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KR930010525B1 - 수소함유 플론냉매용 윤활유와 조성물 - Google Patents

수소함유 플론냉매용 윤활유와 조성물 Download PDF

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Publication number
KR930010525B1
KR930010525B1 KR1019880013972A KR880013972A KR930010525B1 KR 930010525 B1 KR930010525 B1 KR 930010525B1 KR 1019880013972 A KR1019880013972 A KR 1019880013972A KR 880013972 A KR880013972 A KR 880013972A KR 930010525 B1 KR930010525 B1 KR 930010525B1
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KR
South Korea
Prior art keywords
hydrogen
lubricating oil
cst
oil composition
viscosity
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Application number
KR1019880013972A
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English (en)
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KR890006799A (ko
Inventor
마사또 카네꼬
Original Assignee
이데미쓰 고산 가부시끼가이샤
이데미쓰 쇼스께
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Priority claimed from JP62270390A external-priority patent/JP2590143B2/ja
Priority claimed from JP62270389A external-priority patent/JPH01115998A/ja
Application filed by 이데미쓰 고산 가부시끼가이샤, 이데미쓰 쇼스께 filed Critical 이데미쓰 고산 가부시끼가이샤
Publication of KR890006799A publication Critical patent/KR890006799A/ko
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Publication of KR930010525B1 publication Critical patent/KR930010525B1/ko

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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M111/04—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 macromolecular organic compound
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    • C10M7/00—Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
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    • C10M101/02—Petroleum fractions
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    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
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    • C10M169/00—Lubricating 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
    • C10M169/04—Mixtures of base-materials and additives
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Abstract

내용 없음.

