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EP0477186A1 - Melanges compatibles de caoutchouc d'ethylene-propylene et caoutchoucs de polychloroprene ou de nitrile - Google Patents

Melanges compatibles de caoutchouc d'ethylene-propylene et caoutchoucs de polychloroprene ou de nitrile

Info

Publication number
EP0477186A1
EP0477186A1 EP19900906707 EP90906707A EP0477186A1 EP 0477186 A1 EP0477186 A1 EP 0477186A1 EP 19900906707 EP19900906707 EP 19900906707 EP 90906707 A EP90906707 A EP 90906707A EP 0477186 A1 EP0477186 A1 EP 0477186A1
Authority
EP
European Patent Office
Prior art keywords
composition
acid
weight
elastomer
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19900906707
Other languages
German (de)
English (en)
Inventor
Robert Charles Keller
Marc Richard Kuhnhein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0477186A1 publication Critical patent/EP0477186A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to compatible blends of ethylene-propylene rubber and polychloroprene and/or nitrile rubber and covulcanizates thereof having improved resistance to the deleterious effects of ozone, oxygen and heat while retaining outstanding tensile strength and abrasion resistance.
  • elastomers such as polybutadiene or polyisoprene may be, in some cases reasonably compatible with olefin/diene elastomers and may be readily covulcanized because of the high availability of sites of ethylenic unsaturation
  • other elastomers such as polychloroprene, butadiene/acrylonitrile copolymers (nitrile) and like materials containing polar groups along the chain and/or a relatively low degree of ethylenic unsaturation are not so readily covulcanized.
  • Ethylene/propylene copolymers and ethylene/ propylene/diene terpolymers which have been chemically treated by free-radical grafting thereon of unsaturated acid monomers are also disclosed in the art as additives in polymeric compositions.
  • European Patent 0183493 to Mitsui Petrochemical Industries, Ltd. discloses liquid olefin copolymers or olefin/diene terpolymers having a molecular weight (Mn) of 200 to 10,000 which have been modified by graft copolymerization with an unsaturated carboxylic acid compound.
  • graft copolymers are disclosed to be useful as tackifier additives to various resinous compositions or as additives to curable rubbery polymers such as ethylene/propylene/diene elastomers and mixtures thereof with other elastomers.
  • US Patent 4307204 to DuPont discloses an expandable, curable elastomeric sponge composition based on ethylene/propylene/diene terpolymer (EPDM) elastomer or polychloroprene elastomer, which composition further contains a minor amount of an ionomer resin which is an ethylene polymer or copolymer containing at least about 50 mole percent acid functional groups, which groups are at least about 50% neutralized by metal ions.
  • EPDM ethylene/propylene/diene terpolymer
  • acid-modified ethylene polymers which may also include acid-modified EPDM terpolymers, are disclosed to improve the balance of curing and expanding properties of the polymer composition when used to prepare cured expanded materials
  • Neither of the aforementioned disclosures addresses the development of a cured polychloroprene or nitrile rubber formulation which not only exhibits improved resistance to ozone or oxygen attack and improved heat stability, but also exhibits a retention and in some cases improvement of important physical properties such as tensile strength, elongation, modulus and resistance to abrasion.
  • the present invention provides for polychloroprene and nitrile rubber compositions and vulcanizates thereof having improved resistance to chemical attack comprising a uniform mixture of polychloroprene or nitrile elastomer and from about 10 to about 60% by weight based on the content of total elastomer in the composition of a carboxylated ethylene-propylene rubber.
  • the blend of this invention may be readily covulcanized and formed into shaped, heat resistant and oil resistant articles such as automotive drive belts and automotive hoses which not only exhibit improved resistance to oxygen and ozone attack but also have retained or enhanced physical properties such as abrasion resistance, modulus, elongation and tensile strength.
  • the carboxylated ethylene-propylene copolymer rubber (EPR) useful for forming the blends of this invention are prepared from ethylene and ethylenically unsaturated hydrocarbons including cyclic, alicyclic and acyclic, containing from 3 to 28 carbons, e.g. 2 to 18 carbons.
  • These ethylene copolymers may contain from 30 to 85 wt. % ethylene preferably 40 to 80 wt. % of ethylene and 15 to 70 wt. %, preferably 20-60 wt. % of one or more C 3 to C 2 g, preferably C 3 to C 18 , more preferably C 3 to Cg, alpha olefins.
  • Copolymers of ethylene and propylene are most preferred.
  • Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc; also branched chain alpha-olefins , such as 4-methyl-l-pentene, 4-methyl-l-hexene, 5-methylpentene-l, 4, 4-dimethyl-l-pentene, and 6-methylheptene-l, etc. and mixtures thereof.
  • copolymer or EPR as used herein, unless otherwise indicated, includes terpolymers, tetrapolymers , etc. , preferably of ethylene, said C 3 _ 28 alpha-olef in and/or a non-conjugated diolefin or mixtures of such diolefins which may also be used.
  • the amount of the non-conjugated diolefin will generally range from about 0.5 to 20 wt. percent, preferably about 1 to about 7 wt. percent, based on the total amount of ethylene and alpha-olef in present.
