KR100827253B1 - High cold cohesion silicone-based grease composition - Google Patents
High cold cohesion silicone-based grease composition Download PDFInfo
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- KR100827253B1 KR100827253B1 KR1020067023288A KR20067023288A KR100827253B1 KR 100827253 B1 KR100827253 B1 KR 100827253B1 KR 1020067023288 A KR1020067023288 A KR 1020067023288A KR 20067023288 A KR20067023288 A KR 20067023288A KR 100827253 B1 KR100827253 B1 KR 100827253B1
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M169/02—Mixtures of base-materials and thickeners
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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
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
- C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
- C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
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- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
- C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
- C10M2211/0225—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
- C10M2229/0415—Siloxanes with specific structure containing aliphatic substituents used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/042—Siloxanes with specific structure containing aromatic substituents
- C10M2229/0425—Siloxanes with specific structure containing aromatic substituents used as base material
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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Abstract
하나 이상의 유성 디오가노폴리실록산 중합체, 10 % 내지 30 % 의 유기금속성 비누(들) 및 5 내지 20 중량% 의 염소화 파라핀을 포함하는 것을 특징으로 하는 고 점착성 그리스. 특히 저온에서 양호한 점착력을 제공하고, 특히 저온에서 구동 장치에 관련된 부품들간의 미끄러짐을 예방할 수 있는, 구동 금속 부품 분야에서의 처리 및/또는 보호 및/또는 윤활제로서의 상기 그리스의 용도.Highly tacky grease comprising at least one oily diorganopolysiloxane polymer, 10% to 30% organometallic soap (s) and 5 to 20% by weight chlorinated paraffin. Use of said grease as a treatment and / or protection and / or lubricant in the field of driving metal parts, in particular providing good adhesion at low temperatures and preventing slipping between the parts involved in the drive device, especially at low temperatures.
Description
본 발명은 특히 저온에서 고 점착성을 가지는 유기금속성-비누-기재 (organometallic-soap-based) 실리콘 그리스에 관한 것이다. 본 발명은 또한 상기 그리스의 제조 방법 및 특히 자동차 산업에서의 그 용도에 관한 것이다.The present invention relates, in particular, to organometallic-soap-based silicone greases having high adhesion at low temperatures. The invention also relates to a process for producing such greases and in particular their use in the automotive industry.
하기를 피하기 위해 특히 저온에서 고 점착성을 가지는 그리스의 적용이 요구되는 자동차 산업에서의 특정 적용예가 공지되어 있다:Particular applications are known in the automotive industry which require the application of grease with high adhesion, especially at low temperatures, to avoid the following:
- 첫 번째로, 운전 장치에 속하는 차량 금속성 부품들 사이의 스케이팅 (skating) 현상, 및Firstly, a skating phenomenon between the metallic parts of the vehicle belonging to the driving device, and
- 두 번째로, 제한되지 않은 (unconfined) 챔버내에 그리스가 있는 경우의 적용에서, 그리스가 하우징(housing)으로부터 흘러서 생길 수 있는 손실.Secondly, in applications where grease is present in an unconfined chamber, losses that can occur due to grease flowing from the housing.
언급할 수 있는 운전 장치의 예는 하기를 포함한다: 차량 클러치 케이블, 변속기 박스 또는 시동 장치.Examples of driving devices that may be mentioned include: vehicle clutch cables, transmission boxes or starting devices.
당해 분야에서, 이는 저온 경계치를 개선시킴으로써 상기 현상의 진행을 피할 수 있는 것과 같은, 운전 장치에 속하는 부품들 사이의 스케이팅 현상을 재현하는 기계적 시험에서의 양태와 그리스의 유동성 경계치 (또는 임계 응력) 사이의 관 계가 수립되어 왔으며, 이는 시험을 위해 선택된 온도에서 (이 경우 -40 ℃) 그리스를 컨디셔닝 할 수 있는 응력 제어 유동계를 사용하는 공지된 방식으로 유동성 경계치를 측정할 수 있다. In the art, this is a rheological threshold (or critical stress) of grease and aspects in a mechanical test that reproduces skating phenomena between parts belonging to the operating device, such as by improving the low temperature threshold, thereby avoiding the development of the phenomenon. A relationship has been established, which can measure the fluidity boundary in a known manner using a stress-controlled flow meter capable of conditioning the grease at the selected temperature (in this case -40 ° C) for the test.
