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EP0296220A1 - Melanges de copolymeres humidifiables, hydrophiles, doux et permeables a l'oxygene - Google Patents

Melanges de copolymeres humidifiables, hydrophiles, doux et permeables a l'oxygene

Info

Publication number
EP0296220A1
EP0296220A1 EP88900859A EP88900859A EP0296220A1 EP 0296220 A1 EP0296220 A1 EP 0296220A1 EP 88900859 A EP88900859 A EP 88900859A EP 88900859 A EP88900859 A EP 88900859A EP 0296220 A1 EP0296220 A1 EP 0296220A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
group
lens
acid
substituted
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Withdrawn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
EP88900859A
Other languages
German (de)
English (en)
Other versions
EP0296220A4 (fr
Inventor
Sing-Hsiung Chang
Mei Zyh Chang
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.)
CHANG SING HSIUNG
Original Assignee
CHANG SING HSIUNG
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 CHANG SING HSIUNG filed Critical CHANG SING HSIUNG
Publication of EP0296220A1 publication Critical patent/EP0296220A1/fr
Publication of EP0296220A4 publication Critical patent/EP0296220A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/008—Hydrogels or hydrocolloids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon

Definitions

  • This invention relates to novel copoly er composition, and more particularly to an increased oxygen permeable, soft, hydrophilic, tear wettable, dehydration resistant, deposition resistant and stable copolymer for contact lens, eye bandage or artificial skin for burn or wound dressing.
  • polymeric materials in some areas of medical application are that they be hydrophilic, soft, oxygen permeable, body fluid wettable, dehydration and deposition resistable and stable.
  • the prior art teaches the use of many different polymer ⁇ ic materials in medical areas such as in contact lens, eye bandage, artificial membranes e.g., surgical and burn dressings, membranes for an artificial lung machine.
  • polymers possess certain desirable properties for their specific medical use, they suffer from other undesirable characeristics which reduce their utility.
  • HGP hard gas permeable lens
  • SGP- soft gas permeable lens
  • the material described in the CHANG patents are highly oxygen permeable, soft and hydrophilic. But surprisingly we discovered that the material just being highly hydrophilic is not good enough for a long term contact lens use.
  • the lens made thereof is highly soft and hydrophilic, but surprisingly is relatively poor in the long term functional (tear) wettabi ⁇ lity, dehydration resistance and/or deposition resistance. Although the lens would be excellent for certain daily wear use, it is highly not suitable for the extended wear use.
  • the material described in the Tanaka or LeBoeuf patent would have a similar defect.
  • the unique properties of the invented material is also highly desirable in the areas of medical applications, such as eye bandage for drug control release or protective devices for cornea injury or disease, bandages for wound treatment or artificial skin as burn dressing, artificial lung membrane for lung machine .
  • the number shown in the Table is designated to each desired feature for a successful contact lens: 1 t oxygen permeability; 2, softness; 3, hydro ⁇ philicity; 4, stability; 5, long term tear wettability; 6, dehydration resistance; and 7, deposition resistance.
  • PMMA is poly methyl methacrylate
  • Poly HEMA is poly 2-hydroxyethyl metha ⁇ crylate.
  • Acrylic silicone such as those described in U.S.P. # 4,152,508; 3,808,178 Acrylic fluorosilicone such as those described in Japan Kokai Tokkyo Koho JP 61,126,052 (Chem. Abstract: 105:191777c).
  • This invention relates to a new copolymer specially adapted for making certain medical devices.
  • the object of this invention is to provide a new and useful copolymer having substantially increased not only oxygen permeability, softness and hydrophilicity but also long term body fluid (tear) wettability, dehydration resistance and deposition resistance for making contact lens, eye bandage, artificial skin or artificial membranes for lung machine.
  • novel copolymers disclosed are prepared by copolymerizing a comonomer composition comprising:
  • % of at least one amide acrylic (B), 1 to 35, preferably 1 to 20 and most preferably 1 to 15, wt.% of at least one vinyl carboxylic acid; (C), 1 to 90, preferably 5 to 75 and most preferably 10 to 65, wt.% of at least one copolymerizable vinylic organosiloxane; and optionally, (D), 1 to 90, preferably 1 to 65 and most preferably 10 to 65 wt.% of "at least one copolymerizable vinylic fluorinated monomer; and further optionally, (E), 1 to 80, preferably 1 to 65 and most preferably 20 to 50, wt.% of at least one acrylic alkanol.
  • Amide acrylic that is suitable for the practice of this invention has the general structure:
