AU9719901A - Cellulosic and lignocellulosic materials and compositions and composites made therefrom - Google Patents

Description

S&FRef: 499935D1

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

a Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Xyleco, Inc.

90 Addington Road Brookline Massachusetts 02146 United States of America Marshall Medoff, Arthur Lagace Spruson Ferguson St Martins Tower,Level 31 Market Street Sydney NSW 2000 (CCN 3710000177) Cellulosic and Lignocellulosic Materials and Compositions and Composites Made Therefrom The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845c Cellulosic and Lignocellulosic Materials and Compositions and Composites Made Therefrom Background of the Invention The invention relates to texturised cellulosic or lignocellulosic materials (including, but not limited to, poly-coated paper) and compositions and composites made from such texturised materials.

Cellulosic and lignocellulosic materials are produced, processed, and used in large quantities in a number of applications. Once used, these materials are usually discarded.

As a result, there is an ever-increasing amount of waste cellulosic and lignocellulosic material. Paper coated with a polymer (poly-coated paper) is used in a number of applications. For example, poly-coated paper is used to make a variety of food containers, including juice cartons and boxes for frozen foods.

Summary of the Invention The invention is based on the discovery that texturised cellulosic and/or 15 lignocellulosic materials can be combined with many different matrix materials, including organic matrices thermosetting resins, elastomers, asphalts, lignins, or tars) to produce useful compositions. In general, the invention features texturised cellulosic or lignocellulosic materials and compositions and composites made therefrom.

~In one embodiment, the invention features a process for preparing a texturised fibrous material. The process involves shearing a cellulosic or lignocellulosic material having internal fibres flax; hemp; cotton; jute; rags; finished or unfinished paper, paper products, including poly-coated paper, or byproducts of paper manufacturing such as pulp board; or synthetic cellulosic or lignocellulosic materials such as rayon), to the extent that the internal fibres are substantially exposed, resulting in texturised fibrous S* 25 material. The cellulosic or lignocellulosic material can be a woven material such as a woven fabric, or a non-woven material such as paper or bathroom tissue. The exposed fibres of the texturised fibrous material can have a length/diameter ratio of at least about 5 (at least about 5, 10, 25, 50, or more). For example, at least about 50% of the fibres can have L/D ratios of this magnitude.

In another embodiment, the invention features a texturised fibrous material that includes a cellulosic or lignocellulosic material having internal fibres, where the cellulosic or lignocellulosic material is sheared to the extent that the internal fibres are substantially exposed.

The texturised fibrous material can, for example, be incorporated into associated with, blended with, adjacent to, surrounded by, or within) a structure or carrier [1:\DAYLIB\ibaa]09339.doc:sak a netting, a membrane, a flotation device, a bag, a shell, or a biodegradable substance). Optionally, the structure or carrier may itself be made from a texturised fibrous material a texturised fibrous material of the invention), or of a composition or composite of a texturised fibrous material.

The texturised fibrous material can have a bulk density less than about 0.5 grams per cubic centimeter, or even less than about 0.2 g/cm 3 Compositions that include the texturised fibrous materials described above, together with a chemical or chemical formulation a pharmaceutical such as an antibiotic or contraceptive, optionally with an excipient; an agricultural compound such as a fertilizer, herbicide, or pesticide; or a formulation that includes enzymes) are also within the scope of the invention, as are compositions that include the texturised fibrous materials and other liquid or solid ingredients particulate, powdered, or granulated solids such as plant seed, foodstuffs, or bacteria).

Composites that include thermoplastic resin and the texturised fibrous materials are 15 also contemplated. The resin can be, for example, polyethylene, polypropylene, polystyrene, polycarbonate, polybutylene, a thermoplastic polyester, a polyether, a thermoplastic polyurethane, polyvinylchloride, or a polyamide, or a combination of two or more resins.

i* In some cases, at least about 5% by weight 10%, 25%, 50%, 75%, 95%, 99%, or about 100%) of the fibrous material included in the composites is texturised.

The composite may include, for example, about 30% to about 70% by weight resin and about 30% to about 70% by weight texturised fibrous material, although proportions outside of these ranges may also be used. The composites can be quite strong, in some cases having a flexural strength of at least about 6,000 to 10,000 psi.