  • Representative examples of non-conjugated dienes that may be used as the third monomer in the terpolymer include:
  • a. Straight chain acyclic dienes such as: 1,4-hexadiene; 1,5-heptadiene; 1,6-octadiene.
  • Branched chain acyclic dienes such as: 5-methyl-l, 4-hexadiene; 3 , 7-dimethyl 1, 6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene .
  • c. Single ring alicyclic dienes such as:
  • Multi-single ring alicyclic dienes such as:
  • Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydroindene ; methyl tetrahydroindene; dicyclopentadiene; bicyclo (2.2.1) hepta 2,5-diene; alkyl, alkenyl, alkylidene, ⁇ ycloalkenyl and cycloalkylidene norbornenes such as: ethyl norbornene ; 5-methylene-6-methyl-2-norbornene; 5-methylene-6 , 6-dimethyl-2-norbornene ; 5-propenyl-2-norbornene ;
  • the most preferred EPDM elastomer contains from about 60 to about 80% by weight ethylene, from about 15 to about 35% by weight propylene and from about 3 to about 7% by weight of non-conjugated diene.
  • carboxylated refers to EPR polymers as described above which have been modified by inclusion into the polymer chain of from about 0.05 to about 10% by weight of an unsaturated polycarboxylic acid or lower alkyl esters or anhydrides thereof.
  • the reaction of the EPR with an unsaturated mono or polycarboxylic acid, and derivatives thereof, can be carried out in the presence of a free radical source.
  • the EPR may be reacted with unsaturated mono or polycarboxylic acids, and derivatives thereof, at temperatures generally less than 300° C. , preferably from about 150°-250° C, in the presence of free radical sources.
  • free radical sources are, for example peroxides such as ditertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, p-menthane peroxide, p-menthane hydroperoxide compounds or azo compounds, such as azobis (isobutyronitrile) , or irradiation sources.
  • Suitable irradiation sources include, for example, those from cobalt, uranium, thorium, and the like and ultraviolet light.
  • organic unsaturated polycarboxylic acid, anhydride or esters thereof, based on the weight of the EPR can be used.
  • the amount of peroxide or free radical agent used is generally quite low being of the order of about 0.01 to about 0.5 percent based on the weight of the EPR.
  • Suitable unsaturated mono or polycarboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citaconic anhydride, aconitric anhydride, itaconic anhydride, the half or full esters derived from methyl, ethyl, dimethyl maleate, dimethyl fumarate, methyl ethyl maleate, dibutyl maleate, dipropyl maleate, and the like, or those compounds which form these compounds at elevated reaction temperatures such as citric acid, for example.
  • the reaction may be carried out either in a batchwise or in a continuous manner with contact times in the order of about 10 minutes to about 2 hours.
  • the reaction of the EPR can also be carried out in an extruder or a Banbury mixer. This process can be used for EPR having a melt viscosity greater than 5,000 cp. at 190°C, up to a viscosity of 500,000 cp. at 190° C.
  • the acid functionality may also be incorporated in the EPR polymer chain by copolymerizing the unsaturated polycarboxylic acid or derivative thereof with the olefin or the olefin and diene monomers during the formation of the EPR.
  • Polymers prepared by copolymerization of ethylene and such acid monomers are disclosed in US Patent 3264272.
  • the preferred method for preparing the carboxylated EPR for the purposes of this invention is to graft polymerize the unsaturated acid monomer onto the polymer backbone, preferably in the presence of a free radical generator such as an organic peroxide.
  • the amount of unsaturated polycarboxylic acid monomer or derivative thereof incorporated into the EPR polymer according to this invention may generally range from about 0.05 to 10.0 percent by weight, more preferably from about 0.1 to about 5 percent by weight, and most preferably from about 0.15 to about 1.0 percent by weight, based on the weight of EPR polymer.
  • the acid groups present in the EPR polymer chains are not substantially neutralized, such as by treatment with metal salts, prior to vulcanization of the blend.
  • Partial neutralization of, for example, up to about 25% by weight of the acid groups may be tolerated, but higher levels of neutralization tends to detract from the compatibility of the elastomers and the physical properties of the covulcanizates.
  • the carboxylated EPR polymers used in this invention are solid materials having a number average molecular weight (Mn) in the range of from about 15,000 up to about 150,000, more preferably from about 25,000 to about 90,000, as measured by Gel Permeation Chromatography (GPC) .
  • the polychloroprene elastomer used as the major component in the elastomer blend in one embodiment of the present invention is a commercially available material, commonly referred to as CR or neoprene rubber. It is available in a number of grades and molecular weights, all of which elastomeric grades are suitable for use in the compositions of this invention.
  • the preferred grade is Neoprene GRT which is more resistant to crystallization and is based on a copolymer of chloroprene and 2,3-dichloro-1,3-butadiene.
  • Nitrile rubber used as the major component in the elastomer blend in another embodiment of this invention is also a commercial material available in a number of grades.
