WO1993022125A1 - Polymeric articles and materials - Google Patents
Polymeric articles and materials Download PDFInfo
- Publication number
- WO1993022125A1 WO1993022125A1 PCT/GB1993/000854 GB9300854W WO9322125A1 WO 1993022125 A1 WO1993022125 A1 WO 1993022125A1 GB 9300854 W GB9300854 W GB 9300854W WO 9322125 A1 WO9322125 A1 WO 9322125A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- die
- parts
- water
- mandrel
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
- B29C48/337—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles the components merging at a common location
- B29C48/338—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles the components merging at a common location using a die with concentric parts, e.g. rings, cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/147—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle
- B29C48/1472—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle at the die nozzle exit zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
- B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/007—Using fluid under pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
- B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0056—Biocompatible, e.g. biopolymers or bioelastomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
- B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0092—Other properties hydrophilic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/769—Sanitary equipment
Definitions
- This invention relates to polymeric materials and articles made therefrom, and to methods and apparatus for 5 forming polymeric articles and materials, more particularly polymeric articles and materials which can readily be disposed of when no longer required.
- Polyvinyl acetate is a water-insoluble polymer which is
- the residual vinyl acetate content is typically about 11 wt% corresponding to about 12 mol%. If the reaction is taken further, close to completion, the crystallinity of the polyvinyl alcohol increases and the solubility in cold water decreases very markedly.
- the invention is based on our surprising finding that a polymeric material of the type described in WO 92/01556 can be prepared with substantial and unexpected advantages in terms of efficiency, speed and cost, by extruding the layers through certain particular die arrangements or by a specific multistep forming process. It is to be noted that "cast coextrusion" mentioned herein does not in any way resemble the non-extrusion casting/moulding processes described in WO 92/01556, as will be explained in more detail below.
- the present invention therefore provides in one aspect a process for preparing a composite polymeric article or polymeric material comprising a first organic polymer layer (e.g. of partially hydrolysed polyvinyl alcohol) which is water-soluble at a given (suitably low) temperature, typically 20°C, and a second organic polymer layer (e.g.
- a first organic polymer layer e.g. of partially hydrolysed polyvinyl alcohol
- a second organic polymer layer e.g.
- the die may comprise a first inlet port for receiving one of the polymers under pressure; a second inlet port for receiving the other of the polymers under pressure; and a pair of mandrel members, the first
- mandrel member being hollow along its length to encircle the second mandrel member and the arrangement being such that a first annular conduit is defined around the outer circumference of the first mandrel member, for conveying the said one of the organic polymers over the outer
- polymer guide channel associated with one or each of the conduits, for conveying polymer from the respective inlet port to the respective conduit around substantially all of the outer circumference of the respective mandrel member.
- the present invention therefore provides in a further east aspect a die assembly for coextruding a composite polymeric article or material including first and second
- the die assembly comprising: an elongate housing having a first inlet port for receiving one of the polymers under pressure, a second inlet port for receiving the other of the polymers under pressure and an outlet port downstream of the inlet ports for discharging the composite polymeric material; and a pair of mandrel members provided within the housing, the first mandrel member being hollow along its length to encircle the second mandrel member and the arrangement being such that a first annular conduit is defined around the outer circumference of the first mandrel member, for conveying the one organic polymer over the outer surface of the first mandrel member towards the housing outlet port, and a second annular conduit is defined around the outer circumference of the second mandrel member, for conveying the other organic polymer over the outer surface of the second mandrel member towards the housing outlet port, the first and second conduits terminating together in such a way that the two polymers are discharged from the housing outlet port as a composite polymeric material including polymer layers
- each guide channel is associated with each of the conduits and most preferably each guide channel provides two paths for the polymer entering through the respective inlet port? namely, a first path to convey the polymer in one direction around the respective mandrel and a second path to convey the polymer in the other direction around the mandrel.
- each path half-encircles the mandrel and they meet behind the mandrel (as viewed from the inlet port).
- the guide channels are preferably cut into the outer surfaces of the mandrels.
- the width of the guide channels preferably tapers inwards away from the inlet port, most preferably down to a width identical to the conduit being supplied.
- each guide channel is open throughout its length to the conduit it is supplying.
- each guide channel may worm forwards (i.e. downstream) along its respective mandrel, so that polymer that has already travelled along the channel to the back of the mandrel (as viewed from the inlet port) before entering the respective conduit is substantially at the same or similar longitudinal distance along the mandrel as polymer that has entered the conduit relatively soon after entering the assembly through the relevant inlet port.
- the second mandrel may conveniently be hollow so that compressed air can be blown through the centre of the die to expand the film as it leaves the die.
- the cast die or die(s) may comprise a first inlet port for receiving one of the polymers under pressure; a second inlet port for receiving the other of the polymers under pressure, and respective elongate slots in the die(s) through which each sheet is extruded.
- the present invention therefore provides in a further aspect a die assembly for coextruding a composite polymeric article or material including first and second organic polymer layers adjacent to one another, the die assembly comprising: a housing having a first inlet port for receiving one of the polymers under pressure, a second inlet port for receiving the other of the polymers under pressure and an outlet port downstream of the inlet ports for discharging the composite polymeric material; die means defining a first elongate slot aperture and first manifold channel means being provided to connect the first inlet port to said first slot aperture, the manifold channel means widening towards the slot aperture and being arranged to spread the polymer across the mouth of the slot aperture; die means defining a second elongate slot aperture and second manifold channel means being provided to connect the second inlet port to said second slot aperture, the manifold channel means widening towards the slot aperture and being arranged to spread the polymer across the mouth of the slot aperture
- the die assembly used may suitably be an appropriate number of conventional cast extrusion dies providing an appropriate number of slot die apertures and feeder conduits therefor, depending upon the number of layers desired to be formed in the composite material.
