KR100339777B1 - 윤활제조성물 - Google Patents

윤활제조성물 Download PDF

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KR100339777B1
KR100339777B1 KR1019960705962A KR19960705962A KR100339777B1 KR 100339777 B1 KR100339777 B1 KR 100339777B1 KR 1019960705962 A KR1019960705962 A KR 1019960705962A KR 19960705962 A KR19960705962 A KR 19960705962A KR 100339777 B1 KR100339777 B1 KR 100339777B1
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조나단 막슨 앤드류
윌리엄 안토니 프라그넬 존
안토니 에드워즈 마크
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캐스트롤 리미티드
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Abstract

헬레콥터 변속용 윤활제로서 적합한 윤활제 조성물은 100℃의 온도에서 5.0에서 10.0cSt 범위인 점도를 갖는 합성의 기본 원료, 산화방지성분, 중성 유기인산염성분, 디카복실산성분, 모노카복실산성분, 트리아졸성분 그리고 극단 압력첨가제를 함유하는 인 등으로써 구성되어져 있다.

Description

윤활제 조성물
본 발명은 윤활제 조성물에 관한 것이며, 특히 예를 들면 헬리콥터 변속 시스템에 적합한 변속 윤활제에 관한 것이다.
예를 들면 헬리콥터를 위한 새로운 변속 시스템의 개발은 필요한 로드 캐링(load carrying) 및 부식 보호 기준을 만족시킬 수 있는 이러한 목적을 위해 공헌하는 윤활제을 위한 요구 조건이 발생되었다. 예를 들면, 영국 국방성 및 미합중국 해군에 의해 추천된 규격은 현존하는 항공 터빈 엔진 윤활제로 충족될 수 없는 새롭게 공헌하는 헬리콥터 변속 윤활제에 부합되는 요구 조건을 제시한다. 따라서, 이러한 목적을 위해 새롭고 개량된 윤활제 조성물을 개발하는 것이 필요하다. 본 발명은 이러한 요구 조건을 충족시키려고 노력한다.
DE-A-2039785는 가스 터빈 엔진을 위한 로드 캐링 첨가 조성물을 나타낸다. 로드 캐링 첨가 조성물은 99 ℃(210 ℉)에서 5.6 내지 6.0 cs. 의 점도를 갖는 합성 에스테르 기본 원료 액체(synthetic ester base stock fluid)를 포함한다(예 참조).
US-A-3694382는 가스 터빈 엔진용 윤활제를 나타낸다. 상기 윤활제는 99℃(210 ℉)에서 4.0 내지 9.1 cs. 범위인 점도를 갖는 합성 에스테르 기본 원료를 포함한다.
FR-A-2215462는 기본 원료로서 광물성 오일을 갖는 윤활제를 나타낸다.
WO-A-9410270은 100 ℃에서 적어도 4.9 cSt의 점도를 갖는 합성 기본 원료를 포함하는 부식 방지 윤활제 조성물을 나타낸다.
따라서, 본 발명은 다음을 포함하는 윤활제 조성물을 제공한다:
a) 1 또는 그 이상의 합성 기본 원료를 포함하는 기본 성분, 여기에서 기본 100 ℃에서 8.5 내지 9.5 cSt 범위의 점도를 갖는다;
b) 방향족 아민 및 힌더드 페놀(hindered phenolics)로부터 선택되는 적어도 1개의 산화 방지제;
c) 분자식 (R10)3PO 중 적어도 1개의 중성 유기 인산염, 여기에서 R1은 톨릴, 페닐, 크실릴, 알킬 또는 시클로알킬족, 10개 까지의 탄소 원자를 갖는 알킬 또는 시클로알킬족이다;
d) 다음의 일반적인 식 중 적어도 1개의 포화 및/또는 불포화 디카르복시산