본 발명의 근본적인 목적은, -40 ℃ 에서 600 P 초과의 높은 유동성 경계치를 가지는 실리콘 그리스를 제안하는 것이다.It is a fundamental object of the present invention to propose a silicone grease having a high flow threshold above 600 P at −40 ° C.
다른 목적은 그리스의 표준 특성, 특히 23 ℃ 의 상온에서 그 경도, 휘발성 물질의 낮은 함량 및 고온, 즉, 100 ℃ 내지 170 ℃ 범위의 온도에서의 삼출 (또는 블리딩(bleeding)) 에 대한 양호한 저항성을 해치지 않으면서, 높은 저온 유동성 경계치를 가질 수 있는 실리콘 그리스를 제안하는 것이다. Another object is that the grease's standard properties, in particular its hardness, low content of volatiles at room temperature of 23 ° C. and good resistance to exudation (or bleeding) at high temperatures, ie in the range from 100 ° C. to 170 ° C. It is to propose a silicone grease that can have a high low temperature fluidity threshold without harming.
다른 목적은, 경제적인 비용 조건하에서 당업자에게 공지된 방법을 통해서 제조할 수 있는 실리콘 그리스를 제안하는 것이다. Another object is to propose a silicone grease which can be prepared by methods known to those skilled in the art under economical cost conditions.
본 발명의 하나의 대상은 따라서, 하나 이상의 유성 디오가노폴리실록산 (diorganopolysiloxane) 중합체, 10 % 내지 30 % (그리스의 중량에 대해 표현된 중량%) 의 유기금속성 비누(들) 및 5 내지 20 중량% 의 할로겐화 파라핀(들) 를 포함하는 고 점착성 실리콘 그리스이며, 상기 그리스는, 하기 3 분류 중 하나 및/또는 다른 것에 속하는, 염소화된 석유 증류물-기재 선형 탄화수소로 본질적으로 이루어진 클로로파라핀이 사용되는 것으로 특징지어진다: C10-C13 짧은-사슬 클로로파라핀, C14-C17 중간-사슬 클로로파라핀 및 C18-C30 긴-사슬 클로로파라핀, 각 상기 분류는 30 % 내지 70 중량% 범위의 염소를 가질 수 있음.One subject of the present invention is therefore one or more oily diorganopolysiloxane polymers, from 10% to 30% (% by weight expressed by weight of grease) of organometallic soap (s) and from 5 to 20% by weight. Highly tacky silicone greases comprising halogenated paraffin (s), characterized in that chloroparaffins consisting essentially of chlorinated petroleum distillate-based linear hydrocarbons, belonging to one of the following three classes and / or the other, are used. Built: C10-C13 short-chain chloroparaffins, C14-C17 medium-chain chloroparaffins and C18-C30 long-chain chloroparaffins, each of which may have a chlorine in the range of 30% to 70% by weight.
그리스의 기본 구성체인 유성 디오가노폴리실록산 중합체는 하기 일반식에 해당한다:Oily diorganopolysiloxane polymers, the basic constituents of grease, correspond to the following general formula:
[식 중, 동일 또는 상이할 수 있는 기호 R 은, 지방족 불포화가 없고, 탄소수 13 이하인 탄화수소-기재 라디칼을 나타내고, 기호 n 은 30 내지 1500 범위의 임의의 수를 나타냄].[Wherein, the symbol R, which may be the same or different, represents a hydrocarbon-based radical having no aliphatic unsaturation and no more than 13 carbon atoms, and the symbol n represents any number ranging from 30 to 1500].
이러한 선형 중합체는 따라서 본질적으로, 말단 단위는 제외하고, 화학식 (R)2SiO 의 단위의 연속으로 이루어지나; 소량의 다른 단위, 예컨대 (R)2SiO 단위의 갯수에 대하여 1 % 이하 비율의 화학식 SiO2 및 (R)SiO1 . 5 의 존재를 제외하지는 않는다.Such linear polymers thus consist essentially of a series of units of formula (R) 2 SiO, with the exception of the terminal units; Small amounts of other units, such as the formula SiO 2 at a rate of 1% or less relative to the number of (R) 2 SiO units And (R) SiO 1 . Does not exclude the presence of 5 .
