KR100519143B1 - 자동변속기용윤활유조성물 - Google Patents

자동변속기용윤활유조성물 Download PDF

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KR100519143B1
KR100519143B1 KR1019970023749A KR19970023749A KR100519143B1 KR 100519143 B1 KR100519143 B1 KR 100519143B1 KR 1019970023749 A KR1019970023749 A KR 1019970023749A KR 19970023749 A KR19970023749 A KR 19970023749A KR 100519143 B1 KR100519143 B1 KR 100519143B1
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South Korea
Prior art keywords
acid
automatic transmission
phosphate
lubricating oil
oil composition
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KR1019970023749A
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English (en)
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KR980002220A (ko
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도시히코 이치하시
히데오 이가라시
주니치 데시마루
도시키 이케다
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이데미쓰 고산 가부시키가이샤
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Publication of KR980002220A publication Critical patent/KR980002220A/ko
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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Abstract

본 발명은 자동 변속기의 클러치부의 마찰재의 셔더(shudder; 차체 이상진동) 방지 성능이 우수하고, 셔더 방지 성능을 장기간에 걸쳐 유지할 수 있는 자동 변속기용 윤활유 조성물에 관한 것이다.
본 발명은 기본유에 (A) 황 함유 산화방지제 또는 아민계 산화방지제, (B) 인산 에스테르류 또는 이의 아민염, 및 (C) 카복실산과 아민의 반응생성물을 배합하여 제조되는 자동 변속기용 윤활유 조성물을 제공한다.

Description

자동 변속기용 윤활유 조성물{LUBRICATING OIL COMPOSITION FOR AUTOMATIC TRANSMISSIONS}
본 발명은 자동 변속기용 윤활유 조성물에 관한 것으로, 상세하게는 자동 변속기의 클러치부의 마찰재의 셔더(shudder; 차체 이상진동) 방지 성능이 우수하고, 셔더 방지 성능을 장기간에 걸쳐 유지할 수 있는 자동 변속기용 윤활유 조성물에 관한 것이다.
자동 변속기(AT)의 클러치부에서 발생하는 셔더를 방지하는 성능이 특히 연속 슬립(slip) 기구를 갖는 자동 변속기에 요구되고 있다. 종래부터 사용되어 온 자동 변속기유(ATF)로는 셔더가 발생하여 차체가 격렬하게 진동한다. 이 셔더를 방지하기 위해 다양한 시도가 행해지고 있다. 예를 들면, 일본 특허공개 제 95-305082 호 공보에는 기본유에 ① 디티오인산 아연 및/또는 염기성 디티오인산 아연, ② 인산 에스테르, 산성 인산 에스테르 및 아인산 에스테르 등의 그룹으로부터 선택된 한 종류 이상의 화합물, 및 ③ 분자중에 특정 결합 및/또는 작용기를 도입한 구조를 갖는 유기계 마찰 조정제를 배합한 자동 변속기용 윤활유 조성물이 개시되어 있으나, 초기의 셔더 방지에 대해서는 양호하지만, 장기간 사용한 경우 디티오인산 아연이 습식 클러치 표면에 부착하여 셔더 방지수명이 현격하게 저하되어 초기의 성능을 유지할 수 없게 된다는 단점이 있다. 또한, 일본 특허공개 제 88-254196 호 공보에는 ATF의 첨가제로서 인산 에스테르, 지방산 에스테르, 지방산 아미드 등의 마찰 조정제를 사용하는 것이 개시되어 있으나, 초기의 셔더 방지 성능이 불충분하다.
본 발명은 상기 관점에서 이루어진 것으로, 자동 변속기의 클러치부의 마찰재의 셔더 방지 성능이 우수하고, 셔더 방지 성능을 장기간에 걸쳐 유지할 수 있는 자동 변속기용 윤활유 조성물을 제공하는 것을 목적으로 한다.
본 발명자들은 예의 연구를 계속한 결과, 기본유에 특정의 산화방지제, 인산 에스테르류 또는 이의 아민염, 및 카복실산과 아민의 반응물을 배합함으로써 본 발명의 목적을 효과적으로 달성할 수 있음을 발견하고 본 발명을 완성하였다.