여기에서, x+y+z는 2 내지 22를 포함하는 범위인 정수이고 그룹 Rl내끼 R5중 적어도 하나는 카르복시산 그룹이고 나머지 그룹 R1내지 R5는 알킬, 히드록시, 니트로, 아미노, 카르복실, 수소 또는 이의 알킬 유도체로부터 선택되고, 여기에서 알킬은 탄소 원자가 5개 까지인 짧은 체인이다; 및/또는 3개의 식 중 하나는 디카르복시산.
여기에서, R1'는 -COOH, 알킬, 히드록시, 니트로, 아미노, 카복실, 수소 또는 이의 알킬 유도체이다; R2'는 -COOH이다; n은 Rl'가 -COOH일 때 1 내지 4를 포함하는 정수이거나 또는 Rl'가 -COOH가 아닐 때 2 내지 4를 포함하는 정수이다.
e) 35 중량 %까지 일 수 있는 양에서 선택적으로 황화되는 적어도 1개의 직렬(straight) 및/또는 분기(branched) 체인 포화 또는 불포화 모노 카르복시산; 및/또는 이러한 산의 에스테르; 및
f) 다음 식 중 적어도 1개의 트리아졸:
여기에서, Rl"는 -COOH 또는 이의 알킬 유도체, 또는 탄소 원자가 5개 까지인 짧은 체인 알킬이다; n은 0 또는 1 내지 3을 포함하는 정수이다; 및 R2"는 수소, 모르필리노, 알킬, 아미돌, 아미노, 히드록시 또는 알킬 또는 이의 아릴 치환 유도체이다; 또는 1,2,4 트리아졸, 1,2,3 트리아졸, 5-아닐로-1,2,3, 4-티아트리아졸, 3-아미노-1,2,4 트리아졸, 1-H-벤조트리아졸-1-y1-메틸이소시아나이드, 메틸렌-비스-벤조트리아졸 및 나프토트리아졸로부터 선택되는 트리아졸이다; 및
g) 극압(extreme pressure) 첨가제를 함유하는 적어도 1개의 인.
상술한 d)의 성분에서, 이원적인 구조식은 그룹 R2가 어느 한쪽 또는 양쪽 방향족 링에 부착될 수 있는 것을 표시하고자 한 것이다.
기본 성분 중 적어도 1개의 기본 원료는 합성 에스테르 기본 원료, 특히 폴리올(polyol) 에스테르 기본 원료인 것이 바람직하다. 본 발명의 윤활제 조성물의 기본 원료를 바람직하게 형성하는 합성 폴리올 에스테르는 네오펜틸글리콜, 디메틸올프로판, 트리메틸올프로판, 펜타에리트리톨 또는 디펜타에리트리톨과 같은 폴리올 또는 폴리올 에스테르로 에스테르화되는 C5내지 Cl2단일 카르복시산으로 제조될 수 있다. 이것은 종래의 합성 에스테르 기본 원료이다. 바람직한 에스테르는 미국 특허 4826633에 기술되어 있는 것이다.
점도는 1 또는 그 이상의 점도 지수 향상제(improvers)의 포함으로 필요한 범위내에 놓여지게 조정될 수 있다.
변속 윤활제로서의 적절한 성능을 위해, 기본 성분은 100 ℃에서 8.5 내지 9.5 cSt, 바람직하게는 8.75 내지 9.25 cSt 범위인 점도를 가져야 한다. 기본 성분은 단일 폴리올 에스테르를 포함할 수 있지만 더 일반적으로는 폴리올 에스테르의 혼합물, 예를 들면, 100 ℃에서 약 12.0 cSt의 점도를 갖는 폴리올 에스테르와 100℃에서 약 4.0 cSt의 점도를 갖는 폴리올 에스테르의 혼합물이다. 바람직한 합성 폴리올 에스테르는 펜타에리트리톨 및/또는 트리메틸올프로판, 및 C5내지 C10의 직렬 및 분기 체인산을 포함하는 산 혼합물의 반응 생성물이다.
산화 방지 성분 b)는 윤활제 조성물 중 0.01 내지 5 중량 % 바람직하게는 0.4 내지 0.8 중량 %의 양으로 적절하게 주어지는 부틸화된 히드록시톨루엔과 같은 힌더드 페놀 산화 방지제일 수 있다. 택일적으로, 또는 부가하여, 성분 b)은 단독으로 또는 혼합하며 사용되는 모노-옥틸페닐알파나프틸아민 또는 P,P-디옥틸디페닐아민과 같은 방향족 아민 산화 방지제를 포함할 수 있다. 아민 산화 방지 성분은 윤활제 조성물 중 0.01 내지 5 중량 %, 더 바람직하게는 0.5 내지 1.5 중량 % 범위 내에서 적절하게 주어진다.
분자식의 성분 c)를 형성하는 중성 유기 인산염은 조성물 중 0.01 내지 4 중량 %, 바람직하게는 1.5 내지 2.5 중량 %의 양으로 주어질 수 있다. 중성 유기 인산염은 또한 윤활제 조성물의 종래 성분이고 이전에 정의된 바와 같이 식에 해당되는 이러한 임의의 중성 유기 인산염이 사용될 수 있다. 트리-크레실 인산염은 본 발명의 사용에 바람직한 인산염이다.
