WO1993011193A1 - Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions - Google Patents

Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions Download PDF

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Publication number
WO1993011193A1
WO1993011193A1 PCT/US1992/009076 US9209076W WO9311193A1 WO 1993011193 A1 WO1993011193 A1 WO 1993011193A1 US 9209076 W US9209076 W US 9209076W WO 9311193 A1 WO9311193 A1 WO 9311193A1
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WO
WIPO (PCT)
Prior art keywords
ethylenically unsaturated
vaporizable
percent
polymerizable
unsaturated monomer
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.)
Ceased
Application number
PCT/US1992/009076
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English (en)
French (fr)
Inventor
Terry Wayne Cowley
Mary Louise Newman White
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Dow Chemical Co
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Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Priority to JP51010293A priority Critical patent/JP3159988B2/ja
Priority to DE69210625T priority patent/DE69210625T2/de
Priority to EP19920922270 priority patent/EP0614476B1/en
Priority to BR9206960A priority patent/BR9206960A/pt
Priority to FI942399A priority patent/FI942399L/fi
Publication of WO1993011193A1 publication Critical patent/WO1993011193A1/en
Priority to NO941921A priority patent/NO941921L/no
Anticipated expiration legal-status Critical
Ceased 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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/902—High modulus filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2738—Coating or impregnation intended to function as an adhesive to solid surfaces subsequently associated therewith
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/659—Including an additional nonwoven fabric
    • Y10T442/67—Multiple nonwoven fabric layers composed of the same inorganic strand or fiber material