기호 R 로 나타내어지는 탄화수소-기재 라디칼은 하기에서 선택된다:The hydrocarbon-based radical represented by the symbol R is selected from:
- 탄소수 1 내지 13 의 알킬 라디칼, 특히 예컨대 메틸, 에틸, 프로필, 부틸, 펜틸, 헥실, 2-에틸헥실, 옥틸, 데실 및 도데실 라디칼;Alkyl radicals having 1 to 13 carbon atoms, in particular methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl and dodecyl radicals;
- 탄소수 6 내지 10 의 벤젠핵을 하나만 가지는 방향족 라디칼, 특히 예컨대 페닐, 톨릴, 자일릴, 에틸페닐, 쿠메닐 및 부틸페닐 라디칼이며, 이들 라디칼은 염소를 포함하는 하나 이상의 치환체를 지닐 수 있음.Aromatic radicals having only one benzene nucleus having 6 to 10 carbon atoms, in particular phenyl, tolyl, xylyl, ethylphenyl, cumenyl and butylphenyl radicals, which may have one or more substituents including chlorine.
그러나 각 중합체의 분자에서, 모든 탄화수소-기재 라디칼 R 의 45 % 수치 이상은 알킬 라디칼이다. 이들 디오가노폴리실록산 중합체는, 실질적으로 25 ℃ 에서 100 mPa.s 내지 500,000 mPa.s 범위의 점도를 가지는 유성 액체이다(라디칼 R 의 특성 및 n 의 값에 따라). 이는 대부분 실리콘 생산자들에 의해 산업적으로 생산되며; 게다가 그 제조는 화학적 문헌, 예를 들어 프랑스 특허 978 058, 1 025 150 및 1 108 964 에 주어진다.However, in the molecules of each polymer, at least 45% of all the hydrocarbon-based radicals R are alkyl radicals. These diorganopolysiloxane polymers are oily liquids having a viscosity substantially in the range of 100 mPa · s to 500,000 mPa · s at 25 ° C. (depending on the properties of the radicals R and the value of n). It is mostly produced industrially by silicon producers; Furthermore the preparation is given in the chemical literature, for example in French patents 978 058, 1 025 150 and 1 108 964.
사용될 수 있는 중합체의 가이드로서 하기 식으로 나타내어지는 것을 언급할 수 있다: As guides for the polymers that can be used may be mentioned those represented by the following formulas:
ni 및 n'i (i = 1 내지 7) 의 값은 주어진 범위 내에서, 각 중합체 분자의 메틸 라디칼의 수가, 이미 제시된 바와 같이, 이러한 중합체의 규소 원자에 부착된 모든 라디칼의 45% 수치 이상을 나타내도록 각각 가변한다.The values of ni and n'i (i = 1-7) range within 45% of the number of methyl radicals of each polymer molecule, as previously indicated, of all radicals attached to the silicon atoms of such polymers, as given above. Each variable to indicate.
바람직하게 사용되는 유성 디오가노폴리실록산 중합체는 단독 또는 혼합물로서, 화학식 (III) 내지 (VII) 로 표시되는 것이다.The oily diorganopolysiloxane polymers which are preferably used are those represented by the formulas (III) to (VII) alone or as a mixture.
유성 디오가노폴리실록산 중합체 이외에, 본 발명에 따른 실리콘 그리스는 겔화제로서 유기금속성 비누를 함유한다. In addition to the oily diorganopolysiloxane polymers, the silicone greases according to the invention contain organometallic soaps as gelling agents.
그리스 형성을 위해 사용되는 겔화제는 지방산 비누일 수 있다. 비누화가능한 물질은 탄소수 10 내지 32 의 고급 지방산으로부터 유도될 수 있으며, 이러한 산은 하이드록실화 또는 비하이드록실화될 수 있으며, 포화 또는 불포화될 수 있다.The gelling agent used to form the grease may be a fatty acid soap. Saponifiable materials can be derived from higher fatty acids having 10 to 32 carbon atoms, and these acids can be hydroxylated or unhydroxylated and can be saturated or unsaturated.
비하이드록실화 지방산, 특히 하기와 같은 것들의 비누가 바람직하게 사용된다: 카프르산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세르산, 미리스톨레산, 팔미톨레산, 올레산, 리놀레산 및 에루스산; 목화씨 오일, 팜 오일 및 수소화 생선 오일로부터의 지방산, 임의로 그의 혼합물 및/또는 글리세리드, 예컨대 라드 오일, 쇠고기 오일, 평지씨 오일, 팜 오일, 멘헤이든 (menhaden) 오일 또는 청어 오일; 액화 석유 및 왁스의 산화로부터 유도된 산; 수지성 산; 중유 산; 아비에트산; 나프텐산; 술폰산.Non-hydroxylated fatty acids, in particular soaps of the following, are preferably used: capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, Myristoleic acid, palmitoleic acid, oleic acid, linoleic acid and erucic acid; Fatty acids from cottonseed oil, palm oil and hydrogenated fish oil, optionally mixtures and / or glycerides such as lard oil, beef oil, rapeseed oil, palm oil, menhaden oil or herring oil; Acids derived from oxidation of liquefied petroleum and waxes; Resinous acid; Heavy oil acid; Abietic acid; Naphthenic acid; Sulfonic acid.