성분 d), e) 및 f)는 부식 방지 3가지 성분계를 제공하도륵 하는 것이다. 상기 조합은 50% 부식되지 않은 시편의 결과가 만족스러운 부식 방지 요구 조건으로 여겨지는 미합중국 해군 부식 방지 요구 조건(볼 부식 시험(Ball Corrosion Test)-ARP 4249)을 합격할 수 있는 윤활제 조성물을 제공할 수 있는 것으로 발견되었다.
부식 방지 조합의 제 1 성분을 형성하는 디카르복시산은 이전에 주어진 정의에 해당되는 임의의 디카르복시산일 수 있다. 디카르복시산은 조성물 중 0.15 중량 %까지의 비율로 주어질 수 있다. 그러나, 세바스산 또는 이와 동등한 것은 상술한 정의에 해당되는 다른 디카르복시산이 주어질지라도 세바스산 또는 이와 동등한 것이 볼 부식 시험 이외에 예를 들면 만족스러운 납 내식성을 위한 규격 부분을 만족시키는 것이 필요하므로 조성물에 항상 존재하는 것이 바람직하다는 것을 주목해야 한다.
본 발명에 사용될 수 있는 세바스산 이외에 이염기산의 예는 아디프산, 아젤라산, 도데카네디오익산, 3-메틸아디프산, 3-니트로프탈릭산, 1,10-데카네디카르복시산, 및 퓨마르산이다.
부식 방지 조합의 제 2 성분은 양에 있어서 35 중량 %까지 선택적으로 황화될 수 있는 직렬 또는 분기-체인으로 된 포화 또는 불포화 모노카르복시산, 또는 이의 에스테르이다. 상기 산은 C4내지 C22직렬 체인 불포화 모노카르복시산인 것이 바람직하다. 이러한 첨가제의 바람직한 농도는 전체 윤활제 조성물 중 0.001 중량 % 에서 0.35 중량 % 까지이다. 바람직한 모노카르복시산은 황화된 올레산이다.
그러나, 다른 적합한 재료는 올레산 그 자체이다; 즉 길초산 및 에루크산.
부식 방지 조합의 제 3 성분은 이전에 정의된 바와 같은 트리아졸이다. 상기 트리아졸은 전체 조성물 중 0.005 중량 %에서 0.25 중량 % 까지의 농도로 사용되어야 한다. 바람직한 트리아졸은 벤조트리아졸이다.
조성물 중 성분 g)는 극압 첨가제를 함유하는 적어도 1개의 인을 포함한다. 이러한 첨가제의 예는 상표명 IRGALUBE 349로 알려진 것과 같은 아민 인산염 극압 첨가제 및/또는 상표명 IRGALUBE TPPT로 알려진 것과 같은 트리페닐 포스포로티오 네이트 극압/내마모 첨가제이다. 이러한 아민 인산염은 윤활제 조성물 중 0.01 내지 2 중량 %, 바람직하게는 0.2 내지 0.6 중량 % 까지의 양으로 적절하게 주어지는 한편, 이러한 포스포로티오네이트는 윤활제 조성물 중 0.01 내지 3 중량 %, 바람직하게는 0.5에서 1.5 중량 % 까지의 양으로 적절하게 주어진다. 아민 인산염 및 포스포로티오네이트의 혼합물이 사용되는 것이 바람직하다.
헬리콥터 변속용 윤활제의 제공을 위해, 첨가제의 양은 100℃에서 수행되며, (6회 중 평균) 200(상대비, 기준 용액으로서 % 헤르코(Herco) A)의 라이더 기어 시험(Ryder gear test)에 대한 미합중국 해군 요구 조건에 따르도록 선택된다.
다음의 예는 본 발명에 따른 바람직한 윤활제 조성물을 설명하기 위한 것이다.
중량 %
모노-옥틸페닐알파나프틸아민 0.5%
부틸화된 수산화 톨루엔 0.5%
벤조트리아졸 0.1%
황화된 올레산 0.05%
세바스산 0.01%
트리-크레실 인산염 2.0%
아민 인산염 0.4%
트리페닐 포스포로티오네이트 1.0%
실리콘 거품 방지제 2 ppm
조성물을 위해 8.75 내지 9.25 cSt의
점도를 주기 위한 기본 합성 에스테르 혼합 용액 95.44 %
합성 조성물은 100 ℃, 라이더 기어 시험에서 204.7(상대비로서, % Herco A)의 값을 얻었고 볼 부식 시험(ARP 방법 4249에 따른)에 통과 등급이었다.

