AU615647B2 - Creation of Inventions and Patents with Artificial Intelligence

AU615647B2 – Polytetrafluoroethylene coating of polymer surfaces
– Google Patents

AU615647B2 – Polytetrafluoroethylene coating of polymer surfaces
– Google Patents
Polytetrafluoroethylene coating of polymer surfaces

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Publication number
AU615647B2

AU615647B2
AU12942/88A
AU1294288A
AU615647B2
AU 615647 B2
AU615647 B2
AU 615647B2
AU 12942/88 A
AU12942/88 A
AU 12942/88A
AU 1294288 A
AU1294288 A
AU 1294288A
AU 615647 B2
AU615647 B2
AU 615647B2
Authority
AU
Australia
Prior art keywords
international
document
date
ptfe
particles
Prior art date
1987-07-17
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.)

Ceased

Application number
AU12942/88A
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AU1294288A
(en

Inventor
Frieder K. Hoffman
Karol J. Mysels
Wolfgang J. Wrasidlo
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.)

Pall Filtration and Separations Group Inc

Original Assignee
Memtec America Corp
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.)
1987-07-17
Filing date
1988-01-27
Publication date
1991-10-10

1988-01-27
Application filed by Memtec America Corp
filed
Critical
Memtec America Corp

1989-02-13
Publication of AU1294288A
publication
Critical
patent/AU1294288A/en

1991-10-10
Application granted
granted
Critical

1991-10-10
Publication of AU615647B2
publication
Critical
patent/AU615647B2/en

1992-01-23
Assigned to MEMTEC AMERICA CORPORATION
reassignment
MEMTEC AMERICA CORPORATION
Alteration of Name(s) of Applicant(s) under S113
Assignors: BRUNSWICK CORPORATION

2008-01-27
Anticipated expiration
legal-status
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Status
Ceased
legal-status
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Classifications

B—PERFORMING OPERATIONS; TRANSPORTING

B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL

B01D—SEPARATION

B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus

B01D67/0081—After-treatment of organic or inorganic membranes

B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation

B—PERFORMING OPERATIONS; TRANSPORTING

B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL

B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL

B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials

B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J3/00—Processes of treating or compounding macromolecular substances

C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques

C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances

C08J7/04—Coating

C08J7/0427—Coating with only one layer of a composition containing a polymer binder

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances

C08J7/04—Coating

C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers

C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment

C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers

Abstract

Adherent, PTFE coatings on polymer surfaces can be produced at temperatures well below the sintering temperature of PTFE, by contacting the surface with a dilute dispersion of PTFE particles and heating the surface to its softening point (in the vicinity of its glass transition temperature) to dry it and to cause the individual particles to become embedded in and surrounded by the polymer.

