KR19990067513A - 냉동기오일, 냉동기작동유체, 및, 냉동시스템의 윤활방법 - Google Patents

냉동기오일, 냉동기작동유체, 및, 냉동시스템의 윤활방법 Download PDF

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KR19990067513A
KR19990067513A KR1019980703535A KR19980703535A KR19990067513A KR 19990067513 A KR19990067513 A KR 19990067513A KR 1019980703535 A KR1019980703535 A KR 1019980703535A KR 19980703535 A KR19980703535 A KR 19980703535A KR 19990067513 A KR19990067513 A KR 19990067513A
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South Korea
Prior art keywords
oil
polyhydric alcohol
refrigeration
refrigerant
alcohol ester
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KR1019980703535A
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English (en)
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다카시 가이마이
히토시 다카하시
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노미야마 아키히코
가부시키가이샤 쟈판 에나지
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Publication of KR19990067513A publication Critical patent/KR19990067513A/ko

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    • C10M171/00—Lubricating 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
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    • C10M105/44—Complex 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 derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
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    • C10N2040/50—Medical uses

Abstract

본 발명은, 냉동시스템 내에 잔류한 가공오일에 기인하는 석출을 억제할 수 있는 냉동기오일, 냉동기작동유체, 또, 냉동시스템의 윤활방법을 제공한다.
그리고, 상기 냉동기오일은, 다가알코올에스테르화합물을 윤활유기초오일로 하고, 적어도 1종의 폴리옥시알킬렌화합물을 0.5∼4.5중량% 포함한다. 상기 냉동기작동유체는, 상기 냉동기오일과 하이드로플루오로카본냉매를 포함한다. 또한, 상기 윤활방법은, 다가알코올에스테르화합물 또는 플루오로카본냉매에 용해되기 어려운 성분을 포함한 금속가공오일, 혹은, 다가알코올에스테르화합물 또는 하이드로플루오로카본냉매와 반응성이 높은 성분을 포함한 금속가공오일이 계내에 잔류한 냉동시스템의 윤활에 있어서, 상기 냉동기작동유체를 사용하는 것이다. 본 발명에 의해 냉동시스템 내의, 특히 계내의 세관내에서의 석출물 발생을 억제할 수 있다.