- the extrudable polymeric composition is fed to a so-called "clothes-hanger” or “fish-tail” die having a relatively large diameter entry channel which rapidly widens into a manifold channel to spread the extrudable composition across the mouth of the single slot die.
- the manifold channel is configured so as to encourage spreading of the composition towards the extremities of the slot die.
- the width of the slot is suitably adjustable by means of externally accessible adjuster screws.
- the extruded sheet material is typically hauled off under a suitable tension and passed through conventional rollers and cutters for finishing.
- nip lamination is suitably performed by nip rollers, and optionally at elevated temperature.
- Surface effects between the polymers, and/or electrostatic effects, and/or the effects of external air pressure are all believed to assist lamination, and the use of adhesives or fusion of the layers at the interface may not be necessary.
- the first (relatively water-soluble) polymer layer is formed by extrusion or blow-moulding in any conventional manner and the second (relatively water- soluble) polymer layer is subsequently applied as a coating in any conventional manner.
- Spray-coating of a liquid composition of the second polymer is particularly mentioned.
- the second polymer layer may be substituted by the dry residue of an ink which dissolves more slowly than the first polymer (or not at all) at the given temperature (e.g. 20°C).
- the above method is particularly suitable for making degradable rigid blow- moulded containers and bottles of the first (relatively water-soluble) polymer, for holding non-aqueous materials such as oil or petrol, and externally coated with the relatively insoluble ink to protect against water- degradation during use.
- the present invention provides a polymeric article or polymeric material comprising an organic polymer which is water-soluble at a given (suitably low) temperature, typically 20°C, wherein the surface of the article or material is wholly or partially coated with an ink which dissolves more slowly or not at all in water at the same given temperature to form a water-resistant barrier coating.
- the coated portion of the surface of the article or material will suitably be all of that portion of the surface that may be expected or intended to become exposed to water during normal use of the article.
- the article or material is suitably formed in any conventional manner (e.g. extrusion, moulding, blow- moulding, casting etc) from the polymer, and the ink coating subsequently applied in liquid form (e.g. by spraying, dipping, painting or rolling, for example using a conventional film printing press) and then dried.
- any conventional manner e.g. extrusion, moulding, blow- moulding, casting etc
- the ink coating subsequently applied in liquid form (e.g. by spraying, dipping, painting or rolling, for example using a conventional film printing press) and then dried.
- the preferred soluble polymer is partially hydrolysed polyvinyl alcohol.
- the ink coating is preferably the dry residue of a flexographic alcohol-based hydrocarbon-free liquid ink such as the commercially available inks sold for flexo- printing polyolefin films.
- a flexographic alcohol-based hydrocarbon-free liquid ink such as the commercially available inks sold for flexo- printing polyolefin films.
- the inks sold under the trade mark "ORION" by Coates Lorilleux Limited, Essex, England, may be particularly mentioned as examples of suitable liquid inks from which the ink coating of the present invention may be obtained.
- the article or material is laminar.
- a form of the invention could be a polymer film or sheet to be used in industrial production processes.
- Further forms of this aspect of the invention are articles comprising pieces of such polymer sheet or film.
- the pieces of polymer or film may be shaped to have curvature in more than one direction, e.g. bottles.
- an exposed surface of the polymer dissolves but where a polymer surface is overlaid by the ink layer that surface is protected.
- the ink acts as a barrier and protects the first polymer against dissolution if the protected surface gets wet.
- the articles and materials of the invention can be used where it can be arranged that at first the ink layer acts, as a barrier protecting the water-soluble polymer from a material which is, or might be, wet and then at a later stage an unprotected surface of the water-soluble polymer is allowed to come into contact with water. The consequence of this is that dissolution of the soluble polymer takes place when desired but premature dissolution is prevented by the ink.
- the article comprises a polymeric film
- suitably all of one or both faces of the film is coated with the insoluble ink.
- the polymeric film should be sufficiently thick to provide the required mechanical strength, for example from about 5 ⁇ m to 1 mm, more typically from lO ⁇ m to 200 ⁇ m, for example about 50 ⁇ m.
- the ink layer is typically from about l ⁇ m to 7 ⁇ m in thickness, for example about 3um.
- Non-film articles may comprise a "core" of the soluble polymer, substantially or entirely covered by the ink. Such an article can resist attack by water, but when the ink layer is broken water can dissolve the exposed core and hence the entire article may be disintegrated.
- a method of forming a polymeric article comprising an organic polymer which is water-soluble at a given temperature, typically 20°C, wherein there is applied to the article a whole or partial surface coating of a liquid ink and the said coating is subsequently allowed to dry to form a water-resistant ink barrier coating which dissolves more slowly or not at all in water at the same given temperature.
- the liquid ink may suitably be applied initially to a blank roller of a conventional film printing press and then a film of the liquid ink rolled onto a roll of polymeric film in conventional manner.
- the ink may be used in any desired colour or combination of colours to provide an attractive external appearance of the article. If desired, different inks may be applied sequentially to create a desired effect.
- the speed with which the more rapidly soluble (first) polymer dissolves can be altered by selection of the polymer and also by selection of processing conditions»
- the length of time for this polymer to dissolve can be chosen according to the use envisaged or the article or material and can range from a matter of seconds to several hours.
- the soluble polymer will generally have a speed of solution such that when a sheet of the polymer with at least one side face of the sheet is exposed is placed in distilled water at 20°C, the sheet dissolves sufficiently to break up within a period of time not longer than 24 hours, usually not longer than 8 hours and possibly very much shorter than this e.g. less than 10 sees for a test sheet 50 ⁇ m thick.