Description

i ,61564 AU-AIl-12942/ 8 W ORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau 0 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 11) International Publication Number: WO 89/ 00592 C08J 7/04, B01D 13/04 A l (43) International Publication Date: 26 January 1989 (26.01.89) (21) International Application Number: PCT/US88/00227 (74) Agent: GREIF, Arthur; Brunswick Corporation, 2000 Brunswick Lane, DeLand, FL 32724 (US).
(22) International Filing Date: 27 January 1988 (27.01.88) (81) Designated States: AT (European patent), AU, BE (Eu- (31) Priority Application Number: 074,635 ropean patent), CH (European patent), DE (European patent), DK, FR (European patent), GB (Euro- (32) Priority Date: 17 July 1987 (17.07.87) pean patent), IT (European patent), JP, KR, LU (Europeai patent), NL (European patent), SE (European (33) Priority Country: US patent), SU.
(71) Applicant: RRUNSWIG-K-GOR-POR-A-T-0IN [US/US]; Published iOne.Brunswick-P-laza,-Skokie-L-6007-7(US).. With international search report.
obo tu c oai St, A4L -1001 \Ca.Yry ci’d Qtlo3 (72)Inventors: WRASIDLO, Wolfgang, J. 307 Prospect Uldc S .kso, Street, LaJolla, CA 92037 HOFFMAN, Frieder, AAe-~tc.
K. 2630 Autumn Drive, Oceanside, CA 92056 (US).
MYSELS, Karol, J. 8327 LaJolla Scenic Drive, La- A Jolla, CA 92037 0- APR 1989
SAUSTRALAN
1 3FEB 1989 PATENT OFFICE (54) Title: POLYTETRAFLUOROETHYLENE COATING OF POLYMER SURFACES (57) Abstract Adherent, PTFE coatings on polymer surfaces can be produced at temperatures well below the sinterirg temperature of PTFE, by contacting thu surface with a dilute dispersion of PTFE particles and heating the surface to its softening point (in the vicinity of its glass transition temperature) to dry it and to cause the individual particles to become embedded in and surrounded by the polymer.
S WO 89/00592 PCT/LS88/00227 -1- POLYTETRAFLUOROETHYLENE COATING OF POLYMER SURFACES Technical Field This invention relates to a method for coating polymer surfaces with fluoroplastics: and is particularly related to a method for increasing the water repellency of such surfaces by coating with dispersions of polytetrafluoroethylene polymers.
Background Art Fluoroplastics are known to offer a unique combination of chemical, electrical, and mechanical’properties which makes them useful over a broad range of applications.
One such fluoroplastic, polytetrafluoroethylene (PTFE), exhibits exceptional resistance to chemicals. Aqueous dispersions of PTFE have been used to impregnate fabrics to impart hydrophobic properties and resistance to chemicals, as shown, for example, in U.S. Patent 4,342,675.
PTFE coatings are most commonly achieved by contacting the surface to be coated with a dispersion containing about 45-50% solids, drying, and heating the resin particles to temperatures of 357-400 0 C to cause the particles to sinter and thereby bond to the surface.
It has also been suggested that coatings with a degree of useful properties can be achieved at temperatures below that of the sintering temperature of TFE resin particles by either: spray-coating the polymer surface with a volatile solvent for the polymer, sufficient to soften the surface, causing it to become tacky and thereby penetrable by the PTFE particles, as shown in U.S. Patent 3,200,006; (ii) the use of pressure to embed the particles into the substrate, see for example DuPont Product Information Bulletin No. X-0OG; or (iii) the use of chemical coupling agents (heavy metal organic complexes) which are capable of bonding both to the PTFE particles and the surface to be coated, see U.S.
I-s~i -2ii Patents 3, 68,297 and 4,232,087. However, these procedures will be of limited value for those substrates in which the dissolution thereof, the use of compressive forces, or the use of contaminating chemicals would be a serious detriment to the coated surface, for membranes employed in filtration-And.medicinal applications.
Disclosure of Invention I has now been found that a substantial degree of hydrophobicity can be imparted to polymer surfaces, whether 10 in the form of cast films or membranes, or woven or nonwoven fabrics, by coating such surfaces with aqueous dispersions of PTFE homopolymers or TFE copolymers utilizing: (i) temperatures within a narrow range, to achieve a novel type of bonding between the substrate and the coating particles; 15 preferably in combination with (ii) dispersions having a dilution about an order of magnitude lower than has most commonly been employed; and (iii) wetting agents which can be evaporated at temperatures below that at which bonding of the particles is effected. The dilute dispersions contain PTFE particles, dispersing agents in sufficient amounts to maintain the particles in suspension, wetting agents to permit uniform distribution of the particles on the surface anda -vehicle; further, the dispersion has a solids content within the range of 0.1 to 6.0% and it is essentially devoid of heavy metal organic complexes. Thus, the invention comprises the use of aqueous PTFE dispersions (in which the particles are essentially within the range 0.05 to 3pm, preferably and having 0.3 to 1 p the surfac evaporate segmental the result: to be drawi bond which 10 which exhi above meth a transfor o• 2 O* 1 I 1-‘ -2a- 0.1 to 0.5pm) containing a volatile wetting agent a solids content of 0.1 to 6 percent, preferably ercent, wherein such dispersions are contacted with e to be coated, which is then heated both to the wetting agent and to achieve softening or mobility. Once the wetting agent has been removed, ing softening permits the molecules of the surface n around the base of the particles, to produce a has been found to provide an adherent coating bits a superior degree of hydrophobicity. The od can be employed with any polymer which exhibits mation from a solid to a more or N \WO 89/00592 PCT/US88/00227 -3less viscous liquid state over a comparatively broad temperature range rather than the abrupt change associated with purely crystalline materials. With the exception of a few materials melamine and silicone), most polymers exhibit such a transformation, known as the glass transition, in which the polymer viscosity decreases rapidly as temperature is increased. Surface softening is generally associated with the onset of that transformation. To the extent that requisite surface softening is achieved, the bonding mechanism of this invention could be employed up to the temperature 357 0 C) at which the PTFE particles will sinter. However, because it can provide bonding while avoiding surface degradation, the instant method will be of particular benefit in coating polymers: which exhibit softening at temperatures below 2500°C, and more generally below 200°C; and (ii) in the absence of substantial compressive force, pressure of a degree which would cause the particles to be embedded absent softening of the polymer surface.