Description

냉동기오일, 냉동기작동유체, 및, 냉동시스템의 윤활방법
냉매압축기는, 냉장고, 카 에어콘, 산업용냉동기, 룸 에어콘 등의 냉동시스템에 사용되고 있고, 그 냉매로서 하이드로플루오로카본냉매(비염소계, 즉, 염소를 포함하지 않고 수소의 적어도 일부분이 불소로 치환된 수소-불소탄화수소, 이하, HFC냉매라고 한다)가 주목받고 있다. HFC냉매로서, R134a, R125, R32, R143a, R152a 등의 단독 또는 R407C, R410A 등의 혼합물이 제안되어 있다. 하이드로플루오로카본냉매와 함께 사용되는 냉동기오일의 기초오일로서는, 다가(多價)알코올에스테르화합물이 뛰어난 특성을 가진 것이 알려져 있다.
냉동시스템은, 냉매압축기, 콘덴서, 팽창기구(팽창밸브, 모세관 등), 증발기 등이 직렬로 접속된 계(系)로 이루어진다. 이들 각 기기의 부품의 제조나 시스템의 조립 등을 위해서는 여러가지의 금속가공오일이 사용되고, 조립된 냉동시스템의 계내에는 이들 금속가공오일이 잔류하고 있다. 금속가공오일은, 디스루피드 등의 유황계 극압제나, 인산에스테르 등의 인계 극압제 등의 첨가제를 포함하고 있다.
〔발명의 개시〕
유황계나 인계의 극압제를 포함하는 금속가공오일은, 하이드로플루오로카본냉매에 용해되기 어렵다. 또한, 이 금속가공오일은, 다가알코올에스테르화합물 또는 하이드로플루오로카본냉매와 반응성이 높은 성분을 포함하고 있는 경우도 있다. 이 때문에, 유황계 극압제나 인계 극압제 등이 용해되기 어려운 금속가공오일의 첨가제 성분이나, 냉동기오일 등의 반응생성물이, 냉동시스템의 계내의 일부분에 석출하기도 한다. 이러한 석출물은, 냉동시스템의 운전과 함께, 계내의 모세관 등 세관의 관벽에 축적하고, 냉매의 유량저하 및 차압상승을 일으켜 효율을 저하시켜서, 충분한 특성을 얻을 수 없게 되는 경우도 있다.
본 발명은, 상기 문제를 해결하는 것으로, 본 발명의 목적은, 냉동기오일의 기초오일로서 다가알코올에스테르화합물을 사용한 경우, 잔류한 금속가공오일에 기인하는 계내의, 특히 세관부에서의 석출을 억제할 수 있는 냉동기오일, 냉동기작동유체, 또한, 냉동시스템의 윤활방법을 제공하는 것이다.
본 발명자는, 상기 과제를 해결하기 위해, 예의 연구를 진행시킨 결과, 기초오일로서는 다가알코올에스테르화합물을 사용하고, 특정한 폴리옥시알킬렌화합물을 첨가함으로써, 계내의 석출을 억제할 수 있는 것을 발견하여, 본 발명에 생각이 이르렀다.
즉, 본 발명에 의한 냉동기오일은, 다가알코올에스테르화합물을 윤활유 기초오일로 하고, 다음식 (1)에서 나타내는 적어도 1종의 폴리옥시알킬렌화합물을 0.5∼4.5중량% 포함하는 것이다.
R1-O-(R2-O-)n-R3(1)
(여기서, R1은 탄소수 1∼8의 알킬기, R2는 탄소수 1∼4의 알킬렌기, R3는 수소 또는 탄소수 1∼8의 알킬기이고, n은 중합도를 나타내는 수이다.) 본 발명에 의한 냉동기작동유체는, 상기 냉동기오일과 하이드로플루오로카본냉매를 포함하는 것이다. 또한, 본 발명에 의한 냉동시스템의 윤활방법은, 다가알코올에스테르화합물 또는 하이드로플루오로카본냉매에 용해되기 어려운 성분을 포함한 금속가공오일, 또는, 다가알코올에스테르화합물 또는 하이드로플루오로카본냉매와 반응성이 높은 성분을 포함한 금속가공오일이 계내에 잔류한 냉동시스템의 윤활에 있어서, 상기 냉동기작동유체를 사용하는 것이다.
본 발명은, 가정용 냉장고 등의 냉매압축기에 사용되는 냉동기오일에 관하며, 특히, 하이드로플루오로카본냉매를 사용한 냉매압축기용으로서 유용한 냉동기오일, 냉동기작동유체, 또, 그것을 사용한 윤활방법에 관한 것이다.
도 1은, 기초오일에 첨가하는 PAG (폴리옥시알킬렌화합물)의 첨가량을 변화시킨 경우의 전기절연성의 측정결과를 나타낸 도면이다.
〔발명을 실시하기 위한 최량의 형태〕
[다가알코올에스테르화합물]
본 발명에 사용되는 다가알코올에스테르화합물로서는, 수산기수 2∼6의 다가알코올과 지방산으로 얻어지는 다가알코올에스테르를 사용할 수 있다. 이들 다가알코올에스테르로부터 열안정성, 가수분해안정성, 내금속부식성에 뛰어난 조성을 적절히 선택할 수 있다. 특히, 5개의 탄소의 네오형 골격을 가진 다가알코올과 1가포화지방산 혹은 1가포화지방산과 2가포화지방산의 혼합물과의 반응으로 얻어지는 중성 에스테르가 특히 바람직하다. 에스테르의 산치는, 0.lmgKOH/g, 특히 0.02 mgKOH/g 이하가 바람직하다.
다가알코올로서는, 네오펜틸글리콜, 트리메티롤프로판, 펜타에리트리톨, 디펜타에리트리톨 등을 사용할 수 있고, 2가 또는 4가의 다가알코올이 바람직하게 사용된다. 특히, HFC 냉매에 대한 용해성이 양호하고, 적절히 점도를 조정할 수 있는 네오펜틸글리콜에스테르와 펜타에리트리톨에스테르와의 혼합물이 바람직하다.