- the weight ratio of the more soluble to the less soluble polymer will preferably be at least 2:1, more preferably at least 3:1, still more preferably at least 5:1 and perhaps above 10:1 up to even 100:1, particularly for thick articles.
- the less soluble polymer covers the more soluble polymer with a general thickness which is preferably not more than 20 ⁇ m, more preferably not more than lO ⁇ m, most preferably not more 5 than 5 ⁇ m. It may be as thin as 2 ⁇ m or thinner.
- the total film thickness may range typically from 5 ⁇ m to 1mm, more typically from lO ⁇ m to 200 ⁇ m.
- Each polymer may be used in admixture with other 10. substances.
- colours and/or fillers may be used if desired, in one or both layers. These may be conventional.
- Articles may take various forms; for example, a composite film may comprise just two layers, one of each kind of 15 polymer. Alternatively, the composite film may be a sandwich of more soluble polymer between layers of less soluble polymer. Layers of other materials may, of course, additionally be present.
- the first (or only), 20 water-soluble, polymer is preferably partially hydrolysed polyvinyl alcohol.
- the second, relatively water- insoluble, polymer may be fully hydrolysed polyvinyl alcohol.
- the extrudable and blow-mouldable precursor compositions are preferably plasticised compositions of 25 the respective polymers.
- the plasticised composition of the first (water-soluble) polymer preferably comprises from about 1 to 60, suitably about 5 to 35 parts (by weight or volume), more preferably from about 10 to 20 parts, most 30 preferably about 15 parts, of plasticiser per 100 parts of polymer; up to about 30, suitably about 0 to 15, more suitably about 1 to 15, parts (by weight or volume), more preferably from about 3 to 15 parts, most preferably about 5 parts, of water per 100 parts of polymer; and up to about 5, suitably about 0.01 to 5, parts (by weight or volume), more preferably from about 0.01 to 3 parts, most preferably about 0.25 parts, of a slip agent such as powdered silica (to promote flow of the composition) per 100 parts of polymer.
- a slip agent such as powdered silica (to promote flow of the composition) per 100 parts of polymer.
- the plasticised composition of the second polymer preferably comprises from about 1 to 80, suitably about 5 to 60 parts (by weight or volume), more preferably from about 15 to 35 parts, most preferably about 25 parts, of plasticiser per 100 parts of polymer; up to about 30, suitably about 0 to 15, more suitably about 1 to 15, parts (by weight or volume), more preferably from about 3 to 15 parts, most preferably about 5, suitably about 0.01 to 5, parts, of water per 100 parts of polymer; and up to about 3 parts (by weight or volume), more preferably from about 0.01 to 3 parts, most preferably about 0.25 parts, of a slip agent such as powdered silica per 100 parts of polymer.
- a slip agent such as powdered silica per 100 parts of polymer.
- the plasticiser may be- selected from any conventional plasticiser for the polymer in question.
- the plasticiser should be a polyhydric alcohol, such as glycerol, a glycol, an alkanediol (e.g. an ethanediol, propanediol ⁇ butanediol, pentanediol or hexanediol), an alkanetriol (e.g. a hexanetriol or trimethylol propane), a fatty acid monoglyceride, or a mixture thereof.
- glycerol such as glycerol, a glycol, an alkanediol (e.g. an ethanediol, propanediol ⁇ butanediol, pentanediol or hexanediol), an alkanetriol (e.g. a hexanetriol or trimethylol propane), a fatty acid monog
- compositions described above are generally solid and granular, in contrast to the aqueous compositions indicated for extrusion in WO 92/01556. It is to be noted particularly that the compositions of the present invention employ significantly less water than comparable known compositions. For other forming methods, however, higher levels of water may be required. Such judgements are, however, within the capacity of one of ordinary skill in this art.
- ingredients of the compositions are suitably mixed_ together at an elevated temperature (e.g. about 110°C), but this is not essential, and lower temperatures may be used for the mixing, which will result in a longer mixing time.
- an elevated temperature e.g. about 110°C
- the extrusion is performed under pressure and suitably at elevated temperature.
- the precise pressure and temperature conditions may be selected by a skilled worker, according to the melting and degradation conditions of the polymers employed.
- Processing aids such as antifoamers and lubricants may be used if desired.
- each polymer composition is suitably supplied to the die by means of a short screw extruder having a trickle feeder to prevent blockage.
- the extruders should be arranged to avoid excessive shearing forces on the compositions while delivering the compositions to the die inlet under the desired compression and within a sufficiently short time so that significant degradation of the polymer does not take place (about 4 minutes under normal extrusion conditions for PVA compositions).
- an apparatus for delivering an extrudable plasticised composition of an organic polymer to an extrusion die in a process for forming a composite polymeric article or material comprising a screw extruder having two or more compression zones in the extruder barrel and being vented between some or all zones, and temperature control means whereby the barrel is capable of being maintained at a controlled temperature or series of temperatures along its length.
- the extrusion die may be a coextrusion die for receiving both polymers or may comprise dies having separate apertures for extruding each polymer separately and nipping means provided downstream of the die apertures to laminate the polymer layers after extrusion.
- each polymer is preferably delivered via its own screw extruder as described above.
- the die may be a single die for extruding only a relatively water-soluble polymer for subsequent coating.
- the positions of the compression zones along the barrel are chosen to suit the particular composition being carried. It is preferred that the first compression zone is far enough down the barrel so that the composition has achieved significant momentum before entering the compression zone, for ease of feeding and to prevent blockage (to further reduce the possibility of blockage in the compression zone, and to reduce shear of the composition, the compression on the composition suitably increases gradually into the compression zone).
