KR900005107B1 - 윤활유 조성물 - Google Patents

윤활유 조성물 Download PDF

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KR900005107B1
KR900005107B1 KR1019880700458A KR880700458A KR900005107B1 KR 900005107 B1 KR900005107 B1 KR 900005107B1 KR 1019880700458 A KR1019880700458 A KR 1019880700458A KR 880700458 A KR880700458 A KR 880700458A KR 900005107 B1 KR900005107 B1 KR 900005107B1
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South Korea
Prior art keywords
oil
lubricating oil
oil composition
viscosity
weight
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KR1019880700458A
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English (en)
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KR880701769A (ko
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히로미찌 세이끼
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이데미쓰 고산 가부시끼가이샤
이데미쓰 쇼스께
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Publication of KR880701769A publication Critical patent/KR880701769A/ko
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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Abstract

내용 없음.

Description

윤활유 조성물
본 발명은 윤활유 조성물에 관한 것이며, 상세하게는 자동변속기, 트랙터 등의 습식브레이크나 습식클러치를 포함하는 부분의 윤활에 적절하게 사용되는 윤활유 조성물에 관한 것이다.
습식브레이크나 습식클러치를 포함하는 부분의 윤활에 사용되는 습식브레이크나 습식클러치용 윤활유는 시동성을 고려하여 저온점도가 낮아야 한다.
일반적으로 기유(base oil) 전체의 점도를 낮게하면, 그 목적을 달성하기 쉽지만 반대로 고온시에 점도가 너무 낮으면 윤활성능이 저하되어 실제로 사용할 수 없게 되는 문제가 있다.
그래서, 저점도 기유에 고분자 화합물 등의 점도 지수향상제를 배합하는 방법이 많이 사용되고 있으나, 사용함에 따라 고분자가 전단에 받게되어 저점도화되기 때문에 본질적인 해결이 되지 않는다.
본 발명의 첫 번째 목적은, 기유 자체의 특성으로서 고온에서의 점도가 일정하게 유지되면서도, 저온점도가 낮은 기유를 제공하는 것이다. 물론, 이 기유는 산화안정성이 우수하고, 내고무밀봉성(seal rubber compatibility)도 우수하여야 한다.
본 발명의 두 번째 목적은, 기유 그 자체로 습식브레이크나 습식클러치에 대한 마찰특성을 향상시킬 수 있는 윤활유 조성물을 제공하는 것이다.
즉, 본 발명은 100℃에서의 동점도가 2-50센티스토크스(cst), 유동점(JIS k-2269에 준거)이 -5~-30℃, 점도지수(JIS K-2283에 준거)가 80 이상이며, %CA(방향족 탄화수소의 함량)가 3 이하인 광물유 97-60중량% 및 폴리에스테르 3-40중량%로 이루어지는 윤활유 조성물을 제공하는 것이다.
본 발명의 윤활유 조성물은, 고온에서의 점도가 적절하며, 더욱이 저온점도가 낮다.
더구나, 본 발명의 윤활유 조성물은 마찰특성에 있어서도 우수하다. 게다가, 본 발명의 윤활유 조성물은 산화안정성이 우수한 동시에 내고무밀봉성도 우수한 것이다.
본 발명의 윤활유 조성물의 주성분을 이루는 광물유는, 100℃에서의 동점도가 2-50cst, 바람직하게는 5-30cst이며, 유동점이 -5~-30℃ 바람직하게는 -7.5~-3.0℃이고, 점도지수가 80 이상, 바람직하게는 85 이상이며, %CA가 3 이하, 바람직하게는 1 이하의 것이다.
상기의 범위를 벗어나게되면, 원하는 윤활유 조성물을 얻을 수가 없다. 또한, 광물유로서는 산화안정성을 고려하여 유황성분이 0.01중량% 이하, 바람직하게는 0.001중량% 이하인 것이 바람직하다.
상술한 바와 같은 특성을 갖는 광물유는, 파라핀계 원유 또는 중간기(intermediate base)원유를 증류하여 얻은 증류유(대기압 하에서의 비등점, 약 250-450℃)를 고도로 정제하여 얻을 수 있다. 또한, 증류유라고 하는 것은 원유를 상압증류하던가, 혹은 상압증류의 잔류유를 감압증류하여 얻은 것을 의미한다.