즉, 본 발명은 기본유에 (A) 황 함유 산화방지제 또는 아민계 산화방지제, (B) 인산 에스테르류 또는 이의 아민염, 및 (C) 카복실산과 아민의 반응생성물을 배합하여 제조되는 자동 변속기용 윤활유 조성물을 제공한다.
이하에, 본 발명의 실시 형태를 설명한다.
먼저, 본 발명의 자동 변속기용 윤활유 조성물에 있어서, 기본유로서 광유 및/또는 합성유가 사용된다. 이 광유 또는 합성유에 대해, 일반적으로 변속기유의 기본유로서 사용되고 있는 것이면 무방하고 특별히 제한되지는 않으나, 100℃에서의 동점도가 1 내지 20mm2/s, 특히 2 내지 10mm2/s의 범위의 것이 바람직하다. 기본유의 동점도가 너무 높으면 저온 점도가 악화되고, 역으로 너무 낮으면 자동 변속기의 기어 축수, 클러치 등의 접동부에 있어서 마모가 증가하여 바람직하지 않다. 또한, 이 기본유의 저온 유동성의 지표인 유동점에 대해서는 특별히 제한은 없으나, -10℃ 이하가 바람직하다.
이러한 광유, 합성유는 다양한 종류가 있으며, 용도 등에 따라 적절히 선택할 수 있다. 광유로는 예를 들면 파라핀계 광유, 나프텐계 광유, 중간기계 광유 등을 들 수 있으며, 구체적으로는 용매 정제 또는 수소첨가 정제에 의한 경질 중성(neutral)유, 중(medium)질 중성유, 중(heavy)질 중성유, 브라이트 스톡(bright stock) 등을 들 수 있다.
한편, 합성유로는 예를 들면 폴리α-올레핀, α-올레핀 공중합체, 폴리부텐, 알킬벤젠, 폴리올 에스테르, 이염기산 에스테르, 폴리옥시알킬렌글리콜, 폴리옥시알킬렌글리콜 에스테르, 폴리옥시알킬렌글리콜 에테르, 실리콘 오일 등을 들 수 있다.
이들 기본유는 각각 단독으로 또는 2종류 이상을 조합하여 사용할 수 있으며, 광유와 합성유를 조합하여 사용할 수도 있다.
하기에, 기본유에 배합되는 (A) 내지 (C) 성분에 대해 설명한다.
(A) 성분
황 함유 산화방지제로는 황을 함유하고 있는 산화방지제라면 어떤 것이든 무방하며, 예를 들면 디라우릴티오디프로피오네이트, 디스테아릴티오디프로피오네이트 등의 디알킬티오디프로피오네이트; 디알킬디티오카밤산 유도체(금속염은 제외됨), 비스(3,5-디-t-부틸-4-하이드록시벤질)설파이드, 머캅토벤조티아졸, 오황화인과 올레핀의 반응생성물, 황화디세틸 등을 들 수 있으며, 이중에서도 디라우릴티오디프로피오네이트, 디스테아릴티오디프로피오네이트 등의 디알킬티오디프로피오네이트가 바람직하다.
아민계 산화방지제로는 예를 들면 모노옥틸디페닐아민, 모노노닐디페닐아민 등의 모노알킬디페닐아민계; 4,4'-디부틸디페닐아민, 4,4'-디펜틸디페닐아민, 4,4'-디헥실디페닐아민, 4,4'-디헵틸디페닐아민, 4,4'-디옥틸디페닐아민, 4,4'-디노닐디페닐아민 등의 디알킬디페닐아민계; 테트라부틸디페닐아민, 테트라헥실디페닐아민, 테트라옥틸디페닐아민, 테트라노닐디페닐아민 등의 폴리알킬디페닐아민계; α-나프틸아민, 페닐-α-나프틸아민, 부틸페닐-α-나프틸아민, 펜틸페닐-α-나프틸아민, 헥실페닐-α-나프틸아민, 헵틸페닐-α-나프틸아민, 옥틸페닐-α-나프틸아민, 노닐페닐-α-나프틸아민 등의 나프틸아민계를 들 수 있으며, 이들중에서 디알킬디페닐아민계가 바람직하다.
황 함유 산화방지제 및 아민계 산화방지제는 기본유에 대해 조성물 총중량 기준으로 0.01 내지 5 중량%, 바람직하게는 0.03 내지 3 중량%의 비율로 배합된다.