In another embodiment, the invention features a composite including a resin, such as a thermoplastic resin, and at least about 2% by weight, more preferably at least about by weight, texturised cellulosic or lignocellulosic fibre. The invention also features a composite that includes polyethylene and at least about 50% by weight texturised cellulosic or lignocellulosic fibre.

The invention further features composites, including a resin and cellulosic or lignocellulosic fibre, that have flexural strengths of at least about 3,000 psi, or tensile strengths of at least about 3,000 psi.

In addition, the invention features a process for manufacturing a composite; the process includes shearing cellulosic or lignocellulosic fibre to form texturised cellulosic [I:\DAYLB\Iibaa]09339.doc:sak or lignocellulosic fibre, then combining the texturised fibre with a resin. A preferred method includes shearing the fibre with a rotary knife cutter. The invention also features a process for manufacturing a composite that includes shearing cellulosic or lignocellulosic fibre and combining the fibre with a resin.

The composites can also include inorganic additives such as calcium carbonate, graphite, asbestos, wollastonite, mica, glass, fibre glass, chalk, talc, silica, ceramic, ground construction waste, tire rubber powder, carbon fibres, or metal fibres stainless steel or aluminum).

The inorganic additives can represent about 0.5% to about 20% of the total weight of the composite.

In one embodiment, the invention features a composition that includes a matrix reinforced with at least about 2% fibre 10%, 30%, 50%, 70%, 90% or more, 10 to 90%, 30 to where the fibre is a lignocellulosic or cellulosic material that has been sheared to the extent that the internal fibres are substantially 15 exposed. Material thus sheared is termed "texturised." At least 5% 5% 10%, 10%, 25%, 50%, 75%, 90%, 95%, 99%, or substantially all) of the material by weight can be texturised. Generally, at least about 5% or 10%, more preferably at least about 50%, or 70%, of these fibres have a length/diameter ratio of at least 5, more •*•oo preferably at least 10 or 25, or at least The matrix can include, for example, a thermosetting resin an alkyd, a diallyl phthalate, an epoxy, a melamine, a phenolic, a silicone, a urea, a thermosetting polyester, or their derivatives, or a combination of two or more such thermoplastic resins), an elastomer natural rubber, isoprene rubber, styrene-butadiene copolymers, neoprene, nitrile rubber, butyl rubber, ethylene propylene copolymer ethylene propylene 25 diene terpolymer hypalon, acrylic rubber, polysulfide rubber, silicones, urethanes, fluoroelastomers, butadiene, or epichlorohydrin rubber, or combinations or derivatives thereof), a tar or asphalt, or a lignin lignins that have been extracted and/or isolated and/or purified from their natural sources, or synthetic or modified lignins and their derivatives). The matrix can be prepared from natural or synthetic components, or combinations of both.

The composition can also include optional additives such as pharmaceuticals; agricultural compounds; enzymes; particulate, powdered, or granulated solids; plant seeds; foodstuffs for human consumption or animal feed); bacteria; and/or aatditives such as calcium carbonate, graphite, asbestos, wollastonite, mica, glass, fibre glass, chalk, talc, silica, ground construction waste, tire rubber powder, carbon fibres, metal fibres, [1:\DAYLIB\ibaa]09339.doc:sak c 4 plasticizers, lubricants, antioxidants, opacifiers, heat stabilizers, colorants, impact modifiers, photostabilizers, biocides, antistatic agents, organic or inorganic flame retardants, biodegradation agents, dispersants, emulsion polymers, accelerators, extenders, retardants, antifoaming agents, thixotropic agents, or waterproofing agents. In some cases, such additives can constitute from about 0.5% to about 20% 2%, 10%, 15%, or or more, of the total weight of the composition.

The composite or composition can be in a bulk form, or can be in the form of articles such as pallets injection molded pallets), pipes, panels, decking materials, boards, housings, sheets, poles, straps, fencing, members, doors, shutters, awnings, shades, signs, frames, window casings, backboards, wallboards, flooring, tiles, railroad ties, forms, trays, tool handles, stalls, bedding, dispensers, staves, films, wraps, totes, barrels, boxes, packing materials, baskets, straps, slips, racks, casings, binders, dividers, walls, indoor and outdoor carpets, rugs, wovens, and mats, frames, bookcases, sculptures, chairs, tables, desks, art, toys, games, wharves, piers, boats, masts, pollution control 15 products, septic tanks, automotive panels, substrates, computer housings, above- and below-ground electrical casings, hoses, polymeric foams, furniture, picnic tables, tents, playgrounds, benches, shelters, sporting goods, beds, bedpans, thread, filament, cloth, plaques, trays, hangers, servers, pools, insulation, caskets, bookcovers, clothes, canes, •crutches, and other construction, agricultural, material handling, transportation, automotive, industrial, environmental, marine, naval, electrical, electronic, recreational, S* medical, textile, and consumer products. The composites can also be in the form of a fibre, filament, or film.