  • R 7 which can be the same or different, substituted or not substituted, are selected from a group consisting essentially of H, C ⁇ -C- alkyl, phenyl and cyclohexyl.
  • amide acrylic is a N,N-dialkyl methacrylamide and most preferably ⁇ a N,N-dimethylmethacrylamide.
  • Amide acrylic selected is preferably in liquid form at ambient condition.
  • VCA Vinyl carboxylic acid
  • VCA comprises at least a carboxylic acid group (-COOH) and a polymerizable vinylic prefer ⁇ ably selected from a group of acryloxy and styrenyl.
  • VCA is selected from a group consisting essentially of: methacrylic acid, acrylic acid, itaconic acid, methacryloxybenzoic acid, methacryloxyethanoic acid, and vinylic benzoic acid.
  • VCA selected is preferably in_l_iquid form at ambient condition.
  • VCA can be used singly or in admixture.
  • VCA such as methacrylic acid is used, its amount in the composition is preferably kept below 20%, more preferably below 15% and most preferably below 10 wt.%.
  • Copolymerizable vinylic organosiloxane (hereafter referred to as COS) that can be used in the practice of this invention is liquid and comprises a polysiloxanyl , one polymerizable acrylic and one chain connecting with these two groups.
  • COS Copolymerizable vinylic organosiloxane
  • X is selected from a group consisting of alkyl, alkenyl, phenyl and cyclohexyl, substituted or not substituted; preferably X is an alkylene, -(CH 2 ) n - wherein n is an integer of at least one, prefer ⁇ ably of from 1 to 10 t a is an integer of 0 to 2 inclusive and b is an integer of from 0 to 3 inclusive; each COS includes at least one M and the molar ratio of N to M is at least one, preferably selcected from a range of one to 25.
  • P is a polymerizable vinylic group, such as viny, acrylamido, styrenyl, methacryloxy
  • chain is a chain of chemical bonds which may be linear or branched, however, the chain length is at least one chemical bond;
  • each COS include!- at least one M' and the value of the molar ratio of N 1 to M' is at least one;
  • R' and R" are selected from a group consisting of H, substituted and nonsubstituted alkyl, alkenyl, cyclohexyl and phenyl, such as, -CH 3 , -CF 2 CF 3 , -CH 2 C00R, -CH 2 CH 2 C0N- (CH,) 2 , -CH 2 0H etc-; preferably, said chain contains 1 to 12 chemical bonds.
  • molar ratio is not used herein as based upon the actual molecular weight of the copolymer per se, but rather as based upon the molecular weight of the unit or average molecular weight of the units which are present in such copolymer, as is the common polymer practice.
  • H 2 C C(CH 3 )C0 2 -(CH 2 ) 3 -Sj[-0-Si(CH 3 ) 2 -0-Si(CH 3 ) 3 ]-
  • COS includes:
  • reaction products of r-methacryloxypropyl tri ethoxysilane with trimethylacetoxysilane, pentamethylacetoxydisiloxane and/or heptamethyl acetoxytrisiloxane catalyzed by an acid (Based on GC analysis, the product contains at least one COS having one M group and one COS having two M groups..)
  • Copolymerizable vinylic fluorinated monomer (hereinafter referred to as CVFM) that can be used in the practice of this invention has the general structure: PVG"-Y wherein PVG" is selected from a group consisting essen ⁇ tially of vinyl, methacryloxy, methacrylamido and styrenyl, preferably selected from a methacryloxy; Y is selected from a group consisting of fluorinated alkyl, cyclohexyl and phenyl, substituted or not substituted.
  • the fluorination can be carried out by the techniques knownin the art.
  • the preferred CVFM's are such as those described in "U.S.P.
  • alkyl is selected from C, to C 20
  • Acrylic alkanol that can be used in this invention is selected from a group consisting of acryloxy alkanol and acrylamido alkanol, wherein alkanol is an alcohol of C- ] -C .
  • Preferably acrylic alkanol is selected from a group of 2-acryloxyethaol , 3-acryloxypropanol and 3-acryloxy, 1,2-propan-diol .
  • the novel body fluid or tear wetting system of this invention is to modify the copolymer rendering not only highly oxygen permeable, soft and hydro ⁇ philic but also stable, long term body fluid wettable, dehydration resis ⁇ tant and deposition resistant.
  • #4,343,927 can substantially improve the body fluid or tear wettability of the material or lens made thereof.
  • fluorinated acrylate and acrylic alkanol of this invention into such copolymer, the resistance to protein deposition is substantially increased.
  • acrylic alkanol into the copolymer can substantially improve the highly desired tintability of the lens.
  • some of the other physical properties, such as strength, optical, hardness, surface property of the copolymer in this invention can be modified, if desired, by copolymerizing the composition with (F), 1 to 30 wt.% of at least one copolymerizable property modifier which is selected from a group consisting of C. -C 2Q alkyl methacrylate, styrene, acrylonitrile and methacrylamide.