Definitions

  • the present invention concerns low styrene emission vinyl ester and polyester formulations
  • ceresin wax as a styrene emission depressant and drying oil and epoxidized drying oil as secondary adhesion promoters.
  • vinyl ester resins and unsaturated polyester resins contain polymerizable, vaporizable, ethylenically unsaturated monomers such as styrene as a reactive diluent. Since styrene or other polymerizable, vaporizable, ethylenically unsaturated monomer is a volatile component which tends to be released to the atmosphere during storage and/or curing of the
  • thermosettable vinyl ester and unsaturated polyester resins it is becoming more and more desirable to reduce the level of styrene or other polymerizable, vaporizable monomer which is released to the atmosphere during storage and/or cure.
  • One method for reducing the release of styrene or other polymerizable, vaporizable monomer into the atmosphere is to include ceresin wax in the formulation. While this does indeed reduce the amount of styrene released into the atmosphere, the composition suffers from a loss in secondary adhesion.
  • formulations containing ceresin wax as a polymerizable, vaporizable, ethylenically unsaturated monomer emission suppressant can be accomplished by incorporating into the formulation a combination of corn oil and epoxidized soybean oil.
  • the present invention concerns an improvement in vinyl ester and unsaturated polyester resin
  • compositions containing a polymerizable, vaporizable, ethylenically unsaturated monomer and a polymerizable, ethylenically unsaturated monomer emission suppression amount of ceresin wax which improvement comprises employing in said compositions a secondary adhesion promoting amount of at least one drying oil and at least one epoxidized drying oil.
  • Another aspect of the present invention pertains to a polymerizable, vaporizable, ethylenically unsaturated vinyl monomer suppressant/secondary adhesion promoter additive composition
  • a polymerizable, vaporizable, ethylenically unsaturated vinyl monomer suppressant/secondary adhesion promoter additive composition comprising (1) at least one vaporizable ethylenically unsaturated monomer, (2) ceresin wax, (3) at least one drying oil, and (4) at least one epoxidized drying oil.
  • Another aspect of the present invention pertains to a curable composition comprising (A) at least one vinyl ester resin or at least one unsaturated polyester resin or a combination thereof; (B) at least one polymerizable, vaporizable, ethylenically
  • a further aspect of the present invention pertains to a substrate material saturated or
  • a further aspect of the present invention pertains to the product or article resulting from shaping one or more plies of the aforementioned
  • the present invention may suitably comprise, consist of, or consist essentially of, the
  • the vaporizable ethylenically unsaturated vinyl monomer suppressant/secondary adhesion promoter additive composition of the present invention usually comprises (1) from 20 percent to 40 percent, preferably from 20 percent to 35 percent, more preferably from 25 percent to 35 percent percent by weight of at least one
  • vaporizable ethylenically unsaturated monomer (2) from 10 percent to 25 percent, preferably from 10 percent to 20 percent, more preferably from 13 percent to 17 percent percent by weight ceresin wax, (3) from 10 percent to 30 percent, preferably from 18 percent to 28 percent, more preferably from 20 percent to 26 percent percent by weight of at least one drying oil, and (4) from 20 percent to 40 percent, preferably from 20 percent to 35 percent, more preferably from 25 percent to 35 percent by weight of at least one epoxidized drying oil.
  • Suitable vinyl ester resins which can be employed herein include any such resin prepared by the reaction of an epoxy resin having an average of more than one vicinal epoxy group per molecule with an unsaturated carboxylic acid.
  • the reactants are usually employed in amounts which provide a ratio of acid groups per epoxy group of from 0.95:1 to 1.05:1, preferably from 1:1.
  • Suitable epoxy resins include those which contain an average of more than one glycidyl group per molecule such as for example glycidyl derivatives of aliphatic, cycloaliphatic or aromatic compounds
  • epoxy resins include, for example, the glycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol K, fluorene, phenol- or cresol-aldehyde resins, halogenated, particularly bromine substituted derivatives thereof, or any combination thereof.
  • Suitable unsaturated carboxylic acids which can be employed in the preparation of the vinyl ester resins include, for example, acrylic acid, methacrylic acid, glacial methacrylic acid, or any combination thereof.
  • the reaction between the epoxy resin and the unsaturated acid is usually conducted at temperatures of from 90°C to 130°C, preferably from 100°C to 120°C, more preferably from 105°C to 115°C for a time sufficient to complete the reaction.
  • the reaction is usually conducted at temperatures of from 90°C to 130°C, preferably from 100°C to 120°C, more preferably from 105°C to 115°C for a time sufficient to complete the reaction.
  • the reaction is usually conducted at temperatures of from 90°C to 130°C, preferably from 100°C to 120°C, more preferably from 105°C to 115°C for a time sufficient to complete the reaction.