Modes for Carrying Out the Invention Although PTFE coatings are known to enhance chemical resistance, the principal objective of the instant invention is to impart hydrophobic or anti-wetting properties to the polymer surfaces. Initial trials were conducted by coating a commercially available polysulfone filtration membrane. To prevent destruction or degradation of the pores of this membrane, experimentation was conducted to determine if adherence could be achieved at temperatures well below that at which actual flow (Tm) was encountered. For polysulfone, it was determined that a temperature of 1800°C was sufficient to achieve a desirable degree of surface softening. It should be noted that this temperature is somewhat below the glass transition temperature, Tg, of VWO 89/00592 PCT/US88/00 2 2 7 -4polysulfone, variedly reported to be, for example, 1870, 1900, and 195 0 C in the literature. Hydrophobicity, the degree of adhesion of water droplets to the coated surface, was determined by the visual observation and characterization of the contact angle, the degree of beading, of small water droplets on the coated surface. Using such visual observation, the degree of hydrophobicity imparted could be set forth in three categories: “superior” in which the contact angle was very steep, of the order of 900; (II) “satisfactory” in which the contact angle was of the order of 450; and (III) “unsatisfactory” those in which the contact angle was markedly shallow.
The dip coating of the polysulfone membrane with a commercial PTFE dispersion (TEFLON 30, sold by DuPont Company, Wilmington, Delaware, containing about percent solids and about 6 percent of a wetting agent) proved comparatively ineffective in imparting hydrophobic properties. Utilizing Scanning Electron Micrographs (SEM), it was determined that lower PTFE solids concentrations would produce a discontinuous, monolayer of adherent particles which exhibited enhanced hydrophobicity in comparison with the essentially continuous, smooth layer of particles, which resulted from the use of the high PTFE concentrations. A set of experiments was run in which the TEFLON 30 was diluted with: an aqueous solution containing 0.5 percent perfluorooctanoic acid (PFOA) neutralized with ammonium hydroxide (rather than NaOH so as to maintain requisite volatility) to a pH of 7.3; and an aqueous solution of 16 percent isopropanol, to produce dispersions of varying solids content. The polysulfone membranes were soaked in the PTFE dispersions for about one second and thereafter heated to 180 0 C, both to evaporate the CI~ V \O 89/00592 PCT/LCSF8/00227 wetting agent and soften the surface. The results are reported in the Table below:
TABLE
wetting agent PFOA neutralized to pH of 7.3 PTFE Solids concentration Hydrophobicity 0.3 II 0.42 I 0.54 I 0.66 II 0.78 II wetting agent isopropanol PTFE Solids concentration Hydrophobicity 0.2 II 0.4 II 0.8
I
1.6 I 3.2 I It is seen from the results above, utilizing a temperature, 180 0 C, far below that suggested in the literature (for dispersions devoid of organo-metallic complexes to achieve bonding), that “superior” hydrophobicity could be achieved by utilizing dilute dispersions of PTFE particles in which the optimum solids concentration is, to some extent, a function of the wetting agent employed. Thus, with PFOA at a pH of 7.3, superior anti-wetting is achieved in a narrow concentration range of about 0.5 percent PTFE particles; while, for the isopropanol wetting agent, the optimum solids concentration would be about 1-3 percent.
For those end-uses in which melting of the polymer surface would be detrimental, it is, of course, necessary that the surface be heated to a temperature well below t L i i. i. ,i i r InA~~? NN( 0 89/00592 P’ TL t1 /uu- i -6the melting point (Tm) of the polymer. The maximum temperature at which the surface should be heated will depend largely on the degree of surface degradation which can be tolerated. Even in those instances in which a substantial degree of degradation is tolerable, there will be little need to maintain the temperature of the surface at a value more than 200C above the softening point, to achieve a desired degree of bonding.
Generally, such bonding will be achieved with a temperature no more than J00C thereabove. In any event, the surface must, however, be heated to a temperature high enough and long enough to evaporate the wetting agent and to achieve a sufficient degree of softening or segmental mobility, whereby the colloidal PTFE particles can become embedded into the surface. Scanning Electron Micrographs (SEM) suggest that an intermolecular type of force, such as van der Waals interaction, appears to draw the surface molecules (capable of movement at the “softening” temperature) around the base of each particle.
The enhanced bonding apparently results from attraction between the enlarged contact area of the two surfaces, the coated polymer surface which is in contact with and surrounds the surface quadrant of the PTFE particle embedded therein.
The specific temperature at which optimum “softening” will occur for each polymer cannot be predetermined with complete specificity; although it will generally be in the vicinity of Tg the glass transition temperature. However, use of Tg’s variedly reported in the literature for a particular polymer may, in some instances, be insufficient to achieve the segmental mobility necessary to achieve the desired adherence; while in many instances, the reported Tg may be too high and detrimental to the surface. Thus, Tg can vary not only with the structural and morphological parameters i i I rF- NVO 89/00592 PCT/US88/00227 -7degree of substitution, molecular-weight distribution, degree of chain entanglement) of a given polymer, but also with the experimental parameters (heating and/or penetration rate) employed in its determination.
Therefore, for any given polymer surface and heating method to be employed, it will be preferable to determine, empirically, the requisite surface “softening” temperature, at which segmental mobility is sufficient to permit the molecules of the surface to be drawn around the base of the PTFE particles. In this regard, it must be borne in mind that such surface-particle interaction can only occur after the wetting agent has evaporated. The above notwithstanding, Tg can nevertheless serve as a guide, or starting point, in determining the optimum “softening” temperature particularly when Tg has been determined by measuring volume expansion (at conventional heat-up rates) of the polymer as a function of temperature, such that Tg is the temperature at which the volume expansion coefficient shows an abrupt change. Requisite softening wi.ll generally be achieved by heating the polymer surface to a temperature below the Tg determined by the above volume expansion procedure.