The terms "texturised cellulosic or lignocellulosic material" and "texturised fibrous i material" as used herein, mean that the cellulosic or lignocellulosic material has been •25 sheared to the extent that its internal fibres are substantially exposed. Generally, at least about 10%, more preferably at least about 25%, 50%, or 70%, of these fibres have a length/diameter ratio of at least 5, more preferably at least 25, or at least 50. An example of texturised cellulosic material is shown in Fig. 1.

The term "matrix", as used herein, refers to the continuous phase of the compositions described herein and can include, for example, thermoplastic resins, thermosetting resins, elastomers, tars, lignins, or asphalts, or mixtures of any of these or other materials. Other components contaminants, metal filings) may also be present in the matrix.

The term "thermosetting resin", as used herein, refers to plastics organic polymers) that are cured, set, or hardened into a permanent shape. Curing is an [I:\DAYLIB\ibaa09339.doc:sak irreversible chemical reaction typically involving molecular cross-linking using heat or irradiation UV irradiation). Curing of thermosetting materials can be initiated or completed at, for example, ambient or higher temperatures. The cross-linking that occurs in the curing reaction is brought about by the linking of atoms between or across two linear polymers, resulting in a three-dimensional rigidified chemical structure.

Examples of thermosetting resins include, but are not limited to, silicones, alkyds, diallyl phthalates (allyls), epoxies, melamines, phenolics, certain polyesters, silicones, ureas, polyurethanes, polyolefin-based thermosetting resins such as TELENETM (BF Goodrich) and METTON T M (Hercules).

The term "elastomer", as used herein, refers to macromolecular materials that rapidly return to approximate their initial dimensions and shape after deformation and subsequent release.

Examples of elastomers include, but are not limited to, natural rubber, isoprene rubber, styrene-butadiene copolymers, neoprene, nitrile rubber, butyl rubber, ethylene 15 propylene copolymer "EPM") and ethylene propylene diene terpolymer "EPDM"), hypalon, acrylic rubber, polysulfide rubber, silicones, urethanes, fluoroelastomers, butadiene, and epichlorohydrin rubber.

The term "tar", as used herein, means a typically thick brown to black liquid Smixture of hydrocarbons and their derivatives obtained by distilling wood, peat, coal, shale, or other vegetable or mineral materials. An example is coal tar, which is made by destructive distillation of bituminous coal or crude petroleum containing naphthalene, toluene, quinoline, aniline, and cresols).

The term "lignin", as used herein, refers to an amorphous substance, mixture, or powder isolated from wood, plants, recycled wood or plant products, or as a byproduct of paper making. In nature, lignins,, together with cellulose, form the woody cell walls of plants and the cementing material between them. They are typically polymeric and may be distinguished from cellulose by a higher carbon content than cellulose, and the inclusion of propyl-benzene units, methoxyl groups, and/or hydroxyl groups. They are generally not hydrolyzed by acids but may be soluble in hot alkali and bisulfite, and may be readily oxidizable. Lignins can be recovered from the liquor that results from the sulfate or soda process of making cellulosic pulp, or from sulfite liquor. The term lignin thus includes sulfite lignin, or lignin-sulfonates.

The term "asphalt", as used herein, refers, for example, to an amorphous, solid, or semisolid mixture of hydrocarbons, brownish-black pitch, or bitumen, produced from the higher-boiling point minerals oils by the action of oxygen. Asphalts include both [I:\DAYLIB\Iibaa]09339.doc:sak 3 asphaltenes and carbenes. Asphalts are commonly used for paving, roofing, and waterproofing materials.

The texturised fibrous materials of the invention have properties that render them useful for various applications. For example, the texturised fibrous materials have absorbent properties, which can be exploited, for example, for pollution control. The fibres are generally biodegradable, making them suitable, for example, for drug or chemical delivery in the treatment of humans, animals, or in agricultural applications). The texturised fibrous materials can also be used to reinforce polymeric resins.