  • the rigidity of the copolymer in this invention can also be improved, if desired, by incorporating into the material with (G), 0.1 to 30, preferably 0.1 to 10, wt.% of at least one crosslinking monomer known in the art.
  • the cross!inker contains at least two polymerizable vinylic or acrylic groups.
  • Representatives of crosslinking monomers which are suitable for the practice of this invention are polyol dimethacr late or a polyo!
  • methacrylic ester of higher functionality for example, mono-, di-, tri-, or tetraethylene glycol dimeth cr late, butylene glycol dimethacry- late, neopentyl diacrylate and pentaerythritol triacrylate or tetracrylate and the like.
  • the COS described above containing at least two M groups can also be used as crosslinking monomers as described here.
  • the novel copolymer system of this invention can provide the desired features of a successful contact lens. Not only the lens has substantial- ly increased oxygen permeability, softness and hydrophilicity but also stability, long term body fluid or tear wettability, dehydration resistance and deposition resistance. Thus, the wearing comfort is substantially improved.
  • the lens can continuously be worn for a long period of time.
  • the copolymer can be fabricated into soft gas permeable ( SGP ) lens.
  • the water content of this SGP lens is controlled between 30 and 75 wt.% after hydration.
  • the water content can be controlled by adjusting the amount of the comonomers (A) and (B) listed above.
  • this novel . copolymer can also be prepared for the use of a hard gas permeable (HGP) lens.
  • the water content of the HGP lens of this invention is controlled between 1 and 8 wt.% by controlling the amount of comonomer (A) and (B) listed above, and by adding certain amount of crosslinking monomer.
  • the softness of the lens surface is substantially increased and so are the long term tear wettability, dehydration resistance and deposition resistance. Thus, the wearing comfort and wearing period of the lens is substantially improved.
  • the unique properties of the invented material is also highly desirable in certain areas of medical applications, such as eye bandage for drug control release or protective devices for cornea injury or disease; bandage for wound treatment or artificial skin as burn dressing, artificial lung membrane etc.
  • the invented copolymer is fabricated into thin film or membranes by the technology known in the art such as a thin film casting from the liquid comonomers.
  • the transparent copolymer is required; otherwise, it is not the case.
  • This example illustrates the general procedure to prepare the copolymer of this invention.
  • the lens can absorb ca. 4% water as compared to ca. 0.5% of the PMMA lens.
  • the desired hydro ⁇ philicity and high oxygen permeability of the lens increase the soft feeling and comfort for a successful extended wear of a contact lens.
  • the tear wettaility of a contact lens on a human eye can be reflected in the tear breakup time (BUT) ofthe tear film on the lens surface.
  • BUT tear breakup time
  • BUT here is the time visually monitored before the tear film breakup or before a dried spot appearing on the lens surface after an individual eye with the lens is open.
  • the BUT of the lens made of the above copolymer after fully hydrated in a physiological saline is ca. 2 minutes in a human eye testing.
  • the BUT of a lens made of the copolymer of 20 (wt.)% NNDMA, 15% TMPT and 65% MPTS as described in the closest prior art, U.S.P. #4,343,927, after fully hydrated is about 0.5 minute.
  • a substantial increase or in this example about 400% increase of BUT of this inventi.on over the closest prior art is highly desirable for a successful extended wear of a contact lens.
  • Both lenses have similar water content or hydrophilici- ty but the tear wettability or BUT is dramatically different. So this example also illustrates that the body fluid or tear wettability of a lens or the copolymer is not only dependent on the hydrophilicity of the material .
  • This example further illustrates the novelty of this invention showing the lens is substantially increased in functional (body or tear) wettabili ⁇ ty, dehydration resistance and deposition resistance.
  • a lens was made of the composition of 50 (wt.)% NNDMA, 5% MA, 4% MAA (methacrylamide) and 41% MPTS and 0.1% .TMPT of this invention. After equilibrated in a physiological saline, the lens was subject to a human eye testing. Its BUT is about 2 minutes. The lens could very comfortably be worn for one week continuously on the same tested eye. No tear wettabi ⁇ lity problem, dehydration problem, deposition problem, stability problem was experienced during wearing or at the end of wearing.
  • the lens prepared from a similar composition of the above closest prior art having 55% NNDMA, 5% MMA (methyl ' methacrylate) and 40% MPTS after full hydration in a physiological saline is not suitable for an overnight extended wear.