(B) 성분
본 발명의 인산 에스테르류는 하기 일반식 (1) 내지 (5)의 인산 에스테르, 산성 인산 에스테르, 아인산 에스테르, 산성 아인산 에스테르를 포함한다:
Figure pat00001
Figure pat00002
Figure pat00003
Figure pat00004
Figure pat00005
상기 식에서,
R1 내지 R3은 탄소수 4 내지 30의 알킬기, 알케닐기, 알킬아릴기 및 아릴알킬기이며, 이들은 동일하거나 상이할 수 있다.
인산 에스테르로는 트리아릴포스페이트, 트리알킬포스페이트, 트리알킬아릴포스페이트, 트리아릴알킬포스페이트, 트리알케닐포스페이트 등이 있고, 구체적으로는 예를 들면 트리페닐포스페이트, 트리크레실포스페이트, 벤질디페닐포스페이트, 에틸디페닐포스페이트, 트리부틸포스페이트, 에틸디부틸포스페이트, 크레실디페닐포스페이트, 디크레실페닐포스페이트, 에틸페닐디페닐포스페이트, 디에틸페닐페닐포스페이트, 프로필페닐디페닐포스페이트, 디프로필페닐페닐포스페이트, 트리에틸페닐포스페이트, 트리프로필페닐포스페이트, 부틸페닐디페닐포스페이트, 디부틸페닐페닐포스페이트, 트리부틸페닐포스페이트, 트리헥실포스페이트, 트리(2-에틸헥실)포스페이트, 트리데실포스페이트, 트리라우릴포스페이트, 트리미리스틸포스페이트, 트리팔미틸포스페이트, 트리스테아릴포스페이트, 트리올레일포스페이트 등을 들 수 있다.
산성 인산 에스테르로는 구체적으로는 예를 들면 2-에틸헥실산성포스페이트, 에틸산성포스페이트, 부틸산성포스페이트, 올레일산성포스페이트, 테트라코실산성포스페이트, 이소데실산성포스페이트, 라우릴산성포스페이트, 트리데실산성포스페이트, 스테아릴산성포스페이트, 이소스테아릴산성포스페이트 등을 들 수 있다.
아인산 에스테르로는 구체적으로는 예를 들면 트리에틸포스파이트, 트리부틸포스파이트, 트리페닐포스파이트, 트리크레실포스파이트, 트리(노닐페닐)포스파이트, 트리(2-에틸헥실)포스파이트, 트리데실포스파이트, 트리라우릴포스파이트, 트리이소옥틸포스파이트, 디페닐이소데실포스파이트, 트리스테아릴포스파이트, 트리올레일포스파이트 등을 들 수 있다.
산성 아인산 에스테르로는 구체적으로는 예를 들면 디부틸하이드로겐포스파이트, 디라우릴하이드로겐포스파이트, 디올레일하이드로겐포스파이트, 디스테아릴하이드로겐포스파이트, 디페닐하이드로겐포스파이트 등을 들 수 있다.
이상의 인산 에스테르류 중에서 올레일산성포스페이트, 트리크레실포스페이트가 바람직하다.
또한, 이들과 아민염을 형성하는 아민류로는 예를 들면 하기 일반식 (6)의 단일치환 아민, 이치환 아민 또는 삼치환 아민을 들 수 있다:
RnNH3-n
상기 식에서,
R은 탄소수 3 내지 30의 알킬기 또는 알케닐기, 탄소수 6 내지 30의 아릴기 또는 아릴알킬기, 또는 탄소수 2 내지 30의 하이드록시알킬기이며, 복수인 경우 복수의 R은 동일하거나 상이할 수 있고;
n은 1, 2 또는 3이다.
상기 일반식 (6)의 R 중에서 탄소수 3 내지 30의 알킬기 또는 알케닐기는 직쇄상, 분지상 및 환상중 임의의 것일 수 있다.