- the final compression zone, before the composition enters the die may similarly be arranged so that the compression on the composition increases gradually into the zone (in addition to reducing shear, this prevents back-flow of composition out of the vent in the region of substantially zero compression immediately before the final compression zone).
- plasticised insoluble PVA composition may suitably be delivered under a compression ratio of from 1.1:1 to 5.6:1 (more preferably about 2.15:1) whereas plasticised soluble PVA composition may suitably be delivered under a compression ratio of from 1.5:1 to 6:1 (more preferably about 3:1).
- Plasticised insoluble PVA composition is desirably delivered to the coextrusion die at a relatively high screw speed and low barrel diameter, compared with plasticised soluble PVA composition. More particularly, plasticised insoluble PVA may be delivered at a screw speed of about 70 rpm through a screw barrel of 18mm diameter, and plasticised soluble PVA at a screw speed of about 50 rpm through a screw barrel of 25mm diameter.
- the temperature conditions along the barrel are controlled.
- the temperature of each successive portion of the barrel may increase, remain substantially constant or decrease towards the die.
- the temperature of each successive third of the barrel should increase towards the die, suitably in the steps 180 ⁇ 30°C, 230 ⁇ 30°C and 250 ⁇ 30°C; and for a screw carrying plasticised soluble PVA composition, the temperature of each successive third should remain substantially constant or decrease slightly towards the die, suitably in the steps 203 ⁇ 30°C, 202 ⁇ 30°C and 199 ⁇ 30°C.
- the laminar articles prepared by means of the present invention include disposable packaging material and barrier layers in sanitary products e.g. nappies and bed-pan liners. These need to be able to withstand wetness on one side; by using film embodying the present invention they can after use be dropped, with their contents, into a WC bowl to disintegrate. The whole can then be flushed away.
- sanitary products e.g. nappies and bed-pan liners.
- a further application lies in water-disintegratable containers, e.g. rigid oil containers.
- These can suitably be formed by blow-moulding the water-soluble first polymer into container form in conventional manner, and applying an external coating of the water-soluble second polymer or of a water-insoluble ink (e.g. by spraying).
- Fig. 1 shows a longitudinal sectional view of a coextrusion die assembly
- Fig. 2 shows a top view of the die assembly of Fig. 1;
- Fig. 3 shows (a) a top view and (b) a longitudinal sectional view of a lower housing block part of the assembly of Fig. 1;
- Fig. 4 shows (a) a bottom view and (b) a front view of a first mandrel part of the assembly of Fig. 1;
- Fig. 5 shows a side view of the mandrel part of Fig. 4 (b) looking down from the left;
- Fig. 6 shows (a) a bottom view and (b) a front view of a second mandrel part of the assembly of Fig. 1;
- Fig. 7 shows a side view of the mandrel part of Fig. 6 (b) looking from the right;
- Fig. 8 shows (a) a top view and (b) a longitudinal sectional view (with a detail enlarged) of a top housing block part of the assembly of Fig. 1;
- Fig. 9 shows a longitudinal sectional view of a die bush part of the assembly of Fig. 1;
- Fig. 10 shows (a) a top view and (b) a front view of a pin part of the assembly of Fig. 1;
- Fig. 11 shows (a) a top view and (b) a longitudinal sectional view of a clamp ring part of the assembly of Fig. 1;
- Fig. 12 shows a semi-schematic vertical sectional view of a cast coextrusion die assembly
- Fig. 13 shows a sectional view of the die assembly of Fig. 12, taken along the line AA looking in the direction of the arrows;
- Fig. 14 shows a schematic view of a first coextrusion apparatus
- Fig. 15 shows a schematic view of a second coextrusion apparatus
- Fig. 16 shows a side view of a screw part of an extruder for use in the apparatus of Fig. 14 or 15;
- Fig. 17 shows in cross-section a film protected by an ink barrier ' layer on one side
- Fig. 18 shows in cross-section a film protected by an ink barrier layer on both sides.
- both the insoluble and soluble layers were made from PVA.
- the PVAs used were "Mowiol” (Registered Trade Mark) obtainable from Hoechst AG.
- the soluble layers were made using Mowiol 26-88, a partially-hydrolysed PVA having a mean molecular weight of 103000, an 88 mol% degree of hydrolysis and whose viscosity, measured as a 4% aqueous solution, is 26 mPa.s 2 .
- the insoluble layers were made using a 50:50 blend of Mowiol 56/98 and Mowiol 28/99 which are fully- hydrolysed grades having viscosities and hydrolysis values substantially as indicated by their respective specification numbers, as before.
- the plasticised Mowiol 26-88 composition had the following composition (proportions are parts by weight per 100 parts of Mowiol 26-88):
- the powdered silica R972 was present as a slip agent, manufactured by Aerosil.
- the ingredients were all placed initially into a Baker Perkins High Speed Mixer (manufactured by Baker Perkins Limited), which was preheated to 110°C.
- the mixer was then run at approximatel 600 rpm for about 6 minutes, whereupon the material began to lift on the side of the mixer.
- the composition was then dumped into a cooler for approximately 15 minutes or until the temperature fell below 40°C.
- the glycerine plasticiser and the silica slip agent coat "he Mowiol granules and the distilled water is absorbed into the Mowiol granules. The process is accompanied by a rise in temperature.
- the plasticised 50:50 Mowiol 56-98:Mowiol 28-99 composition had the following composition (proportions are parts by weight per 100 parts of Mowiol mixture):
- the ingredients were placed initially into a Baker Perkins High Speed Mixer which was preheated to 110°C.
- the mixer was run at approximately 600 rpm for 30 seconds and then at 1000-1200 rpm for approximately 15-17 minutes, whereupon the material began to lift on the side of the mixer.