비누 제조에 사용되는 비누화제는 금속성 Li, Na, K, Cs, Mg, Ca, Sr, Cd, Zn, Pb 또는 Co 화합물일 수 있고, 바람직하게는 상기 언급된 알칼리 금속 및 알칼리성 토금속 중 하나의 옥시드, 하이드록시드 또는 카르보네이트이다. 비누의 혼합물도 사용될 수 있으며, 이러한 비누는 인시츄 (in situ) 에서 제조되거나, 또는 미리 제조되어 그리스를 형성할 수 있다.The saponifying agent used in the soap preparation may be metallic Li, Na, K, Cs, Mg, Ca, Sr, Cd, Zn, Pb or Co compounds, preferably jade of one of the above-mentioned alkali metals and alkaline earth metals. Seed, hydroxide or carbonate. Mixtures of soaps may also be used, such soaps may be prepared in situ or may be prepared in advance to form grease.
단독 또는 혼합물로 사용되는 비누의 특정 예는: 스테아르산의 리튬 비누; 수소화 생선 오일 지방산의 리튬 비누; 스테아르산의 소듐 비누; 올레산의 소듐 비누; 올레산의 포타슘 비누; 스테아르산의 칼슘 비누; 스테아르산의 바륨 비누; 혼합 스테아르산 및 올레산의 바륨 비누; 스테아르산의 복합 리튬 및 소듐 비누이다.Specific examples of soaps used alone or in admixture include: lithium soaps of stearic acid; Lithium soaps of hydrogenated fish oil fatty acids; Sodium soap of stearic acid; Sodium soap of oleic acid; Potassium soap of oleic acid; Calcium soap of stearic acid; Barium soap of stearic acid; Barium soap of mixed stearic acid and oleic acid; Complex lithium and sodium soap of stearic acid.
단독 또는 혼합물로 사용되는 특히 적합한 비누는 스테아르산의 리튬 비누 및 스테아르산의 복합 리튬 및 소듐 비누이다.Particularly suitable soaps used alone or in admixture are lithium soaps of stearic acid and complex lithium and sodium soaps of stearic acid.
본 발명에 따른 그리스의 비누 함량은 10 중량% 내지 30 중량% 를 나타내며; 이 함량이 15 중량% 내지 25 중량% 를 나타내는 것이 추천된다.The soap content of the greases according to the invention represents 10% to 30% by weight; It is recommended that this content represents 15% to 25% by weight.
또한, 그 목적이 그리스의 제조를 용이하게 (충전물의 보다 양호한 분산, 혼합 시간의 감소) 하고/하거나, 그 내부 점착을 개선하고/하거나, 착색을 제공하는 것인 보조 첨가제는 유성 디오가노폴리실록산 중합체 및 유기금속성 비누와 혼입될 수 있다. 가이드로서 언급될 수 있는 첨가제는 하기를 포함한다: 폴리알킬렌 글리콜; 붕산 및 알킬 보레이트; 펜타에리트리톨; 25℃ 에서 10 내지 500 mPa.s 범위의 낮은 점도를 갖는 하이드록실화 디오가노폴리실록산 오일; 착색 안료. 도입된 상기 첨가제의 총량은, 사용되는 경우, 그리스의 중량에 대해 보통 1 중량% 내지 8 중량% 범위에 있다.In addition, auxiliary additives whose purpose is to facilitate the preparation of grease (better dispersion of the filling, reduction of mixing time), and to improve the internal adhesion thereof and / or to provide coloring are oily diorganopolysiloxane polymers. And organometallic soaps. Additives that may be mentioned as guides include: polyalkylene glycols; Boric acid and alkyl borate; Pentaerythritol; Hydroxylated diorganopolysiloxane oils having a low viscosity in the range of 10 to 500 mPa · s at 25 ° C .; Coloring pigments. The total amount of said additive introduced, when used, is usually in the range of 1% to 8% by weight relative to the weight of the grease.
본 발명에 따른 실리콘 그리스의 구성에 포함된 클로로파라핀은 이러한 유형의, 다수의 기술되고 시판되는 이러한 유형의 유기 화합물로부터 선택될 수 있다.The chloroparaffins included in the construction of the silicone greases according to the invention can be selected from a number of these types of organic compounds of this type which are described and commercially available.