Those composites that include texturised fibrous material and resin are strong, lightweight, and inexpensive. The raw materials used to make the composites are available as virgin or recycled materials; for example, they may include discarded containers composed of resins, and waste cellulosic or lignocellulosic fibre.

The new compositions have properties that render them useful for various 15 applications. Compositions that include texturised fibrous material and matrices are, for example, strong, lightweight, and inexpensive.

Other advantages afforded by the texturised fibres include: Reduced densities of matrix materials such as elastomers and thermosetting resins.

Higher impact resistance due to increased interfacial area between matrix and :texturised fibre and increased energy absorbed when texturised fibre delaminates from matrices.

Reduced surface friction.

Higher lubricity surfaces.

25 Enhanced tolerance for and compatibilization of both the hydrophobic and hydrophilic constituents in the matrices.

Enhanced ability to custom tailor the properties of the composition for specific requirements.

Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.

Brief Description of the Drawing Fig. 1 is a photograph of a texturised newspaper, magnified fifty times.

Detailed Description of the Invention The invention is directed to texturised cellulosic and/or lignocellulosic materials, which can optionally be combined with many different matrix materials, including [L:\DAYLIB\ibaa]09339.doc:sak organic matrices thermosetting resins, elastomers, asphalts, lignins, or tar-like materials).

Examples of cellulosic raw materials include paper and paper products such as newsprint, poly-coated paper, and effluent from paper manufacture; examples of lignocellulosic raw materials include wood, wood fibres, and wood-related materials, as well as materials derived from kenaf, grasses, rice hulls, bagasse, cotton, jute, other stem plants hemp, flax, bamboo; both bast and core fibres), leaf plants sisal, abaca), and agricultural fibres cereal straw, corn cobs, rice hulls, and coconut hair). Aside from virgin raw materials, post-consumer, industrial offal), and processing waste effluent) can also be used as fibre sources.

The fibres can optionally be chemically treated, for example, with silanes, stearates, surfactants, or other compounds to render them lipophilic, lipophobic, more adherent, and/or dispersible or processible for a given product application within polymeric, elastomeric, tar, asphalt, or lignin matrices). Other additives, or mixtures of matrix 15 materials, can also be used.

The mechanical properties of matrices are influenced by the condition of the :'reinforcing fibre and the quality of the preparation process. In general, the greater the fibre length in the product, the higher certain mechanical moduli will be. The fibre-tomatrix weight ratio in the final product can also affect mechanical properties tensile 20 strength, flexural strength, and/or compressive strength). Texturised fibre has the :advantage of having lower specific gravity than traditional reinforcing materials such as glass fibre, resulting in strong, lightweight, economical products.

The resulting compositions include a network of fibres, encapsulated within a matrix. The fibres are thought to form a lattice network, which provides the composition 25 with strength. Since the cellulosic and/or lignocellulosic material is texturised, the amount of surface area available to bond to the matrices increased, in comparison with compositions prepared with un-texturised cellulosic or lignocellulosic material. The matrix material binds to the surface of the exposed fibres, creating an intimate blend of the fibre network and the resin matrix. The intimate blending of the fibres and the matrix further strengthens the compositions.

Preparation of Texturised Fibrous Material If scrap cellulosic or lignocellulosic materials are used, they should be clean and dry. The raw material can be texturised using any one of a number of mechanical means, or combinations thereof. One method oftexturizing includes first cutting the cellulosic or lignocellulosic material into 1/4- to 1/2-inch pieces, if necessary, using a standard cutting [I:\DAYLIB\ ibaa]0933 9.doc:sak 8 apparatus. Counter-rotating screw shredders and segmented rotating screw shredders such as those manufactured by Munson (Utica, NY) can also be used, as can a standard document shredder as found in many offices.

The cellulosic or lignocellulosic material is then sheared with a rotary cutter, such as the one manufactured by Sprout, Waldron Companies, as described in Perry's Chem.

Eng. Handbook, 6th Ed., at 8-29 (1984). Although other settings can be used, the spacing between the rotating knives and bed knives of the rotary cutter is typically set to 0.020" or less, and blade rotation is set to 750 rpm or more. The rotary cutter can be cooled to 100C or lower during the process, for example, using a water jacket.