- the composition was then dumped into a cooler for approximately 15 minutes or until the temperature fell below 40°C.
- the liquid ink used was an alcohol-based and hydrocarbon- free flexographic ink sold for printing polyolefin films, having the trade mark "ORION” (Coates Lorilleux Limited, Essex, England). Such inks have low odour and solvent retention, are relatively quick drying when applied to a polymeric surface, with good adhesion to the surface, are resistant to freezing temperatures and show acceptable anti-static and slip properties.
- the liquid ink may be admixed with conventional additives, diluents, colouring agents or solvents if desired.
- a coextrusion die assembly having a lower housing block part 1 surrounded by an electrical heating jacket (approx. 600W; 240V) 2; a first (outer) mandrel part 3; a second (inner) mandrel part 4 located within a hollow interior of the first mandrel 3; a top housing block part 5; a die bush part 6; a pin 7 located within the die bush 6; and a top clamp ring part 8.
- the metal housing block 1 is cylindrical in form and is provided near its base with a pair of inlet ports 9,10 angled at approximately 120° to each other.
- the top face of the block is provided with six tapped holes 11 to receive bolts 12 for securing the top block 5 to the lower block 1; a similar number of holes are provided in the bottom face of the block 1 to receive bolts 14 for securing a base portion 15 of inner mandrel 4 in position.
- Each inlet port 9,10 is provided with an adaptor piece 16,17 to connect the wider diameter screw extruders (discussed in more detail below with reference to Figs. 12 and 13) to the inlet ports.
- the adaptor pieces are of metal and are provided with electrical heating jackets 18 which enable their temperature to be controlled. Most typically the temperature maintained by heating jackets 2 and 18 will be substantially the same, the adaptors 16,17 thereby also functioning as regulators of the temperature of the incoming polymer compositions.
- the first (outer) mandrel 3 is generally cylindrical in form, being arranged to fit snugly within the housing block 1 and having itself a hollow central channel 19 to receive the second (inner) mandrel 4, as will be described in greater detail below.
- the outer mandrel 3 is formed of metal and has machined into its external surface by means of a bull-nose cutter a polymer guide channel 20 which starts relatively near the base of the mandrel, at a point adjacent the inlet port 9 of the housing, and worms up and around the mandrel in both the clockwise and the anticlockwise directions, tapering inwards in width as it does so, to terminate on the opposite side of the mandrel.
- a polymer composition entering the die through inlet port 9 encounters the relatively wide portion 21 of guide channel 20 and divides its flow to follow the guide channel in both its directions.
- the channel 20 markedly assists in achieving an even circumferential distribution of the polymer around the mandrel 3.
- the mandrel 3 is provided in its wall near its base with a radial hole 25 for communicating between the second inlet port 10 and the second (inner) mandrel 4, as will be described in greater detail below. Furthermore, the base of the outer mandrel 3 is provided with six holes 26 to receive bolts for securing the base portion 15 of the inner mandrel 4 in position.
- the second (inner) mandrel 4 is also generally cylindrical in form, but smaller than the first mandrel 3, being arranged to fit snugly within the central channel 19 of the first mandrel.
- the second mandrel 4 also has a central channel 27, however, for conveying compressed air in the extrudate blowing stage, as will be described in more detail below.
- the inner mandrel 4 is of generally similar form and function to mandrel 3, having a similar polymer guide channel 28 cut into the mandrel 4 for conveying polymer, from the second housing inlet port 10 and the hole 25 of mandrel 3, circumferentially around the mandrel 4 to spill out into a second annular conduit 29 defined by the upper portion 30 of the interior wall of the first mandrel 3 and the upper portion 31 of the second mandrel, which is of somewhat reduced diameter and is therefore spaced apart from the upper portion 30 of the interior wall of the first mandrel.
- the guide channel 28 tapers inwardly in width away from the inlet port 10 and follows a two-directional worm path over the mandrel 4, analogously to guide channel 20 of mandrel 3.
- the base portion 15 ⁇ Of inner mandrel 4 is provided with a radially outer set of six holes 31 to receive bolts 14 for securing the mandrel 4 to the housing block 1.
- the base portion 15 is also provided with a radially inner set of six holes 32 to receive bolts for securing the mandrel 4 to the outer mandrel 3.
- each conduit 24,29 are provided constrictions 33,34 which adjust the thickness and evenness of each polymer film prior to the films meeting and adhering together to form the desired bilayer.
- constriction 33 is provided by a bulbous portion 35 provided on an interior portion of the cylindrical top block part 5 of the assembly.
- the block 5 has an inner wall 36 which tapers inwards towards the top, so guiding the extruded polymer passing through the constriction 33 radially inwards to meet the other polymer emerging from the second conduit 29 via constriction 34.
- Block 5 is bolted to the top of housing block 1, via six holes 37, six smaller holes 38 also being provided in the upper rim of block 5 to receive bolts for securing the clamp ring 8 to the block 5, as will be described in more detail below.
- Block 5 is also provided with four side holes 39a through its upper portion, to receive bolts 39b for securing the die bush 6 in position within the hollow interior of block 5, as will be described in more detail below.
- the die bush 6 is of hollow cylindrical construction having an internal surface tapering outwards in the up direction to form a chamber 40 which houses the pin 7.
- the pin 7 is hollow to receive a hollow bolt (not shown) which passes down through the pin and into a widened top portion of the central channel 27 of the inner mandrel 4 to secure the pin in position.
- the central channel 27 and the central channel of the hollow bolt together provide a passage through the centre of the die assembly to permit the passage of compressed air through the die assembly.
- the pin 7 has an outwardly tapering outer surface which guides the composite polymeric film out of the die housing through an exit port 41 to a film blowing region above the assembly.
