WO1991013955A1 - Composition de graisse lubrifiante - Google Patents
Composition de graisse lubrifiante Download PDFInfo
- Publication number
- WO1991013955A1 WO1991013955A1 PCT/EP1991/000407 EP9100407W WO9113955A1 WO 1991013955 A1 WO1991013955 A1 WO 1991013955A1 EP 9100407 W EP9100407 W EP 9100407W WO 9113955 A1 WO9113955 A1 WO 9113955A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- grease composition
- composition according
- grease
- lithium
- acid
- Prior art date
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
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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
- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
- C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/06—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having more than one carboxyl group bound to an acyclic carbon atom or cycloaliphatic carbon atom
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- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/08—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- 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
- C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
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- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C10M169/06—Mixtures of thickeners and additives
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
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Definitions
- This invention relates to a lubricating grease composition and, more especially, to grease compositions thickened with lithium soap.
- Lithium soap greases are well known and are used in the lubrication of many automotive and industrial applications, for example bearings, gears and couplings. Whilst lithium soap greases, and particularly lithium soap complex greases, are often favoured for higher temperature applications, the greases have the disadvantage that they have a limited lifetime at temperatures exceeding about 120°C as the oil tends to separate ("bleed") from the grease, and thus frequent reapplication of the grease is required.
- the present invention provides a lithium complex grease with prolonged lifetime at high temperatures. More specifically the invention provides a lubricating grease composition comprising a major proportion of a lubricating base oil, a thickening amount of a lithium soap comple and an effective amount of an organic metal compound wherein the metal is selected from molybdenum, tungsten, vanadium, niobium and tantalum.
- the grease according to the invention has the advantage that it has a significantly improved lifetime at high temperatures, the improvement being particularly evident at temperatures between about 120 and 160°C.
- the grease has a lower tendency to bleed oil compared with other lithium soap-containing greases.
- the number of reapplications necessary to maintain satisfactory lubrication of the mechanical part to which the grease is applied can be considerably reduced.
- the grease can provide "lifetime" lubrication, i.e. it need not be renewed for the lifetime of the mechanical part. Examples of such applications include automotive antifriction bearings and sliding bearings.
- the amount of lithium soap complex present in the grease is preferably from 2 to 30 wt %, preferably 5 to 20 wt % based on the total weight of the composition. It is preferred that the lithium complex soap comprises a lithium soap of a C12 to C24 hydroxy fatty acid and at least one other lithium compound. This other lithium compound is advantageously either a lithium soap of a C2 to C12 aliphatic dicarboxylic acid or a lithium salt of boric acid, or a mixture of both.
- the lithium soap of the hydroxy fatty acid is a Cig to C2 0 hydroxy fatty acid.
- a particularly preferred hydroxy fatty acid is hydroxystearic acid, for example 9-hydroxy-, 10-hydroxy-, or 12-hydroxystearic acid, more preferably the latter.
- Ricinoleic acid which is an unsaturated form of 12-hydroxystearic acid having a double bond in the 9-10 position, can also be used.
- Other suitable hydroxy fatty acids include 12-hydroxybehenic acid and 10-hydroxypalmitic acid.
- the proportion of dicarboxylic acid to hydroxy fatty acid employed is generally a weight ratio of between 0.05 and 1, usually between 0.1 and 0.8, parts dicarboxylic acid per part hydroxy fatty acid.
- the dicarboxylic acid is preferably a C4 to C12 - more preferably C - to C1 0 , aliphatic dicarboxylic acid.
- suitable acids include oxalic, malonic, succinic, glutaric, adipic, suberic, pimelic, azelaic, dodecanedioic and sebacic acids. Azelaic and sebacic acids are especially preferred.
- the proportion of hydroxy fatty acid to boric acid employed is generally a weight ratio of between 3 and 100 parts, usually between 5 and 80 parts, hydroxy fatty acid per part boric acid.
- the lithium soap complex may also include a second hydroxycarboxylic acid.
- This generally has 3 to 14 carbon atoms and an -OH group not more than 6 carbon at atoms away from the carboxyl group.
- This acid can be either an aliphatic acid such as lactic acid, 6-hydroxydecanoic acid, 3-hydroxybutanoic acid, 1-hydroxycaproic acid, 4-hydroxybutanoic acid, 6-hydroxy-alpha-hydroxystearic acid, etc.