여기에서, 단일치환 아민의 예로는 부틸아민, 펜틸아민, 헥실아민, 사이클로헥실아민, 옥틸아민, 라우릴아민, 스테아릴아민, 올레일아민, 벤질아민 등을 들 수 있고; 이치환 아민의 예로는 디부틸아민, 디펜틸아민, 디헥실아민, 디사이클로헥실아민, 디옥틸아민, 디라우릴아민, 디스테아릴아민, 디올레일아민, 디벤질아민, 스테아릴ㆍ모노에탄올아민, 데실ㆍ모노에탄올아민, 헥실ㆍ모노프로판올아민, 벤질ㆍ모노에탄올아민, 페닐ㆍ모노에탄올아민, 톨릴ㆍ모노프로판올아민 등을 들 수 있다. 또한, 삼치환 아민의 예로는 트리부틸아민, 트리펜틸아민, 트리헥실아민, 트리사이클로헥실아민, 트리옥틸아민, 트리라우릴아민, 트리스테아릴아민, 트리올레일아민, 트리벤질아민, 디올레일ㆍ모노에탄올아민, 디라우릴ㆍ모노프로판올아민, 디옥틸ㆍ모노에탄올아민, 디헥실ㆍ모노프로판올아민, 디부틸ㆍ모노프로판올아민, 올레일ㆍ디에탄올아민, 스테아릴ㆍ디프로판올아민, 라우릴ㆍ디에탄올아민, 옥틸ㆍ디프로판올아민, 부틸ㆍ디에탄올아민, 벤질ㆍ디에탄올아민, 페닐ㆍ디에탄올아민, 톨릴ㆍ디프로판올아민, 크실릴ㆍ디에탄올아민, 트리에탄올아민, 트리프로판올아민 등을 들 수 있다.
인산 에스테르류 또는 이의 아민염은 기본유에 대해 조성물 총중량 기준으로 0.03 내지 5 중량%, 바람직하게는 0.1 내지 4 중량%의 비율로 배합된다.
(C) 성분
아민과 반응시키는 카복실산으로는 지방족 카복실산, 이가 카복실산(이염기산), 방향족 카복실산이 있고, 여기에서 지방족 카복실산은 탄소수 8 내지 30이고, 포화 또는 불포화일 수 있으며, 직쇄 또는 분지쇄일 수 있다. 지방족 카복실산의 구체예로는 펠라르곤산, 라우르산, 트리데칸산, 미리스트산, 팔미트산, 스테아르산, 이소스테아르산, 에이코산산, 베헨산, 트리아콘탄산, 카프롤레산, 운데실렌산, 올레산, 리놀렌산, 에루크산, 리놀산 등을 들 수 있다. 이가 카복실산의 구체예로는 옥타데실숙신산, 옥타데세닐숙신산, 아디프산, 아젤라산, 세바스산 등을 들 수 있다. 또한, 방향족 카복실산에 대해서는 살리실산이 있다.
한편, 카복실산과 반응시키는 아민으로는 디에틸렌트리아민, 트리에틸렌테트라아민, 테트라에틸렌펜타아민, 펜타에틸렌헥사아민, 헥사에틸렌헵타아민, 헵타에틸렌옥타아민, 디프로필렌트리아민, 테트라프로필렌펜타아민, 헥사부틸렌헵타아민 등의 폴리알킬렌폴리아민; 모노에탄올아민, 디에탄올아민 등의 알칸올아민을 들 수 있다.
이중에서도, 이소스테아르산과 테트라에틸렌펜타아민, 올레산과 디에탄올아민의 조합이 바람직하다. 카복실산과 아민의 반응생성물은 기본유에 대해 조성물 총중량 기준으로 0.01 내지 5 중량%, 바람직하게는 0.03 내지 3 중량%의 비율로 배합된다.
본 발명의 조성물은 기본유에 상기 (A) 내지 (C) 성분을 배합함으로써 수득되며, 통상 윤활유의 물성 향상을 위해 점도지수 향상제, 무회분 분산제, 청정제, 극압제, 소포제, 녹 방지제 등을 적절히 첨가할 수 있다.
실시예
하기에, 본 발명을 실시예에 의해 보다 상세하게 설명하고 있으나, 본 발명이 이들 예에 의해 한정되는 것은 아니다.
실시예 및 비교예의 각종 성능 시험법
(1) 셔더 방지성
자동 변속기유의 성능 시험방법(JASO M349-95)에 기초하여 μ1/μ50으로 평가하였다.
μ1 : 미끄러짐 속도 1rpm시의 마찰계수
μ50 : 미끄러짐 속도 50rpm시의 마찰계수
(2) 셔더 방지수명
JASO M349-95에 기초하여 하기 조건에서 내구 시험을 실시하고, 매 8시간마다 마찰특성을 평가하여 μ1/μ50이 1 이상이 될 때까지를 수명시간으로 하였다.