Claims (5)

4. The method of claim 3, in which said surface is a porous membrane and said particles have a particle size within the range 0.1 to 0.5 pm. 9 -9- The method of claim 4, in which said surface heating temperature is not more than 100 C. above the “softening” temperature.

6. The method of claim 5, in which said dispersion: contains a non-ionic or anionic wetting agent which can be volatilized during said heating; and is devoid of heavy metal organic complexes.

7. The method of claim 4, in which said surface heating temperature is below the glass transition, as determined by volume expansion, of said polymer. S8. The method of claim 3, in which the content of PTFE particles within said dispersion is within the range 0.3 to S” 1 percent. DATED this 8th day of January, 1991 MEMTEC AMERICA CORPORATION S” WATERMARK PATENT TRADEMARK ATTORNEYS 2ND FLOOR, “THE ATRIUM”, S: 290 BURWOOD ROAD HAWTHORN, VICTORIA 3122 AUSTRALIA AL:DBM:(1.22) c? ‘4e :2/6?g INTERNATIONAL SEARCH REPORT International Arplication NoDCT/US 88 /00227 1. CLASSIFICATION OF SUBJECT MATTER lif several ciassificotion symools aooty, indicate Bill According to International Patent Classification (IPC) or to both National Classification and IPC 4 IPC C 08 J 7/04; B 01 D 13/04

11. FIELDS SEARCHED Minimum Documentation Searched Classification System jCiassification Symbols 4 IPC C 08 J; B 01 D; C 09 D; B 05 D Documentation Seatched other than Minimum Documentation to the Extant that such Documents arv, inciuded In the Fields Searched