- an aromatic acid such as parahydroxy-benzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid); 2,6-dihydroxybenzoic acid (gamma resorcyclic acid); 4-hydroxy-4-methoxybenzoic acid, etc. or a hydroxyaromatic aliphatic acid such as orthohydroxyphenyl, metahydroxyphenyl, or parahydroxyphenyl acetic acid.
- a cycloaliphatic hydroxy acid such as hydroxycyclopentyl carboxylic acid or hydroxynaphthenic acid could also be used. Particularly useful hydroxy acids are lactic acid, salicylic acid, and parahydroxybenzoic acid.
- a lower alkyl ester usually, a Ci to C 4 alkyl ester of the above second hydroxycarboxylic acid can be used instead of the free acid.
- boric acid is employed as the ester aids dispersion of the insoluble salt.
- a preferred ester is methyl salicylate.
- the proportion is generally a weight ratio of 0.1 to 10 parts, usually 0.5 to 5 parts, second hydroxycarboxylic acid per part of the acid component of the said other lithium-containing compound, for example boric acid.
- the metal of the organic metal compound is preferably molybdenum.
- the organic component of this compound is preferably a thiocarba ate or xanthate.
- preferred organic metal compounds are molybdenum thiocarbamate and molybdenum xanthate compounds.
- the preferred amount of the organic metal compound present in the grease composition is from 0.1 to 10 wt %, more preferably 0.5 to 5 wt %, based on the total weight of the composition.
- the organic metal compound acts as an antiwear agent and prolongs the high temperature lifetime of the grease.
- the grease according to the invention also contains an antioxidant, which is generally present in an amount from 0.1 to 5 wt %, preferably 0.5 to 3 wt %, based on the total weight of the composition.
- the antioxidant employed is preferably an a ine based antioxidant compound, an example being alkyldiphenylamine.
- the lubricating base oil employed in the grease composition can be any of the conventionally used lubricating oils and is preferably a mineral oil or a blend of mineral and synthetic oils. In general these lubricating oils have a viscosity in the range of 35 to 300 SUS at 210°F, and a viscosity index in the range of 30 to 170, preferably 30 to 140.
- Mineral lubricating oil base stocks used in preparing the greases can be any conventionally refined base stocks derived from paraffinic, naphthenic and mixed base crudes.
- Synthetic lubricating oils that can be used include esters of dibasic acids, such as a di-2-ethylhexyl sebacate, esters of glycols such as C13 oxo acid diester or tetraethylene glycol, or complex esters such as one formed from 1 mole of sebacic acid and 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.
- Other synthetic oils that can be used include synthetic hydrocarbons such as alkyl benzenes, e.g. alkylate bottoms from the alkylation of benzene with tetrapropylene, or the polymers and copolymers of alpha olefins; silicone oils, e.g.
- ethyl phenyl polysiloxanes methyl polysiloxanes, etc.
- polyglycol oils e.g. those obtained by condensing butyl alcohol with propylene oxide
- carbonate esters e.g. the product of reacting C ⁇ oxo alcohol with ethylcarbonate to form a half ester followed by reaction of the latter with tetraethylene glycol, etc.
- suitable synthetic oils include the polyphenyl ethers, e.g. those having from about 3 to 7 ether linkages and about 4 to 8 phenyl groups (see US Patent 3,424,678, column 3).
- the grease according to the invention also has the advantage that the usual benefits associated with lithium complex greases may be retained, together with the additional benefit of prolonged lifetime at high temperatures.
- Usual benefits associated with lithium soap greases include good water resistance, high dropping point, and good mechanical and chemical stability.
- the grease according to the invention can also be employed in low temperature, as well as high temperature, applications.
- Examples 1-3 demonstrate grease composition according to the invention based on lithium complexes comprising a lithium soap of a hydroxy fatty acid and a lithium soap of an aliphatic discarboxylic acid.
- Example 4 is comparative, using the same lithium soap complex.
- a lithium complex grease was formulated with the following components:
- Fio which represents the time after which the first ten percent of the bearings are starved of lubricant
- F50 which represents the time after which fifty percent of the bearings are starved of lubricant.
- a grease which has an F50 value of at least 100 hours at a given temperature is regarded as a lifetime lubricant at that temperature.
- a grease composition was formulated as in Example 1 except that MDDC employed was supplied as Molyvan A from Vanderbilt Company Inc.
