WO1992001556A1 - Composite polymeric articles - Google Patents
Composite polymeric articles Download PDFInfo
- Publication number
- WO1992001556A1 WO1992001556A1 PCT/GB1991/001237 GB9101237W WO9201556A1 WO 1992001556 A1 WO1992001556 A1 WO 1992001556A1 GB 9101237 W GB9101237 W GB 9101237W WO 9201556 A1 WO9201556 A1 WO 9201556A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- soluble
- water
- insoluble
- layer
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/728—Hydrophilic
Definitions
- Polyvinyl acetate is a water-insoluble polymer which is obtained by polymerization of vinyl acetate. This polymer is used for the production of polyvinyl alcohol by hydrolysis or alcoholysis to remove the acetyl groups from polyvinyl acetate. This removal of acetyl groups may be carried to partial completion so as to give a product which is a copolymer of vinyl alcohol and vinyl acetate. If vinyl alcohol predominates, but there is still a substantial quantity of vinyl acetate present. such a copolymer is soluble in cold water and 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. Material of this type is referred to as "fully
- hydrolysed polyvinyl alcohol Its content of residual vinyl acetate is typically no greater than 3 mol% .
- Polyvinyl alcohol can be made into film or sheet form.
- US-A-4444839 Hoechst ) describes PVA labels which are soluble only in hot water, but which have an adhesive fixing layer which can dissolve in cold water enabling easy detachment of the label.
- the adhesive may be a polyvinyl alcohol.
- this invention provides an article or material comprising a first organic polymer which is water-soluble at a given temperature, typically 20°C, and a second organic polymer located directly adjacent thereto, which second organic polymer dissolves more slowly or not at all in water at the same given
- the first, water-soluble, polymer is preferably partially hydrolysed polyvinyl alcohol.
- the water-insoluble organic polymer may be fully hydrolysed polyvinyl
- both polymers will feel dry, not tacky, to the touch.
- the article or material is laminar with adjacent layers of the two polymers.
- Such a form of the invention could be polymer film or sheet to be used in industrial production processes.
- Further forms of the invention are articles comprising pieces of such polymer sheet or film.
- the pieces of polymer sheet or film may be shaped to have curvature in more than one direction.
- Articles and materials of this invention have the property that if an exposed surface of the first polymer is brought into contact with water, it dissolves but where a first polymer surface is overlaid by the second polymer that surface is protected.
- the second polymer acts as a barrier and protects the first polymer against dissolution if the protected surface gets wet.
- the article or material e.g. a continuous uniform multilayer laminate film, or a body of the soluble polymer substantially surrounded by a coat of the insoluble polymer.
- the second polymer can be a surprisingly thin layer, so thin that it does not remain intact after the first polymer dissolves. Then the first polymer is relied upon to provide mechanical strength while the second polymer is relied on for a water-barrier.
- the articles and materials of the invention can be used where it can be arranged that at first the slower-dissolving second polymer 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 second polymer 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.
- dissolution cf the soluble polymer takes place when desired but premature dissolution is prevented by the second polymer.
- laundry bags made from polymer film which is watersoluble with a very thin layer of water-insoluble polymer on the inside of the bags. If the laundry happens to be wet, it will not cause the bags to dissolve prematurely because of the barrier function of the very thin
- insoluble polymer in the sewage system need not be a problem because the preferred material, namely fully hydrolysed polyvinyl alcohol, is bio-degradable.
- Another possibility is to have a piece or layer of the first polymer surrounded by the second polymer, so that the article can maintain its integrity in the presence of water unless broken or ruptured, allowing water to attack the first polymer.
- the preferred soluble polymer is partially
- hydrolysed polyvinyl alcohol As already mentioned above this is a copolymer of polyvinyl alcohol with vinyl acetate. Generally these copolymers are hydrolysed to an extent between 75 and 95 mol%, more commonly between 80 and 90 mol%. Thus, the mol ratio of vinyl alcohol to vinyl acetate lies between 75:25 and 95:5, more
- polyvinyl alcohol is fully bio-degradable. This has the considerable benefit that if the polymer is allowed to dissolve in water which is then run to waste, the polymer which enters the sewage system will degrade into
- the soluble polymer does not
- 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. as will be mentioned below.