  • Nitrile rubber is a random copolymer of a major proportion of butadiene and a minor proportion of acrylonitrile and is generally produced by free radical catalysis.
  • the polychloroprene or nitrile rubber preferably constitutes the major component of the mixture of elastomers of the present invention, but may be generally present in a range of from about 40 about 90% by weight based on total elastomer content.
  • the carboxylated EPR polymer is correspondingly present at a level of from about 10 to about 60% by weight based on total elastomer content. It is also within the scope of the present invention to provide elastomer compositions based on blends of the polychloroprene and nitrile rubber components.
  • the vulcanizable composition of the present invention also includes a conventional mixed vulcanizing system for EPR, polychloroprene and nitrile rubber.
  • vulcanizing systems include a metal oxide such as zinc oxide, magnesium oxide and mixtures thereof, used either alone or mixed with one or more organic accelerators or supplemental curing agents such as an amine, a phenolic compound, a sulfonamide, thiazole, a thiuram compound, thiourea or sulfur.
  • organic accelerators or supplemental curing agents such as an amine, a phenolic compound, a sulfonamide, thiazole, a thiuram compound, thiourea or sulfur.
  • Organic peroxides may also be used as curing agents.
  • the zinc or magnesium oxide is normally present at a level of from about 1 to about 10 parts by weight per 100 parts by weight of elastomer blend, and the sulfur and supplemental curing agents or curing accelerators, where used, may be present at a level of from about 0.1 to about 5 parts by weight per 100 parts by weight of elastomer blend.
  • the elastomer polymer composition may also contain other additives such as lubricants, fillers, plasticizers, tackifiers, coloring agents, blowing agents, and antioxidants.
  • fillers examples include inorganic fillers such as carbon black, silica, calcium carbonate, talc and clay, and organic fillers such as high-styrene resin, ⁇ oumarone-indene resin, phenolic resins, lignin, modified melamine resins and petroleum resins.
  • lubricants examples include petroleum-type lubricants such as oils, paraffins and liquid paraffins, coal tar-type lubricants such as coal tar and coal tar pitch; fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as licinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; and synthetic polymeric substances such as petroleum resins.
  • petroleum-type lubricants such as oils, paraffins and liquid paraffins
  • coal tar-type lubricants such as coal tar and coal tar pitch
  • fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil
  • tall oil waxes such as beeswax, carnauba wax and lanolin
  • plasticizers examples include hydrocarbon oils, e.g. paraffin, aromatic and naphtheni ⁇ oils, phthalic acid esters, adipic acid esters, sebacic acid esters and phosphoric acid-type plasticizers.
  • tackifiers are petroleum resins, coumarone-indene resins, terpene-phenol resins, and xylene/ formaldehyde resins .
  • coloring agents are inorganic and organic pigments.
  • blowing agents examples include sodium bicarbonate, ammonium carbonate, N, N' -dinitrosopentamethylenetetramine, azocarbonamide, azobis isobutyronitrile, benzenesulf onyl hydrazide, toluenesulfonyl hydrazide, calcium amide, p-toluenesulfonyl azide, salicylic acid, phthalic acid and urea.
  • the vulcanizable composition may be prepared and blended on any suitable mixing device such as an internal mixer (Brabender Plasticorder) , a Banbury Mixer, a kneader or a similar mixing device. Blending temperatures and times may range from about 45 to 180 °C and from about 4 to 10 minutes respectively. After forming a homogeneous mixture of the elastomers and optional fillers, processing aids, antioxidants and the like, the mixture is then vulcanized by the further mixing-in of crosslinking agents and accelerators followed by heating the resulting blend to a temperature of from about 100° to 250°C, more preferably from about 125 to 200°C for a period of time ranging from about 1 to 60 minutes. Molded articles such as belts and hoses are prepared by shaping the pre-vulcanized formulation using an extruder or a mold, and subjecting the composition to temperatures and curing times as set forth above.
  • suitable mixing device such as an internal mixer (Brabender Plasticorder) , a Banbury Mixer,
  • the EPR polymer employed is a terpolymer comprising about 70 weight percent ethylene, 25 weight percent propylene and 5 weight percent 5-ethylidene-2-norbomene.
  • This terpolymer has a number average molecular weight (Mn) of about 70,000 as measured by Gel Permeation Chromatography (GPC) , a dispersity (Mw/Mn) of less than 4, and a Mooney Viscosity at 1+4, 125°C of 60.
  • the EPDM terpolymer identified as "Modified EPDM” is the same terpolymer except that it also contains 0.25% by weight of maleic anhydride grafted along the polymer chain by the free radical grafting technique described above.
  • the polychloroprene rubber employed is a commercially available material resistant to crystallization sold by DuPont under the trade name Neoprene GRT and is a copolymer of chloroprene and 2,3-dichloro-l,3-butadiene.