이러한 화합물은 대기압 및 실온 (23 ℃) 에서 액체이고; 이들의 점도는 500 내지 100 000 mPa.s 범위, 바람직하게는 1000 내지 20 000 mPa.s 범위인 것으로 공지되어 있다. Such compounds are liquid at atmospheric pressure and at room temperature (23 ° C.); Their viscosity is known to be in the range of 500 to 100 000 mPa · s, preferably in the range of 1000 to 20 000 mPa · s.
본 출원인은, 본 발명의 조건 하에서, 사용되는 클로로파라핀이 바람직하게는 염소의 중량% 가 40% 내지 60% 범위인 C14-C17 중간-사슬 및 C18-C30 긴-사슬 클로로파라핀임을 발견하였다. Applicants have found that under the conditions of the present invention, the chloroparaffins used are preferably C14-C17 medium-chain and C18-C30 long-chain chloroparaffins, wherein the weight percent of chlorine ranges from 40% to 60%.
특히 적절한 클로로파라핀의 구체적인 예로는, Ineos Chlor 사에서 상표명 S54, S56, E56, M50, 42SS 및 48 하에 판매되는 제품을 특히 언급할 수 있다. As specific examples of particularly suitable chloroparaffins, mention may be made especially of the products sold under the trade names S54, S56, E56, M50, 42SS and 48 by Ineos Chlor.
본 발명에 따른 그리스 중 클로로파라핀(들)의 함량은 5 중량% 내지 20 중량% 로 나타나는데; 상기 함량은 10 중량% 내지 15 중량% 를 나타낼 것이 추천된다. The content of chloroparaffin (s) in the grease according to the invention is represented by 5 to 20% by weight; It is recommended that the content represent 10% to 15% by weight.
상기 그리스는 유성 디오가노폴리실록산 중합체(들) 중 비누의 용융/재결정에 의해서, 및 용융/재결정 단계 전 또는 후의, 하지만 바람직하게는 용융/재결정 후의 클로로파라핀(들)의 혼입 및 그리스의 냉각 단계에 의해서 제조된다. 상기 절차는 점성 혼합물의 블렌딩을 위해 고안된 장치 내에서 수행되는데; 따라서, 예를 들면, 블렌더 및 밀이 상기 제조에 특히 적절하다. 후속 단계에서, 필요하다면, 그리스를, 예를 들면 롤 밀 또는 콜로이드 밀에서 작동시켜 분쇄함으로써, 그리스의 유동성 및/또는 외관을 원하는 용도에 적합하도록 하는 것이 가능하다. The grease is subjected to melting / recrystallization of soap in the oily diorganopolysiloxane polymer (s) and to incorporation of the chloroparaffin (s) before or after the melting / recrystallization step, but preferably after the melting / recrystallization and cooling of the grease. Is manufactured by. The procedure is carried out in a device designed for the blending of the viscous mixture; Thus, for example, blenders and mills are particularly suitable for the preparation. In a subsequent step, if necessary, it is possible to make the grease's fluidity and / or appearance suitable for the desired application by operating the grinder, for example in a roll mill or a colloid mill.
본 발명에 따른 그리스는 -40 ℃ 에서 600 Pa 를 초과하는 높은 유동성 경계치를 가지면서, 예를 들면, 침투도, 휘발성 화합물의 함량 및 삼출 양태에 관하여 바람직한 특징을 동시에 제공할 수 있다. The greases according to the invention can at the same time provide the desired characteristics with respect to permeability, the content of volatile compounds and the exudation aspect, while having a high flow threshold above 600 Pa at −40 ° C.
이들 그리스는 특히 저온에서 양호한 점착성을 가지며, 그 결과로 특히 저온에서, 운전 장치에 관여하는 부품들, 예를 들면 자동차 분야에서 차량 클러치 케이블, 변속기 박스 또는 시동 장치에 관여하는 성분들 사이에서의, 특히는 스케이팅 현상을 방지하는 것이 가능하기 때문에; 구동 금속성 차량 부품의 분야에서 처리 및/또는 보호 및/또는 윤활제로서 성공적으로 사용된다. These greases have good adhesion, especially at low temperatures, and as a result, in particular at low temperatures, between the components involved in the driving device, for example in the automotive field, among the components involved in a vehicle clutch cable, transmission box or starting device, In particular, because it is possible to prevent the skating phenomenon; It is successfully used as a treatment and / or protection and / or lubricant in the field of drive metallic vehicle parts.