The texturised material is passed through a discharge screen. Larger screens up to 6 mm) can be used in large-scale production. The cellulosic or lignocellulosic feedstock is generally kept in contact with the blades of the rotary cutter until the fibres are pulled apart; smaller screens 2 mm mesh) provide longer residence times and *ie more complete texturization, but can result in lower length/diameter aspect ratios.

A vacuum drawer can be attached to the screen to maximize and maintain fibre "•.length/diameter aspect ratio.

The texturised fibrous materials can be directly stored in sealed bags or may be dried at approximately 105C for 4-18 hours until the moisture content is less than about immediately before use. Fig. 1 is an SEM photograph of texturised newspaper.

Alternative texturizing methods include stone grinding, mechanical ripping or tearing, and other methods whereby the material's internal fibres can be exposed pin grinding, air attrition milling).

Uses of Texturised Fibrous Material 0:9. 025 Texturised fibrous materials and compositions and composites of such fibres with other chemicals and chemical formulations can be prepared to take advantage of the material's properties. The materials can be used to absorb chemicals, for example, potentially absorbing many times their own weight. Thus, the materials could, for instance, be used to absorb spilled oil, or for clean-up of environmental pollution, for example, in water, in the air, or on land. Similarly, the material's absorbent properties, together with its biodegradability, also make them useful for delivery of chemicals or chemical formulations. For example, the materials can be treated with solutions of enzymes or pharmaceuticals such as antibiotics, nutrients, or contraceptives, and any necessary excipients, for drug delivery for treatment of humans or animals, or for use as or in animal feed and/or bedding), as well as with solutions of fertilizers, [I:\DAYLIB\libaa]09339.doc:sak 'herbicides, or pesticides. The materials can optionally be chemically treated to enhance a specific absorption property. For example, the materials can be treated with silanes to render them lipophilic.

Compositions including texturised materials combined with liquids or particulate, powdered, or granulated solids can also be prepared. For example, texturised materials can be blended with seeds with or without treatment with a solution of fertilizer, pesticides, etc.), foodstuffs, or bacteria bacteria that digest toxins). The ratio of fibrous materials to the other components of the compositions will depend on the nature of the components and readily be adjusted for a specific product application.

In some cases, it may be advantageous to associate the texturised fibrous materials, or compositions or composites of such materials, with a structure or carrier such as a netting, a membrane, a flotation device, a bag, a shell, or a biodegradable substance.

Optionally, the structure of carrier may itself be made of a texturised fibrous material a material of the invention), or a composition or composite thereof.

15 Composites and Compositions of Texturised Fibrous Material and Resin Texturised fibrous materials can also be combined with resins to form strong, lightweight composites. Materials that have been treated with chemicals or chemical formulations, as described above, can similarly be combined with biodegradable or nonbiodegradable resins to form composites, allowing the introduction of, for example, •g 20 hydrophilic substances into otherwise hydrophobic polymer matrices. Alternatively, the composites including texturised fibrous materials and resin can be treated with chemicals or chemical formulations.

Compositions containing texturised fibrous material and matrices of thermosetting resins, elastomers, tars, lignins, or asphalts can be used in the manner of other fibre- 25 reinforced materials, for example, for unidirectional or multi-directional reinforcement, and for improved impact resistance, mechanical integrity after impact, stiffness-to-weight ratio, strength-to-weight ratio, stiffness per unit cost, strength per unit cost, overall cost efficiency, weight reduction, and other benefits.

The texturised cellulosic or lignocellulosic material provides the composite with strength. The composite may include from about 10% to about 90%, for example from about 30% to about 70%, of the texturised cellulosic or lignocellulosic material by weight.

The resin (whether thermoplastic, thermosetting, elastomer, tar, lignin or asphalt) encapsulates the texturised cellulosic or lignocellulosic material in the composites, and helps control the shape of the composites. The resin also transfers external loads to the [I:\DAYLB\Iibaa]09339.doc:sak fibrous materials and protects the fibre from environmental and structural damage.

Composites can include, for example, about 10% to about 90%, more preferably about to about 70%, by weight, of the resin.