  • the nitrile rubber employed is a commercially available copolymer of butadiene and acrylonitrile sold by Uniroyal under the trademark PARACRIL B and may be characterized by an acrylonitrile content of about 29 mole percent and a nominal Mooney Viscosity ML-4 at 212°F of 82.
  • the milled elastomer composition was then sheeted off the mill at a thickness of about 0.1 inch, placed in a 6 inch by 6 inch by .075 inch mold and cured at a temperature of about 160°C for a period of 20 minutes.
  • Example 2 The process of Example 1 was repeated except that the elastomer compos ition consisted of a mixture of polychloroprene and unmodified EPDM. Other ingredients are as set forth in Table 1, Ex. 2.
  • Example 1 The process of Example 1 was repeated except that the elastomer composition consisted of a mixture of polychloroprene and the modified EPDM of this invention. Other ingredients are as set forth in Table 1, Ex. 3.
  • Example 5 The process of Example 1 was repeated except that the elastomer composition consisted of a mixture of polychloroprene and unmodified EPDM. The other ingredients are as set forth in Table 1, Ex. 4. The sulfur and vulcanization accelerators additionally present in this formulation were added to the elastomer mixture at the same time as the zinc oxide/magnesium oxide mixture.
  • Example 5 The sulfur and vulcanization accelerators additionally present in this formulation were added to the elastomer mixture at the same time as the zinc oxide/magnesium oxide mixture.
  • Example 2 The process of Example 1 was repeated except that the el astomer compos it ion consisted of a mixture of polychloroprene and the modified EPDM elastomer of this invention. Other ingredients are as set forth in Table
  • Aromatic hydrocarbon process oil 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5
  • Hardness Shore A (ASTM D-2240) 70 75 73 75 73
  • Example 2 and 4 which are based on the blend of polychloroprene and unmodified EPDM elastomer (outside of the scope of this invention) show a significant tensile strength loss and lower physical properties after heat aging as compared with the control formulation of Example 1 containing 100% polychloroprene as the cured elastomeric component.
  • the formulation of Example 3 which contains the modified EPDM of this invention yields only a small decrease in tensile strength with slightly higher physical properties after heat aging.
  • the vulcanized composition of the present invention also exhibits both good abrasion resistance and dynamic ozone resistance.
  • the enhancement of these properties is demonstrated in the following Examples. TABLE 2
  • Aromatic hydrocarbon process oi 10 10 10
  • Example 6 contains no added EPDM terpolymer elastomer; the formulation of Example 7 contains the unmodified EPDM terpolymer; and the formulation of Example 8 contains the modified (carboxylated) EPDM terpolymer of this invention.
  • the composition of this invention (Example 8) exhibited both improved hardness and 100% Modulus when compared with the composition of Example 6 which does not contain EPDM elastomer, and also exhibited better tensile strength and elongation than the composition of Example 7 which contains the unmodified EPDM.
  • the dynamic ozone resistance and abrasion resistance of the composition of Example 8 were also superior to those properties for the composition of Example 7. It is also noteworthy that the static and dynamic ozone resistance of the EPDM blends are superior to the polychloroprene composition compounded with antioxidants, even though the antioxidants were not included in he blend formulations of the invention.
  • Paracril B (UniRoyal) 100 70 70
  • antioxidant based on the reaction product of diphenyl amine and acetone.
  • Example 9 contains no added EPDM terpolymer elastomer; the formulation of Example 10 contains the unmodified EPDM terpolymer; and the formulation of Example 11 contains the modified (carboxylated) EPDM terpolymer of this invention.
  • the composition of this invention (Example 11) exhibited improved hardness, modulus and resistance to crack when compared with the composition of Example 9 which does not contain EPDM elastomer, and also exhibited better tensile strength, elongation, modulus and resistance to crack than the composition of Example 10 which contains the unmodified EPDM.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention prévoit des compositions en élastomère et des vulcanisats de celles-ci, présentant une résistance accrue à l'attaque chimique, comprenant un mélange uniforme d'élastomère en caoutchouc de polychloroprène ou de nitrile et d'environ 10 à environ 60 % en poids, en fonction de la teneur en élastomère total présent dans la composition d'un copolymère carboxylé d'éthylène, une alpha-oléfine supérieure et, éventuellement, un diène non conjugué. Le mélange en élastomère ainsi obtenu est facilement covulcanisé et réalisé sous forme d'articles résistants à la chaleur et à l'huile telles que des courroies de transmission et des durites d'automobiles, lesdits articles présentant non seulement une résistance accrue à l'attaque par l'oxygène ou par l'ozone mais possédant également des propriétés physiques existantes ou améliorées telle que résistance à l'usure, module d'élasticité, allongement et résistance à la traction.
EP19900906707 1989-04-28 1990-04-25 Melanges compatibles de caoutchouc d'ethylene-propylene et caoutchoucs de polychloroprene ou de nitrile Withdrawn EP0477186A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34514989A 1989-04-28 1989-04-28
US345149 1989-04-28

