characterized in that it comprises a polyol ester, and the polyol ester has very good miscibility with a refrigerant having a low global warming potential (GWP) and a high polarity among refrigerants for a refrigerating machine. It may have a high viscosity to increase wear resistance in

구체적으로, 본 발명의 폴리올 에스테르는 지구 온난화 지수가 0 내지 2,500의 다양한 냉동기용 극성 냉매와 혼화성이 우수하고, 특히 지구 온난화 지수가 0 내지 750인 친환경성 냉매와의 우수한 혼화성을 가진다. 예를 들어, 상기 냉매는 냉장 시스템에서 사용 빈도가 높은 R134a, 공기조화기술 시스템에서 사용 빈도가 높은 R410A 및 친환경성 냉매인 R32로 구성되는 군에서 선택되는 1종 이상의 HFC계 냉매를 포함할 수 있으나, 반드시 이에 제한되는 것은 아니다. 예를 들어, 상기 HFC계 냉매 외에, HC계 냉매 및 HFO계 중 1종 이상의 냉매와 혼합하거나, HC계 냉매 및 HFO계 냉매 단독에도 적용할 수 있다.Specifically, the polyol ester of the present invention has excellent miscibility with various polar refrigerants for refrigerators having a global warming potential of 0 to 2,500, and particularly has excellent miscibility with eco-friendly refrigerants having a global warming potential of 0 to 750. For example, the refrigerant may include one or more HFC-based refrigerants selected from the group consisting of R134a, which is frequently used in refrigeration systems, R410A, which is frequently used in air conditioning systems, and R32, which is an environmentally friendly refrigerant. , but is not necessarily limited thereto. For example, in addition to the HFC-based refrigerant, it may be mixed with at least one refrigerant selected from among HC-based refrigerants and HFO-based refrigerants, or may be applied to HC-based refrigerants and HFO-based refrigerants alone.

상기 3가지 냉매 외에 적용 가능성이 있는 냉매의 구체적인 예로는, R1234yf (HFO계 냉매), R454B (HFC계 냉매/ HFO계 냉매의 혼합), R513A (HFC계 냉매/ HFO계 냉매의 혼합) 등을 들 수 있으나, 반드시 이에 제한되는 것은 아니다.Specific examples of refrigerants that can be applied in addition to the above three refrigerants include R1234yf (HFO-based refrigerant), R454B (HFC-based refrigerant/HFO-based refrigerant mixture), R513A (HFC-based refrigerant/HFO-based refrigerant mixture), and the like. It may be, but is not necessarily limited thereto.

상기 폴리올 에스테르는 하기 측정방법 (1)에 따라 측정한 플록 포인트(floc point)가 -30℃ 이하인 것이 바람직하며, 상기 플록 포인트의 값이 낮을수록 대상 냉매와의 혼화성이 우수한 것을 의미한다.The polyol ester preferably has a floc point of -30 ° C or less, measured according to the following measurement method (1), and the lower the floc point value, the better the miscibility with the target refrigerant.

[측정방법 (1)] 폴리올 에스테르 및 냉매와의 총 100vol%를 기준으로 할 때, 상기 냉매를 80vol% 혼합하는 것을 기준으로 하여, ASHRAE STANDARD 86에 의거하여 플록 포인트(Floc point)를 측정함.[Measurement method (1)] Floc point is measured in accordance with ASHRAE STANDARD 86, based on a mixture of 80 vol% of the refrigerant, based on a total of 100 vol% of the polyol ester and the refrigerant.

이와 같은 우수한 혼화성과 동시에, 냉동기 압축기의 마모 보호 성능 발현을 위해 높은 점도를 필요로 하는 바, 본 발명에 따른 폴리올 에스테르는 40℃에서의 동점도(kinematic viscosity 40℃; KV40)가 95~105 cSt인 것이 요구되고 있다.At the same time as such excellent miscibility, high viscosity is required for the expression of wear protection performance of refrigerator compressors, and the polyol ester according to the present invention has a kinematic viscosity of 40 ° C; something is being demanded

상기 기술적 요구를 달성하기 위하여 예의 연구한 결과, 본 발명에서는 하이드록실기를 5개 이상 포함하는 다가 알코올; 탄소수 4 내지 6의 직쇄형 지방산인 제1지방산; 탄소수 4 내지 6의 분지형 지방산인 제2지방산; 및 탄소수 7 내지 10의 직쇄형 또는 분지형 지방산인 제3지방산;으로 합성되는 폴리올 에스테르를 도출하였으며, 이를 냉동기유 조성물의 베이스 오일로서 사용하였다.As a result of intensive research to achieve the above technical requirements, in the present invention, a polyhydric alcohol containing 5 or more hydroxyl groups; A first fatty acid that is a straight chain fatty acid having 4 to 6 carbon atoms; A second fatty acid that is a branched fatty acid having 4 to 6 carbon atoms; And a third fatty acid, which is a straight-chain or branched fatty acid having 7 to 10 carbon atoms; a polyol ester synthesized from it was derived, and it was used as a base oil of a refrigeration oil composition.