ㆍ유온 : 120℃
ㆍ면압 : 1.00±0.05MPa
ㆍ회전수 : 200rpm
(3) 전달 토크(torque) 용량
JASO M349-95에 기초하여 마찰특성 시험을 수행하고, 정마찰계수(μs)를 평가하였다.
[실시예 1]
기본유로서 파라핀계 광유(100℃에서의 동점도 5mm2/s)를 사용하고, (A) 성분으로서 디라우릴티오디프로피오네이트 0.5 중량%, (B) 성분으로서 트리크레실포스페이트 0.5 중량%, 및 (C) 성분으로서 이소스테아르산 테트라에틸펜타미드 0.5 중량%를 배합하고, 또한 기타 첨가제로서 폴리메타크릴레이트(점도지수 향상제) 9.5 중량%, 폴리부테닐숙신산이미드(무회분 분산제) 2 중량%, 칼슘 설포네이트(청정제) 2 중량%, 및 황화유지(극압제) 0.5 중량%(합계 14 중량%)를 배합하여 자동 변속기용 윤활유 조성물을 수득하고, 상기의 각종 성능시험을 수행하였다. 그 결과를 하기 표 1a에 나타내었다.
[실시예 2 내지 6 및 비교예 1 내지 8]
실시예 1에 있어서 기본유의 양 및 (A) 내지 (C) 성분과 그 양을 하기 표 1에 기재한 것으로 변화시킨 것 이외에는 동일하게 자동 변속기용 윤활유 조성물을 수득하고, 동일하게 각종 성능시험을 수행하였다. 그 결과를 하기 표 1a 내지 표 1e에 나타내었다.
Figure pat00006
Figure pat00007
Figure pat00008
Figure pat00009
Figure pat00010
실시예와 비교예에 의해 하기 사항을 알 수 있다. 실시예에 있어서, μ1/μ50은 0.82 내지 0.86을 나타내어 1 이하의 충분한 셔더 방지성을 갖는다. 또한, 셔더 방지수명은 소정의 시험에 대해 50 내지 62시간을 나타내어 비교예의 2배 이상이 된다. 또한, 이의 전달 토크용량도 0.1 이상을 가져 자동 변속기유로서 우수한 성능을 갖는다.
한편, 비교예 1 및 6에 있어서는, (B) 및 (C) 성분을 소정량 배합한 것으로 셔더 방지수명이 극히 짧아 본 발명의 목적을 달성하지 않는다. 또한, 비교예 2 및 7은 (C) 성분이 없기 때문에 셔더 방지 성능을 만족시키지 않고, (B) 성분이 없는 비교예 3 및 8은 셔더 방지수명이 짧다. 또한, 비교예 4 및 5에 있어서는, (B) 및 (C) 성분을 다량으로 배합하여 셔더 방지수명을 연장시킨 예이지만, 셔더 방지수명은 비교적 길어진 반면 실시예에 비해 수명은 1/2 이하이다. 또한, 전달 토크용량도 0.1 이하가 되어 자동 변속기유로서 불충분하다. 따라서, (B) 및 (C) 성분을 단순히 증가시켜 셔더 방지수명의 연장을 나타내어도 토크 용량의 부족을 초래하여 자동 변속기유로서 실용상 제공할 수 없다.
본 발명의 자동 변속기용 윤활유 조성물은 셔더 방지 성능이 우수하고, 셔더 방지 성능을 장기간에 걸쳐 유지할 수 있으며, 또한 전달 토크용량이 높다.

Claims (1)

  1. 기본유에, 조성물의 총중량을 기준으로 (A) 황 함유 산화방지제 또는 아민계 산화방지제 0.01 내지 5중량%, (B) 인산 에스테르류 또는 이의 아민염 0.03 내지 5중량%, 및 (C) 카복실산과 아민의 반응생성물 0.01 내지 5중량%를 배합하여 제조되는 자동 변속기용 윤활유 조성물.
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JPH09328697A (ja) 1997-12-22
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US5972854A (en) 1999-10-26
EP0812900A3 (en) 1998-04-15
EP0812900A2 (en) 1997-12-17

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