고도 정제법은 특별한 제한은 없지만, 다음의 ①-⑤의 어느 것인가의 처리에 의하여 얻을 수가 있다.
① 증류유를 수소화처리하던가, 또는 수소화처리한 후, 알칼리증류 또는 황산세정을 행한다.
② 증류유를 용제정제 처리하던가, 또는 용제정제 처리한 후, 알칼리 증류 또는 황산세정을 행한다.
③ 증류유를 수소화 처리한 후, 이어서 제2단계의 수소화 처리를 행한다.
④ 증류유를 수소화 처리한 후, 제2단계의 수소화 처리를 하고, 다시 제3단계의 수소화 처리를 행한다.
⑤ 증류유를 수소화 처리한 후, 제2단계의 수소화 처리를 행하고, 다시 알칼리증류 또는 황산세정을 행한다.
이하에 처리법의 일예를 나타낸다.
파라핀계 원유나 중간기 원유로부터 통상적인 방법에 의하여 윤활유 조원료를 제조하고, 가혹한 수소화 처리를 행한다.
이 처리에 의하여, 방향족 성분등의 윤활유 증류분에 바람직하지 않은 성분을 제거하거나, 유효한 성분으로 변화시킨다. 이와 동시에 유황성분이나 질소성분도 거의 제거된다.
이어서, 감압증류에 의하여 필요한 점도를 얻기 위한 분별증류를 행한다. 그후, 기지의 용제 탈납을 행하고, 통상적인 파라핀계 기유가 갖는 유동점, 즉 -15~10℃ 정도에서 탈납시킨다.
이 탈납 처리 후, 필요에 따라서 더욱 수소화 처리를 행하고, 방향족 성분의 대부분을 수소화시켜 포화성분으로 만들고, 기유(base oil)의 열적, 화학적이 안정성을 향상시킨다.
그후, 원하는 유동점을 갖도록 하기 위하여 탈납 처리를 행한다. 이 처리에서는 용제탈납법, 심탈납법이 사용될 수 있다.
수소화 처리는 원료유의 특성 등에 따라 다르지만, 통상적으로는 반응온도 200-480℃, 바람직하게는 250-450℃, 수소압력 5-300kg/cm2, 바람직하게는 30-250kg/cm2, 수소도입량(공급증류유 1kl당) 30-3000Nm3, 바람직하게는 100-2000Nm3의 조건으로 행하여 진다. 또한, 이때에 사용되는 촉매는 담체로서 알루미나, 실리카, 실리카, 알루미나, 제올라이트, 활성탄, 보오크사이크 등을 사용하고, 주기율표 제Ⅵ족, 제Ⅷ족 등의 금속, 바람직하게는 코발트, 니켈, 몰리브덴, 텅스텐 등의 촉매성분을 기지의 방법으로 담지시킨 것이 사용된다. 또한, 촉매는 미리 예비황화시킨 것이 바람직하다.
상기한 바와 같이, 증류유를 수소화 처리한 후, 각종의 처리를 하게 되지만, 제2단계 또는 제3단계의 수소화 처리를 행할 경우, 수소화 처리 조건은 상기한 범위내로 설정되면 좋으며, 제1-3단계의 각 조건은 동일하거나 상이하여도 무방하다.
그러나, 통상적으로는 제1단계보다는 제2단계, 제2단계 보다는 제3단계의 조건을 엄격하게 하여 행한다.
그 다음, 알칼리 증류는 미량의 산성물질을 제거하여 증류성분의 안정성을 개량시키는 공정으로서 행하여 지며, NaOH, KOH 등의 알칼리를 가하여 감압 증류하는 것에 의하여 행하여진다.
또한, 황산세정은 일반적으로 석유제품의 마무리 공정으로서 행하여지며, 방향족 탄화수소, 특히 다환의 방향족 탄화수소나 올레핀류, 유황 화합물 등을 제거하여 증류유의 특성을 개선시키기 위하여 사용된다.
구체적으로는, 처리유에 0.5-5중량%의 진한 황산을 가하여 실온 -60℃의 온도로 처리하는 것에 의하여 행하여지며, 그후, NaOH등으로 중화시킨다. 또한, 증류유의 처리는 상기한 조작을 조합하는 것에 의하여 전기한 바와 같은 ①-⑤의 구체적인 방법이 있지만, 이들의 방법중에서도 특히 ①, ③, ④의 방법이 적합하다.