Resins are used in a variety of applications, for example, in food packaging. Food containers made of resins are typically used once, then discarded. Examples of resins that are suitably combined with texturised fibres include polyethylene (including, low density polyethylene and high density polyethylene), polypropylene, polystyrene, polycarbonate, polybutylene, thermoplastic polyesters PET), polyethers, thermoplastic polyurethane, PVC, polyamides nylon) and other resins. It is preferred that the resins have a low melt flow index. Preferred resins include polyethylene and polypropylene with melt flow indices of less than 3 g/10 min, and more preferably less than 1 g/10 min.

The resins can be purchased as virgin material, or obtained as waste materials, and can be purchased in pelletized or granulated form. One source of waste resin is used polyethylene milk bottles. If surface moisture is present on the pelletized or granulated "•resin, however, it should be dried before use.

The composites can also include coupling agents. The coupling agents help to bond the hydrophilic fibres to the hydrophobic resins. Examples of coupling agents suitable for •use with thermoplastic resin-containing composites include maleic anhydride modified polyethylenes, such those in the FUSABOND® (available from DuPont, Delaware) and POLYBOND® (available from Uniroyal Chemical, Connecticut) series. One suitable coupling agent is a maleic anhydride modified high density polyethylene such as FUSABOND® MB 100D.

*The composites can also contain additives known to those in the art of 25 compounding, such as plasticizers, lubricants, antioxidants, opacificers, heat stabilizers, colorants, flame retardants, biocides, impact modifiers, photostabilizers, antistatic agents, biodegradation agents, and dispersants. Special fibre surface treatments and additives can be used when a specific formulation requires specific property improvement.

The composites can also include inorganic additives such as calcium carbonate, graphite, asbestos, wollastonite, mica, glass, fibre glass, chalk, silica, talc, flame retardants cush as alumina trihydrate or magnesium hydroxide, ceramic, ground construction waste, tire rubber powder, carbon fibres, or metal fibres aluminum, stainless steel). These additives can reinforce, extend, change electrical or mechanical or compatibility properties, and can provide other benefits. When such additives are included, they are typically present in quantities of from about 0.5% up to about 20-30% [1:\DAYL1B\ibaa09339.doc:sak by weight. For example, submicron calcium carbonate can be added to the composites of fibre and resin to improve impact modification characteristics or to enhance composite strength.

Preparation of Compositions Compositions containing the texturised cellulosic or lignocellulosic materials and chemicals, chemical formulations, or other solids can be prepared, for example, in various immersion, spraying, or blending apparatuses, including, but not limited to, ribbon blenders, cone blenders, double cone blenders, and Patterson-Kelly blenders.

For example, a composition containing 90% by weight texturised cellulosic or lignocellulosic material and 10% by weight ammonium phosphate or sodium bicarbonate can be prepared in a cone blender to create a fire-retardant material for absorbing oil.

Preparation of Composites of Texturised Fibre and Resin Composites of texturised fibrous material and resin can be prepared as follows. A standard rubber/plastic compounding 2-roll mill is heated to 325-400F. The resin (usually 15 in the form of pellets or granules) is added to the heated roll mill. After about 5 to

S

minutes, the coupling agent is added to the roll mill. After another five minutes, the texturised cellulosic or lignocellulosic material is added to the molten resin/coupling agent mixture. The texturised material is added over a period of about 10 minutes.

•The composite is removed from the roll mill, cut into sheets and allowed to cool to room temperature. It is then compression molded into plaques using standard compression molding techniques.

Alternatively, a mixer, such as a Banbury internal mixer, is charged with the ingredients. The ingredients are mixed, while the temperature is maintained at less than about 190 0 C. The mixture can then be compression molded.

25 In another embodiment, the ingredients can be mixed in an extruder mixer, such as a twin-screw extruder equipped with co-rotating screws. The resin and the coupling agent are introduced at the extruder feed throat; the texturised cellulosic or lignocellulosic material is introduced about 1/3 of the way down the length of the extruder into the molten resin. The internal temperature of the extruder is maintained at less than about 190 0 C. At the output, the composite can be, for example, pelletized by cold strand cutting.

Alternatively, the mixture can first be prepared in a mixer, then transferred to an extruder.

In another embodiment, the composite can be formed into fibres, using fibreforming techniques known to those in the art, or into filaments for knitting, warping, [I:\DAYLB\ibaa]09339.doc:sak weaving, braiding, or making non-wovens. In a further embodiment, the composite can be made into a film.