폴리올 에스테르(polyol ester; POE)는 일반적으로 다가 알코올(폴리올)과 지방산을 합성하여 제조하는데, 본 발명에서는 특히 극성이 높은 냉매와도 혼화성이 우수할 것을 목적으로 한다. 따라서, 극성 냉매와의 혼화성을 높이기 위해서는 폴리올 에스테르도 극성이 높을 것이 요구되며, 이와 함께, 윤활성을 확보하기 위해 고점도로 합성되는 것도 필요하다.Polyol ester (POE) is generally prepared by synthesizing a polyhydric alcohol (polyol) and a fatty acid, and in the present invention, it is aimed to have excellent miscibility even with a highly polar refrigerant. Therefore, in order to increase miscibility with polar refrigerants, polyol esters are also required to have high polarity, and at the same time, to secure lubricity, it is also necessary to synthesize them with high viscosity.

따라서, 본 발명에서는 합성되는 폴리올 에스테르의 극성을 높이기 위하여, 바람직하게는 다가 알코올로서 하이드록실기(-OH)를 5개 이상 포함하는 것을 사용할 수 있고, 예를 들어 하이드록실기를 5개~10개 포함하는 것을 사용할 수 있으며, 예를 들어 디펜타에리스리톨(di-pentaerythritol; di-PE), 트리펜타에리스리톨(tri-pentaerythritol; tri-PE) 등을 포함할 수 있다.Therefore, in the present invention, in order to increase the polarity of the polyol ester to be synthesized, preferably, a polyhydric alcohol containing 5 or more hydroxyl groups (-OH) can be used, for example, 5 to 10 hydroxyl groups One containing dog may be used, and for example, di-pentaerythritol (di-PE), tripentaerythritol (tri-PE), and the like may be included.

또한, 본 발명에서는 지방산으로서, 탄소수 4 내지 6의 직쇄형 지방산인 제1지방산; 탄소수 4 내지 6의 분지형 지방산인 제2지방산; 및 탄소수 7 내지 10의 직쇄형 또는 분지형 지방산인 제3지방산;의 3 종류의 지방산을 혼합하여 폴리올 에스테르를 합성할 수 있다. In addition, in the present invention, as a fatty acid, a first fatty acid that is a straight-chain fatty acid having 4 to 6 carbon atoms; A second fatty acid that is a branched fatty acid having 4 to 6 carbon atoms; And a third fatty acid that is a straight-chain or branched fatty acid having 7 to 10 carbon atoms; a polyol ester may be synthesized by mixing three types of fatty acids.

상기 제1지방산 및 제2지방산처럼 탄소수 4 내지 6의 지방산은 비교적 짧은 탄소수를 가진 지방산으로서 극성의 냉매와 혼화성 확보를 위해 폴리올 에스테르의 극성을 높이는데 기여할 수 있고, 상기 제3지방산처럼 탄소수 7 내지 10의 지방산은 윤활성, 고점도를 확보하는데 기여할 수 있다.Like the first fatty acid and the second fatty acid, the fatty acid having 4 to 6 carbon atoms is a fatty acid having a relatively short carbon number, and may contribute to increasing the polarity of the polyol ester to secure miscibility with a polar refrigerant, and, like the third fatty acid, having a carbon number of 7 to 10 fatty acids can contribute to securing lubricity and high viscosity.

또한, 지방산의 탄소수(사슬의 길이)와 무관하게 분지형의 지방산은 직쇄형 지방산에 비하여 폴리올 에스테르의 극성을 높일 수 있고 다가 알코올을 보호하여 화학적 안정성 및 가수분해 안정성을 높일 수 있으나 비교적 비용이 높다는 단점과 마찰계수가 높다는 단점이 존재하므로, 직쇄형 지방산과 혼합하는 것이 바람직하다.In addition, regardless of the number of carbon atoms (chain length) of the fatty acid, branched fatty acids can increase the polarity of polyol esters compared to straight-chain fatty acids and protect polyhydric alcohols to increase chemical and hydrolytic stability, but relatively expensive. Since there are disadvantages of high friction coefficient and disadvantages, it is preferable to mix with straight-chain fatty acids.