  • the reaction is usually
  • the reaction time is usually from 3 to 6 hours.
  • a catalyst for promoting the reaction between the epoxy resin and the unsaturated acid can be employed.
  • Suitable such catalysts include, tris(dimethylaminomethyl)phenol, tetraethyl ammonium bromide, or any combination thereof.
  • Particularly suitable such catalysts include, for example, or any combination thereof.
  • Particularly suitable such catalysts include, for example
  • the catalysts are usually employed in amounts of from 0.05 to 0.08, preferably from 0.055 to 0.075, more preferably from 0.065 parts of catalyst per 100 parts of resultant mixture of the carboxylic acid and epoxy resin.
  • Suitable unsaturated polyester resins which can be employed herein include, for example, those prepared by reacting a compound having an average of more than one, preferably two, aliphatic, cycloaliphatic or aromatic hydroxyl groups per molecule with a compound having an average of more than one aliphatic,
  • cycloaliphatic or aromatic carboxyl groups per molecule with the proviso that there be present at least one reactant which contains polymerizable unsaturated groups.
  • the reactants are usually employed in amounts which provide a ratio of acid groups per hydroxyl group.
  • Particularly suitable compounds containing an average of more than one hydroxyl group per molecule from which unsaturated polyester resins can be prepared include, for example, those compounds having aliphatic, cycloaliphatic or aromatic hydroxyl groups.
  • Particularly suitable such compounds include, for example propylene glycol, ethylene glycol, bisphenol A, or any combination thereof.
  • Suitable compounds containing an average of more than one carboxylic acid group per molecule from which unsaturated polyester resins can be prepared include, for example, fumaric acid, maleie anhydride, succinic anhydride, chlorendic anhydride, orthophthalic acid or anhydride isophthalic acid or anhydride,
  • terephthalic acid or anhydride or any combination thereof.
  • the reaction between the hydroxyl containing compound and the acid is usually conducted at
  • temperatures of from 150°C to 190°C, preferably from
  • reaction 170°C to 190°C, more preferably from 175°C to 185°C for a time sufficient to complete the reaction.
  • the reaction is usually considered complete when the acid number has reached a value of 50 or below.
  • the reaction time is 6 to 16 hours.
  • a catalyst for promoting the reaction between the hydroxyl-containing compound and the catalyst can be employed.
  • Suitable such catalysts include, butyl stannoic acid, para-toluene sulfonic acid, or any combination thereof.
  • Particularly suitable such catalysts include, for example butyl stannoic acid, or any combination thereof.
  • the catalysts are usually employed in amounts of from 0.05 to 1.0, preferably from 0.05 to 0.1, more preferably from 0.075 parts of
  • ethylenically unsaturated monomers which can be employed herein include, for example, styrene, alpha-methyl styrene, chlorostyrene, vinyl benzene, vinyl toluene, p- methylstyrene, divinylbenzene, or any combination thereof. Also suitable are the C 1 -C 8 alkyl esters of acrylic and methacrylic acid. Styrene is the preferred polymerizable, vaporizable, ethylenically unsaturated vinyl monomer.
  • the polymerizable, vaporizable, ethylenically unsaturated monomers are usually employed in amounts of from 20 to 60, preferably from 35 to 55, more preferably from 40 to 50 percent by weight based upon the combined, weight of the resin and the polymerizable, vaporizable, ethylenically unsaturated monomer.
  • Ceresin Wax is usually employed in amounts of from 20 to 60, preferably from 35 to 55, more preferably from 40 to 50 percent by weight based upon the combined, weight of the resin and the polymerizable, vaporizable, ethylenically unsaturated monomer.
  • Ceresin wax employed herein is a mixture of hydrocarbons of complex composition purified by
  • ceresin wax ozokerite wax 170-D
  • ozokerite wax 170 M.B. white ozokerite wax
  • yellow ozokerite wax yellow ozokerite wax
  • S&P ozokerite wax yellow etc.
  • Strahl & Pitsch Inc. a producer of ceresin wax, defines ozokerite as a
  • hydrocarbon wax derived from mineral or petroleum sources hydrocarbon wax derived from mineral or petroleum sources.
  • the ceresin wax is employed in any amount which will suppress emission of styrene or other volatile polymerizable ethylenically unsaturated monomers
  • ceresin wax examples include, for example, from 0.15 percent to 0.4 percent,
  • any other reactive diluent polymerizable ethylenically unsaturated monomer which may be present, and resin.
  • drying oil as employed herein means any naturally occurring oil which contains glycerides of linoleic and/or linolenic acids. Suitable drying oils will have an Iodine value of from 100 to 210, preferably from 115 to 150, more preferably from 115 to 140.
  • drying oils include , for example, corn oil, linseed oil, safflower oil, soybean oil, sunflower oil, cottonseed oil, rapeseed oil, perilla oil, hempseed oil, or any combination thereof. Corn oil and soybean oil are preferred.
  • the drying oil is employed in any amount which in combination with the epoxidized drying oil will enhance the secondary adhesion of the formulation.