- the length of time for this polymer to dissolve can be chosen according to the use envisaged for the article or material and can range from a matter of seconds to several hours.
- the more rapidly soluble polymer used in the present invention will generally have a speed of solution such that when a sheet of the polymer with at least one side face of the sheet 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 50um thick.
- the relatively less soluble polymer should of course dissolve more slowly than the more soluble polymer.
- the polymer is essentially insoluble, to the extent that if a test sheet of the material with sufficient thickness to be handled, e.g. 50 ⁇ m, is placed in sterile distilled water at 20°C, the sheet remains undissolved and intact for a period exceeding 8 hours and perhaps more than 24 hours.
- the relatively slowly dissolving polymer is
- Fullyhydrolysed polyvinyl alcohol or a suitably insoluble polyvinyl alcohol copolymer are over 96 mol% hydrolysed; commonly over 98 mol%. They are in fact appreciably watersoluble at raised temperatures, e.g. over about 50°C, and usually highly soluble over about 80°C, although some special types can withstand such temperatures for some time without dissolving. At about room temperature, however, solubility is sparing and particularly so for the more highly polymerised PVAs.
- both polymers are biodegradable, meaning that when discarded into sewage or otherwise exposed to water and natural
- the articles of the invention will usually have the "insoluble" polymer exposed to the exterior.
- the soluble polymer may also be exposed, or may be enclosed by the insoluble polymer.
- the insoluble layer will usually contact only the exterior and the more soluble polymer; not any adhesive or other type of layer.
- 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 or three-dimensional 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 10 ⁇ m, most preferably not more 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 10 ⁇ m to 200 ⁇ m.
- Each polymer may be used in admixture with other substances.
- a plasticiser is usually desirable to achieve a piiable film product.
- Glycerol, trimethylol propane, and glycols are suitable
- plasticisers Colours and/or fillers may also be used if desired, in one or both layers. These may be
- Articles may take various forms, for example, a film may comprise just two layers, one of each kind of
- the film may be a sandwich of more soluble polymer between layers of less soluble polymer.
- Non-film articles may comprise a "core" of the soluble polymer substantially or entirely covered by the less soluble polymer. Such an article can resist attack by water, but when it is broken water can dissolve the exposed core and hence the entire article may be
- the invention provides processes for preparing composite articles and materials as
- a cast/mould process for film or sheet involves forming a first of the layers - the less soluble one if PVA - on a flat or shaped surface and subsequently applying the second layer on top of it.
- Application may be e.g. by spraying or by a dripped feed.
- PVA can be applied with water e.g. as an aqueous solution or
- dispersion optionally containing plasticisers, thickeners etc. as appropriate, from which water is evaporated in forming the two layers of polymer.
- Extrusion preferably involves co-extrusion of the two layers. Blown film co-extrusion is preferred.
- the process can be an adaptation of the known process for forming a blown film from a single PVA polymer.
- the conventional production of PVA film by extrusion entails feeding a plasticised volume e.g. an aqueous solution or dispersion of the PVA, to a die with an annular extrusion orifice surrounding an air inlet.
- the plasticised polyvinyl alcohol is extruded from the orifice it forms a tube which is blown out into a larger diameter tube by the pressure of air introduced through the air inlet.
- the blown tube is drawn off between a pair of nip rollers which close off the air space.
- a high pressure, short screw extruder is suitable. This usually has a smooth bush, and e.g. a vibrating trickle feeder to avoid overloading the screw, which can be a problem with PVA.
- a film-blowing process which is one aspect cf this invention comprises supplying an appropriate extrudable form e.g. solution or dispersion of the polymers to respective extrusion orifices of a die, the orifices being annular and one within the other, so as to extrude tubes of the polymers from the orifices, while also supplying gas pressure to the interior of the inner tube thereby expanding both tubes and uniting the inner tube with the outer tube to form a single tube made up from layers of the two polymers.