Description

수소함유 플론냉매용 윤활유와 조성물
본 발명은 수소함유 플론(Flon) 냉매용 윤활유 및 조성물에 관한 것이며, 상세하게는 수소함유 플론 화합물과 접촉되는 계의 윤활제, 특히 이 수소함유 플론 화합물을 냉매로 하는 냉동기 등의 윤활제로서 유용한 윤활유 및 조성물에 관한 것이다.
현재, 냉동기유로는 트리클로로모노플루오로메탄(플론-11)이나 다이클로로다이플루오로메탄(플론-12)등의 수소를 함유하지 않는 플론 화합물이 냉매로서 주로 사용되고 있다. 그러나, 이러한 종류의 플론 화합물은 대기 중에 방출되면, 그 대부분이 분해되지 않고 성층권에 도달하며, 이것이 오존층을 파괴하므로, 국제적으로 사용이 규제되어가고 있다. 그 때문에, 장래적으로는 비교적 분해되기 용이한 수소함유 플론 화합물을, 냉매로서 사용하는 것이 고려되고 있지만, 그 경우, 냉매와 윤활유, 특히 광물유계 윤활유와의 2층 분리 온도가 높고, 양층이 분리되기 쉽다라고 하는 문제가 생긴다. 또한, 종래부터, 냉동기유로서 사용되고 있는 알킬벤젠으로는, 윤활성, 특히 내소 부성이 부족하고, 또한 증발에 의한 오일 소비량이 많다고 하는 문제도 생긴다.
본 발명의 목적은, 수소 함유 플론 화합물을 냉매로서 사용하는 계의 윤활제로서 바람직한 윤활유를 제공하는 것에 있다.
본 발명의 다른 목적은, 수소 함유 플론 화합물을 냉매로서 사용하는 냉동기, 쿨러, 히트 펌프 등에 바람직한 윤활제를 제공하는 것에 있다.
더우기, 본 발명의 다른 목적은, 수소함유 플론 화합물에 대하여 2층 분리 온도가 낮고, 또한 내소부성이 높으며, 증발에 의한 오이 소비량이 적고, 더구나 안정성이 양호한 윤활유를 제공하는 것에 있다.
본 발명은 다음의 제1 내지 제4의 발명의 관한 것이다. 즉, 제1발명은 ,40℃에 있어서의 동점도가 50cSt 이상의 고점도 알킬 벤젠을 주성분으로 하는 수소 함유 플론 냉매용 윤활유이며, 제2발명은, 상기의 고점도 알킬벤젠을 (A)성분으로 하고, 이것과 (B) 40℃에 있어서의 동점도가 50cSt 이상, 유동점이 -15℃ 이하이며, 또한 질소 함유량이 100ppm 이하인 광물유를 주성분으로 하는 수소 함유 플론 냉매용 윤활유 조성물이고, 제3발명은, 상기의 (A)성분과 (C) 40℃에 있어서의 동점도가 50cSt 이상이며, 또한 점도 지수가 150 이상인 폴리글리콜을 주성분으로 하는 수소 함유 플론 냉매용 윤활유 조성물이고, 제4발명은, 상기의 (A) 성분과 (B') 40℃에 있어서의 동점도가 5-600cSt, 유동점이 -15℃ 이하이며, 또한 질소 함유량이 100ppm 이하인 광물유 및 (C') 폴리글리콜을 중성분으로 하는 수소 함유 플론 냉매용 윤활유 조성물이다.
제1발명의 윤활유는, 상술한 바와 같이 고점도 알킬벤젠을 주성분으로 하는 것이지만, 이 알킬 벤젠은, 종래 냉동기유 등에 사용되고 있는 알킬벤젠에 비하여 점도가 높은 것이며, 통상적으로는 40℃에 있어서의 동점도가 50cSt 이상, 바람직하게는 60-300cSt, 더욱 바람직하게는 70-250cSt인 것이다. 여기서, 동점도가 50cSt 미만인 것으로는, 증발에 의한 오일 소비량이 많고, 또한 씨일성이 열악한 등의 각종 부적합성이 생김과 동시에, 내소부성이 불충분하고, 윤활성이 부족하다.
이와 같은 고점도 알킬벤젠으로서는, 각종의 것들이 있지만, 알킬기의 총 탄소수(알킬기가 복수인 경우는, 각각의 알킬기의 탄소수의 합계)가 20 이상인 알킬벤제(모노알킬벤젠, 다이 알킬벤젠, 트리알킬벤젠등), 바람직하게는 총 탄소수가 20 이상으로서, 더구나 알킬기를 2개 이상 갖는 것(다이알킬벤젠 등)이 바람직하게 사용된다. 또한, 이 고점도 알킬벤젠은, 동점도가 상기 범위에 드는 것이라면, 1종류 단독인 것이라도, 혹은 2종류 이상을 혼합한 것이라도 좋다.
이 제1발명의 윤활유는, 상기의 고점도 알킬벤젠을 주성분으로 하는 것이지만, 더욱더, 필요에 따라서 마찰방지제, 염소 포촉제, 산화방지제, 금속 불활성화제, 소포제 등을 적량 배합하는 것도 유효하다.