  • drying oil examples include, for example, from 0.1 percent to 0.7, preferably from 0.2 percent to 0.5 percent, more preferably from 0.25 percent to 0.4 percent percent by weight based upon the combined weight of the styrene (polymerizable
  • epoxidized drying oil includes any naturally occurring oils which contains glycerides of linoleic and or linolenic acids and which have been epoxidized. Suitable such epoxidized drying oils include, for example, epoxidized soybean oil, epoxidized corn oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized sunflower oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized perilla oil, epoxidized hempseed oil, or any combination thereof.
  • Epoxidized soybean oil and epoxidized corn oil are preferred.
  • the epoxidized drying oils can be prepared by reacting an epihalohydrin with the desired drying oil and then dehydrohalogenating the resultant halohydrin intermediate with a suitable basic-acting compound such as, for example, an alkali metal halide, alkali metal carbonate. Sodium hydroxide is preferred.
  • a suitable basic-acting compound such as, for example, an alkali metal halide, alkali metal carbonate.
  • Sodium hydroxide is preferred.
  • epoxidized drying oils are available commercially such as, for example epoxidized soybean oil is available from Atochem North America as VIKOFLEX 7170, epoxidized Linseed Oil is available from Atochem North America as VIKOFLEX 7190.
  • the epoxidized drying oil is employed in any amount which in combination with the drying oil will enhance the secondary adhesion of the formulation and retard styrene volatilization some.
  • Particularly suitable amounts of epoxidized drying oil include, for example, from .2 to .7, preferably from .3 to .6, more preferably from 0.35 to 0.55 percent by weight based upon the combined weight of the styrene (polymerizable ethylenically unsaturated monomer), any other reactive diluent (polymerizable ethylenically unsaturated
  • compositions of the present invention can be cured by any means suitable for curing vinyl ester resins and unsaturated polyester resins. They can be suitably cured by means of azo compounds, peroxides, or any combination thereof. Particularly suitable curing agents include, for example, methyl ethyl ketone
  • the curing catalysts are usually employed in amounts of from 1 to 2.5, preferably from 1 to 1.5, more preferably from 1 to 1.25 percent by weight based upon the weight of the resin.
  • curing accelerators or promoters can be employed. Suitable such curing accelerators or promoters include, for example, cobalt naphthenate, cobalt octoate, N,N-dimethylaniline, N,N- dimethylacetoacetamide, or any combination thereof.
  • the curing accelerators or promoters are usually employed in amounts of from 0.05 to 0.6, preferably from 0.1 to 0.4, more preferably from 0.1 to 0.3 percent by weight based upon the weight of the resin.
  • Suitable substrate materials which can be saturated or impregnated with the curable compositions of the present invention include natural or synthetic fibers in woven, mat or multifilament strand form.
  • Suitable such materials can be nylon, rayon, cotton, glass , graphite , carbon , aramid , polyester , or any combination thereof.
  • compositions of the present invention such as, for example, pigments, dyes, fillers, or any combination thereof.
  • the curable compositions are useful in the preparation of laminates, coatings, polymer concrete.
  • Vinyl Ester Resin (VER) A was a vinyl ester resin prepared from a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 380 to 420 and methacrylic acid in an equivalent ratio of acid per epoxy group of 1:1. The resin contained 45 percent styrene by weight.
  • Polyester Resin (PER) A was a rigid, low reactivity, low viscosity, thixotropic, orthophthalic laminating resin commercially available from Reichhold as POLYLITETM Polyester Resin 33-087. The resin was prepromoted for room temperature curing with the addition of methyl ethyl ketone peroxide. The resin contained 43-47 percent styrene by weight.
  • the test was based on a completely catalyzed, curable, system since it was under curing conditions that most of the volatile ethylenically unsaturated monomer was lost.
  • the secondary adhesion promotion test was a cycle flexing test conducted on cured laminates at 70% of the flexural strength determined by ASTM D 790-86.
  • the secondary adhesion test was determined by ASTM D 3479-76(82).
  • the primary laminate was prepared by saturating 6" x 12" glass layers in the following sequence,
  • the secondary laminate was then prepared on top of the primary laminate by saturating 6" X 12" glass layer in the following sequence, CSM/WR/CSM.
  • CSM 1.5 oz. chopped strand mat
  • the secondary laminate was then cured at a temperature of approximately 25°C for at least 20-24 hours.
  • the resultant cured laminate was then subjected to the aforementioned ASTM tests.
  • a paste concentrate for addition to vinyl ester and unsaturated polyester resins was prepared by blending the following: styrene 30.8 percent ceresin wax 15.3 percent corn oil 23.1 percent
  • the blending operation was conducted in a 7-gallon (26.5 L) glass vessel using an air driven stirrer at a
  • This paste concentrate was employed as an additive to vinyl ester resin A and polyester resin A and tested for styrene loss.
  • the formulations and results are given in Table II.