- an appropriate extrudable form e.g. solution or dispersion of the polymers to respective extrusion orifices of a die, the orifices being annular and one within the other, so as to extrude tubes of the polymers from the orifices, while also supplying gas pressure to the interior of the inner tube thereby expanding both tubes and uniting the inner tube with the outer tube to form a single tube made up from layers of the two polymers.
- the extrusion machinery can resemble conventional machinery for forming blown films of polyvinyl alcohol except however that its extrusion die has two annular orifices instead of the usual single orifice and a feed screw for each orifice with associated means for supply to each feed screw.
- the gas which is blown in is suitably hot air, via an inlet within the inner annular slit.
- the heated air can also evaporate water from the PVA so that the film bubble dries and can be passed through e.g. nip rollers above the die.
- Extrusion of PVA including blown film extrusion, is known technology and the skilled man will be able to select suitable conditions, for example a die temperature in the region of 150°C, etc.
- the relative rates of feed to the die orifices and concentrations of the polymers can be adjusted to achieve the desired ratio of thickness of the two layers.
- Processing aids such as antifoamers and lubricants may be used if desired.
- the invention provides a coextrusion apparatus adapted for producing bubble-blown film as described above.
- the laminar articles 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.
- Fig 1 is a schematic side view of a blown film coextrusion apparatus
- Fig 2 is a schematic top view of the apparatus
- Fig 3 is a schematic cross-section of the coextrusion die of the apparatus
- Fig 4 shows steps in making a baby's potty liner
- Fig 5 shows a disposable nappy.
- Fig 6 shows a two layer film
- Fig 7 shows a three-layer laminar article
- Fig 8 shows a three-dimensional moulded article.
- 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 (i) Mowiol
- each of these was made up in a respective aqueous composition containing, by weight, 15% PVA granules
- the PVA granules were added to the water and glycerine and then heated at 93°C for fifteen to twenty minutes to form a solution.
- the make-up of the individual PVA compositions can be selected in accordance with known criteria.
- An experimental apparatus was set up as shown schematically in Figs 1 to 3.
- a pair of heated supply tanks 1 were provided, one for each PVA type, and
- nip rollers 16 were mounted with a take off to a collecting point (not shown) for the film produced.
- Aqueous extrudable PVA compositions are prepared as described above e.g. from Mowiol 26-88 and Mowiol 20-98, and each put in a respective heated tank 1 of the
- the tank of Mowiol 26-88 (soluble, partially hydrolysed) composition communicates via its feed screw 2 with the outer, wider extrusion slit 10.
- the Mowiol 2098 (insoluble, fully hydrolysed) composition communicates via its feed screw 2 with the inner, narrower extrusion slit 11.
- the die is heated to 150°C and the heated PVA compositions then fed to the die by their respective screws 2 at rates of e.g. 5:1 (soluble:insoluble).
- warm air is blown to the air inlet 17 and out through the hole in the centre of the die 5.
- a blown film bubble 20 can thereby be formed above the die, with the thin insoluble PVA layer on the inside. Cooling air is blown, again in conventional manner, over the outside of the bubble above the die.
- the two extruded layers emerging from their respective slits 10,11 coalesce to form the composite film within a few millimeters of exiting the die.
- the blown air dries the bubble rapidly to a nontacky state such that it can be flattened between the nip rollers 16 and collected folded flat, to be cut open into single sheet form subsequently.
- a convex mould surface 25 (see Fig 4a) was prepared, made from a shaped metal sheet. This had a hat shape, with an upwardly-projecting central portion 26 and a surrounding bottom rim 27 for forming the rim of the liner.
- An insoluble PVA layer was formed by spraying a solution of Mowiol 20-98 onto the outer, convex mould surface.
- the solution was as described previously under “Materials Used", but with the substitution of 10% cellulose ether thickener ( “Tylose” (Registered Trade Mark)) for 10% of the water to improve adhesion of the PVA layer to the sloping sides of the mould 25.