Properties of the Composites of Texturised Fibrous Material and Resin The resulting composites include a network of fibres, encapsulated within a resin matrix. The fibres form a lattice network, which provides the composite with strength.

Since the cellulosic or lignocellulosic material is texturised, the amount of surface area available to bond to the resin is increased, in comparison to composites prepared with untexturised cellulosic or lignocellulosic material. The resin binds to the surfaces of the exposed fibres, creating an intimate blend of the fibre network and the resin matrix. The intimate blending of the fibres and the resin matrix further strengthens the composites.

Preparation of Compositions of Texturised Fibrous Material and Matrices The following are non-limiting examples of compositions: Thermosetting Resins: Compositions of texturised fibrous material and thermosetting resins can be prepared as bulk molding compounds (BMCs), sheet molding s15 compounds (SMCs), or as other formulations.

Bulk molding compounds (BMCs) are materials made by combining a resin and chopped fibres in a dough mixer, then mixing until the fibres are well wetted and the material has the consistency of modeling clay. Most BMCs are based on polyesters, but vinyl esters and epoxies are sometimes used. A pre-weighed amount of the compound is 20 placed in a compression mold, which is then closed and heated under pressure to cross- S. link the thermosetting polymer. Many electrical parts are made using BMC compounds and processing. Other applications include microwave dishes, table tops, and electrical

S

insulator boxes.

I Sheet molding compounds (SMCs) are made by compounding a polyester resin with 25 fillers, pigments, catalysts, mold release agents, and/or special thickeners that react with the polymer to greatly increase the viscosity. The resin mixture is spread onto a moving nylon film. The resin passes under feeders which disperse the texturised fibres. A second film is placed on top, sandwiching the compound inside. The material then passes through rollers that help the resin to wet the fibres, and the material is rolled up. Prior to use, the nylon films are removed and the compound is molded.

Other techniques and preparation procedures can be used to prepare and cure thermosetting systems.

Elastomers: Compositions of texturised fibrous material and elastomers can be prepared by known methods. In one method, for example, the elastomer is added to a rubber/plastic compounding two-roll mill. After a couple of minutes, the other [1:\DAYLB\Iibaa09339.doc:sak ingredients, including a vulcanizing agent, are added to the roll mill. Once the elastomer has been compounded, the texturised fibrous material is added to the roll mill. The texturised fibrous material is added over a period of about 10 minutes. The compounded material is removed from the roll mill and cut into sheets. It is then compression molded into the desired shape using standard compression molding techniques.

Alternatively, a mixer, such as a Banbury internal mixer or appropriate twin or single screw compounder can be used. If a Banbury mixer is used, the compounded mixture can, for example, be discharged and dropped onto a roll mill for sheeting. Single or twin screw compounders produce a sheet as an extrudate. The mixture can then be compression molded. Likewise, single- or twin-screw compounders can extrude a shaped profile that can be directly vulcanized. The composition can be molded, extruded, compressed, cut, or milled.

Uses of the Composites of Texturised Fibrous Material and Resin The resin/fibrous material composites can be used in a number of applications. The composites are strong and light weight; they can be used, for example, as wood substitutes. The resin coating renders the composites water-resistant, so they may be used in outdoor applications. For example, the composites may be used to make pallets, which are often stored outdoors for extended periods of time, wine staves, rowboats, furniture, oO° skis, and oars. Many other uses are contemplated, including panels, pipes, decking S 20 materials, boards, housings, sheets, poles, straps, fencing, members, doors, shutters, •awnings, shades, signs, frames, window casings, backboards, wallboards, flooring, tiles, railroad ties, forms, trays, tool handles, stalls, bedding, dispensers, staves, films, wraps, S* totes, barrels, boxes, packing materials, baskets, straps, slips, racks, casings, binders, dividers, walls, indoor and outdoor carpets, rugs, wovens, and mats, frames, bookcases, sculptures, chairs, tables, desks, art, toys, games, wharves, piers, boats, masts, pollution control products, septic tanks, automotive panels, substrates, computer housings, aboveand below-ground electrical casings, furniture, picnic tables, tents, playgrounds, benches, shelters, sporting goods, beds, bedpans, thread, filament, cloth, plaques, trays, hangers, servers, pools, insulation, caskets, bookcovers, clothes, canes, crutches, and other construction, agricultural, material handling, transportation, automotive, industrial, environmental, naval, electrical, electronic, recreational, medical, textile, and consumer products. Numerous other applications are also envisioned. The composites may also be used, for example, as the base or carcass for a veneer product. Moreover, the composites can be, for example, surface treated, grooved, milled, shaped, imprinted, textured, compressed, punched, or colored. The surface of the composites can be smooth or rough.