하기 실시예는 본 발명을 예시한다. The following examples illustrate the invention.
실시예 1Example 1
본 발명에 따른 실리콘 그리스의 제조를 하기한다.The preparation of the silicone grease according to the invention is as follows.
본 그리스 제제를 하기 표 1에 기재한다.This grease formulation is shown in Table 1 below.
(1) 프리믹스 35/65: 35중량%의 리튬 스테아레이트 및 65중량%의 오일 510V100으로 이루어진 혼합물로, 이 혼합물은 암 (arm) 블렌더에서 작업하여 수득되고, 이는, 하기 조건하에서 용융/재결정 사이클을 거친 것이다: 약 200℃에서 비누의 용융 이후 23℃로 냉각;(1) Premix 35/65: A mixture consisting of 35% by weight of lithium stearate and 65% by weight of oil 510V100, which is obtained by working in an arm blender, which melt / recrystallization cycles under the following conditions Was passed through: cooling to 23 ° C. after melting the soap at about 200 ° C .;
(2) 오일 510V100: 25℃에서 점도 100mPa.s인 폴리(디메틸)(메틸페닐)실록산 공중합체로, 15중량%의 Si(C6H5)(CH3)O 단위 함유;(2) oil 510V100: poly (dimethyl) (methylphenyl) siloxane copolymer having a viscosity of 100 mPa · s at 25 ° C., containing 15% by weight of Si (C 6 H 5 ) (CH 3 ) O units;
(3) 클로로파라핀: 상품명 E56으로 Ineos Chlor 회사에서 시판되고, 하기 특성을 소지함: C14-C17 사슬; 25℃에서 점도는 11 868 mPa.s; 몰질량 459.6g 및 Cl2 중량%는 55.75.(3) Chloroparaffin: sold by the Ineos Chlor company under the trade name E56 and possesses the following properties: C14-C17 chain; The viscosity at 25 ° C. was 11 868 mPa.s; The molar mass of 459.6 g and Cl 2 wt% is 55.75.
그리스는 DAC 150FV-K 스피드 믹서TM 블렌더로 제조하는데 (Hauschild Engineering 사 시판), 35중량%의 리튬 스테아레이트 및 65중량%의 오일 H510V100으로 이루어진 그리스 프리믹스로부터 시작한다. 클로로파라핀 첨가제를 가하고, 오일 H510V100으로 제제를 완성하여 최종 스테아레이트 함량이 22.4중량% 및 최종 클로로파라핀 함량이 12중량%가 되게한다.Grease is made with a DAC 150FV-K Speed Mixer ™ blender (available from Hauschild Engineering), starting with a grease premix consisting of 35% by weight lithium stearate and 65% by weight oil H510V100. Chloroparaffin additives are added and the formulation is completed with oil H510V100 to have a final stearate content of 22.4% by weight and a final chloroparaffin content of 12% by weight.
2. 단락 1에서 제조한 그리스의 일반 성질을 하기한다.2. The general properties of the grease prepared in paragraph 1 are given below.
(4) 흐름 경계치:(4) flow threshold:
사용 장치:Device used:
- 유량 과학용 SR5 응력 제어 유량계;SR5 stress controlled flow meters for flow science;
- Julabo F25 항온조;Julabo F25 thermostat;
- 25mm 콘/플레이트, 0.0984rad의 각:-25mm cone / plate, angle of 0.0984rad:
+ 간격; 0.0559mm,+ Spacing; 0.0559mm,
+ 시리얼 번호 4144.+ Serial number 4144.
방법:Way:
1) 플레이트를, 냉각조 및 카디스 (cardice)를 조합 사용하여 -40℃로 유지시킨 에탄올 기재 액체 순환으로 -40℃로 냉각한다.1) The plate is cooled to -40 ° C with an ethanol based liquid circulation maintained at -40 ° C using a combination of a cooling bath and a cardice.
2) 장치를 영점화시키고, 간격이 일단 조절되면, 빈 스핀들 (empty spindle) 의 관성이 일정해질 때까지 체크한다.2) Zero the device and once the clearance has been adjusted, check until the inertia of the empty spindle is constant.
3) 플레이트 상의 응축을 아세톤으로 제거한다.3) Remove condensation on the plate with acetone.
4) 제품을 삽입하고 이후 간격을 조절한다.4) Insert the product and adjust the gap afterwards.