- annular rib 42 by which the above mentioned constriction 34 in second conduit 29 is obtained when the rib 42 is in position near the upper portion 30 of the interior wall of the first mandrel 3.
- the die bush 6 is retained to the top block 5 by means of a top clamp ring 8 overlying both the top block 5 and a shoulder 43 of the die bush 6 and bolted to the top block 5 through six holes 44 in the clamp ring 8 (only one such hole is shown in the sectional view of Fig. 11(b), for clarity).
- the top block 5 is then suitably surrounded by an electric heating jacket 45.
- a two- slot cast coextrusion die assembly having two housing block parts 50a,50b including conventional heating means (not shown); an upper slot die 51 having associated adjuster and feed means as described in more detail below; and a lower slot die 53 having similar associated adjuster and feed means.
- Each slot die 51,52 is defined by respectively an upper 53 and lower 54 variable lip spaced apart from a fixed central double-edged lip 55, each variable lip being moveable to and fro with respect to the fixed lip 55 to alter the width of the respective slot by means of conventional adjusting screws 56,57.
- composition initially enters the housing through inlet port 58 which enlarges laterally to form a manifold channel 59 which guides the composition laterally outwards into the mouth of an elongate and relatively narrow slot conduit 60 which constitutes the exit from the manifold channel.
- the manifold channel 59 tapers inwards in diameter and turns somewhat forwards (in the direction of the flow of extrudable composition) towards its extremities (the dotted ellipses in Fig. 13 represent the changing profile of the manifold channel) and by this means spreads the composition across the upstream mouth of the slot conduit 60 formed in the housing block 50a,50b. Viewed from above as in Fig.
- the upstream edge of this conduit is arcuate in shape, as indicated by line 61, so that composition which has already passed laterally outwards along the manifold channel has correspondingly less distance to travel through this conduit 60 before exiting the conduit into a pre-entry zone 62 in which a flex- adjustable restrictor bar 63 (adjustable by means of a screw 64) may if desired constrict the width of the zone to control the flow. 5
- Fig. 13 represent the width of the conduit 60 and pre-entry zone 62 (as illustrated the width is constant and somewhat narrower than the manifold channel, but nevertheless wider than the final die exit at lips 53,54 and 54,55).
- the composition passes to the upstream mouth of each slot die at lips 53,54 and 54,55 and then out through the die, forming thereby a coextrusion in the form of a laminate of cast coextruded sheets to be processed through rollers, cutters and haul- off systems in conventional manner.
- a coextrusion apparatus comprising respectively a die assembly 70 of the form shown in Figs. 1 to 11 and a die assembly 71 of the form shown in Figs. 12 and 13 and described above.
- the first inlet port of the die assembly 70 is supplied with the plasticised composition of a soluble polyvinyl alcohol previously described, through first adaptor piece 16 by means of a 25mm barrel diameter medium compression extrusion screw 72 connected between a first heated supply chamber 73 and the adaptor piece 16.
- the second inlet port of the die assembly 70 is supplied with the plasticised composition of an insoluble polyvinyl alcohol previously described, through second adaptor piece 17 by means of an 18mm barrel diameter low compression screw 74 connected between a second heated supply chamber 75 and the adaptor piece 17.
- the upper inlet port of the die assembly 71 is supplied with the plasticised composition of a soluble polyvinyl alcohol previously described, through first adaptor piece 80 by means of a 25mm barrel diameter medium compression extrusion screw 72 connected between a first heated supply chamber 73 and the adaptor piece 80.
- the lower inlet port of the die assembly 71 is supplied with the plasticised composition of an insoluble polyvinyl alcohol previously described, through second adaptor piece 81 by means of an 18mm barrel diameter low compression screw 74 connected between a second heated supply chamber 75 and the adaptor piece 81.
- the extrusion screw 72 was a Betol short screw having a length/diameter ratio (L/D) of 25:1 and a compression ratio of 3:1.
- the screw had two compression zones 76,77 separated by a zone 78 in which no compression of polymer composition took place and in which a vent 79 in the barrel wall allows the escape of steam.
- the screw operated at a speed of 53-54 rpm.
- the extrusion screw 74 was of generally similar construction to the screw 72, although it had an L/D ratio of 18:1, a compression ratio of 2.15:1 and a screw speed of 71.4 rpm.
- a pair of nip rollers 83 were mounted a distance of about 0.75 to 1 metre vertically above the die, with a take off to a collecting point (not shown) for the film produced.
- the extruded film is taken up by conventional haul-off apparatus, rollers and cutters for finishing (not shown).
- the screw flights continue along the entire length of the extruder, although for simplicity only the first and last few flights are illustrated in Fig. 16.
- the Mowiol compositions were prepared as described above and dumped the respective hoppers 90,91 of the extruder supply chamber 73,75.
- a trickle feeder is used to prevent blockage of the hopper mouths.
- the composition is taken up by the first screw portion in region 92 and passes into the barrel of the extruder. In this region the barrel temperature is maintained at about 203 ⁇ 30°C in the case of the soluble polymer and about 180 ⁇ 30°C in the corresponding case of the insoluble polymer.
- the root diameter of the screw begins to taper outwards towards the barrel wall (region 93) and then remains parallel with the barrel wall for a distance about equal to the distance of taper.
- the composition is compressed.
- the barrel temperature is maintained at about 202 ⁇ 30°C in the case of the soluble polymer and about 230 ⁇ 30° in the corresponding case of the insoluble polymer.
- region 96 of the extruder The compression is then repeated in region 96 of the extruder, before passing into the adaptor piece and the die.
- the barrel temperature is maintained at about 199 ⁇ 30°C in the case of the soluble polymer and about 250 ⁇ 30° in the case of the insoluble polymer.