Claims (17)

  1. a) 1 또는 그 이상의 합성 기본 원료를 포함하는 기본 성분, 여기에서 기본 성분은 100 ℃에서 8.5 내지 9.5 cSt 범위의 점도를 가지며;
    b) 방향족 아민 및 힌더드 페놀로부터 선택되는 적어도 1개의 산화 방지제;
    c) 분자식 (R1O)3PO 중 적어도 1개의 중성 유기 인산염, 여기에서 R1은 톨릴, 페닐, 크실릴, 알킬 또는 시클로알킬족, 10개 까지의 탄소 원자를 갖는 알킬 또는 시클로 알킬족이며;
    d) 다음의 일반적인 식 중 적어도 1개의 포화 또는 불포화 디카르복시산
    여기에서, x+y+z는 2 내지 22를 포함하는 범위인 정수이고 그룹 R1에서 R5중 적어도 하나는 카르복시산 그룹이고 나머지 그룹 R1내지 R5는 알킬, 히드록시, 니트로, 아미노, 카르복실, 수소 또는 이의 알킬 유도체들로부터 선택되고, 여기에서 알킬은 탄소 원자가 5개 까지인 짧은 체인; 또는 다음 세개의 식 중 하나인 디카르복시산이며;
    여기에서, Rl'는 -COOH, 알킬, 히드록시, 니트로, 아미노, 수소 또는 이의 알킬 유도체이며; R2'는 -COOH이며; n은 Rl'가 -COOH일 때 1 내지 4를 포함하는 정수이거나 또는 Rl'가 -COOH가 아닐 때 2 내지 4를 포함하는 정수이며;
    e) 35 중량 % 까지 일 수 있는 양에서 선택적으로 황화되는 적어도 1개의 직렬 또는 분기 체인 포화되거나 불포화된 모노 카르복시산, 또는 이러한 산의 에스테르; 및
    f) 다음 식 중 적어도 1개의 트리아졸 :
    여기에서, Rl"는 -COOH 또는 이의 알킬 유도체, 또는 탄소 원자가 5개 까지인 짧은 체인 알킬이며; n은 0 또는 1 내지 3을 포함하는 정수이며; 및 R2"는 수소, 모르필리노, 알킬, 아미돌, 아미노, 히드록시 또는 알킬 또는 이의 아릴 치환 유도체이며; 또는 1,2,4 트리아졸, 1,2,3 트리아졸, 5-아닐로-1,2,3, 4-티아트리아졸, 3-아미노-1,2,4 트리아졸, 1-H-벤조트리아졸-1-y1-메틸이소시아나이드, 메틸렌-비스-벤조트리아졸 및 나프토트리아졸로부터 선택되는 트리아졸이며; 및
    g) 극압 첨가제를 함유하는 적어도 1개의 인
    을 포함하는 윤활제 조성물.
  2. 제 1 항에 있어서,
    기본 성분 중 적어도 1개의 기본 원료는 폴리올 에스테르인 윤활제 조성물.
  3. 제 2 항에 있어서,
    폴리올 에스테르 기본 원료는 1 또는 그 이상의 폴리올 또는 폴리올 에테르로 에스테르화되는 1 또는 그 이상의 C5내지 C12모노카르복시산을 포함하는 윤활제 조성물.
  4. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,
    기본 성분은 100 ℃에서 8.75에서 9.25 cSt 까지의 범위인 점도를 가지는 윤활제 조성물.
  5. 제 1 항에 있어서,
    산화 방지제는 조성물 중 0.4 내지 0.8 중량 % 까지의 양으로 주어지는 힌더드 페놀 산화 방지제를 포함하는 윤활제 조성물.
  6. 제 1 항에 있어서,
    산황 방지제는 조성물 중 0.5 내지 1.5 중량 % 까지의 양으로 주어지는 방향족 아민 산화 방지제를 포함하는 윤활제 조성물.
  7. 제 1 항에 있어서,
    중성 유기 인산염은 조성물 중 1.5 내지 2.5 중량 % 까지의 양으로 주어지는 윤활제 조성물.
  8. 제 1 항에 있어서,