다음에, 제2발명의 윤활유 조성물은, 상기의 고점도 알킬벤젠을 (A)성분으로 하고, 이것과 (B) 광물유를 주성분으로 하는 것이다. 여기서 (B)성분으로서의 광물유는, 40℃에 있어서의 동점도가 50cSt 이상, 바람직하게는 60cSt 이상인 것이다. 동점도가 50cSt 미만인 것으로는, 증발에 의한 오일의 손실이 많고, 또한 씨일성이 저하된다고 하는 등의 부적합성이 생긴다. 또한, 이 광물유는, 유동점이 -15℃이하, 바람직하게는 -20℃ 이하, 더욱 바람직하게는 -30℃ 인 것이다.
유동점이 -15℃를 초고하면, 저온 상승이 저하되기 때문에, 본 발명이 대상으로 하는 냉동기 등의 윤활제로서는 만족할 수 없는 것으로 된다. 더우기, 이 광물유는, 질소 함유량이 100ppm 이하, 바람직하게는 50ppm 이하, 더욱 바람직하게는 30ppm 이하이다. 질소함유량이 100ppm을 초과하는 것으로는, 내열성이 저하되고, 또한 변색되기 쉽다고 하는 문제가 생긴다. 이러한 (B)성분으로서의 광물유는 동점도, 유동점 및 질소 함유량이 상술한 범위에 드는 것이라면 좋지만, 그 밖에, 유황함유량이 1중량% 이하인 것이 바람직하다.
이와 같은, 광물유로서는, 다양한 것이있지만, 구체적으로는 파라핀기계원유, 중간기계원유 혹은 나프텐 기계원유를 상압증류하던가, 혹은 상압 증류의 잔사유를 감압증류하여 얻어지는 유출유 또는 이것을 통상적인 방법에 따라서 정제하는 것에 의하여 얻어지는 정제유, 예컨대 용제정제유, 수소첨가 정제유나 탈납 처리유 등을 들 수 있다.
제2발명의 윤활유 조성물은, (A)성분인 고점도 알킬벤젠과 (B)성분인 광물유의 배합 비율에 관하여는, 특별한 제한은 없지만, 바람직하게는 (A)성분 100중량부에 대하여 (B)성분을 150중량부 이하, 특히 110-5중량부가 최적이다.
다음에, 제3발명의 윤활유 조성물은 (A)성분인 고점도 알킬벤젠과 (C)폴리글리콜을 주성분으로 하는 것이며, 이러한 (C)성분인 폴리글리콜은, 통상적으로는 40℃에 있어서의 동점도가 50cSt 이상, 바람직하게는 60cSt-800cSt이고 또한, 점도지수가 150 이상, 바람직하게는 170 이상인 것이다. 여기서, 동점도가 50cSt 미만인 폴리글리콜로는, 증발에 의한 오일 소비량이 많고, 씨일성이 열악하다고 하는 문제가 있으며, 또한 점도 지수가 150미만인 것으로는, 고온에서의 윤활성이 저하된다고 하는 문제가 생긴다.
제3발명의 윤활유 조성물은, (A)성분인 고점도 알킬벤젠과 (C)성분인 폴리글리콜의 배합비율에 관하여는, 특별한 제한은 없지만, 바람직하게는 (A)고점도 알킬벤젠 97-3중량%및 (C) 폴리글리콜 3-97중량%의 비율이다.
또한, 제4의 발명의 윤활유 조성물은, (A)성분인 고점도 알킬벤젠, (B')성분인 광물유 및 (C')성분인 폴리글리콜을 주성분으로 하는 것이다. 여기서 (A)성분인 고점도 알킬벤젠은 전술한 바와 같은 것이다. 또한, (B')성분인 광물유는, 40℃에 있어서의 동점도가 50cSt 이상인 것에 한정되지 않고, 5-600cSt인 것이 널리 사용될 수 있고, 또한 (C')성분인 폴리글리콜에 관하여는, 동점도는 특별히 제한은 없고, 일반적으로 40℃에 있어서의 동점도가 10-1000cSt인 것이 사용된다.
이 제4발명의 윤활유조성물은, (A),(B') 및 (C')성분의 배합 비율에 관하여는, 특별한 제한은 없지만, 바람직하게는 (A)고점도 알킬벤젠 2-20중량%, (B')광물유 2-15중량% 및 (C')폴리글리콜 96-65중량%의 비율이다.
제1발명의 윤활유 조성물 및 제2,3,4 발명의 조성물에는, 더욱더, 필요에 따라서 마모방지제, 염소포촉제, 산화방지제, 금속불활성화제, 소포제 등을 적량 배합하는 것도 유효하다.
상기 본 발명의 윤활유 및 윤활유 조성물은, 수소함유 플론 냉매를 사용하는 냉동기, 쿨러, 히트펌프 등의 윤활제로서 유효하지만, 여기서 냉매의 수소함유 플론으로서는, 1,1-다이클로로-2,2,2-트리플루오로에탄(플론-123), 1,1,1,2-테트라플루오로에탄(플론-134a), 1-클로로-1,1-다이플루오로에탄(플론-142b), 1,1-다이플루오로에탄(플론-152a), 트리플루오로메탄(플론-23) 혹은 모노클로로다이플루오로메탄(플론-22)을 들 수 있고, 이것들의 냉매에 대하여 특히 유효하다.