1가포화지방산으로서는, 탄소수 5∼8의 직쇄 1가포화지방산, 탄소수 5∼9의 비네오형 분기 1가포화지방산, 또는, 탄소수 5∼9의 비네오형 분기 1가포화지방산과 탄소수 5∼8의 직쇄 1가포화지방산의 혼합물 등을 바람직하게 사용할 수 있고, 분기 1가포화지방산은 α 위치 혹은 β 위치의 탄소에 메틸 혹은 에틸기가 분기한 것이 바람직하다. 또, 탄소수가 1∼4의 지방산으로부터 얻어진 다가알코올에스테르는 윤활성, 내가수분해성, 내금속부식성에 난점이 있다. 이와 같은 분기 1가포화지방산으로서, 구체적으로는 2-메틸펜탄산, 2-에틸펜탄산, 2-메틸헥산산, 2-에틸헥산산, 2-메틸헵탄산, 2-에틸헵탄산, 3,5,5-트리메틸헥산산이, 또한, 직쇄 1가포화지방산으로서는 n-펜탄산, n-헥산산, n-헵탄산, n-옥탄산이 예시된다. 또한, 2가포화지방산으로서, 호박산, 글루타릭산, 아디핀산, 피멜릭산 등을 l가포화지방산과 병용하여, 비교적 점도가 높은 합성에스테르의 윤활유기초오일을 얻을 수도 있다.
[폴리옥시알킬렌화합물]
본 발명에서 사용되는 폴리옥시알킬렌화합물은, 식 (1)의 구조를 가진 것이다.
R1-O-(R2-O-)n-R3(1)
R1는 탄소수 1∼8의 알킬기이고, 메틸기, 에틸기, 부틸기가 바람직하다. R2는 탄소수 l∼4의 알킬렌기이며, 메틸렌기, 에틸렌기, 프로필렌기 및 부틸렌기를 들 수 있다. 따라서, -R2-O-로서는 옥시메틸렌기, 옥시에틸렌기, 옥시프로필렌기 및 옥시부틸렌기의 옥시알킬렌기를 들 수 있고, -(R2-O-)n으로서는 이들이 단독중합체여도 상기 옥시알킬렌기가 2종 이상 중합한 공중합체여도 된다. 공중합체인 경우, 블록(block)공중합체라도 랜덤(random)공중합체라도 좋다. 중합체부분은 옥시프로필렌기 또는 이것이 포함되어 있는 것이 바람직하고, 특히 옥시에틸렌기와 옥시프로필렌기의 공중합체가 바람직하다. 이 공중합체는, 블록공중합체라도 랜덤공중합체라도 되지만 블록공중합체가 특히 바람직하고, 옥시프로필렌기의 비율이 50%이상, 특히 70%이상인 것이 바람직하다. R3은 수소 또는 탄소수 1∼8의 알킬기이고, 특히 수소, 즉, 말단이 수산기인 것이 바람직하다. n 은 중합도를 나타내는 수이다. 상기의 폴리옥시알킬렌화합물은, 분자량이 크면 용해성이 감소하는 경향이 있고, 또 작으면 증발하기 쉽게 되므로, n 은 분자량이 300∼3,000에 상당하는 수인 것이 바람직하다. 보다 바람직하게는 300∼1,500, 더는 300∼1,200에 상당하는 수이다.
폴리옥시알킬렌화합물은, 냉동기오일의 중량에 대하여 0.5∼4.5중량% 첨가한다. 첨가량이 적으면, 계내에서의 금속가공오일의 첨가제 등에 기인한 석출을 충분히 억제할 수 없다. 1중량% 이상 첨가하는 것이 보다 바람직하다.
한편, 4.5중량%를 넘어 많이 첨가해도 그 첨가량에 알맞는 석출억제효과를 얻을 수 없으므로, 비경제적이다. 보다 바람직하게는 3.5중량% 이하 첨가한다.
또한, 가정용 냉장고와 같은 밀폐형냉동기는, 압축기와 모터가 일체화되어 있으므로, 사용하는 냉동기오일의 전기절연성은 큰 쪽이 바람직하다. 폴리옥시알킬렌화합물을 첨가하면 전기절연성이 저하한다. 특히 폴리옥시알킬렌화합물이 공중합체로 되는 경우, 옥시알킬렌기 중에 차지하는 옥시에틸렌기의 비율이 많을수록 전기절연성은 저하하는 경향이 있고, 또한 이 경향은 폴리옥시알킬렌화합물의 분자량이 작아질수록 조장된다. 이 점으로 부터도 첨가량은, 4.5중량% 이하가 바람직하고, 또한, 냉동기오일의 전기절연성으로서 1012∼ 1013Ωcm이상, 보다 바람직하게는 1013Ωcm 이상의 부피저항율을 얻을 수 있도록, 상기 첨가량의 범위내에서, 조정하는 것이 보다 바람직하다.
[하이드로플루오로카본냉매]
본 발명에 사용되는 하이드로플루오로카본냉매는, 1,1,1,2-테트라플루오로에탄(R134a), 펜타플루오로에탄(R125), 디플루오로메탄(R32), 1,1,1-트릴플루오로에탄(R143a), 1,1-디플루오로에탄(R152a) 등의 탄소수 1∼2의 탄화수소의 수소를 불소로 치환한 하이드로플루오로카본냉매이다. R407C, R410A 등의 혼합냉매라도 좋다.
[냉동기오일]
본 발명의 냉동기오일의 점도는 적절히 조정하면 되며, 통상, 40℃점도로 5∼500 cSt이고, 특히, 냉장고용으로서는 40℃점도가 8∼32 cSt, 룸 에어콘용이나 산업용으로서는 40℃점도가 25∼100 cSt, 카 에어콘용으로서는 100℃점도가 8∼30 cSt가 사용된다.
다른 첨가제로서, 내마모제로서 트리아릴포스페이트, 트리알킬포스페이트 등의 포스페이트화합물, 금속불활성화제로서 벤조트리아졸 유도체 혹은 알케닐호박산에스테르, 산화방지제로서 DBPC(2, 6-디타샤리-부틸-p-크레졸) 혹은 p, p'-디옥틸디페닐아민, HFC냉매의 안정화제로서 2-에틸헥실구리시딜 에테르, 세콘다리부틸페닐그리딜에테르, 탄소수 5∼10의 아실기를 함유하는 모노글리시딜에테르 등의 엑폭시화합물 등 공지의 첨가제를 필요에 따라 배합할 수도 있다.