- This first layer was then dried to tackiness by blowing it with warm air, and a second layer of a corresponding thickened aqueous solution of Mowiol 26-88 was sprayed over it to a considerably greater thickness.
- a pronouncedly thick layer was formed on the brim 27 of the former, to strengthen the rim of the liner.
- the insoluble inner layer of the liner was able to contain the potty contents for an extended period without leaking.
- the release paper 33 was lifted off and two opposing sides of the rim stuck together face-to-face using the PVA adhesive coat 32, so as to form a sealed bag
- a backing sheet 40 for a disposable nappy was made by sequential spraying and drying of two different PVA layers as described above for the liner, but this time on a flat steel surface and without the Tylose thickener.
- the thicker, soluble layer formed the outside of the nappy and the thin, insoluble layer the inside (uppermost in Fig 5).
- the more soluble layer may be about 0.1 mm thick and the less soluble layer about 0.02 mm, but these can be adjusted according to the required strength.
- a conventional cellulosic absorbent pad 41 was affixed to the thin insoluble layer using a commercial PVA adhesive.
- aqueous liquid was poured onto the padding and the nappy was then rolled up. After being left for eight hours, the nappy was still intact and there was no leakage. However, on putting the rolled-up nappy into a bowl of water, it broke up in seconds and dispersed.
- FIGS 6 to 8 illustrate schematically various forms of article embodying the invention.
- Figure 6 shows a two-layer flexible film comprising a layer 50 of fully-hydrolysed PVA, 3 ⁇ m thick,
- Figure 7 shows a disposable drinking cup made from a three layer laminar product. This has a thick
- intermediate layer 61 of partially-hydrolysed PVA, perhaps 0.5mm thick, giving mechanical strength to the cup.
- the inner and outer surfaces of the cup have a thin, 5 ⁇ m coating 60 of fully-hydrolysed PVA which prevents outside moisture, and liquid in the cup, from attacking the intermediate layer 61. To render the cup disposable it need only be torn up, whereupon the
- intermediate layer is exposed and can be dissolved.
- Fig. 8 shows a moulded golf tee having a central core 71 of partially-hydrolysed PVA forming the basic shape of the tee. 5 ⁇ m coating 70 of insoluble PVA covers the tee. The coating may be applied to the moulded
- soluble tee by conventional methods.
- the tee can withstand normal use. If it is lost, any natural wear or damage will allow natural moisture to destroy it quickly and hence avoid a litter problem.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR919106667A BR9106667A (en) | 1990-07-24 | 1991-07-24 | COMPOSITE POLYMERIC ITEMS |
CA002091365A CA2091365C (en) | 1990-07-24 | 1991-07-24 | Composite polymeric articles |
AU82281/91A AU656731B2 (en) | 1990-07-24 | 1991-07-24 | Composite polymeric articles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB909016151A GB9016151D0 (en) | 1990-07-24 | 1990-07-24 | Composite polymeric articles |
GB9016151.4 | 1990-07-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992001556A1 true WO1992001556A1 (en) | 1992-02-06 |
Family
ID=10679521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1991/001237 WO1992001556A1 (en) | 1990-07-24 | 1991-07-24 | Composite polymeric articles |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0540593A1 (en) |
JP (1) | JPH05509045A (en) |
AU (1) | AU656731B2 (en) |
BR (1) | BR9106667A (en) |
CA (1) | CA2091365C (en) |
GB (1) | GB9016151D0 (en) |
WO (1) | WO1992001556A1 (en) |
ZA (1) | ZA915792B (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2033572A1 (en) * | 1990-05-02 | 1993-03-16 | Rhone Poulenc Agriculture | Soluble sachets |