이상과 같이, 본 발명의 윤활유 및 윤활유 조성물은, 플론-123, 플론-134a, 플론-142b, 플론-152a, 플론-23, 플론-22 등의 수소함유 플론 화합물에 대하여 2층분리온도가 낮고, 또한 내소부성분이 높으며, 증발에 의한 오일 소비량도 적고, 더구나 안정성이 양호하다.
따라서, 본 발명의 윤활유 및 윤활유 조성물은, 이들 수소함유 플론 화합물을 냉매로서 사용하는 냉동기, 쿨러, 히트 펌프등의 윤활제로서 유효하게 이용된다.
다음에, 본 발명을 실시예 및 비교예에 의하여 더욱 상세히 설명한다.
[실시예 1-8 및 비교예 1-6]
제1표에 나타낸 광물유 및 알킬 벤젠을 사용하여, 윤활유 혹은 윤활유 조성물을 조제하고, 이것을 시료유로서 하기의 방법에 따라서 그 성능 평가를 행하였다. 결과를 제2표에 나타낸다.
[플론-22의 2층 분리 온도]
시료유와 플론-22를 2 : 8(중량)로 혼합하고, 2층으로 분리되는 온도를 측정하였다. ×는 10℃ 이상, ○은 10-0℃, ◎는 0℃ 이하를 나타낸다.
[화렉스 소부시험]
ASTM D 3233에 준거하여, 소부하중(파운드)으로 평가하였다.
[씨일드 튜브 시험]
시료유와 플론-22와의 2 : 1(중량) 혼합물을 철, 동, 알루미늄의 촉매와 함께, 유리관에 봉입하고, 175℃에 있어서 720시간 가열 후, 그 외관 및 석출물의 유무를 측정하였다.
[표 1]
Figure kpo00001
*1 알킬 벤젠(알킬기의 총 탄소수 19이하) : 알킬벤젠(알킬기의 총 탄소수 20이상)=50 : 50(중량비)
*2 알킬 벤젠(알킬기의 총 탄소수 19이하) : 알킬벤젠(알킬기의 총 탄소수 20이상)=30 : 70(중량비)
*3 알킬 벤젠(알킬기의 총 탄소수 19이하) : 알킬벤젠(알킬기의 총 탄소수 20이상)=10 : 90(중량비)
[표 2]
Figure kpo00002
[실시예 9-10 및 비교예 7-10]
제3표에 나타낸 광물유, 알킬벤젠 및 폴리글리콜을 사용하여, 윤활유 혹은 윤활유 조성물을 조제하고, 이것을 시료유로 하여 전술한 바와 같은 방법에 따라서 성능 평가를 행하였다.
결과는 제4표에 나타낸다.
[표 3]
Figure kpo00003
*1 알킬기의 총 탄소수가 19이하인 알킬벤젠(A)와 알킬기의 탄소수 20이상인 알킬벤젠(B)의 비,
A : B=50 : 50(중량비)
*2 알킬기의 총 탄소수가 19이하인 알킬벤젠(A)와 알킬기의 탄소수 20이상인 알킬벤젠(B)의 비,
A : B=30 : 70(중량비)
*3 알킬기의 총 탄소수가 19이하인 알킬벤젠(A)와 알킬기의 탄소수 20이상인 알킬벤젠(B)의 비,
A : B=10 : 90(중량비)
*4 폴리옥시프로필렌글리콜모노부틸에테르 분자량 1900
[표 4]
Figure kpo00004
[실시예 11-18]
제5표에 나타내는 광물유, 알킬벤젠 및 폴리글리콜을 사용하여, 윤활유 혹은 윤활유 조성물을 조제하고, 이것은 시료 유포하여 전술한 바와 같은 방법에 따라서, 그 성능 평가를 행하였다.
결과를 제5표에 나타낸다. 단, 내마모성 시험은, ASTM D 2670에 준거하여, 하중 150파운드로 1시간, 냉매로서 플론-22를 사용하고, 주입량 10ℓ/시간의 조건으로 평가하였다.
[표 5]
Figure kpo00005
*1 제1표의 시료 No. VI와 같다(40℃의 동점도 56cSt)
*2 제1표의 시료 No. Ⅶ와 같다(40℃의 동점도 90cSt)
*3 알킬벤젠(알킬기의 총 탄소수 19이하) : 알킬벤젠(알킬기의 총 탄소수 20이상)=90 : 10(중량비)(40℃의 동점도 14cSt)
*4 나프텐계 광물유 40℃의 동점도 9cSt, 질소함량 10ppm, 유황함량 0.5중량%, 유동점 -35℃
*5 나프텐계 광물유 40℃의 동점도 32cSt, 질소함량 10ppm, 유황함량 0.35중량%, 유동점 -30℃
*6 폴리옥시프로필렌글리콜모노부틸에테르, 분자량 700, 40℃의 동점도 32cSt
*7 폴리옥시프로필렌글리콜모노부틸에테르, 분자량 1000, 540℃의 동점도 56cSt