5) 분석을 선택한다: 6.28rad/s 의 고정 진동에서 1-5000 Pa의 다이내믹 스트레스 모드로 스캐닝.5) Select analysis: scanning in dynamic stress mode of 1-5000 Pa at a fixed vibration of 6.28 rad / s.
6) 플레이트가 -40℃로 안정화되면 분석을 개시한다.6) Start assay when plate is stabilized at -40 ° C.
7) 각 샘플을 2회 측정하여 측정의 반복성을 체크한다.7) Measure each sample twice to check the repeatability of the measurement.
1Hz 진동, -40℃에서 분석이 실시됨을 언급할 수 있다. 이는, 주변온도에서 약 3000rpm의 진동수와 관련되는 것으로 보인다.It can be mentioned that the analysis is performed at 1 Hz vibration, -40 ° C. This seems to be related to a frequency of about 3000 rpm at ambient temperature.
(5) 작업 침투도: 특정 기구내에서 벗겨진 그리스의 일정성 (consistency)를, 표준 NF T 60132 (ASTM 표준 D217과 동등)에 기재된 조건하에서 그리스 내로 콘의 침투도를 측정하여 평가한다.(5) Work Penetration: The consistency of the grease peeled off within a specific instrument is evaluated by measuring the penetration of the cone into the grease under the conditions described in standard NF T 60132 (equivalent to ASTM standard D217).
(6) 휘발물%: 10g의 그리스로 작업하여, 24시간 동안 150℃ 오븐 내에 놓인 그리스의 중량 손실을 측정한다.(6)% volatiles: Work with 10 g of grease to measure the weight loss of the grease placed in the 150 ° C. oven for 24 hours.
(7) 삼출: 표준 FTMS 791321의 요건에 따라 작업하여, 24시간 동안 150℃에서 유지시킨 그리스 10그램이 놓여진 메탈 그릴을 통해 삼출되는 오일의 양을 측정한다.(7) Exudation: Work in accordance with the requirements of standard FTMS 791321 to determine the amount of oil exuded through a metal grill with 10 grams of grease maintained at 150 ° C. for 24 hours.
3. 단락 1에서 제조된 그리스의 자동차 내에서의 수행능을 하기에 기재한다.3. The performance in the motor vehicle of the grease produced in paragraph 1 is described below.
단락 1에 따라 제조된 그리스로 수개의 운전 배열 및 수개의 시동 장치상에서 수행된 기계적 시험은 긍정적이다; 즉, -40℃에서 스케이팅이 부재하며, 시험 벤치 상의 고온에서 시동 장치가 올바르게 작동함.With greases prepared in accordance with paragraph 1, mechanical tests performed on several operating arrangements and several starting devices are positive; That is, there is no skating at -40 ° C and the starting device works correctly at high temperatures on the test bench.
본 출원에서, 자동차의 시동 장치 자체를 연소 엔진으로 연결하는 커플링 또는 비(非)커플링 장치로 그리스가 도입됨을 지적하여야만 한다.In the present application, it should be pointed out that grease is introduced into a coupling or non-coupling device which connects the starting device of the motor vehicle itself to the combustion engine.
실시예 2 내지 5Examples 2-5
본 발명의 기타 실리콘 그리스의 제조를 하기에 기재한다.The preparation of other silicone greases of the present invention is described below.
이들 그리스는;These greases;
- 실시예 1의 1 부분에 기재된 바와 동일한 방법으로 제조되나, 단 다소 변형된 다른 클로로파라핀의 비율이 사용되며 (하기 실시예 3 참조), 그리고,Prepared in the same manner as described in part 1 of example 1 except that a slightly modified proportion of other chloroparaffins is used (see example 3 below), and
-하기의 성질을 제공한다 (하기 실시예 3 참조).It provides the following properties (see Example 3 below).
(8): 상품명 S54로 Ineos Chlor 회사에서 시판되고, 하기 특성을 소지하는 제품: C14-C17 사슬; 25℃에서 점도는 4400 mPa.s; 몰질량 443.2g 및 Cl2 중량%는 54.(8): a product sold by the Ineos Chlor company under the trade name S54 and having the following properties: C14-C17 chain; The viscosity at 25 ° C. was 4400 mPa · s; Molar mass 443.2 g and Cl 2 The weight percent is 54.
(9): 상품명 S56으로 Ineos Chlor 회사에서 시판되고, 하기 특성을 소지하는 제품: C14-C17 사슬; 25℃에서 점도는 11 868 mPa.s; 몰질량 459.6g 및 Cl2 중량%는 55.75.(9): A product sold by the Ineos Chlor company under the trade name S56 and having the following characteristics: C14-C17 chain; The viscosity at 25 ° C. was 11 868 mPa.s; The molar mass of 459.6 g and Cl 2 wt% is 55.75.
