WO2003006536A1 - Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same - Google Patents
Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same Download PDFInfo
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- WO2003006536A1 WO2003006536A1 PCT/US2002/021031 US0221031W WO03006536A1 WO 2003006536 A1 WO2003006536 A1 WO 2003006536A1 US 0221031 W US0221031 W US 0221031W WO 03006536 A1 WO03006536 A1 WO 03006536A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/268—Monolayer with structurally defined element
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Definitions
- the present invention relates to environmentally stable breathable and water weakenable films, fibers, and articles of novel polymer blends and the methods for making those films, fibers, and articles.
- the present invention relates to environmentally stable breathable, water weakenable polymer films, fibers, and articles that demonstrate improved stability and enhanced strength when exposed to environmental conditions of increased humidity and elevated temperature.
- Disposable products are a great convenience and provide the benefit of one time, sanitary use. Such products can be useful for applications including, but not limited to, personal care items, diapers and training pants, feminine care products, adult incontinence products, hospital garments, wound care products, hospital bed linens, surgical fabrics, medical fabrics, and the like.
- disposal of these products because of traditional disposal methods. For instance, incineration of these products is not desirable because of increasing concerns about air quality, and the costs and difficulties associated with separating these products from other disposed, non- incineratable articles. Dumping of these products is also undesirable due to limited landfill space and increasing land cost. Consequently, there is a need for disposable products which may be quickly and conveniently disposed of by means other than dumping or incineration.
- these disposable products are breathable in order to increase the level of comfort of the consumers of these products.
- Many disposable articles are not designed for the comfort of the user. Many of these articles use thermoplastic polymers which do not have high water vapor transmission rates and therefore do not have good breathability. In the case of many disposable products, breathability is especially desirable in order to avoid the build-up of perspiration.
- breathability is especially desirable in order to avoid the build-up of perspiration.
- the skin wellness of the user is also increased. It is desirable for the water vapor to pass through the film and move away from the skin rather than becoming trapped against the skin where it can cause possible rashes or other skin maladies. However, it would not be desirable for the film to disintegrate when exposed to the water vapor.
- the article it is desirable for the article to be comprised of a breathable material which has mechanical integrity when it is dry, yet it is readily water weakenable upon immersion in water. Furthermore, it is highly desirable if the film demonstrates the stability and strength to withstand the environmental conditions of elevated temperature and increased humidity that are often experienced in many end-use situations, such as, for instance, in the use of personal care products.
- PEO Polyethylene oxide
- PEO Because of its water-responsive properties, PEO is desirable for flushable applications.
- commercially available PEO resins are very sensitive to high humidity and elevated temperature environments which limits its use in many disposable products. Because of today's global market, it is necessary to manufacture, ship and store product components, and end-use products all over the world, encompassing a multitude of climatic conditions.
- PEO films dramatically lose strength and rigidity when the humidity is above about 65% Relative Humidity (RH) and at temperatures of between about 35-55°C because of the resulting increased moisture absorption. As a result, PEO films experience more failure and tear more easily during manufacturing and storage under these conditions of increased humidity and elevated temperatures. Especially noticeable are stress induced environmentally accelerated cracking and tearing which increases as the material ages.
- RH Relative Humidity
- Shipping and storage of finished products can also cause environmentally induced tearing and cracking when the end use products are exposed to increased humidity and elevated temperature during shipment throughout the world and storage in distribution warehouses in various climates. Controlling the shipping and storage environment would significantly increase the cost of distribution.
- the current state of the art includes disposable articles consisting of a liquid impermeable, vapor permeable film consisting of a crystallizable, stretched polyolefin-based film and a rattle-reducing additive which is polyfethylene oxide).
- these liquid impermeable, vapor permeable films require at least one nucleating agent which is described as talc or calcium carbonate. Further, stretching is required to generate porosity and hence breathability and subsequent leaching of the rattle-reducing agent is desired.
- These are also coated, transparent plastic articles that may consist of poly(ethylene oxide).
- An inorganic, protective coating is applied as a separate layer over the transparent plastic article to improve surface hardness, increase stretch resistance, and facilitate non-fogging.
- the inorganic, protective coating can comprise various metal oxides. However, the coating forms a separate, discrete, glass-like layer from the transparent plastic article and the resulting coating and articles are not breathable or flushable.
- Multilayered or coated recording sheets are available electrostatic printing processes.