  • the problem likely resulted from the synergetic effect of the relatively poor quality in tear wettability, dehydration resistance and deposition resistance of the lens of the closest prior art.
  • This example further illustrates the novelty of this invention substantial ⁇ ly increasing the lens stability, long term tear wettability, dehydration resistance and deposition resistance.
  • a lens was made of the composition of 24 (wt,)% NNDMA, 6% MA, 10% EGDM (ethylene glycol dimethacr late) and 60% MPTS of this invention. After saturated in a physiological saline, the lens was subject to a human eye testing. Its BUT is about 2 minutes. The lens could very comfortably be worn for about 20 days continuously. No problem in tear wettability, dehydration resistance and deposition resistance was experienced during the wearing. The lens has substantially increased oxygen permeability, DK unit ca. 53, sofness and hydrophilicity. EXAMPL E 5
  • a lens was made of the composition of 39 (wt.)% NNDMA, 2.2% MA, 46% MPTS and 12.8% HEMA of this invention. After fully hydrated in a physiolo ⁇ gical saline, the lens was subject to a human eye testing. It had excel ⁇ lent BUT and the lens could very comfortable be worn for about 30 days continuously, reflecting the excellency in tear wettability, dehydration resistance and deposition resistance of this invention.
  • a thin film (ca. 20-50 micron) cast from a comonomer composition of 50 wt.% of r-methacryloxypropyl, tris(trimethylsiloxy)silane, 10% methacrylic acid, 40% NNDMA and 0.1% TMPT is very oxygen permeable, soft, hydrophilic, body fluid wettable, thus compatible, after hydrated in a physiological saline.
  • the film should be excellent as burn or wound dressing. This film should not only provide the required physiological response but also provide comfort for patient and transparency of the dressing for progress monitoring by attending doctor. This film can also be used as eye protective membrane for corneal injury, disease or drug release-
  • compositions of this invention are shown in Table II and III.
  • MN N,N-dimethylmethacrylamide
  • NN N,N-dimethylacrylamide
  • MA methacrylic acid
  • IA itaconic acid
  • HM HEMA
  • S1 ⁇ r-methacryloxypropyl tris(pentamethyldisiloxanyl)silane
  • S2 trimethylsilyl methylmethacrylate
  • S3 reaction product of ⁇ -methacryloxypropyl trimethoxysilane with trimethylacetoxysilane
  • S4 methacryloxyme thyl heptamethylcyclotetrasiloxane
  • S5 pentamethyldisiloxanylmethyl methacrylate
  • FPM 1,1-dihydrofluoroprop methacrylate
  • MMA methyl methacrylate
  • St. styrene
  • TMPT as defined in specification.
  • MN, MA, S. , MMA and TMPT are the same as those used in Table II;
  • R. fluorostyrene;
  • F trifluoroethyl methylate;
  • F 3 1, l-bis(pentafluorophenyl ) methyl methacrylate;
  • F. 1, 1, 18-trihydro fluorooctadecanyl methacrylate;
  • HP 3-methacryloxy propanol ;
  • HG 3-methacryloxy, 1,2-propan- diols.
  • This invented copolymer is extremely desirable and useful for making extended war contact lens for vision correction.
  • the copoly ⁇ mer should also be highly useful for making eye bandage, artificial skin for burn or wound dressing or artificial membrances for lung machine.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Hematology (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Copolymère spécialement adapté à certaines applications médicales, telles que: lentilles de contact, bandages de l'oeil, peau artificielle pour les brûlés ou bandages de blessures, composés de comonomères dont la proportion, en poids, est la suivante: A - 1 à 85 % d'une amide acrylique au moins; B - 1 à 35 % d'un acide vinyle carboxylique au moins, C - 1 à 90 % d'un organosiloxane vinylique copolymérisable et, éventuellement, de 1 à 90 % d'un monomère vinylique fluoruré copolymérisable au moins, E - 1 à 80 % d'un alcanol acrylique.
EP19880900859 1987-01-07 1988-01-05 Melanges de copolymeres humidifiables, hydrophiles, doux et permeables a l'oxygene. Withdrawn EP0296220A4 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US114987A 1987-01-07 1987-01-07
US1149 1987-01-07
US2683687A 1987-03-17 1987-03-17
US26836 1987-03-17
US13217487A 1987-12-14 1987-12-14
US132174 1987-12-14

Publications (2)

Publication Number Publication Date
EP0296220A1 true EP0296220A1 (fr) 1988-12-28
EP0296220A4 EP0296220A4 (fr) 1989-05-11

Family

ID=27356847

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880900859 Withdrawn EP0296220A4 (fr) 1987-01-07 1988-01-05 Melanges de copolymeres humidifiables, hydrophiles, doux et permeables a l'oxygene.

Country Status (4)

Country Link
EP (1) EP0296220A4 (fr)
JP (1) JPH01503072A (fr)
AU (1) AU1156688A (fr)
WO (1) WO1988005060A1 (fr)

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AU1156688A (en) 1988-07-27
WO1988005060A1 (fr) 1988-07-14
JPH01503072A (ja) 1989-10-19
EP0296220A4 (fr) 1989-05-11

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