상기한 바와 같은 처리에 의하여, 전기한 특성을 갖는 광물유를 얻을 수가 있지만, 더욱 이것을 백토(clay)처리할 수도 있다.
본 발명에 있어서, 다른 성분으로서 사용되는 폴리에스테르로서는, 힌더드 에스테르(hindered ester) 또는 다이카복실산에스테르가 있다.
여기서 힌더드 에스테르로서는, 유동점이 -30℃ 이하, 바람직하게는 -40℃ 이하의 것이 사용된다.
유동점이 -30℃를 초과하게 되면 저온점도가 높아지게 되므로 바람직하지 않다. 힌더드 에스테르의 화학적 구조는, 동점도, 점도지수, 유동점을 고려하여 다음의 것들이 바람직하다.
즉 힌더드 에스테르를 구성하는 폴리울로서는, 네오펜틸글리콜, 트리메틸롤에탄, 트리메틸롤프로판, 팬타에리스리톨 등의 알콜의 β탄소가 제4급인 것이 사용된다.
한편, 상기의 폴리올과 함께 힌더드 에스테르를 구성하는 지방산으로서는, 탄소수 3-18, 바람직하게는 탄소수 1-14의 직선상 또는 가지상의 지방산이 바람직하고, 특히 가지상의 지방산이 바람직하다.
구체적으로는 헥산산, 헵탄산, 옥탄산, 노난산, 데칸산 등의 직선상의 지방산과, 2-에틸헥산산, 아이소옥탄산, 아이소노난산, 아이소데칸산 등의 가지상인 지방산을 들 수 있다.
또한, 주성분이 탄소수 4-14의 혼합지방산도 바람직하게 사용될 수 있다. 가지상인 지방산, 혼합지방산을 사용하는 것은, 저온유동성을 향상시킨다는 점에서 바람직하다.
그 다음, 다이카복실산 에스테르로서는 유동점이 -30℃ 이하, 바람직하게는 -40℃ 이하인 것이 사용된다.
유동점이 -30℃를 초과하게 되면 저온점도가 높아지게 되므로 바람직하지 않다. 다이카복실산 에스테르의 화학적 구조는, 동점도, 점도지수, 유동점을 고려하여 다음의 것들이 바람직하다.
즉, 다이카복실산 에스테르를 구성하는 알콜로서는, 탄소수가 3-18, 특히 4-13이며, 가지상의 알콜이 바람직하다.
구체적으로는, 아이소부틸알콜, 아이소아밀알콜, 아이소헥실알콜, 아이소옥틸알콜, 아이소노닐알콜, 아이소데실알콜, 아이소트리데실알콜 등을 들 수가 있다. 한편, 상기의 알콜과 함께 다이카복실산 에스테르를 구성하는 이염기산으로서는, 탄소수 4-16의 이염기산으로서는, 아디핀산, 아젤라인산, 세바신산, 도데칸다이카복실산 등을 들 수가 있다.
본 발명의 윤활유 조성물은, 상기한 바와 같이 광물유의 폴리에스테르로부터 이루어지는 것이다.
여기서, 양자의 배합비율은 전자 97-60중량%에 대하여 후자, 3-40중량%, 바람직하게는 전자 90-70중량에 대하여, 후자 10-30중량%이다.
후자의 배합 비율이 3중량% 미만이면, 후자를 배합하는 것에 의한 효과를 볼 수가 없으며, 반면에 후자의 배합 비율이 40중량%를 초과하면, 고무팽윤성 및 마찰특성이 저하되기 때문에 바람직하지 않다.
본 발명의 윤활유 조성물은 상술한 성분으로 이루어지는 것이지만, 목적등에 따라서 산화방지제, 청정분산제, 점도지수 향상제, 소포제(defoaming agent), 극압제(extreme pressure agent), 유동점 강하제 등을 첨가할 수가 있다.
더욱이, 습식브레이크나 습식클러치를 포함하는 윤활부분의 윤활유로서는 마찰조성제를 첨가할 수가 있다.