- the recording sheets consist of a base sheet with an anti-static layer, which can be made from polyethylene oxide).
- the recording sheets consist of an additional toner- receiving layer, which consists of inorganic oxides such as silicon dioxide, titanium dioxide, calcium carbonate, or the like.
- the poly(ethylene oxide) and inorganic oxides are contained in separate layers, the anti-static layer and the toner-receiving layer respectively. Further, the recording sheets are not breathable or flushable.
- the invention relates to environmentally stable, water weakenable and breathable films, fibers, and articles that demonstrate improved stability and enhanced strength when exposed to environmental conditions of increased humidity and elevated temperature.
- the invention also relates to processes and methods for manufacturing the films, fibers, and articles.
- the films fibers and articles can be useful for manufacturing products that require disposal, including but not limited to, personal care items, diapers and training pants, feminine care products, adult incontinence products, hospital garments, wound care products, hospital bed linens, surgical fabrics, medical fabrics, and the like.
- the films, fibers and articles can be composed of novel polymer blends of chemically modified PEO resin and thermoplastic synthetic resins.
- films, fibers, and articles of the present invention are environmentally stable, breathable and water weakenable and demonstrate improved stability and enhanced strength when exposed to environmental conditions of increased humidity and elevated temperature.
- the films of the present invention do not require stretching and/or addition of filler to provide breathability.
- the novel polymer blends that are used can provide stronger films, fibers and articles with significantly enhanced tensile yield load, to prevent cracking and tearing when subjected to environmental stress during manufacturing, shipping and storage.
- the films, fibers and articles are water weakenable, making them desirable for disposable applications such as flushable products.
- Figure 1 shows a process diagram for forming the polymer blends including a twin screw extruder for compounding components, an air cooled belt for collecting and cooling a water weakenable blend, and a pelletizer.
- the present invention is directed to films, fibers, and articles that are water weakenable and breathable and demonstrate improved stability and enhanced strength when exposed to environmental conditions of increased humidity and temperature.
- the films, fibers, and articles can be used to make disposable products.
- the structure of these films, fibers and articles will weaken when placed in water and allow disposal by flushing in a standard toilet.
- the enhanced strength and improved stability in environments of elevated temperature and increased humidity that is demonstrated by these films, fibers and articles significantly delays the tearing and cracking associated with other polymers exposed to those conditions.
- the water vapor transmission capabilities provide for breathability of the article and results in consumer comfort.
- the use of novel polymer blends produce a breathable film that does not require stretching and/or addition of filler to provide breathability.
- the invention relates to films, fibers, and articles comprising novel blends of water-responsive polymers and non-water soluble polymers. More preferably, the invention relates to films, fibers, and articles comprising blends of PEO with non-water soluble thermoplastic synthetic resins. Most preferable are blends of PEO with ethylene acid copolymers and ionomer resins.
- the films, fibers and articles developed from the PEO blends used in the invention can be especially useful, for example, for disposable applications including but not limited to personal care items, diapers and training pants, feminine care products, adult incontinence products, hospital garments, wound care products, hospital bed linens, surgical fabrics, medical fabrics, and the like.
- the invention can be used for flushable applications such as personal care items, disposable diapers and training pants, feminine care products, adult incontinence products, and the like.
- Articles comprising the novel polymer blend film can comprise at least one layer of the film.
- Articles comprising novel polymer blend fiber may be partially or totally constructed of the fiber.
- Fiber related articles may comprise woven or nonwoven fibrous material.
- water-responsive refers to polymers, films, fibers, articles, and the like that are water-soluble, water-dispersible, water-disintegratible or water-weakenable.
- water-weakenable refers to the ability of a polymer, film, fiber and article, to remain in one piece, but weaken, lose rigidity after five minutes of immersion in water, and become drapeable. In other words, the article bends without an external force applied thereto when it is held by one corner in a horizontal position.
- water-stable refers to a polymer, film, fiber and article, which does not become drapeable after five minutes of immersion in water and remains in one piece after a water response test.
- water-dispersible refers to the ability of a polymer, film, fiber and article, to dissolve or break into pieces smaller than 20 mesh after being immersed in water for approximately thirty minutes.
- water- disintegratable refers to the ability of a polymer composition, film, fiber, and article to break into multiple pieces within thirty minutes of immersion in water, wherein that some of the pieces are caught by a 20 mesh screen without slipping through.