상기와 같은 각 지방산의 특징으로 인해 본 발명에서 요구되는 폴리올 에스테르를 합성하기 위해서는, 상기 제1지방산, 제2지방산 및 제3지방산의 총 중량을 100wt%를 기준으로, 바람직하게는 상기 제1지방산 및 제2지방산을 합하여 50~80wt%를 사용할 수 있고, 상기 제3지방산은, 상기 제1지방산 및 제2지방산을 합한 함량의 이하인 20~50wt%를 사용할 수 있으나, 지방산의 구체 종류에 따라 상기 함량은 조절될 수 있다.In order to synthesize the polyol ester required in the present invention due to the characteristics of each fatty acid as described above, the total weight of the first fatty acid, the second fatty acid, and the third fatty acid is preferably based on 100 wt%. and 50 to 80 wt% of the second fatty acid may be used, and the third fatty acid may be used in an amount of 20 to 50 wt% less than the sum of the first fatty acid and the second fatty acid. Content can be adjusted.

보다 구체적으로는, 상기 제1지방산, 제2지방산의 총 중량을 100wt%로 했을 때, 바람직하게는 상기 제1지방산은 30~50wt%를 사용하고, 상기 제2지방산은 50~70wt%를 사용하여 폴리올 에스테르를 합성함으로써 본 발명에서 요구하는 폴리올 에스테르의 극성, 높은 점도, 윤활성, 내마모성 및 화학적 안정성을 모두 달성할 수 있다. 상기와 같이 제1지방산의 함량은 제2지방산의 함량의 이하이며, 지방산의 구체 종류에 따라 상기 함량은 조절될 수 있다.More specifically, when the total weight of the first fatty acid and the second fatty acid is 100 wt%, preferably, the first fatty acid is used in an amount of 30 to 50 wt% and the second fatty acid is used in an amount of 50 to 70 wt%. By synthesizing the polyol ester, it is possible to achieve all of the polarity, high viscosity, lubricity, wear resistance and chemical stability of the polyol ester required in the present invention. As described above, the content of the first fatty acid is less than that of the second fatty acid, and the content may be adjusted according to the specific type of fatty acid.

냉동기유 조성물Refrigeration Oil Composition

본 발명의 냉동기유 조성물은, 상기 폴리올 에스테르를 함유하는 베이스 오일(base oil)에 다른 첨가제를 더 혼합하여 제조된다. 예를 들어, 첨가제로서는 부식 방지제 및 산포착제로 구성되는 군에서 선택되는 1종 이상을 더 포함할 수 있고, 그 외에 마모성능 개선제, 산화방지제 등의 첨가제를 더 포함할 수 있다. The refrigeration oil composition of the present invention is prepared by further mixing other additives with the base oil containing the polyol ester. For example, the additive may further include at least one selected from the group consisting of a corrosion inhibitor and a scattering agent, and may further include additives such as a wear performance improver and an antioxidant.

본 발명에 따른 냉동기유 조성물은 40℃에서의 동점도(kinematic viscosity 40℃; KV40)가 70~90 cSt이고, 전산가(total acid number; TAN)는 0.010~0.100 mgKOH/g일 수 있다. 이때의 전산가는 총 산가로서, ASTM D664 『Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration』에 의거하여 측정한 산가를 의미한다.The refrigeration oil composition according to the present invention may have a kinematic viscosity of 40° C. (KV40) of 70 to 90 cSt and a total acid number (TAN) of 0.010 to 0.100 mgKOH/g. The total acid value at this time is the total acid value, and means the acid value measured in accordance with ASTM D664 『Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration』.

폴리올 에스테르를 함유하는 베이스 오일에 첨가제를 혼합하게 되면, 제조된 냉동기유 조성물의 점도는 다소 낮아지게 되는데, 본 발명에서는 높은 점도의 냉동기유 조성물을 제조하는 것을 목적으로 하며, 이와 동시에 충분한 윤활성도 확보하는 것이 필요하다. 이러한 관점에서, 본 발명에 따른 폴리올 에스테르를 함유하는 베이스 오일(base oil)의 40℃에서의 동점도(kinematic viscosity 40℃; KV40)는 95~105 cSt인 것이 바람직하다.When the additive is mixed with the base oil containing polyol ester, the viscosity of the prepared refrigeration oil composition is somewhat lowered. In the present invention, the object of the present invention is to prepare a high viscosity refrigeration oil composition, and at the same time, sufficient lubricity is secured. it is necessary to do From this point of view, the kinematic viscosity at 40 ° C. (KV40) of the base oil containing the polyol ester according to the present invention is preferably 95 to 105 cSt.