- Example 3 The grease was tested as described in Example 1 and the results are given in Table 1 below.
- a grease composition was formulated as in Example 1 except that the alkyldiphenylamine was omitted and the amount of MDDC increased to 3 wt %. The balance was made up by increasing the amount of base oil to 81.5 wt %.
- the greases of Examples 1-3 were compared with a conventional lithium complex soap grease.
- This grease contained the same base oil and lithium complex as the above Examples, but contained no molybdenum compound nor alkyldiphenylamine.
- a grease composition was formulated with the following components:
- the base oil and lithium soap complex components were formulated as described in Example 2 of US Patent 3,758,497.
- the MDDC and alkyldiphenylamine additives were then added, and the grease was milled using a conventional grease mill.
- a grease composition was formulated as in Example 2 except that the paraffinic base oil was replaced with a base oil blend of 28.5 wt %, based on the total grease composition, of a poly-alpha-olefin (V 4 o-48mm 2 /s, VIQO - 7.9mm2/s) and 52 wt %, based on the total grease composition, of a paraffinic oil base (V 4 o ⁇ 110mm 2 /s, V 100 - 12mm 2 /s) .
- the blended base oil yielded the following viscosities:
- the grease was tested as described in Example 1 at 160°C.
- the F]_o result was 101 hours and the F 50 result was 134 hours.
- This grease also demonstrated long lifetime at high temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69101376T DE69101376T2 (de) | 1990-03-07 | 1991-03-05 | Schmierfettzusammensetzung. |
AT91904931T ATE102644T1 (de) | 1990-03-07 | 1991-03-05 | Schmierfettzusammensetzung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9005104.6 | 1990-03-07 | ||
GB9005104A GB2241707A (en) | 1990-03-07 | 1990-03-07 | Lubricating grease composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991013955A1 true WO1991013955A1 (fr) | 1991-09-19 |
Family
ID=10672172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/000407 WO1991013955A1 (fr) | 1990-03-07 | 1991-03-05 | Composition de graisse lubrifiante |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0523064B1 (fr) |
JP (1) | JP2964165B2 (fr) |
CA (1) | CA2077555A1 (fr) |
DE (1) | DE69101376T2 (fr) |
GB (1) | GB2241707A (fr) |
WO (1) | WO1991013955A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994011470A1 (fr) * | 1992-11-14 | 1994-05-26 | Gkn Technology Limited | Graisses |
WO1995007963A1 (fr) * | 1993-09-13 | 1995-03-23 | Exxon Chemical Patents Inc. | Composition antioxydante melangee |
EP0696636A1 (fr) * | 1993-04-30 | 1996-02-14 | Tonen Corporation | Composition d'huile lubrifiante |
CN101200670B (zh) * | 2006-12-12 | 2010-05-19 | 中国石油天然气集团公司 | 一种复合锂基润滑脂及其制备方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3370829B2 (ja) * | 1995-04-21 | 2003-01-27 | 株式会社日立製作所 | 潤滑グリース組成物 |
JP2001187891A (ja) * | 1995-04-21 | 2001-07-10 | Hitachi Ltd | 潤滑油組成物及び潤滑グリース組成物 |
US6482779B2 (en) | 2000-03-21 | 2002-11-19 | Nsk Ltd. | Lubricating grease composition and rolling apparatus comprising same |
JP2001335792A (ja) * | 2000-03-21 | 2001-12-04 | Nsk Ltd | 潤滑グリース組成物及びそれを用いた転がり軸受、転動装置 |
CN101880582A (zh) * | 2010-06-29 | 2010-11-10 | 濮阳市航天化工有限公司 | 高温润滑脂及其制备方法 |
CN101880581A (zh) * | 2010-06-29 | 2010-11-10 | 濮阳市航天化工有限公司 | 通用锂基润滑脂及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3248325A (en) * | 1964-08-21 | 1966-04-26 | Phillips Petroleum Co | Lubricating composition |
GB1097372A (en) * | 1964-08-07 | 1968-01-03 | Vanderbilt Co R T | Dithiocarbamates, the manufacture and use thereof, and compositions containing the same |
EP0176202A1 (fr) * | 1984-08-22 | 1986-04-02 | Mobil Oil Corporation | Composition de graisse |