- environmentally stable refers to the ability of a film or fiber to retain shape and strength properties under load, and at elevated temperature and humidity.
- the term “elevated temperature” refers to temperatures between greater than about 25° C and about 37°C.
- the term “elevated humidity” refers to the relative humidity greater than about 50% to about 80%.
- under load refers to any load between about 15% up to about 30% of normalized yield load (NYL).
- the films, fibers and articles of the present invention can comprise an environmentally stable polymer blend having a water-responsive polymer.
- the selection of the water-responsive polymer is based on consideration of key variables such as water solubility, average molecular weights, melt processability, strength and ductility.
- the water-responsive polymer comprises a polymer of ethylene oxide.
- the term "polymer” includes homopolymers, copolymers, terpolymers and modifications thereof.
- Such water-responsive polymers include, but are not limited to, polymers of ethylene oxide, and polymers of poly vinyl alcohol. Most preferable are polymers of ethylene oxide, particularly homopolymers and modified homopolymers of ethylene oxide.
- the water-responsive polymer is poly(ethylene oxide) ("PEO").
- PEO poly(ethylene oxide)
- the PEO is in the form of high molecular weight PEO resins.
- the PEO resins useful for this invention preferably have a molecular weight from greater than about 100,000 g/mol to about 8,000,000 g/mol.
- high molecular weight PEO resins are desirable for mechanical and physical properties
- low molecular weight PEO resins provide the best balance between the mechanical/physical properties and the film- forming properties.
- the more preferred range of molecular weights of PEO resins ranges from about 300,000 g/mol. to about 1,000,000 g/mol.
- the composite films, fibers and articles of the present invention may also comprise other water-responsive polymers.
- PEO resins having a molecular weight higher than 600,000 g/mol have poor melt processability in both filler compounding and in film extrusion. This causes high melt pressure and the resulting films have severe melt fracture. Films thinner than 8 mils cannot be obtained. Therefore, the unmodified PEO resins have limited utility in making thin breathable films. Thin films are desired for personal care product applications due to better flexibility of the material and reduced finished product weight and cost. o resolve these problems, it was discovered that chemically modified PEO resins are especially useful and preferred for the breathable flushable films applicable to the present invention. These. PEO resins have been modified by grafting a polar vinyl monomer onto the PEO.
- modified PEO resins have lower molecular weights than the unmodified high-strength PEO resins.
- the modified PEO resins have lower melt viscosities, higher melt strengths and higher melt elasticity than the unmodified low- strength PEO resins, thereby allowing the formation of very thin films of thickness of about 1 mil.
- the grafting modification method imparts stretchability to the PEO resin as compared to unmodified PEO resin.
- the process for making modified PEO resins and examples of such compositions are described in U.S. Patent No. 6,172,177 to Wang et al., issued January 9, 2001, and U.S. Patent No. 6,117,947 issued September 12, 2000 to Wang et al, both of which are herein incorporated by reference.
- PEO resins suitable for this invention are available from Union Carbide
- PEO resins available from Union Carbide include, but are not limited to, resins sold under the following trade designations and reported average molecular weights: POLYOX® WSR N-
- PEO powder and pellets of PEO were utilized in the examples of the present invention.
- PEO can be blended with any water insoluble polymer which provides the resulting film, fiber, or article of the blend with the properties of increased strength and improved environmental stability in increased humidity and elevated temperature, and can impart these environmentally stable properties to water weakenable and breathable film, fiber, or articles for disposable applications.
- thermoplastic copolymers that are water insoluble. More preferable are ionomer resins, and polystyrene copolymers. Most preferable are ionomer resins and polystyrene acrilonitrile resins.
- the blends can be comprised of chemically modified PEO resin and non-water-soluble ionomer or styrene acrylonitrile resin. While not proposing to be bound by any particular theory, both non-water-soluble resins are believed to provide strong intermolecular interactions with PEO thus stabilizing it in high humidity and elevated temperature environments. Desirably, the blend comprises from about 5 weight percent to about 45 weight percent of non- water soluble resin to total weight of the polymer blend. Blends containing more than about 45 weight percent can be too stable and lose the water weakenable characteristics. Blends comprising less than about 5 weight percent do not provide enough environmental stability when subjected to elevated temperature and high humidity.