(8): 상품명 M50으로 Ineos Chlor 회사에서 시판되고, 하기 특성을 소지하는 제품: C18-C20 사슬; 25℃에서 점도는 17 700 mPa.s; 몰질량 520.3g 및 Cl2 중량%는 52.2.(8): a product sold by the Ineos Chlor company under the trade name M50 and having the following characteristics: C18-C20 chain; The viscosity at 25 ° C. was 17 700 mPa · s; The molar mass of 520.3 g and Cl 2 wt% is 52.2.
(8): 상품명 42SS로 Ineos Chlor 회사에서 시판되고, 하기 특성을 소지하는 제품: 왁스성 사슬; 25℃에서 점도는 2160 mPa.s; 몰질량 625.1g 및 Cl2 중량%는 41.5.(8): A product sold by the Ineos Chlor company under the trade name 42SS and having the following properties: waxy chain; The viscosity at 25 ° C. is 2160 mPa · s; The molar mass of 625.1 g and Cl 2 wt% is 41.5.
클로로파라핀 기재 첨가제를 가함으로써, 대조군 실리콘 그리스의 흐름 경계치가 실질적으로 증가됨을 상기 표로부터 명백히 알 수 있다.It can be clearly seen from the table that by adding a chloroparaffin based additive, the flow threshold of the control silicone grease is substantially increased.
Claims (10)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0404793A FR2869911A1 (en) | 2004-05-05 | 2004-05-05 | HIGH COHESION SILICONE GREASE WITH COLD |
FR0404793 | 2004-05-05 | ||
PCT/FR2005/000943 WO2005121287A1 (en) | 2004-05-05 | 2005-04-19 | High cold cohesion silicone-based grease composition |
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KR20070034467A KR20070034467A (en) | 2007-03-28 |
KR100827253B1 true KR100827253B1 (en) | 2008-05-07 |
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KR1020067023288A KR100827253B1 (en) | 2004-05-05 | 2005-04-19 | High cold cohesion silicone-based grease composition |
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US (1) | US20080108530A1 (en) |
EP (1) | EP1753850A1 (en) |
JP (1) | JP2007536423A (en) |
KR (1) | KR100827253B1 (en) |
CN (1) | CN101103099A (en) |
FR (1) | FR2869911A1 (en) |
WO (1) | WO2005121287A1 (en) |
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FR2906257A1 (en) * | 2006-09-25 | 2008-03-28 | Rhodia Recherches & Tech | HIGH COHESION SILICONE GREASE WITH COLD |
CN109490441A (en) * | 2018-11-29 | 2019-03-19 | 广东省测试分析研究所(中国广州分析测试中心) | A kind of measuring method of short chain chlorinated paraffin content and its carbochain composition |
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NL75295C (en) * | 1950-03-23 | |||
JPS60106890A (en) * | 1983-11-14 | 1985-06-12 | Shin Etsu Chem Co Ltd | Grease composition |
JPS62283196A (en) * | 1986-06-02 | 1987-12-09 | Shin Etsu Chem Co Ltd | Silicone grease |
JPH07113114B2 (en) * | 1991-03-19 | 1995-12-06 | ダウ コーニング アジア株式会社 | Grease composition |
-
2004
- 2004-05-05 FR FR0404793A patent/FR2869911A1/en active Pending
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2005
- 2005-04-19 JP JP2007512247A patent/JP2007536423A/en not_active Abandoned
- 2005-04-19 KR KR1020067023288A patent/KR100827253B1/en not_active IP Right Cessation
- 2005-04-19 CN CNA200580020051XA patent/CN101103099A/en active Pending
- 2005-04-19 WO PCT/FR2005/000943 patent/WO2005121287A1/en active Application Filing
- 2005-04-19 EP EP05757934A patent/EP1753850A1/en not_active Withdrawn
- 2005-04-19 US US11/579,617 patent/US20080108530A1/en not_active Abandoned
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JP2007536423A (en) | 2007-12-13 |
CN101103099A (en) | 2008-01-09 |
EP1753850A1 (en) | 2007-02-21 |
WO2005121287A1 (en) | 2005-12-22 |
US20080108530A1 (en) | 2008-05-08 |
KR20070034467A (en) | 2007-03-28 |
FR2869911A1 (en) | 2005-11-11 |
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