US4749502A (en) * | 1986-07-14 | 1988-06-07 | Exxon Research And Engineering Company | Grease composition |
EP0286139A1 (fr) * | 1987-04-10 | 1988-10-12 | Gesellschaft für Industrielle Instandhaltungs- und Wartungsprodukte mbH SIWA | Lubrifiant ou concentré de lubrifiant |
GB2215346A (en) * | 1988-03-09 | 1989-09-20 | Exxon Research Engineering Co | Lithium complex lubricating grease |
US4897210A (en) * | 1988-07-12 | 1990-01-30 | Pennzoil Products Company | Lithium complex grease thickener and high dropping point thickened grease |
US4908142A (en) * | 1988-10-21 | 1990-03-13 | Union Oil Company Of California | Extreme pressure lubricating compositions and method of using same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB973580A (en) * | 1962-02-01 | 1964-10-28 | Leybold Anlagen Holding Ag | A parting compound for plastics moulding in moulds |
-
1990
- 1990-03-07 GB GB9005104A patent/GB2241707A/en not_active Withdrawn
-
1991
- 1991-03-05 JP JP3504602A patent/JP2964165B2/ja not_active Expired - Fee Related
- 1991-03-05 CA CA002077555A patent/CA2077555A1/fr not_active Abandoned
- 1991-03-05 EP EP91904931A patent/EP0523064B1/fr not_active Expired - Lifetime
- 1991-03-05 DE DE69101376T patent/DE69101376T2/de not_active Expired - Fee Related
- 1991-03-05 WO PCT/EP1991/000407 patent/WO1991013955A1/fr active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1097372A (en) * | 1964-08-07 | 1968-01-03 | Vanderbilt Co R T | Dithiocarbamates, the manufacture and use thereof, and compositions containing the same |
US3248325A (en) * | 1964-08-21 | 1966-04-26 | Phillips Petroleum Co | Lubricating composition |
EP0176202A1 (fr) * | 1984-08-22 | 1986-04-02 | Mobil Oil Corporation | Composition de graisse |
US4749502A (en) * | 1986-07-14 | 1988-06-07 | Exxon Research And Engineering Company | Grease composition |
EP0286139A1 (fr) * | 1987-04-10 | 1988-10-12 | Gesellschaft für Industrielle Instandhaltungs- und Wartungsprodukte mbH SIWA | Lubrifiant ou concentré de lubrifiant |
GB2215346A (en) * | 1988-03-09 | 1989-09-20 | Exxon Research Engineering Co | Lithium complex lubricating grease |
US4897210A (en) * | 1988-07-12 | 1990-01-30 | Pennzoil Products Company | Lithium complex grease thickener and high dropping point thickened grease |
US4908142A (en) * | 1988-10-21 | 1990-03-13 | Union Oil Company Of California | Extreme pressure lubricating compositions and method of using same |
Non-Patent Citations (1)
Title |
---|
Database WPI, accession no. 77-20680y, Derwent Publications Ltd, (London, GB), & JP-A-52016503 (CHUO YUKA) 7 February 1977 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994011470A1 (fr) * | 1992-11-14 | 1994-05-26 | Gkn Technology Limited | Graisses |
GB2287715A (en) * | 1992-11-14 | 1995-09-27 | Gkn Technology Ltd | Greases |
GB2287715B (en) * | 1992-11-14 | 1996-08-21 | Gkn Technology Ltd | Greases |
EP0696636A1 (fr) * | 1993-04-30 | 1996-02-14 | Tonen Corporation | Composition d'huile lubrifiante |
EP0696636A4 (fr) * | 1993-04-30 | 1996-07-24 | Tonen Corp | Composition d'huile lubrifiante |
WO1995007963A1 (fr) * | 1993-09-13 | 1995-03-23 | Exxon Chemical Patents Inc. | Composition antioxydante melangee |
CN101200670B (zh) * | 2006-12-12 | 2010-05-19 | 中国石油天然气集团公司 | 一种复合锂基润滑脂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH05504369A (ja) | 1993-07-08 |
DE69101376T2 (de) | 1994-07-07 |
JP2964165B2 (ja) | 1999-10-18 |
GB2241707A (en) | 1991-09-11 |
GB9005104D0 (en) | 1990-05-02 |
DE69101376D1 (de) | 1994-04-14 |
EP0523064B1 (fr) | 1994-03-09 |
EP0523064A1 (fr) | 1993-01-20 |
CA2077555A1 (fr) | 1991-09-08 |
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