- blends comprising from about 10 weight percent to about 30 weight percent of non-water soluble resin to total weight of the polymer blend. More preferable are blends comprising from about 10 weight percent to about 20 weight percent of non-water soluble resin to the total weight of the polymer blend.
- the PEO blend technology can be utilized in a wide variety of thermally processable PEO-based materials where enhanced strength, stiffness and environmental stability at high humidity and elevated temperature are desirable.
- Any polystyrene copolymer which increases the stability and enhances the strength of PEO blends in environments of increased humidity and elevated temperature can be used.
- Most preferable are styrene acrylonitrile copolymer (SAN) resins which have glass transition temperatures above the melting temperature of PEO, and below the desired extrusion processing temperature.
- SAN styrene acrylonitrile copolymer
- Dow Chemical SAN copolymer resins under the trade name Tyril® were used.
- the styrene acrylonitrile resin used in this invention was Tyril ® 125.
- Other SAN copolymer resins such as Dow Chemical Tyril ® 880 and Tyril ® 990 can be used.
- ionomer resins made from ethylene acid copolymers in which the acid groups are partially neutralized with either zinc, sodium or other ions can be used for this invention.
- the ionomer resins used for purposes of examples of this invention were Surlyn ® 1601 (sodium ion) and Surlyn ® 1652 (zinc ion) available from DuPont.
- the PEO resins employed in the polymer blends, films, fibers and articles of the present invention can contain various additives including, but not limited to, plasticizers, processing aids, fillers, dispersants, solid state modifiers, rheology modifiers, antioxidants, UV light stabilizers, pigments, colorants, slip additives, antiblock agents, polymer emulsions, and the like.
- the polymer blends of the present invention can include filler.
- a filler material can be organic or inorganic, and are desirably in a form of individual, discreet particles.
- Suitable inorganic filler materials include metal oxides, metal hydroxides, metal carbonates, metal sulfates, various kinds of clay, silica, alumina, powdered metals, glass microspheres, or vugular void-containing particles.
- Particularly suitable filler materials include calcium carbonate, barium sulfate, sodium carbonate, magnesium carbonate, magnesium sulfate, barium carbonate, kaolin, carbon, calcium oxide, magnesium oxide, aluminum hydroxide, and titanium dioxide. Still other inorganic fillers can include those with particles having higher aspect ratios such as talc, mica and wollastonite.
- Suitable organic filler materials include, for example, latex particles, particles of thermoplastic elastomers, pulp powders, wood powders, cellulose derivatives, chitin, chitozan powder, powders of highly crystalline, high melting polymers, beads of highly crosslinked polymers, organosilicone powders, and powders of super absorbent polymers, such as partially neutralized polyacrylic acid, and the like, as well as combinations and derivatives thereof.
- These filler materials can improve toughness, softness, opacity, vapor transport rate (breathability), water dispersability, biodegradability, fluid immobilization and absorption, skin wellness, and other beneficial attributes of the film.
- the filler is added in an amount sufficient to create a composite that can be made into films.
- the filler comprises from about 10 percent to about 90 percent by weight of the film. More preferably, the filler comprises from about 20 percent to about 50 percent by weight of the film.
- PEO resins will effectively disperse the fillers during the melt extrusion process and produce extruded strands of a uniform and smooth surface.
- Suitable commercially available filler materials include the following:
- This material has a top cut particle size of about 8 microns and a mean particle size of about 1 micron and can be coated with a surfactant, such as Dow Corning 193 surfactant, before mixing with the polymer.
- a surfactant such as Dow Corning 193 surfactant
- SUPERCOAT® a coated ultrafme ground CaCO3, which is available from ECC International of Atlanta, Georgia. This material has a top cut particle size of about 8 microns and a mean particle size of about 1 micron.
- OMYACARB® UF high purity, ultrafme, wet ground CaCO3, which is available from OMYA, Inc., of Proctor, Vermont.
- This material has a top cut particle size of about 4 microns and an average particle size of about 0.7 microns and provides good processability.
- This filler can also be coated with a surfactant such as Dow Corning 193 surfactant before mixing with the polymer.
- OMYACARB® UFT CaCO3 an ultrafme pigment surface coated with stearic acid, available from OMYA, Inc. This material has a top cut particle size of about 4 microns and a mean particle size of about 0.7 microns and provides good processability.
- the filler can be coated with liquid additives to reduce coupling at the resin-filler interface.