- Temperature regulation is performed by means of conventional electric jackets.
- the dies 70,71 are heated to 214°C and the heated PVA compositions then fed to the die by their respective screws at rates of e.g. 5:1 (soluble:insoluble).
- the blown-film extrusion (Fig. 14) at the same time, warm air is blown through the hole in the centre of the die 70.
- a blown film bubble can thereby be formed above the die, with the thin insoluble PVA layer on the inside (or optionally on the outside, depending on which inlet port of the die is supplied with which polymer). Cooling air is blown, again in conventional manner, over the outside of the bubble above the die.
- the blown air dries the bubble rapidly to a non-tacky state such that it can be flattened between the nip rollers 83 and collected folded flat, to be cut open into single sheet form subsequently.
- FIG. 17 there is shown a flexible polymeric film comprising a substrate layer 101 of partially-hydrolysed (soluble) PVA having a relatively thin coating 102 on one face, formed of the dried insoluble residue of the ORION ink described above.
- Figure 18 shows a modification of the film of Figure 17 wherein the ink coating 102 is applied to both sides of the substrate 101. In both cases the coating 102 is applied as a liquid by conventional ink printing methods and subsequently allowed to dry in air.
- the ink coating is applicable to all types of polymeric articles but is particularly useful in the case of thin- walled or film articles. After the useful life of the article is completed, simple tearing or other damage to the protective ink coating will lead to dissolution of the polymer by water and subsequent breaking down by the natural action of microorganisms and the ink coating which is present in much lower amounts than the polymer, will also disperse naturally as the polymer breaks down, since the ink coating itself has no inherent mechanical strength.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Peptides Or Proteins (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019940703822A KR950701272A (en) | 1992-04-23 | 1993-04-23 | Peptidoglycan monomer (PGM) and trivalent metal complexes, preparation method thereof and use thereof |
SK1277-94A SK127794A3 (en) | 1992-04-23 | 1993-04-23 | Polymeric articles and materials |
EP93909387A EP0644823A1 (en) | 1992-04-23 | 1993-04-23 | Polymeric articles and materials |
GB9421384A GB2282100A (en) | 1992-04-23 | 1993-04-23 | Polymeric articles and materials |
BR9306286A BR9306286A (en) | 1992-04-23 | 1993-04-23 | Polymeric articles and materials |
JP5519047A JPH07508688A (en) | 1992-04-23 | 1993-04-23 | Polymer products and materials |
FI944958A FI944958A (en) | 1992-04-23 | 1994-10-21 | Polymer products and materials |
NO944003A NO944003L (en) | 1992-04-23 | 1994-10-21 | Polymer articles and materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929208834A GB9208834D0 (en) | 1992-04-23 | 1992-04-23 | Coextrusion die,method and apparatus |
GB9208834.3 | 1992-04-23 | ||
GB9305322.1 | 1993-03-16 | ||
GB939305322A GB9305322D0 (en) | 1993-03-16 | 1993-03-16 | Coextrusion method and apparatus |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993022125A1 true WO1993022125A1 (en) | 1993-11-11 |
Family
ID=26300766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/GB1993/000854 WO1993022125A1 (en) | 1992-04-23 | 1993-04-23 | Polymeric articles and materials |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0644823A1 (en) |
JP (1) | JPH07508688A (en) |
KR (1) | KR950701272A (en) |
AU (1) | AU4021493A (en) |
BR (1) | BR9306286A (en) |
CA (1) | CA2134101A1 (en) |
CZ (1) | CZ261594A3 (en) |
FI (1) | FI944958A (en) |
GB (1) | GB2282100A (en) |
HU (1) | HUT70712A (en) |
NO (1) | NO944003L (en) |
SK (1) | SK127794A3 (en) |
WO (1) | WO1993022125A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5472518A (en) * | 1994-12-30 | 1995-12-05 | Minnesota Mining And Manufacturing Company | Method of disposal for dispersible compositions and articles |
GB2291831A (en) * | 1994-08-03 | 1996-02-07 | British Tech Group Int | Extrusion and moulding apparatus and method |
EP0701490A1 (en) * | 1993-04-29 | 1996-03-20 | HONEYCUTT, Travis W. | Method of disposal of hot water soluble garments and like fabrics |
WO1998046668A1 (en) * | 1997-04-15 | 1998-10-22 | Solplax Limited | Controlled degradation coatings and a method for their manufacture |
US5965624A (en) * | 1997-06-27 | 1999-10-12 | Eval Company Of America | Self purging EVOH compositions, and methods |
US6579814B1 (en) | 1994-12-30 | 2003-06-17 | 3M Innovative Properties Company | Dispersible compositions and articles of sheath-core microfibers and method of disposal for such compositions and articles |
WO2004052746A1 (en) * | 2002-12-07 | 2004-06-24 | Blue Bag (Innovation) Ltd | Method & apparatus for packing powdered or granular material |
US6838504B1 (en) | 1998-05-06 | 2005-01-04 | Solucorp Industries Ltd. | Integrated fixation systems |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2430060A (en) | 2005-09-08 | 2007-03-14 | Hewlett Packard Development Co | Flows for variable data printing |
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US4094947A (en) * | 1976-09-03 | 1978-06-13 | The Dow Chemical Company | Multilayer coextrusion process for producing selective reflectivity |