본 발명의 냉동기유 조성물에서, 부식 방지제는 냉동기유의 열화 및 팽창밸브의 부식을 방지하는 역할을 수행하지만, 너무 과량으로 첨가되면 냉동기유 조성물의 초기 전산가(TAN)가 과도하게 높아지는 문제점이 있을 수 있다. 이러한 관점에서, 냉동기유 조성물의 총 중량을 100wt%로 했을 때, 예를 들어 상기 부식 방지제는 0.03~0.10wt%로 포함되는 것이 바람직하고, 0.03~0.05wt%로 포함되는 것이 더욱 바람직하다.In the refrigeration oil composition of the present invention, the corrosion inhibitor serves to prevent deterioration of the refrigeration oil and corrosion of the expansion valve, but when added in an excessive amount, the initial total acid number (TAN) of the refrigeration oil composition may be excessively high. . From this point of view, when the total weight of the refrigeration oil composition is 100 wt%, for example, the corrosion inhibitor is preferably included in an amount of 0.03 to 0.10 wt%, more preferably 0.03 to 0.05 wt%.

본 발명의 냉동기유 조성물에서, 산기 산포착제는 냉매 분해에 의한 불산 등의 산을 포착하여 냉동기의 작동 안정성을 높이는 역할을 수행하지만, 너무 과량으로 첨가되면 에 따른 냉동기유 조성물을 에이징한 후 전산가(TAN)가 높아질 수 있기 때문에, 냉동기유 총 중량을 100wt%로 했을 때, 상기 산포착제는 0.50~3.00wt%로 포함하는 것이 바람직하고, 1.00wt%~2.00wt%로 포함하는 것이 더욱 바람직하다.In the refrigeration oil composition of the present invention, the acid group acid scavenger serves to increase the operational stability of the refrigerator by capturing acids such as hydrofluoric acid by decomposition of the refrigerant, but if added in an excessive amount, the total acid value after aging the refrigeration oil composition according to Since (TAN) can be high, when the total weight of refrigeration oil is 100 wt%, the scattering agent is preferably included at 0.50 to 3.00 wt%, and more preferably included at 1.00 wt% to 2.00 wt% do.

상기 부식 방지제는 본 기술분야에서 일반적으로 사용되는 것을 사용할 수 있고, 예를 들어 티아졸(thiazole)계 화합물, 트리아졸(triazole)계 화합물, 티아디아졸(thiadiazole)계 화합물 등을 사용할 수 있다. 예를 들면, 트리아졸계 화합물 중에서도, 벤조트리아졸기를 함유하는 벤조트리아졸계 화합물로서 벤조트리아졸기를 제외한 탄소수가 3~12개, 바람직하게는 탄소수 6~10개를 함유하는 화합물을 포함할 수 있으나, 이에 반드시 한정되는 것은 아니다. 구체적인 화합물의 예로는 N,N-bis(alkyl)-AR-methyl-1H-benzotriazole-1-methanamine(CAS No. 94270-86-7) 등을 포함할 수 있다.As the corrosion inhibitor, those generally used in the art may be used, and for example, a thiazole-based compound, a triazole-based compound, or a thiadiazole-based compound may be used. For example, among triazole-based compounds, benzotriazole-based compounds containing a benzotriazole group may include compounds containing 3 to 12 carbon atoms, preferably 6 to 10 carbon atoms excluding the benzotriazole group, It is not necessarily limited to this. Examples of specific compounds may include N,N-bis(alkyl)-AR-methyl-1H-benzotriazole-1-methanamine (CAS No. 94270-86-7) and the like.

상기 산포착제는 본 기술분야에서 일반적으로 사용되는 것을 사용할 수 있고, 예를 들어 에폭시계 화합물, 카르보디이미드 화합물, 글리시딜 에테르계 화합물, 테르펜계 화합물 등을 사용할 수 있다. 예를 들면, 글리시딜 에테르(glycidyl ether)계 화합물을 포함할 수 있고, 구체적으로 트리글리시딜 에테르(triglycidyl ether), 디글리시딜 에테르(diglycidyl ether), 글리시딜 에테르(glycidyl ether), 라우릴 글리시딜 에테르(lauryl glycidyl ether) 등이 있으나 반드시 이에 한정되는 것은 아니다. As the acid trapping agent, those generally used in the art may be used, and examples thereof include epoxy-based compounds, carbodiimide compounds, glycidyl ether-based compounds, and terpene-based compounds. For example, it may include a glycidyl ether-based compound, specifically triglycidyl ether, diglycidyl ether, glycidyl ether, lauryl glycidyl ether and the like, but are not necessarily limited thereto.

상기 조성물이 적용된 냉동기유 조성물은 하기 조건 (A)를 만족할 수 있다:The refrigeration oil composition to which the above composition is applied may satisfy the following condition (A):

[조건 (A)] l (TAN)f - (TAN)i l ≤ 0.03[Condition (A)] l (TAN) f - (TAN) i l ≤ 0.03

상기 (TAN)i는 냉동기유 조성물의 제조 직후 측정한 TAN값을 의미하고, 상기 (TAN)f는 ASHRAE STANDARD 97에 의거하여 냉동기유 조성물의 에이징(aging) 후 측정한 TAN값을 의미함.The (TAN) i means the TAN value measured immediately after preparation of the refrigeration oil composition, and the (TAN) f means the TAN value measured after aging the refrigeration oil composition in accordance with ASHRAE STANDARD 97.