- Decoupling should facilitate debonding of filler from polymer matrix during stretching. This is especially important for the polar PEO matrix, which demonstrates strong interaction with fillers.
- the coating should provide affinity to polymer resin for improved dispersion and deagglomeration.
- additives include silicone glycol copolymers of different Hydrophilic-Lipophilic Balance (hereinafter
- HLB HLB numbers ranging from 0 to about 12.
- silicone glycol copolymers are available from Dow Corning Corporation.
- PEO resin, or additive can be compounded with resin and filler at the melt-blending step. The latter method reduces effectiveness of the coating.
- the environmentally stable water weakenable and breathable films, fibers, and articles produced in the present invention may optionally contain various additives such as plasticizers, processing aids, rheology modifiers, antioxidants, UV light stabilizers, pigments, colorants, slip additives, antiblock agents, etc. which may be added before or after blending with the filler.
- additives such as plasticizers, processing aids, rheology modifiers, antioxidants, UV light stabilizers, pigments, colorants, slip additives, antiblock agents, etc. which may be added before or after blending with the filler.
- the inorganic fillers may include water-soluble fillers including, but not limited to, magnesium sulfate, sodium sulfite, sodium hydrogen sulfite, sodium sulfate, sodium hydrogen sulfate, sodium phosphate, sodium hydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and, where applicable, hydrates thereof.
- water-soluble fillers including, but not limited to, magnesium sulfate, sodium sulfite, sodium hydrogen sulfite, sodium sulfate, sodium hydrogen sulfate, sodium phosphate, sodium hydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and, where applicable, hydrates thereof.
- the process of making flushable breathable environmentally stable, water weakenable films, fibers and articles in accordance with the present invention includes the preparation of a composite formed by blending a water-responsive polymer with a water insoluble resin.
- a water-responsive polymer with a water insoluble resin.
- other known water-responsive polymers may be used as the base polymer component of the blend. These polymers include, but are not limited to, polymers and copolymers of ethylene oxide, particularly homopolymers, modified polymers and graft copolymers of ethylene oxide; polymers of vinyl alcohol; poly(vinyl pyrrolidone), polyethyloxazolme, and water-responsive acrylic acid based copolymers.
- the water-responsive polymer is a polymer or copolymer of ethylene oxide, more particularly a homopolymer of ethylene oxide.
- the selection of the water-responsive polymer is based on consideration of key variables including, but not limited to, water responsiveness, controlled molecular weight, melt processability, strength and- ductility.
- PEO poly(ethylene oxide) resins
- the present invention is demonstrated by the use of PEO as the polymer component, the scope of the present invention is not limited to PEO and can be expanded to other water responsive polymers containing polar, ionic, and cationic functional groups.
- the PEO resin can be chemically modified by grafting, reactive extrusion, block polymerization or branching to improve its processability in a melt and performance in a solid state.
- the PEO resin can be modified by reactive extrusion or grafting as described in more detail in U.S. Patent No. 6,172,177 issued to Wang et al., January 9, 2001, which is incorporated by reference in its entirety herein.
- the selection of water insoluble polymer is based on consideration of key variables including, but not limited to, glass transition temperature, melt processability, strength and ductility.
- Thermoplastic synthetic resins were used in the examples.
- Styrene acrylonitrile copolymer (SAN) resins which have glass transition temperatures above the melting temperature of PEO, or below the desired extrusion processing temperature, are applicable for this invention.
- Dow Chemical manufactures Dow Chemical manufactures
- SAN copolymer resins under the tradename Tyril®.
- the styrene acrylonitrile resin used in these Examples was Tyril® 125.
- Ionomer resins made from ethylene acid copolymer in which the acid groups are partially neutralized with either zinc, sodium or other ions are applicable for this invention.
- Other melt processable ionomer resins may also be appropriate for this invention.
- the ionomer resins used in these Examples were Surlyn® 1601 (sodium ion) and Surlyn® 1652 (zinc ion) available from DuPont.
- process equipment for the preparation of the water weakenable and breathable polymer blends, and films of the following examples is based on major requirements such as high shear melt processing, sufficient residence time for mixing, and potential for high rate processing.
- component materials, the PEO resin, and the thermoplastic synthetic resin are suitably intermixed prior to melting.