    포화 또는 붙포화 디카르복시산 성분 d)는 조성물 중 0.15 중량 % 까지의 양으로 주어지는 윤활제 조성물.
  9. 제 1 항에 있어서,
    포화 또는 불포화 디카르복시산 성분 d)는 세바스산을 포함하는 윤활제 조성물.
  10. 제 1 항에 있어서,
    모노카르복시산 성분 e)는 조성물 중 0.001 내지 0.35 중량 % 까지의 양으로 주어지는 윤활제 조성물.
  11. 제 1 항에 있어서,
    모노카르복시산 성분 e)는 황화된 올레산을 포함하는 윤활제 조성물.
  12. 제 1 항에 있어서,
    트리아졸 성분 f)는 조성물 중 0.005 내지 0.25 중량 % 까지의 양으로 주어 지는 윤활제 조성물.
  13. 제 1 항에 있어서,
    트리아졸 성분 f)는 벤조트리아졸을 포함하는 윤활제 조성물.
  14. 제 1 항에 있어서,
    극압 첨가제 성분 g)는 조성물 중 0.2 내지 0.6 중량 % 까지의 양으로 주어지는 아민 인산염 극압 첨가제를 포함하는 윤활제 조성물.
  15. 제 1 항에 있어서,
    극압 첨가제 성분 g)는 조성물 중 0.5 내지 1.5 중량 % 까지의 양으로 주어지는 포스포로티오네이트 극압 첨가제를 포함하는 윤활제 조성물.
  16. 제 1 항에 규정된 바와 같이 성분 a) 내지 g)를 포함하는 헬리콥터 변속 윤활제.
  17. 제 16 항에 있어서,
    성분 b) 내지 g)는 100℃에서 수행되며, 200(상대비, 기준 용액으로서 % 헤르코 A)의 라이더 기어 시험에 대한 미합중국 해군 요구 조건에 따르도록 선택되는 양으로 주어지는 헬리콥터 변속 윤활제.
KR1019960705962A 1994-04-26 1995-04-25 윤활제조성물 KR100339777B1 (ko)

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GB9408235A GB9408235D0 (en) 1994-04-26 1994-04-26 Lubricant composition
PCT/GB1995/000941 WO1995029214A1 (en) 1994-04-26 1995-04-25 Lubricant composition

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JP5827782B2 (ja) 2009-05-08 2015-12-02 出光興産株式会社 生分解性潤滑油組成物
JP6669343B2 (ja) * 2015-02-27 2020-03-18 出光興産株式会社 生分解性潤滑油組成物
CN106590869A (zh) * 2016-11-28 2017-04-26 广西大学 一种全合成四连杆摆块机构热气机润滑剂组合物

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ES2148513T3 (es) 2000-10-16
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AU695511B2 (en) 1998-08-13
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GR3033741T3 (en) 2000-10-31
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AU2313595A (en) 1995-11-16
CA2188936A1 (en) 1995-11-02

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