111. DOCUMENTS CONSIDERED TO BE RELEVANT’ Category Citation of Document. 11 with Indication, where appropriate, of the relievant Passage$ 12 Relevant to Claim No. 0~ A US, A, 3200006 FITZSIMMTONS) 1 August 1965 see claims A US, A, 4416791 H-AQ) 22 November 1983 1-3 I see claims 1,2,6,7; figure 1; column 3, line~s 21-32; column 5, lines 19-26; example 1, lines 50-57 A GB, A, 862482 8 March 1961 1 see claims Special catigorlee of cited documenta: 10 later document Publiahed atter the International filing date ocumnt efinng tei!or priority date and not in conflict with the application but “A”docmen deinig te eneral state of the art which Is not cited to understand the principle or theory underlying the considered to be of particular relevance Invention earlier document but published on or aftear the International document of particular relevance; the claimed invention fIling date cannot be conaidered novel or cannot be considered to IL” document which may throw doubts on priority claim(s) or Involve an Inventive stop which Is cited to establih the publication date of another document of particular relevance:* the claimed Invention citation or other apecialeaason (as epecified) cannot be considered to Involve an Inventive step when the document referring to an oral dlscoq’,rs, use, exhibition or document Is combined with one or more other such docu- othpr means ments, such combination being obvious to a person skilled document Published prior to the International filing date but In the art. later then the priority date claimed “All document member of the same ptilent family I V. CERTIFICATION Date of the Actual Completion of the International Search Date of M.Wlng of this International Search Report 11th May 1988 13 J U N 1988 International Searching Authority SIg~j~6_IAtal a EUROPEAN PATENT OFFICEI Form PCTIISA/210 (second aheet) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH{AEPORT ON INTERNATIONAL- PATENT APPLICATION US 8800227 -SA 20799 This annex lists the patent family rninbers: relating to thc patent documents cited in the above-mentioned international search report. The members are as contained in the European P’atent Office EDP file on 02/06/88 The European P’atcnt Office is in no say liable for these particulars vihich are mek gi~en for the purpose of information. US-A- 3200006 None US-A- 4416791 22-11-83 EP-A,B 0079248 18-05-83 GB-A,B 2109706 08-06-8? JP-A- 58087050 24-05-83 AU-A- 9022682 19-05-83 CA-A- 1190465 16-07-85 AU-B- 549230 23-01-86 0E-A- 3278073 10-03-88 GB-A- 862482 Non-, A w For more details about this anneX See Official Journal of the European Patent Office, No. 12/82

AU12942/88A
1987-07-17
1988-01-27
Polytetrafluoroethylene coating of polymer surfaces

Ceased

AU615647B2
(en)

Applications Claiming Priority (2)

Application Number
Priority Date
Filing Date
Title

US074635

1987-07-17

US07/074,635

US4855162A
(en)

1987-07-17
1987-07-17
Polytetrafluoroethylene coating of polymer surfaces

Publications (2)

Publication Number
Publication Date

AU1294288A

AU1294288A
(en)

1989-02-13

AU615647B2
true

AU615647B2
(en)

1991-10-10

Family
ID=22120693
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU12942/88A
Ceased

AU615647B2
(en)

1987-07-17
1988-01-27
Polytetrafluoroethylene coating of polymer surfaces

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US
(1)

US4855162A
(en)

EP
(1)

EP0368846B1
(en)

JP
(1)

JP2593094B2
(en)

AT
(1)

ATE103309T1
(en)

AU
(1)

AU615647B2
(en)

CA
(1)

CA1292647C
(en)

DE
(1)

DE3888686T2
(en)

WO
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WO1989000592A1
(en)

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JP
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Also Published As

Publication number
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JPH03501131A
(en)

1991-03-14

US4855162A
(en)

1989-08-08

EP0368846A1
(en)

1990-05-23

DE3888686T2
(en)

1994-10-13

CA1292647C
(en)

1991-12-03

WO1989000592A1
(en)

1989-01-26

ATE103309T1
(en)

1994-04-15

EP0368846B1
(en)

1994-03-23

DE3888686D1
(en)

1994-04-28

JP2593094B2
(en)

1997-03-19

AU1294288A
(en)

1989-02-13

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