- Equipment which can be used includes any suitable mixing device, such as Bradender Plasticorders, Haake extruders, single or multiple screw extruders, or any other mechanical mixing devices which can be used to mix, compound, process or fabricate polymers.
- the components of the compositions of the present invention can be fed separately into the melt processing apparatus.
- Conventional extruders having separate feeders which are suitable for preparing the compositions of the present invention can be used.
- Pelletizing the extruded polymer blend can be performed by any suitable pelletizing equipment, such as, for example, a Conair pelletizer.
- Equipment which can be used for the extrusion of films and fibers can be any suitable melt processing apparatus capable of extruding films, fibers or laminates of polymer sheets. Most preferable, the same extrusion equipment used to process the novel polymer blend is capable of extruding the film or fiber.
- the novel polymer blends were produced by a twin screw extrusion process, as demonstrated in Figure 1.
- a twin screw extrusion process In a first step, it is preferred to blend or mix the components in an extruder, such as a single-screw or twin-screw extruder under appropriate temperature and shear/pressure conditions to ensure mixing.
- the blending process can also be performed in a batchwise mixing device, such as a melt mixer or a kneader.
- Modified PEO and SAN,, ionomer, or EVA resins can be fed into the extruder/mixer (12) either simultaneously or in a sequence to minimize any degradation or discoloration.
- additives such as antioxidants can be included to reduce thermal degradation.
- the blend is extruded and the extruded melt strands are cooled in air using a fan-cooled conveyor belt (20).
- the solidified strands are pelletized.
- the polymer blend pellets can then be extruded into a film.
- the PEO, thermoplastic resins, and additives are extruded into a water-weakenable, breathable blend using a Haake TW-100 co-rotating twin-screw extruder (10).
- the barrel has four temperature zones, each ranging from about 150°C to about 200°C.
- the blend is then pelletized in a Conair pelletizer (30). The pellets
- Example 1 a control blend was formed from 100% by weight of the chemically modified PEO base resin.
- a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length was used to demonstrate the process of preparing the compositions.
- the barrel temperatures were set at 170°C, 180°C, 180°C, 190°C.
- the screw speed was set at 120 rpm.
- Modified PEO was added to the extruder using a gravimetric feeder.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was
- Example 2 80% by weight of modified PEO and 20% by weight of Surlyn® 1601 were dry blended, then added simultaneously to the extruder using a gravimetric feeder.
- the blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at 170°C, 180°C, 180°C, 190°C. The screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt. The solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was
- Example 3 70% by weight of modified PEO and 30% by weight of Surlyn® 1601 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder.
- the blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at 170°C, 180°C, 180°C, 190°C. The screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was 150°C, 160°C, 170°C, 170°C, 170°C.
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- Example 4 For Example 4, 80% by weight of modified PEO and 20% by weight of Surlyn® 1652 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder. The blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- Example 5 70% by weight of modified PEO and 30% by weight of Surlyn® 1652 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder.
- the blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at 170°C, 180°C, 180°C, 190°C. The screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was 150°C, 160°C, 170°C, 170°C, 170°C.
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- Example 6 80% by weight of modified PEO and 20% by weight of Tyril® 125 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder. The blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at
- the screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was 150°C, 160°C, 170°C, 170°C, 170°C.
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- Example 7 70% by weight of modified PEO and 30% by weight of Tyril® 125 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder.
- the blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at 170°C, 180°C, 180°C, 190°C. The screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was 150°C, 160°C, 170°C, 170°C, 170°C.
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- Example 8 30% by weight of the ethylene vinyl acetate (EVA) copolymer resin Levapren® 600, available from Bayer was blended with 70% by weight of modified PEO as a comparative example.
- the modified PEO and Levapren® 600 were dry blended, then added simultaneously, to the extruder using a gravimetric feeder.
- the blend was processed by a Haake TW-100 co-rotating twin-screw extruder with screws of 300 mm in length. Four zones of barrel temperatures were set at 170°C, 180°C, 180°C, 190°C. The screw speed was set at 120 rpm.
- the extruded melt strands were cooled in air at room temperature using a fan-cooled conveyor belt.
- the solidified strands were then pelletized using a Conair pelletizer.
- the pelletized resin was converted into film on the same Haake extruder fitted with a melt pump and 4" film die.
- the temperature profile used for film casting was 150°C, 160°C, 170°C, 170°C, 170°C.