Publications (1)

Publication Number Publication Date
EP0477186A1 true EP0477186A1 (fr) 1992-04-01

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EP19900906707 Withdrawn EP0477186A1 (fr) 1989-04-28 1990-04-25 Melanges compatibles de caoutchouc d'ethylene-propylene et caoutchoucs de polychloroprene ou de nitrile

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EP (1) EP0477186A1 (fr)
AU (1) AU5527790A (fr)
CA (1) CA2051411A1 (fr)
WO (1) WO1990013599A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352739A (en) * 1992-11-06 1994-10-04 Exxon Chemical Patents Inc. Compatibilization of elastomer blends
GB2273711A (en) * 1992-12-23 1994-06-29 Tba Belting Ltd Drive belts
JPH08511810A (ja) * 1993-07-07 1996-12-10 エクソン・ケミカル・パテンツ・インク 官能化エチレン／プロピレン共重合体又はエチレン／プロピレン／ジエン三元共重合体を用いた極性及び非極性エラストマーブレンドの相溶化
US6441303B1 (en) 1998-09-15 2002-08-27 Karin Daume Maschinenteile, Gmbh & Co. Kg Device for electrically contacting and sealing a tubular member
DE10004887A1 (de) * 2000-02-04 2001-08-23 Daume Karin Maschinenteile Einrichtung zum Kontaktieren von insbesondere länglichen, bspw. im wesentlichen zylindrischen Körpern, bspw. Rohren oder Kabeln
JPWO2003046073A1 (ja) * 2001-11-30 2005-04-07 日本ゼオン株式会社 ゴム加硫物およびその製造方法、並びにそれに用いる重合体組成物、ゴム組成物および加硫性ゴム組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA814605B (en) * 1980-07-14 1982-07-28 Uniroyal Inc Nitrile rubber/epdm graft blends
JPH0647634B2 (ja) * 1986-02-27 1994-06-22 日本合成ゴム株式会社 耐油・耐候性ゴム組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9013599A1 *

Also Published As

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WO1990013599A1 (fr) 1990-11-15
CA2051411A1 (fr) 1990-10-29
AU5527790A (en) 1990-11-29

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