[냉동기작동유체]
본 발명에 의한 냉동기작동유체는, 상기 냉동기오일과 냉매를 혼합한 것이며, 냉동기오일과 냉매의 혼합비는, 중량비로 통상 10:90∼90:10이고, 특히 20:80 ∼80:20 이 바람직하다.
또, 냉매로서는, 염소를 포함하지 않은 HFC 냉매의 사용이 바람직하지만, 클로로플루오로카본(염소-불소계탄화수소), 하이드로클로로플루오로카본(염소-불소탄화수소), 암모니아냉매, 탄화수소계 냉매 등을 이용할 수도 있다.
이하, 실시예에 따라 본 발명을 구체적으로 설명하나, 본 발명은 이들의 실시예에만 한정되는 것은 아니다. 실시예 및 비교예로서 공시오일을 조제하여, 평가를 한다.
이들 공시오일의 윤활유기초오일은, 펜타에리트리톨과 탄소수 8과 9의 분기포화지방산의 반응으로 얻어지는 에스테르이고, 40℃ 점도가 68 cSt 이다. 이 기초오일에 다음의 폴리옥시알킬렌화합물인 PAG 1∼4를, 표 1의 비율로 첨가한 것, 또는, 첨가하지 않은 것을 공시오일 1∼6으로 한다.
PAG 1은, CH3-O-(PO)m(EO)n-H의 구조를 갖는 화합물이고, PO는 옥시프로필렌기, EO는 옥시에틸렌기를 나타내며, 중합도를 나타내는 m, n은 m:n= 8:2이고, 평균분자량은 약1000이다.
PAG 2는, C4H3-O-(PO)m(EO)n-H의 구조를 갖는 화합물이고, PO는 옥시프로필렌기, EO는 옥시에틸렌기를 나타내며, 중합도를 나타내는 m, n은 m:n= 5:5이고, 평균분자량은 약500이다.
PAG 3은, CH3-O-(PO)m(EO)n-CH3의 구조를 갖는 화합물이고, PO는 옥시프로필렌기, EO는 옥시에틸렌기를 나타내며, 중합도를 나타내는 m, n은 m:n= 8:2이고, 평균분자량은 약1000이다.
PAG 4는, CH3-O-(BO)m(PO)n-CH3의 구조를 갖는 화합물이고, BO는 옥시부틸렌기, PO는 옥시프로필렌기를 나타내며, 중합도를 나타내는 m, n은 m:n= 5:5이고, 평균분자량은 약1000이다.
가공오일의 석출에 의한 냉동시스템 계내의 오염을 실기로 평가하였다. 평가에는, 이하의 냉장고용 냉동시스템을 사용하였다. 냉매압축기에 의해 냉매와 냉동기오일의 혼합물은 압축되고, 응축기로 냉각되어 액화된다. 그 후, 모세관(내경 0.6 mm, 길이1 m, 동제)을 통해 증발기에 유도되어 감압기화하고, 증발기를 통해 열교환이 행하여진다. 기화한 냉매, 냉동기오일은, 그대로 압축기로 복귀된다.
200W의 냉매압축기를 사용하여, 냉매(R407C; 즉, R32:R125:R134a를 중량비 23:25:52로 혼합한 것) 65g, 공시오일(냉동기오일) 250 ml, 및, 냉장고의 제조에 사용되는 복수의 가공오일을 혼합한 것을 공시오일에 대하여 2중량%을 봉입하고, 기화온도 -20℃∼-25℃로 200시간 운전하였다. 그 후, 모세관 내의 석출물의 양을 평가하였다. 전면에 두텁게 석출한 것을 평점 5로 하고, 석출이 적을수록 평점을 적게 하며, 석출이 없는 것을 평점 0으로 하였다. 평점 1∼4은, 다음의 기준으로 행하였다.
평점 1 : 석출물이 점재한다.
평점 2 : 점재하는 석출물이 일부 연결되어 있다.
평점 3 : 점재하는 석출물이 거의 전부 연결되어 있다.
평점 4 : 석출물이 전면을 엷게 덮고 있다.
그 결과를 표 1에 나타낸다.
공시오일1 공시오일2 공시오일3 공시오일4 공시오일5 공시오일6
첨가제 PAG 1 PAG 1 PAG 2 PAG 3 PAG 4
첨가량 (중량% 4 2 2 4 4 없음
석출의 평점 0 0 0 1 1 5
기초오일에 첨가하는 PAG 1∼PAG 3의 양을 변화시킨 경우의 전기절연성을 평가하여, 결과를 도 1에 나타낸다. PAG의 첨가량이 많아짐에 따라서, 전기절연성은 저하한다. PAG 1 및 PAG 3은, 4.5중량% 이하의 첨가량으로, 실용적인 전기절연성(부피저항율1013Ωcm이상)을 얻을 수 있는 것을 알 수 있다. 또한, 옥시에틸렌기의 비율이 많고(m:n= 50:50), 분자량이 작은 (500) PAG 2는, 약 1중량% 이하의 첨가량으로, 실용적인 전기절연성(부피저항율1013Ωcm이상)을 얻을 수 있는 것을 알 수 있다.
〔산업상의 이용가능성〕
본 발명은, 다가알코올에스테르화합물을 윤활유기초오일로 하여, 특정한 폴리옥시알킬렌화합물을 소정량 함유하는 것이다. 냉동시스템 내에 잔류한 가공오일에 기인하는 계내의 석출을 억제할 수 있고, 냉동시스템의 효율을 저하시키는 등의 문제를 발생시키지 않는다. 특히, 하이드로플루오로카본냉매 등의 냉매의 압축기의 이용에 적합한 것이다.