상기 냉동기유 조성물은 상기 부식 방지제, 산포착제 외 산화방지제 및 마모성능 개선제 중 1종 이상의 첨가제를 더 포함할 수 있으나, 본 발명의 목적을 달성할 수 있다면 이에 반드시 한정되는 것은 아니다.The refrigeration oil composition may further include one or more additives selected from among the anti-corrosion agent, the acid scavenger, the antioxidant and the wear performance improver, but it is not necessarily limited thereto as long as the object of the present invention can be achieved.

본 발명에 관한 냉동기유 조성물은 상술한 냉매가 사용되는 통상 냉동기에 적용할 수 있고, 상기 냉매와 조성물의 비율은 냉동기의 종류 및 운전 조건 등에 따라 조절할 수 있다.The refrigeration oil composition according to the present invention can be applied to ordinary refrigerators using the above-mentioned refrigerant, and the ratio of the refrigerant to the composition can be adjusted according to the type of refrigerator and operating conditions.

일 구현예에 따르면, 본 발명에 관한 냉동기유 조성물은 예를 들어, 에어컨, 냉장고 또는 밀폐형 자동차 에어컨 등에 바람직하게 사용된다. 또한 본 발명에 관한 냉동기유 조성물은 제습기, 급탕기, 냉동고, 냉동 냉장 창고, 자동 판매기, 쇼케이스, 화학 플랜트 등의 냉각 장치 등에 바람직하게 사용된다. 또한 본 발명에 관한 냉동기유 조성물은 원심식의 압축기를 갖는 냉각 장치에도 바람직하게 사용될 수 있다.According to one embodiment, the refrigeration oil composition according to the present invention is preferably used, for example, in air conditioners, refrigerators, or sealed automobile air conditioners. The refrigerating machine oil composition according to the present invention is preferably used in cooling devices such as dehumidifiers, hot water heaters, freezers, cold storage warehouses, vending machines, showcases, and chemical plants. In addition, the refrigeration oil composition according to the present invention can also be suitably used in a refrigeration apparatus having a centrifugal compressor.

이하에서는, 본 발명을 실시예 및 실험예에 의해 더욱 상세하게 설명한다. 그러나, 하기의 실시예 및 실험예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예 및 실험예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following Examples and Experimental Examples are only to illustrate the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

<실시예 1 및 비교예 1~4><Example 1 and Comparative Examples 1 to 4>

하기 표 1에 따른 다가 알코올 및 지방산을 이용하여, 실시예 1 및 비교예 1~4의 폴리올 에스테르를 합성하였다.Polyol esters of Example 1 and Comparative Examples 1 to 4 were synthesized using polyhydric alcohols and fatty acids according to Table 1 below.

상기 합성된 폴리올 에스테르에 대하여 KV40 동점도를 측정하였고, 합성된 폴리올 에스테르 및 냉매를 2 : 8 (부피 기준)로 혼합하여 ASHRAE STANDARD 86에 의거하여 플록 포인트(floc point)를 측정하였으며, 이를 하기 표 1에 나타냈다. 또한, 실시예 1에 따른 폴리올 에스테르에 대해서는 하기 표 2에 기재된 다양한 냉매에 대한 플록 포인트를 각각 측정하여 나타냈다. 본 발명에서 목적하는 냉매와의 우수한 혼화성은 플록 포인트가 -30℃ 이하일 경우 만족하는 것으로 하였으며, 플록 포인트 값이 낮을수록 냉매와의 혼화성이 높은 것을 의미하는 것으로 해석하였다.KV40 kinematic viscosity was measured for the synthesized polyol ester, and the floc point was measured according to ASHRAE STANDARD 86 by mixing the synthesized polyol ester and the refrigerant at a ratio of 2: 8 (by volume), which are shown in Table 1 below. shown in In addition, for the polyol ester according to Example 1, the floc points for the various refrigerants listed in Table 2 were measured and shown. In the present invention, the excellent miscibility with the desired refrigerant was satisfied when the floc point was -30 ° C or less, and it was interpreted that the lower the floc point value, the higher the miscibility with the refrigerant.