US4244914A (en) * | 1976-02-18 | 1981-01-13 | Montedison S.P.A. | Process for preparing gas-, vapor- and odor-proof coupled and coextruded multilayer articles of thermoplastic material and closed-surface bodies comprising the same |
US4407881A (en) * | 1981-05-30 | 1983-10-04 | Dai Nippon Insatsu Kabushiki Kaisha | Decorative sheets and processes for producing decorative articles by using the same |
WO1992001556A1 (en) * | 1990-07-24 | 1992-02-06 | Bhp Plastics Limited | Composite polymeric articles |
WO1992015454A1 (en) * | 1991-03-01 | 1992-09-17 | Clopay Corporation | A compostable polymeric composite sheet and method of making or composting same |
-
1993
- 1993-04-23 CA CA002134101A patent/CA2134101A1/en not_active Abandoned
- 1993-04-23 CZ CZ942615A patent/CZ261594A3/en unknown
- 1993-04-23 WO PCT/GB1993/000854 patent/WO1993022125A1/en not_active Application Discontinuation
- 1993-04-23 JP JP5519047A patent/JPH07508688A/en active Pending
- 1993-04-23 AU AU40214/93A patent/AU4021493A/en not_active Abandoned
- 1993-04-23 GB GB9421384A patent/GB2282100A/en not_active Withdrawn
- 1993-04-23 EP EP93909387A patent/EP0644823A1/en not_active Withdrawn
- 1993-04-23 BR BR9306286A patent/BR9306286A/en not_active Application Discontinuation
- 1993-04-23 HU HU9403063A patent/HUT70712A/en unknown
- 1993-04-23 SK SK1277-94A patent/SK127794A3/en unknown
- 1993-04-23 KR KR1019940703822A patent/KR950701272A/en not_active Application Discontinuation
-
1994
- 1994-10-21 NO NO944003A patent/NO944003L/en unknown
- 1994-10-21 FI FI944958A patent/FI944958A/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2121565A1 (en) * | 1971-01-04 | 1972-08-25 | Kautex Werke Gmbh | |
US4244914A (en) * | 1976-02-18 | 1981-01-13 | Montedison S.P.A. | Process for preparing gas-, vapor- and odor-proof coupled and coextruded multilayer articles of thermoplastic material and closed-surface bodies comprising the same |
US4094947A (en) * | 1976-09-03 | 1978-06-13 | The Dow Chemical Company | Multilayer coextrusion process for producing selective reflectivity |
US4407881A (en) * | 1981-05-30 | 1983-10-04 | Dai Nippon Insatsu Kabushiki Kaisha | Decorative sheets and processes for producing decorative articles by using the same |
WO1992001556A1 (en) * | 1990-07-24 | 1992-02-06 | Bhp Plastics Limited | Composite polymeric articles |
WO1992015454A1 (en) * | 1991-03-01 | 1992-09-17 | Clopay Corporation | A compostable polymeric composite sheet and method of making or composting same |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0701490A4 (en) * | 1993-04-29 | 1996-12-18 | Travis W Honeycutt | Method of disposal of hot water soluble garments and like fabrics |
EP0701490A1 (en) * | 1993-04-29 | 1996-03-20 | HONEYCUTT, Travis W. | Method of disposal of hot water soluble garments and like fabrics |
GB2291831A (en) * | 1994-08-03 | 1996-02-07 | British Tech Group Int | Extrusion and moulding apparatus and method |
GB2291831B (en) * | 1994-08-03 | 1997-06-18 | British Tech Group Int | Extrusion and moulding apparatus and method |
US5630972A (en) * | 1994-12-30 | 1997-05-20 | Patnode; Gregg A. | Method of making dispersible compositions and articles |
US5567510A (en) * | 1994-12-30 | 1996-10-22 | Minnesota Mining And Manufacturing Company | Dispersible compositions and articles and method of disposal for such compositions and articles |
US5472518A (en) * | 1994-12-30 | 1995-12-05 | Minnesota Mining And Manufacturing Company | Method of disposal for dispersible compositions and articles |
US5508101A (en) * | 1994-12-30 | 1996-04-16 | Minnesota Mining And Manufacturing Company | Dispersible compositions and articles and method of disposal for such compositions and articles |
US5763065A (en) * | 1994-12-30 | 1998-06-09 | Minnesota Mining And Manufacturing Company | Water dispersible multi-layer microfibers |
US6579814B1 (en) | 1994-12-30 | 2003-06-17 | 3M Innovative Properties Company | Dispersible compositions and articles of sheath-core microfibers and method of disposal for such compositions and articles |
WO1998046668A1 (en) * | 1997-04-15 | 1998-10-22 | Solplax Limited | Controlled degradation coatings and a method for their manufacture |
US5965624A (en) * | 1997-06-27 | 1999-10-12 | Eval Company Of America | Self purging EVOH compositions, and methods |
US6838504B1 (en) | 1998-05-06 | 2005-01-04 | Solucorp Industries Ltd. | Integrated fixation systems |
WO2004052746A1 (en) * | 2002-12-07 | 2004-06-24 | Blue Bag (Innovation) Ltd | Method & apparatus for packing powdered or granular material |
Also Published As
Publication number | Publication date |
---|---|
HUT70712A (en) | 1995-10-30 |
BR9306286A (en) | 1998-06-30 |
AU4021493A (en) | 1993-11-29 |
NO944003L (en) | 1994-12-20 |
GB2282100A (en) | 1995-03-29 |
KR950701272A (en) | 1995-03-23 |
GB9421384D0 (en) | 1994-12-21 |
SK127794A3 (en) | 1995-07-11 |
JPH07508688A (en) | 1995-09-28 |
FI944958A (en) | 1994-12-12 |
HU9403063D0 (en) | 1995-01-30 |
CZ261594A3 (en) | 1995-06-14 |
FI944958A0 (en) | 1994-10-21 |
EP0644823A1 (en) | 1995-03-29 |
CA2134101A1 (en) | 1993-11-11 |
NO944003D0 (en) | 1994-10-21 |
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