- the screw speed was held constant at 21 rpm; the melt pump speed was adjusted to accommodate the flow properties of the resin. Films with a target thickness of 1 mil were collected.
- the films resulting from Examples 1 through 8 were tested for tensile properties, environmental stress cracking, water vapor transmission, and water responsiveness.
- the tensile properties of the films produced in Examples 1 through 8 were assessed on a Sintech 1/D tensile tester according to ASTM Test Method D 638-91. Table 2 shows the machine. direction tensile properties of the films. Blends with ionomer resins of Examples 2 through 5, and SAN resins of Examples 6 and 7, can provide stronger films with significantly enhanced tensile yield load. The PEO/SAN blends of Examples 6 and 7 demonstrate significantly stiffer films with a tensile modulus enhancement by a factor of 3 or more. Table 2
- the films produced by the methods according to Examples 1-8 were assessed for environmental stress cracking according to a modified version of ASTM Method D 5397.
- ASTM Method D 5397 dogbone shaped test specimens with a length of 64 mm, a width of 3.18 mm, and an 18 mm gauge length were cut from each respective film.
- a 1 mm notch was then made across the narrow portion of the test area on the dogbone. The purpose of the notch was to create a localized failure area and accelerate the environmental stress failure of the films.
- the prepared samples were then clipped to a test apparatus and allowed to hang freely; not touching the apparatus except at the clip. Another clip, which weighed approximately 15 g, was hung from the bottom of the dogbone sample.
- a brass gram test weight with a hook was added to the clip, and the samples were placed in an environmental chamber set at 80% RH and 37°C. The elapsed time before sample failure was recorded. If the sample did not fail, an increased load force was added.
- the films were tested at weights that were significantly lower than their dry, room temperature tensile yield load value. To determine the percentage of yield load that was being applied to the films, it was necessary to do a normalization calculation. For each sample, a normalized yield load (NYL) was calculated by adjusting for the notched width of the test specimen and any difference in thickness compared to the sample used for tensile properties analysis. The test load was then divided by the NYL value to determine the percentage of the NYL tested. This number is important because it shows that the same gram weight can create a much higher % yield load in some films compared to others. Table 3 lists the results of the environmental stress cracking test, including the load tested, the average normalized yield load of the specimens tested, and the time elapsed before the sample failed.
- the modified PEO control film of Example 1 was very unstable in the environment of high humidity (80% RH) and elevated temperature (37°). With a test load of only 25 grams, or 30.3% of NYL, the modified PEO film failed in less than two minutes. Under the same load level, Examples 2, 4, and 5 lasted at least one minute longer. Examples 3, 5, and 7 did not fail at all under the 25 gram load. The comparative Example 8, failed in less than one minute.
- the performance of Examples 3, 5, and 7 demonstrates that adding 30% of SAN or Ionomer resin to modified PEO greatly improves stability of films at increased temperature and high humidity at low load levels. Furthermore, the SAN and Ionomer films of Examples 2-7 had much higher tensile yield load values at low humidity and at room temperature conditions than Examples 1 and 8.
- Example 5 the 70/30 modified PEO/Surlyn 1652 film, performed the best. It was able to withstand a 55 gram load, 35.7% of NYL, without failure. This shows that the developed blended films can support a greater load level without failure and they can also withstand a higher percentage of yield load than the modified PEO control film when exposed to environments of high humidity and elevated temperature.
- the water vapor transmission rates (WVTR) of the films were tested according to ASTM Test Method E 96-80. Circular samples measuring three inches in diameter were cut from each of the test materials and from a control of CELGARD® 2500 microporous film which was available from Hoechst Celanese Corporation. Individual samples of the test materials and a control material were placed across the open tops of the individual vapometer cups that contained one hundred milliliters of distilled water. The screw-on flanges were tightened to form a seal along the edges of the cup. The cups were placed in a convection type oven set at 100°F. The relative humidity within the oven was not specifically controlled.
- the cups were first weighed and then immediately placed into the oven. After 24 hours, the cups were removed from the oven and weighed again.
- the WVTR of each material was calculated based on the weight loss and WVTR of the control film, assuming the WVTR of the CELGARD® 2500 microporous film to be 5000 g m 2 /24 hr under predetermined set conditions. In order to normalize the WVTR readings to allow for variation in the thickness of films, the WVTR is multiplied by the thickness of film in mils. The Normalized WVTR is reported in g/m 2 /24 hr/mil. A mil is defined as 0.001 inch.