WO1993022125A1 (en) * | 1992-04-23 | 1993-11-11 | British Technology Group Inter-Corporate Licensing Limited | Polymeric articles and materials |
US5280835A (en) * | 1990-05-02 | 1994-01-25 | Rhone-Poulenc Inc. | Laminated bags for containerization of toxic and hazardous materials |
EP0610008A1 (en) * | 1993-01-25 | 1994-08-10 | Amcol International Corporation | Multi-layer waterproofing articles including a layer of water-soluble polymer and method |
US5472518A (en) * | 1994-12-30 | 1995-12-05 | Minnesota Mining And Manufacturing Company | Method of disposal for dispersible compositions and articles |
WO1996020831A1 (en) * | 1994-12-30 | 1996-07-11 | Kimberly-Clark Worldwide, Inc. | A water-flushable film |
WO1997009379A1 (en) * | 1995-09-08 | 1997-03-13 | Solplax Limited | Biodegradable plastic material and a method for its manufacture |
WO1998050455A1 (en) * | 1997-05-08 | 1998-11-12 | Polyval Research Limited | Biodegradable materials and products and methods for their manufacture |
GB2376680A (en) * | 2001-06-19 | 2002-12-24 | Procter & Gamble | Laundry bag with water soluble features |
US6544452B1 (en) | 1996-12-18 | 2003-04-08 | Pvaxx Technologies Ltd. | Polymer processing method and tablet-forming apparatus |
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 |
US7026375B1 (en) | 1998-08-26 | 2006-04-11 | Pvaxx Research And Development Limited | PVA-containing compositions |
US7049272B2 (en) | 2002-07-16 | 2006-05-23 | Santrol, Inc. | Downhole chemical delivery system for oil and gas wells |
US7195777B2 (en) | 2000-03-01 | 2007-03-27 | Pvaxx Research & Development Limited | Method and apparatus for blowmoding capsules of polyvinylalcohol and blowmolded polyvinylalcohol capsules |
DE102008063520A1 (en) * | 2008-12-18 | 2010-07-01 | Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg | Rinsable multilayer film |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3546716A (en) * | 1968-06-19 | 1970-12-15 | David H E Laumann | Disposable bedpan liner |
US3790067A (en) * | 1970-12-04 | 1974-02-05 | S Scheier | Container |
EP0010171A1 (en) * | 1978-09-21 | 1980-04-30 | Intermedicat GmbH | Multilayer sheet disintegratable in an aqueous medium, and vessel and bag made from this sheet |
US4348293A (en) * | 1978-11-17 | 1982-09-07 | Lever Brothers Company | Water-insoluble, water-permeable bag having a water-soluble or water-dispersable protective layer and containing a particulate detergent composition |
US4372311A (en) * | 1980-09-12 | 1983-02-08 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
GB2193925A (en) * | 1986-08-18 | 1988-02-24 | Enak Ltd | improvements relating to WC-disposable sheet material |
-
1990
- 1990-07-24 GB GB909016151A patent/GB9016151D0/en active Pending
-
1991
- 1991-07-24 WO PCT/GB1991/001237 patent/WO1992001556A1/en not_active Application Discontinuation
- 1991-07-24 EP EP91913355A patent/EP0540593A1/en not_active Ceased
- 1991-07-24 ZA ZA915792A patent/ZA915792B/en unknown
- 1991-07-24 AU AU82281/91A patent/AU656731B2/en not_active Ceased
- 1991-07-24 JP JP3512569A patent/JPH05509045A/en active Pending
- 1991-07-24 BR BR919106667A patent/BR9106667A/en not_active Application Discontinuation
- 1991-07-24 CA CA002091365A patent/CA2091365C/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3546716A (en) * | 1968-06-19 | 1970-12-15 | David H E Laumann | Disposable bedpan liner |
US3790067A (en) * | 1970-12-04 | 1974-02-05 | S Scheier | Container |
EP0010171A1 (en) * | 1978-09-21 | 1980-04-30 | Intermedicat GmbH | Multilayer sheet disintegratable in an aqueous medium, and vessel and bag made from this sheet |