실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 다가 알코올polyhydric alcohol di-PEdi-PE PEPE di-PEdi-PE di-PEdi-PE di-PEdi-PE 지방산
(wt%)
fatty acid
(wt%)
iso butanoic acidisobutanoic acid 3737 1919 1818 2222
normal butanoic acidnormal butanoic acid 2222 2222 2626 normal valeric acidnormal valeric acid 7777 2-ethyl hexanoic acid2-ethyl hexanoic acid 4141 6060 5252 iso nonanoic acidiso-nonanoic acid 8181 2323 실험예Experimental example KV40 (cSt)KV40 (cSt) 97.9197.91 68.4168.41 68.6868.68 108.0108.0 102.1102.1 Floc point (℃) (R32)Floc point (℃) (R32) -35.7-35.7 -10.7-10.7 -9.6-9.6 -21.7-21.7 -18.1-18.1

실시예 1Example 1 Floc point (℃) (R32)Floc point (℃) (R32) -35.7-35.7 Floc point (℃) (R410A)Floc point (℃) (R410A) -60.4-60.4 Floc point (℃) (R134a) Floc point (℃) (R134a) -59.9-59.9 Floc point (℃) (R1234yf)Floc point (℃) (R1234yf) -56.6-56.6 Floc point (℃) (R454B)Floc point (℃) (R454B) -51.6-51.6 Floc point (℃) (R513A)Floc point (℃) (R513A) -56.4-56.4

<실시예 A~B 및 비교예 A~C><Examples A to B and Comparative Examples A to C>

상기 실시예 1에서 제조된 폴리올 에스테르에 부식 방지제 및 산포착제를 혼합하여 냉동기유 조성물을 제조하였으며, 이 때 하기 표 3에 기재된 대로 부식 방지제, 산포착제의 종류 및 함량을 달리 혼합하여 실시예 A~B 및 비교예 A~C의 냉동기유 조성물을 제조하였다.A refrigeration oil composition was prepared by mixing the polyol ester prepared in Example 1 with a corrosion inhibitor and a acid trapping agent. Refrigeration oil compositions of A to B and Comparative Examples A to C were prepared.

상기 제조된 냉동기유 조성물(New Oil)에 대하여 최초 KV40 및 최초 TAN 값을 측정하였고, ASHRAE STANDARD 97에 의거하여 친환경 냉매인 R32 냉매 환경에서 냉동기유의 에이징 후의 냉동기유 조성물(Aged Oil)의 KV40 및 TAN 값을 측정하였다. 에이징 전 및 후의 TAN 값의 변화량을 계산하여 하기 표 3에 나타냈다.The initial KV40 and initial TAN values were measured for the refrigeration oil composition (New Oil) prepared above, and KV40 and TAN of the refrigeration oil composition (Aged Oil) after aging of the refrigeration oil in the R32 refrigerant environment, which is an eco-friendly refrigerant, in accordance with ASHRAE STANDARD 97 values were measured. Changes in TAN values before and after aging were calculated and shown in Table 3 below.

하기 표 3에서, 반제품은 상기 실시예 1에서 제조된 폴리올 에스테르에 산화방지제 및 마모성능 개선제를 동일한 중량비로 배합하여 제조하였다. 상기 부식방지제는 N,N-bis(2-ethylhexyl)-AR-methyl-1H-benzotriazole-1-methanamine이고, 상기 '산포착제 1'은 Lauryl glycidyl ether이고, '산포착제 2'는 Butyl glycidyl ether이고, '산포착제 3'은 Trimethylolpropane triglycidyl ether이다.In Table 3 below, semi-finished products were prepared by mixing the polyol ester prepared in Example 1 with an antioxidant and a wear performance improver in equal weight ratios. The corrosion inhibitor is N,N-bis(2-ethylhexyl)-AR-methyl-1H-benzotriazole-1-methanamine, the 'dispersion scavenger 1' is Lauryl glycidyl ether, and the 'dispersion scavenger 2' is Butyl glycidyl ether, and 'Scatter 3' is Trimethylolpropane triglycidyl ether.

R32 냉매와 사용함Used with R32 refrigerant 실시예 AExample A 실시예 BExample B 비교예 AComparative Example A 비교예 BComparative Example B 비교예 CComparative Example C 반제품 (wt%)Semi-finished product (wt%) 97.9797.97 97.9797.97 99.0099.00 98.0098.00 99.0099.00 부식 방지제 (wt%)Corrosion inhibitor (wt%) 0.030.03 0.030.03 산포착제scattering agent 산포착제 1 (wt%)Scattering agent 1 (wt%) 2.002.00 1.001.00 1.001.00 2.002.00 산포착제 2 (wt%)Diffusion agent 2 (wt%) 1.001.00 산포착제 3 (wt%)Scattering agent 3 (wt%) 1.001.00 TotalTotal 100.00100.00 100.00100.00 100.00100.00 100.00100.00 100.00100.00 실험예Experimental example New OilNew Oil KV40 (cSt)KV40 (cSt) 83.1583.15 86.8686.86 88.8888.88 83.3683.36 92.6092.60 TAN (mgKOH/g)TAN (mgKOH/g) 0.0560.056 0.0460.046 0.0080.008 0.0160.016 0.0090.009 Aged OilAged Oil TAN (mgKOH/g)TAN (mgKOH/g) 0.0470.047 0.0490.049 0.0650.065 0.0580.058 0.0640.064 TAN Change (mgKOH/g)TAN Change (mgKOH/g) -0.009-0.009 +0.003+0.003 +0.057+0.057 +0.042+0.042 +0.055+0.055