- the WVTR values for the films are listed in Table 4.
- a WVTR value of 1000 or more means that the film is considered "breathable.” With the exception of Example 5, all of the films were breathable. Results indicate that Example 5 may have been affected by the thickness of the samples tested, and it is believed that a thinner film made from the same material may be breathable. Hence, the films with improved environmental stability also retained an acceptable level of breathability.
- the water responsiveness of the films was assessed by a modified snag test.
- the term "snag test” refers to a test method developed by the National Sanitation Foundation for the snag test, a film sample was placed on a straight metal rod and placed in a bath of water. The water was stirred at a specified speed. The amount of time for the film sample to disperse was recorded. The following modifications were made to the snag test to test the films in this invention: 1.) A hook shape rod was used. 2.) The film sample was stapled to itself, over the hook, to insure that it would not float loosely during testing. 3.) Distilled water was used. 4.) The water was stirred at approximately 500 rpm (measured by the dry velocity of the stir bar at the same setting). The results of the modified snag test are found in Table 5.
- water-dispersible means that the composition dissolves or breaks into pieces smaller than a 20 mesh screen.
- water-disintegradible means that the composition breaks into multiple pieces within five minutes and that some of the pieces will be caught by a 20 mesh screen.
- water-weakenable means that the composition remains in one piece but weakens and loses rigidity after five minutes and becomes drapeable, i.e., it bends without an external force applied to the film when it is held by one corner at a horizontal position.
- water-stable means that the composition does not become drapeable after five minutes and remains in one piece after the water response test.
- the films with improved environmental stability are not water- dispersible, they are water-weakenable.
Abstract
Description
Claims
Priority Applications (5)
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GB0402787A GB2393964B (en) | 2001-07-12 | 2002-07-03 | Films,fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
BR0210796-1A BR0210796A (en) | 2001-07-12 | 2002-07-03 | Chemically modified polyethylene oxide composition films, fibers and articles with improved environmental stability and methods of producing them |
MXPA04000255A MXPA04000255A (en) | 2001-07-12 | 2002-07-03 | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same. |
DE10297042T DE10297042T5 (en) | 2001-07-12 | 2002-07-03 | Films, fibers and articles made of chemically modified polyethylene-oxide combinations with improved stability under environmental influences and methods for producing the same |
KR10-2004-7000313A KR20040019051A (en) | 2001-07-12 | 2002-07-03 | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
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US09/903,932 | 2001-07-12 | ||
US09/903,932 US6515075B1 (en) | 2001-07-12 | 2001-07-12 | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
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KR (1) | KR20040019051A (en) |
AR (1) | AR036341A1 (en) |
BR (1) | BR0210796A (en) |
DE (1) | DE10297042T5 (en) |
GB (1) | GB2393964B (en) |
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- 2002-07-03 BR BR0210796-1A patent/BR0210796A/en not_active IP Right Cessation
- 2002-07-03 DE DE10297042T patent/DE10297042T5/en not_active Withdrawn
- 2002-07-03 GB GB0402787A patent/GB2393964B/en not_active Expired - Fee Related
- 2002-07-03 WO PCT/US2002/021031 patent/WO2003006536A1/en not_active Application Discontinuation
- 2002-07-03 MX MXPA04000255A patent/MXPA04000255A/en unknown
- 2002-07-12 AR ARP020102622A patent/AR036341A1/en unknown
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Cited By (2)
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US9766007B2 (en) | 2011-12-22 | 2017-09-19 | Sarah Rothenberg | Coolant device, dispenser and methods |
WO2018146429A1 (en) | 2017-02-10 | 2018-08-16 | Polymerexpert Sa | Aqueous viscoelastic solution and use thereof in an injection device |
Also Published As
Publication number | Publication date |
---|---|
GB2393964A (en) | 2004-04-14 |
GB2393964B (en) | 2005-06-29 |
GB0402787D0 (en) | 2004-03-10 |
US6515075B1 (en) | 2003-02-04 |
KR20040019051A (en) | 2004-03-04 |
BR0210796A (en) | 2004-08-17 |
AR036341A1 (en) | 2004-09-01 |
MXPA04000255A (en) | 2004-05-04 |
DE10297042T5 (en) | 2004-07-29 |
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