US4348293A (en) * | 1978-11-17 | 1982-09-07 | Lever Brothers Company | Water-insoluble, water-permeable bag having a water-soluble or water-dispersable protective layer and containing a particulate detergent composition |
US4372311A (en) * | 1980-09-12 | 1983-02-08 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
GB2193925A (en) * | 1986-08-18 | 1988-02-24 | Enak Ltd | improvements relating to WC-disposable sheet material |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2033572A1 (en) * | 1990-05-02 | 1993-03-16 | Rhone Poulenc Agriculture | Soluble sachets |
US5280835A (en) * | 1990-05-02 | 1994-01-25 | Rhone-Poulenc Inc. | Laminated bags for containerization of toxic and hazardous materials |
WO1993022125A1 (en) * | 1992-04-23 | 1993-11-11 | British Technology Group Inter-Corporate Licensing Limited | Polymeric articles and materials |
GB2282100A (en) * | 1992-04-23 | 1995-03-29 | British Tech Group Int | Polymeric articles and materials |
EP0610008A1 (en) * | 1993-01-25 | 1994-08-10 | Amcol International Corporation | Multi-layer waterproofing articles including a layer of water-soluble polymer and method |
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 |
WO1996020831A1 (en) * | 1994-12-30 | 1996-07-11 | Kimberly-Clark Worldwide, Inc. | A water-flushable film |
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 |
US5630972A (en) * | 1994-12-30 | 1997-05-20 | Patnode; Gregg A. | Method of making dispersible compositions and articles |
US5763065A (en) * | 1994-12-30 | 1998-06-09 | Minnesota Mining And Manufacturing Company | Water dispersible multi-layer microfibers |
US5472518A (en) * | 1994-12-30 | 1995-12-05 | Minnesota Mining And Manufacturing Company | Method of disposal for dispersible compositions and articles |
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 |
WO1997009379A1 (en) * | 1995-09-08 | 1997-03-13 | Solplax Limited | Biodegradable plastic material and a method for its manufacture |
US5948848A (en) * | 1995-09-08 | 1999-09-07 | Solplax Limited | Biodegradable plastic material and a method for its manufacture |
US6544452B1 (en) | 1996-12-18 | 2003-04-08 | Pvaxx Technologies Ltd. | Polymer processing method and tablet-forming apparatus |
WO1998050455A1 (en) * | 1997-05-08 | 1998-11-12 | Polyval Research Limited | Biodegradable materials and products and methods for their manufacture |
US6838504B1 (en) | 1998-05-06 | 2005-01-04 | Solucorp Industries Ltd. | Integrated fixation systems |
US7026375B1 (en) | 1998-08-26 | 2006-04-11 | Pvaxx Research And Development Limited | PVA-containing compositions |
US7195777B2 (en) | 2000-03-01 | 2007-03-27 | Pvaxx Research & Development Limited | Method and apparatus for blowmoding capsules of polyvinylalcohol and blowmolded polyvinylalcohol capsules |
GB2376680A (en) * | 2001-06-19 | 2002-12-24 | Procter & Gamble | Laundry bag with water soluble features |
US7049272B2 (en) | 2002-07-16 | 2006-05-23 | Santrol, Inc. | Downhole chemical delivery system for oil and gas wells |
WO2004052746A1 (en) * | 2002-12-07 | 2004-06-24 | Blue Bag (Innovation) Ltd | Method & apparatus for packing powdered or granular material |
DE102008063520A1 (en) * | 2008-12-18 | 2010-07-01 | Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg | Rinsable multilayer film |
US8597796B2 (en) | 2008-12-18 | 2013-12-03 | Huhtamaki Films Germany Gmbh & Co. Kg | Flushable multilayer film |
Also Published As
Publication number | Publication date |
---|---|
CA2091365C (en) | 2003-05-13 |
CA2091365A1 (en) | 1992-01-25 |
ZA915792B (en) | 1992-04-29 |
EP0540593A1 (en) | 1993-05-12 |
JPH05509045A (en) | 1993-12-16 |
BR9106667A (en) | 1993-06-08 |
AU656731B2 (en) | 1995-02-16 |
AU8228191A (en) | 1992-02-18 |
GB9016151D0 (en) | 1990-09-05 |
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