상기 표 3에서 알 수 있는 것처럼, 본 발명에 따라 부식방지제 및 산 포착제를 일정 비율로 혼합하여 제조된 실시예 A~B의 냉동기유 조성물이, 그렇지 않은 비교예 A~C의 냉동기유 조성물에 비하여, 본 발명에서 목적하는 동점도 및 전산가(TAN) 값을 나타내면서도, 에이징 후에도 전산가 변화량이 낮아 우수한 화학적 안정성을 갖는 것을 알 수 있었다.As can be seen from Table 3, the refrigeration oil compositions of Examples A to B prepared by mixing the corrosion inhibitor and the acid scavenger at a certain ratio according to the present invention were compared to the refrigeration oil compositions of Comparative Examples A to C. In contrast, it was found that, while showing the kinematic viscosity and total acid number (TAN) values desired in the present invention, the change in total acid value was low even after aging, and it had excellent chemical stability.

이상 본 명세서의 실시예를 더욱 상세하게 설명하였으나, 본 명세서는 반드시 이러한 실시예로 국한되는 것은 아니며, 본 명세서의 기술 사상을 벗어나지 않는 범위 내에서 다양하게 변형 실시될 수 있다. 따라서 본 명세서에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 그러므로, 이상에서 기술한 실시예는 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 본 명세서 및 본 발명의 보호 범위는 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 명세서 및 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.Although the embodiments of the present specification have been described in more detail above, the present specification is not necessarily limited to these embodiments, and may be variously modified and implemented without departing from the spirit of the present specification. Therefore, the embodiments disclosed herein are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The protection scope of this specification and the present invention should be construed by the claims, and all technical ideas within the equivalent range should be construed as being included in the scope of this specification and the present invention.

Claims (14)