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/US1992/009076 1991-11-25 1992-10-21 Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions Ceased WO1993011193A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP51010293A JP3159988B2 (ja) 1991-11-25 1992-10-21 揮発性エチレン系不飽和モノマーの放出が少ないビニルエステル樹脂組成物及びポリエステル樹脂組成物
DE69210625T DE69210625T2 (de) 1991-11-25 1992-10-21 Vinylester und polyesterharzzusammensetzungen mit niedriger emission von verdampfbaren äthylenisch-ungesättigten monomeren
EP19920922270 EP0614476B1 (en) 1991-11-25 1992-10-21 Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions
BR9206960A BR9206960A (pt) 1991-11-25 1992-10-21 Composição composição de aditivo supressor material de substrato e produto ou artigo moldado
FI942399A FI942399L (fi) 1991-11-25 1992-10-21 Höyrystyvän etyleenisesti tyydyttymättömän monomeerin matalan emissionomaavia vinyyliesteri- ja polysesterihartsikoostumuksia
NO941921A NO941921L (no) 1991-11-25 1994-05-24 Vinylester - og polyesterharpiks-holdige materialer med lavflyktig etylenisk umetted monomer-emisjon

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US797,640 1991-11-25
US07/797,640 US5206077A (en) 1991-11-25 1991-11-25 Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions

Publications (1)

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WO1993011193A1 true WO1993011193A1 (en) 1993-06-10

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PCT/US1992/009076 Ceased WO1993011193A1 (en) 1991-11-25 1992-10-21 Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions

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US (5) US5206077A (https=)
EP (1) EP0614476B1 (https=)
JP (1) JP3159988B2 (https=)
CN (1) CN1072938A (https=)
AT (1) ATE137787T1 (https=)
AU (1) AU2877992A (https=)
BR (1) BR9206960A (https=)
CA (1) CA2122466A1 (https=)
DE (1) DE69210625T2 (https=)
FI (1) FI942399L (https=)
MY (1) MY130021A (https=)
NO (1) NO941921L (https=)
TW (1) TW221824B (https=)
WO (1) WO1993011193A1 (https=)
ZA (1) ZA929089B (https=)

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ATE137787T1 (de) 1996-05-15
US5340856A (en) 1994-08-23
FI942399A7 (fi) 1994-05-24
TW221824B (https=) 1994-03-21
US5380775A (en) 1995-01-10
JP3159988B2 (ja) 2001-04-23
DE69210625D1 (de) 1996-06-13
ZA929089B (en) 1994-05-24
EP0614476B1 (en) 1996-05-08
BR9206960A (pt) 1995-11-28
AU2877992A (en) 1993-06-28
NO941921L (no) 1994-07-15
US5286554A (en) 1994-02-15
EP0614476A1 (en) 1994-09-14
US5206077A (en) 1993-04-27
DE69210625T2 (de) 1996-09-19
JPH07501570A (ja) 1995-02-16
FI942399A0 (fi) 1994-05-24
NO941921D0 (no) 1994-05-24
US5412010A (en) 1995-05-02
CN1072938A (zh) 1993-06-09
MY130021A (en) 2007-05-31
FI942399L (fi) 1994-05-24
CA2122466A1 (en) 1993-06-10

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