Claims (3)

  1. 다가 알코올에스테르화합물을 윤활유기초오일로 하고,
    다음 식(1)으로 표시되는 적어도 1종의 폴리옥시알킬렌화합물을 0.5∼4.5중량% 포함하는 냉동기오일.
    R1-O-(R2-O-)n-R3(1)
    (여기서, R1은 탄소수1∼8의 알킬기, R2는 탄소수 1∼4의 알킬렌기, R3은 수소 또는 탄소수 1∼8의 알킬기이고, n 은 중합도를 나타내는 수이다.)
  2. 제 1 항에 기재된 냉동기오일과 하이드로플루오로카본냉매를 포함하는 냉동기작동유체.
  3. 상기 다가알코올에스테르화합물 또는 상기 하이드로플루오로카본냉매에 용해되기 어려운 성분을 포함한 금속가공오일, 또는, 상기 다가알코올에스테르화합물 또는 상기 하이드로플루오로카본냉매와 반응성이 높은 성분을 포함한 금속가공오일이 계내에 잔류한 냉동시스템의 윤활에 있어서, 제 2 항에 기재된 냉동기작동유체를 사용하는 냉동 시스템의 윤활방법.
KR1019980703535A 1996-09-12 1997-09-08 냉동기오일, 냉동기작동유체, 및, 냉동시스템의 윤활방법 KR19990067513A (ko)

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