또한, 산화방지제로서는 페놀계 화합물, 아민계 화합물, 다이티오인산 아연 등의 일반적으로 사용되고 있는 것이면 좋다.
구체적으로는 2,6-다이-t-부틸-4-메틸-페놀; 2,6-다이-t-부틸-4-에틸페놀; 4,4'-메틸렌비스(2,6-다이-t-부틸-페놀); 페닐-t-나프틸아민; 다이알킬다이페닐아민; 다이-2-에틸헥실다이티오인산아연; 다이아밀다이티오카바민산아연; 오염화피넨 등을 들 수 있다.
그 다음, 청정분산제로서는, 무회분계 청정제, 금속제 청정제 등도 사용될 수가 있다.
구체적으로는 알케닐호박산이미드, 술포네이트, 페네이트 등이 바람직하고, 예컨데 폴리부테닐호박산이미드, 칼슘술포네이트, 바륨술포네이트, 칼슘페네이트, 바륨페네이트, 칼슐살리시네이트 등을 들 수 있다.
점도지수 향상제로서는 특별한 제한은 없으나, 폴리메타크릴레이트, 폴리부텐 등을 사용할 수가 있다.
[실시예 1-6 및 비교예 1-11]
제1표에 나타낸 특성의 광물유에 제2표에 나타낸 특성의 폴리에스테르를 제3표 에 나타낸 소정비율로 배합하여 윤활유 조성물을 제조하고, 그 성능을 평가하였다.
결과를 제3표에 나타낸다.
또한 시험법은 다음과 같다.
[시험법]
(1) 동점도:JIS K-2283에 준거
(2) 브룩필드(Brookfield:BF) 점도:ASTM D 2983-80에 준거
(3) ISOT(내연 기관용 윤활유 산화안정도 시험)
JIS K 2514, 3-1에 준거(165.5℃×48시간)
(4) SAE No. 2 마찰시험
미국 그린닝사 제(Greening Co., U.S.A.), SAE No. 2 마찰 시험기를 사용하여, 하기의 실험조건하에서 마찰 특성을 평가하였다.
[실험조건]
디스크:일제 자동변속기용 페이퍼계 디스크(3매)
플레이트:일제 자동변속기용 동제플레이트(4매)
모터의 회전수:3000rpm
오일 온도:100℃
이상의 실험조건으로 회전수 1200rpm일때의 동마찰 계수를 μ1200 정지하였을 때의 마찰계수를 μ0로 하여 측정하였다.
(5) 아닐린점(Aniline point):JIS K-2256에 준거
(6) 고무침적 시험
JIS K-6301에 준거하여, 다음의 조건으로 행하였다.
고무:니트릴 고무(일본국 오일씰사 제 A727)
오일 온도:150℃
시간:170시간
[비교예 12]
시판중인 파라핀계 용제 정제유를 사용하여, 실시예 1과 같은 방법으로 성능을 평가하였다.
결과를 제3표에 나타낸다.
[제1표]
Figure kpo00001
* 1:하기한 바와 같이 하여 얻어진 광물유를 사용하였다.
쿠웨이트산 원유를 상압증류한 후, 감압증류하여 얻은 증류성분 및 잔재유를 탈아스팔트시킨 증류성분을 공급원료로하여, 생성물인 탈납유(최초로 탈납처리 한 것)의 점도지수가 약 100이 되도록 가혹한 조건에서 수소화 처리하였다.
상기의 방법으로 얻어진 생성물을 분별증류하고, 100℃에서의 점도가 각각 2.3cst, 5.6cst가 되도록 한 2종의 증류유를 얻었다.
이들 2종의 증류유의 각각을 더욱 용제탈납 처리하였다.
이 단계에서의 처리조건은, 탈납유의 유동점이 -15℃가 되도록 하였다.
이어서, 상기의 탈납유에 방향족성분(젤 크로마토그라피법에 의한)이 1.5중량% 이하가 되도록, 더욱 수소화 처리를 행하였다.
* 2:파라핀계 용제정제유
* 3:파라핀계 용제정제유
* 4:나프텐계유
* 5:나프텐계유
[제2표]
Figure kpo00002
* 1:니뽄 유시(주)제, 유니스타 H-334R, 트리메틸롤프로판과 탄소수 6-12의 혼합지방산의 에스테르.