Claims (17)

  1. 40℃에 있어서의 동점도가 50cSt 이상인 고점도 알킬벤젠을 주성분으로 하는 수소함유 플론 냉매용 윤활유
  2. 제1항에 있어서, 고점도 알킬 벤젠의 40℃에 있어서의 동점도가, 60-300cSt인 수소함유 플론냉매용 윤활유.
  3. 제1항에 있어서, 수소함유 플론 냉매가, 1,1-다이클로로-2,2,2-트리플루오로에탄, 1,1,1,2-테트라플루오로에탄, 1-클로로-1,1-다이플루오로에탄, 1,1-다이플루오로에탄, 트리플루오로메탄 혹은 모노클로로다이플루오로메탄인 수소함유 플론 냉매용 윤활유.
  4. (A) 40℃에 있어서의 동점도가 50cSt 이상인 고점도 알킬벤젠 및 (B) 40℃에 있어서의 동점도가 50cSt 이상, 유동점이 -15℃ 이하이고, 또한 질소 함유량이 100ppm 이하인 광물유를 주성분으로 하는 수소함유 플론 냉매용 윤활유 조성물.
  5. 제4항에 있어서, (A)고점도 알킬벤젠 100중량부에 대하여, (B)광물유를 150중량부 이하의 비율로 배합하여 이루어지는 수소 함유 플론 냉매용 윤활유 조성물.
  6. 제4항에 있어서,(A)고점도 알킬 벤젠의 40℃에 있어서의 동점도가, 60-300cSt인 수소함유 플론 냉매용 윤활유 조성물.
  7. 제4항에 있어서, 수소 함유 플론 냉매가, 1,1-다이클로로-2,2,2-트리플루오로에탄, 1,1,1,2-테트라플루오로에탄, 1-클로로-1,1-다이플루오로에탄, 1,1-다이플루오로메탄, 트리플루오로메탄 혹은 모노클로로다이 플루오로메탄인 수소함유 플론 냉매용 윤활유 조성물.
  8. (A) 40℃에 있어서의 동점도가 50cSt 이상인 고점도 알킬벤젠 및 (C) 40℃에 있어서의 동점도가 50cSt 이상이고, 또한 점도 지수가 150 이상인 폴리글리콜을 주성분으로 하는 수소 함유 플론 냉매용 윤활유 조성물.
  9. 제8항에 있어서, (A)고점도 알킬 벤젠의 40℃에 있어서의 동점도가, 60-300cSt인 수소함유 플론냉매용 윤활유 조성물
  10. 제8항에 있어서, (A)고점도 알킬 벤젠 97-3중량% 및 (C)폴리글리콜 3-97중량 %의 비율로 배합하여 이루어지는 수소 함유 플론 냉매용 윤활유 조성물.
  11. 제8항에 있어서, 수소함유 플론냉매가 1,1-다이클로로-2,2,2-트리플루오로에탄, 1,1,1,2-테트라플루오로에탄, 1-클로로-1,1-다이플루오로에탄, 1,1-다이플루오로에탄, 트리플루오로메탄 혹은 모노클로로다이 플루오로메탄인 수소 함유 플론 냉매용 윤활유 조성물.
  12. (A) 40℃에 있어서의 동점도가 50cSt 이상인 고점도 알킬 벤젠, (B') 40℃에 있어서의 동점도가 5-600cSt, 유동점이 -15℃ 이하이고, 또한 질소 함유량이 100ppm 이하인 광물유 및 (C') 폴리글리콜을 주성분으로 하는 수소함유 플론냉매용윤활유 조성물.
  13. 제12항에 있어서, (A) 고점도 알킬 벤젠의 40℃에 있어서의 동점도가, 60-300cSt인 수소함유 플론 냉매용 윤활유 조성물.
  14. 제12항에 있어서, (A) 고점도 알킬 벤젠 2-20중량%, (B') 광물유 2-15중량%및 (C') 폴리글리콜 96-65중량%의 비율로 배합하여 이루어지는 수소 함유 플론 냉매용 윤활유 조성물.
  15. 제12항에 있어서, 수소 함유 플론 냉매가, 1,1-다이클로로-2,2,2-트리플루오로에탄, 1,1,1,2-테트라플루오로에탄, 1-클로로-1,1-다이플루오로에탄, 1,1-다이플루오로에탄, 트리플루오로메탄 혹은 모노클로로다이플루오로메탄인 수소함유 플론냉매용 윤활유 조성물.
  16. 제12항에 있어서, (B') 광물유의 40℃에 있어서의 동점도가 5-600cSt인 수소함유 플론냉매용 윤활유 조성물.
  17. 제12항에 있어서, (C') 폴리글리콜의 40℃에 있어서의 동점도가, 10-1000cSt인 수소함유 플론 냉매용 윤활유 조성물.
KR1019880013972A 1987-10-28 1988-10-26 수소함유 플론냉매용 윤활유와 조성물 KR930010525B1 (ko)

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JP62270390A JP2590143B2 (ja) 1987-10-28 1987-10-28 水素含有フロン冷媒用潤滑油組成物
JP270389/1987 1987-10-28
JP270389 1987-10-28
JP62270389A JPH01115998A (ja) 1987-10-28 1987-10-28 水素含有フロン冷媒用潤滑油及び組成物
JP270390/1987 1987-10-28
JP270390 1987-10-28

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