하이드록실기를 5개 이상 포함하는 다가 알코올;
탄소수 4 내지 6의 직쇄형 지방산인 제1지방산;
탄소수 4 내지 6의 분지형 지방산인 제2지방산; 및
탄소수 7 내지 10의 직쇄형 또는 분지형 지방산인 제3지방산;으로 합성되는 폴리올 에스테르(polyol ester)를 포함하는 베이스 오일(base oil)을 포함하고,
지구 온난화 지수(GWP)가 0 내지 2,500인 냉매와 사용되고, 40℃에서의 동점도(KV40)가 70~90 cSt이고,
상기 폴리올 에스테르는 하기 측정방법 (1)에 따라 측정한 플록 포인트(floc point)가 -30℃ 이하인, 냉동기유 조성물.
[측정방법 (1)] 폴리올 에스테르 및 냉매와의 총 중량 100vol%를 기준으로 할 때, 상기 냉매를 80vol% 혼합하는 것을 기준으로 하여, ASHRAE STANDARD 86에 의거하여 플록 포인트(Floc point)를 측정함.
Polyhydric alcohol containing 5 or more hydroxyl groups;
A first fatty acid that is a straight chain fatty acid having 4 to 6 carbon atoms;
A second fatty acid that is a branched fatty acid having 4 to 6 carbon atoms; and
A third fatty acid, which is a linear or branched fatty acid having 7 to 10 carbon atoms; a base oil containing a polyol ester synthesized with
Used with refrigerants having a global warming potential (GWP) of 0 to 2,500, and a kinematic viscosity (KV40) at 40 ° C of 70 to 90 cSt,
The polyol ester has a floc point measured according to the following measurement method (1) of -30 ° C or less, a refrigeration oil composition.
[Measurement method (1)] Floc point is measured in accordance with ASHRAE STANDARD 86, based on mixing 80 vol% of the refrigerant based on 100 vol% of the total weight of the polyol ester and the refrigerant .
제1항에 있어서,
상기 냉매는 R32, R410A, R134a, R1234yf, R454B 및 R513A로 구성되는 군에서 선택되는 1종 이상을 포함하는,
냉동기유 조성물.
According to claim 1,
The refrigerant comprises at least one selected from the group consisting of R32, R410A, R134a, R1234yf, R454B and R513A,
Refrigeration oil composition.
제1항에 있어서,
상기 폴리올 에스테르는 40℃에서의 동점도(KV40) 값이 95~105 cSt인,
냉동기유 조성물.
According to claim 1,
The polyol ester has a kinematic viscosity (KV40) value of 95 to 105 cSt at 40 ° C.
Refrigeration oil composition.
삭제delete 제1항에 있어서,
상기 폴리올 에스테르는, 상기 제1지방산, 제2지방산 및 제3지방산의 총 중량을 100 wt%를 기준으로, 상기 제1지방산 및 제2지방산을 합하여 50~80 wt%를 사용하고, 상기 제3지방산은 20~50 wt%를 사용하여 합성되는 것인,
냉동기유 조성물.
According to claim 1,
The polyol ester uses 50 to 80 wt% of the total weight of the first fatty acid, the second fatty acid, and the third fatty acid based on 100 wt% of the total weight of the first fatty acid and the second fatty acid, and the third fatty acid Fatty acid is synthesized using 20 ~ 50 wt%,
Refrigeration oil composition.
제5항에 있어서,
상기 제1지방산 및 제2지방산의 총 중량을 100 wt%로 했을 때, 상기 제1지방산은 30~50 wt%를 사용하고, 상기 제2지방산은 50~70 wt%를 사용하는 것인,
냉동기유 조성물.
According to claim 5,
When the total weight of the first fatty acid and the second fatty acid is 100 wt%, 30 to 50 wt% of the first fatty acid and 50 to 70 wt% of the second fatty acid are used,
Refrigeration oil composition.
제1항에 있어서,
상기 다가 알코올은 디펜타에리스리톨을 포함하는,
냉동기유 조성물.
According to claim 1,
The polyhydric alcohol includes dipentaerythritol,
Refrigeration oil composition.
제1항에 있어서,
부식 방지제 및 산포착제로 구성되는 군에서 선택되는 1종 이상의 첨가제를 더 포함하고,
40℃에서의 동점도(KV40)가 70~90 cSt이고,
전산가(total acid number; TAN)가 0.010~0.100 mgKOH/g인,
냉동기유 조성물.
According to claim 1,
Further comprising one or more additives selected from the group consisting of corrosion inhibitors and acid trapping agents,
Kinematic viscosity (KV40) at 40 ℃ is 70 ~ 90 cSt,
Total acid number (total acid number; TAN) is 0.010 ~ 0.100 mgKOH / g,
Refrigeration oil composition.
제8항에 있어서,
상기 냉동기유 조성물 총 중량을 100 wt%로 했을 때,
상기 부식 방지제는 0.05~0.10 wt%로 포함하고,
상기 산포착제는 0.50~3.00 wt%로 포함하는,
냉동기유 조성물.
According to claim 8,
When the total weight of the refrigeration oil composition is 100 wt%,
The corrosion inhibitor contains 0.05 ~ 0.10 wt%,
The scattering agent contains 0.50 to 3.00 wt%,
Refrigeration oil composition.
제8항에 있어서,
상기 부식 방지제는 벤조트리아졸(benzotriazole)계 화합물을 포함하는,
냉동기유 조성물.
According to claim 8,
The corrosion inhibitor includes a benzotriazole-based compound,
Refrigeration oil composition.
제8항에 있어서,
상기 산포착제는 글리시딜 에테르(glycidyl ether)계 화합물을 포함하는,
냉동기유 조성물.
According to claim 8,
The acid scavenger includes a glycidyl ether-based compound,
Refrigeration oil composition.
제8항에 있어서,
하기 조건 (A)를 만족하는, 냉동기유 조성물:
[조건 (A)] l (TAN)f - (TAN)i l ≤ 0.03
상기 (TAN)i는 냉동기유 조성물의 제조 직후 측정한 TAN 값을 의미하고, 상기 (TAN)f는 ASHRAE STANDARD 97에 의거하여 냉동기유 조성물의 에이징 후 측정한 TAN값을 의미함.
According to claim 8,
A refrigeration oil composition that satisfies the following condition (A):
[Condition (A)] l (TAN) f - (TAN) i l ≤ 0.03
The (TAN) i means the TAN value measured immediately after preparation of the refrigeration oil composition, and the (TAN) f means the TAN value measured after aging the refrigeration oil composition in accordance with ASHRAE STANDARD 97.
제7항에 있어서,
산화방지제 및 마모성능 개선제 중 1종 이상의 첨가제를 더 포함하는,
냉동기유 조성물.
According to claim 7,
Further comprising at least one additive of an antioxidant and a wear performance improver,
Refrigeration oil composition.
제1항에 있어서,
에어컨, 냉장고 및 자동차 에어컨으로 구성된 군에서 선택되는 1종 이상의 제품에 사용되는 것인,
냉동기유 조성물.
According to claim 1,
Used for one or more products selected from the group consisting of air conditioners, refrigerators and automobile air conditioners,
Refrigeration oil composition.
KR1020220131570A 2022-10-13 2022-10-13 Base oil comprising polyol ester and refrigerating machine oil composition comprising the same KR102548607B1 (en)

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