* 2:상껜 카꼬(주)제, DINA, 아디핀산 다이아이소노닐 에스테르.
[제3a표]
Figure kpo00003
[제3b표]
Figure kpo00004
[제3c표]
Figure kpo00005
* 1:청정분산제, 산화방지제, 마찰조정제, 소포제등을 함유하는 패키지 타입 첨가제.
* 2:폴리메타크릴레이트 타입 점도지수 향상제.
표 3으로부터 다음을 알 수 있다.
즉 비교예 1, 2 및 5에서는, 저온점도(ⓐ-40℃)가 각각 23800, 36900, 78700cp이며, 실용상의 요구치 20000cp 이하라야 하는 조건을 만족시키지 못하며, 더구나 비교예 2 및 5에서는 ISOT의 총 산가의 상승이 크고, 열화가 현저한 것을 알 수 있다. 또한, 비교예 3-4 및 비교예 6-7에서는 ISOT에서의 총산가가 크고, 더구나 저온점도가 낮기는 하지만, 역시 실용상의 요구치 20000cp 이하이어야 하는 조건을 만족시키지 못하고 있다. 더구나, 비교예 8-9에서는 아닐린점이 낮고, 고무에 대한 중량 및 체적 변화율이 크며, 팽윤이 크다는 것을 알 수 있다. 또한, 비교예 10, 11은 모두, 배합 비율을 본 발명의 범위외로 한 것이다. 비교예 10과 같이, 폴리에스테르의 배합 비율이 작으면 저온점도(ⓐ-40℃)가 실용상의 요구치 20000cp 이하이어야 조건을 만족시키지 못하며, 반면에 비교예 11과 같이, 폴리에스테르의 배합비율이 크면 아닐린 점이 낮고, 더구나 고무에 대한 중량 및 체적변화율이 커서 팽윤이 크다는 것을 알 수 있다. 더구나, 비교예 12와 같은 시판유를 사용하는 경우, 저온점도(ⓐ-40℃)가 42000cp라서, 실용상의 요구치를 만족시키지 못하며, 더구나 마찰특성도 충분하지 못한 것을 알 수 있다. 이것과 비교하여, 실시예 1-6에서는 저온점도가 20000cp 이하이며, 산화안정성(ISOT) 및 고무팽윤성도 양호한 것을 알 수 있다. 더구나, 마찰특성도 우수하다는 것을 알 수 있다.
본 발명의 윤활유 조성물은, 습식브레이크나 습식클러치를 포함하는 부분의 윤활제, 예컨데 자동변속기용 윤활제, 트랙터유등에 사용될 수 있으며, 더욱이 저온 점도가 낮고, 산화안정성, 고무팽윤성이 양호하기 때문에 파우워 스티어링유, 유압유, 내연기관유 등으로서도 사용할 수가 있다.

Claims (10)

100℃에서의 동점도가 2-50센티스토크스, 유동점이 -5~-30℃, 점도지수가 80 이상이며, %CA가 3 이하인 광물유 97-60중량% 및 폴리에스테르 3-40중량%로 이루어지는 윤활유 조성물.
제1항에 있어서, 광물유의 유황성분이 0.01중량% 이하인 윤활유 조성물.
제1항에 있어서, 광물유의 유황성분이 0.001중량% 이하인 윤활유 조성물.
제1항에 있어서, 100℃에서의 광물유의 동점도가 5-30센티스토크스인 윤활유 조성물.
제1항에 있어서, 광물유의 유동점이 -7.5~-30℃인 윤활유 조성물.
제1항에 있어서, 광물유의 점도 지수가 85 이상인 윤활유 조성물.
제1항에 있어서, 광물유가, %CA가 1 이하인 윤활유 조성물.
제1항에 있어서, 광물유가, 100℃에서의 동점도가 5-30센티스토크스 유동점이 -7.5~-30℃, 점도지수 85 이하, %CA가 1 이하인 윤활유 조성물.
제1항에 있어서, 폴리에스테르가 힌더드(hindered) 에스테르 또는 다이카복실산에스테르인 윤활유 조성물.
제1항에 있어서, 폴리에스테르의 유동점이 -30℃ 이하인 윤활유 조성물.
KR1019880700458A 1986-09-08 1987-09-04 윤활유 조성물 KR900005107B1 (ko)

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