[I:\DAYLIB\Iibaa]09339.doc:sak 14 The following examples illustrate certain embodiments and aspects of the present invention and not to be construed as limiting the scope thereof.

Examples Example 1 A 1500 pound skid of virgin, half-gallon juice cartons made of polycoated white kraft board was obtained from International Paper. Each carton was folded flat.

The cartons were fed into a 3 hp Flinch Baugh shredder at a rate of approximately to 20 pounds per hour. The shredder was equipped with two rotary blades, each 12" in length, two fixed blades, and a 0.3" discharge screen. The gap between the rotary and fixed blades was 0.10".

The output from the shredder, consisting primarily of confetti-like pieces, about 0.1" to 0.5" in width and about 0.25" to 1" in length, was then fed into a Thomas Wiley Mill Model 2D5 rotary cutter. The rotary cutter had four rotary blades, four fixed blades, and a 2 mm discharge screen. Each blade was approximately 2" long. The blade gap was S. 15 set at 0.020".

S•The rotary cutter sheared the confetti-like pieces across the knife edges, tearing the o:ooo pieces apart and releasing a finely texturised fibre at a rate of about one pound per hour.

The fibre had an average minimum L/D ratio of between five and 100 or more. The bulk density of the texturised fibre was on the order of 0.1 g/cc.

S 20 Example 2 Composites of texturised fibre and resin were prepared as follows. A standard rubber/plastic compounding 2-roll mill was heated to 325-400F. The resin (usually in the form of pellets or granules) was added to the heated roll mill. After about 5 to S"minutes, the resin banded on the rolls it melted and fused on the rolls). The coupling S 25 agent was then added to the roll mill. After another five minutes, the texturised cellulosic or lignocellulosic material was added to the molten resin/coupling agent mixture. The cellulosic or lignocellulosic fibre was added over a period of about 10 minutes.

The composite was then removed from the roll mill, cut into sheets, and allowed to .cool to room temperature. Batches of about 80 g each were compression molded into 6" x 6" x 1/8" plaques using standard compression molding techniques.

One composition contained the following ingredients: Composition No. 1 Ingredient Amount(g) High density polyethylene 160 Old newspaper 2 240 [1:\DAYLIB\Iibaa]09339.doc:sak Coupling agent3 8 'Marlex 16007 2 Texturised using rotary cutter with 2 mm mesh SFUSABOND 100D The plaques were machined into appropriate test specimens and tested according to the procedures outlined in the method specified. Three different specimens were tested for each property, and the mean value for each test was calculated. The properties of Composition No. 1 are as follows: Flexural strength (10' psi) 9.81 (ASTM D790) l0 Flexural modulus (105 psi) 6.27 (ASTM D790) A second composition contains the following ingredients: Composition No. 2 Ingredient Amount(g) High density polyethylene' 160 Old magazines 2 240 Coupling agent 3 8 The properties of Composition No. 2 are as follows: Flexural strength (103 psi) 9.06 (ASTM D790) Flexural modulus (105 psi) 6.78 (ASTM D790) 20 A third composition contains the following ingredients: Composition No. 3 Ingredient Amount(g) HDPE' 160 Fibre paper 2 216 25 3.1 mm texturised kenaf 24 Coupling agent 3 8 The properties of Composition No. 3 are as follows: Flexural strength (10' psi) 11.4 (ASTM D790) Flexural modulus (105 psi) 6.41 (ASTM D790) A fourth composition contains the following ingredients: Composition No. 4 Ingredient Amount (g) SUPERFLEX CaCO 3 33 Fibre 24 67 HDPE compatibilizer)'1 3 100 [1:\DAYLIB\Iibaa]09339.doc:sak 4 Virgin polycoated milk cartons The properties of Composition No. 4 are as follows: Flexural strength (105 psi) 8.29 (ASTM D790) Ultimate elongation <5 (ASTM D638) Flexural modulus (105 psi) 10.1 (ASTM D790) Notch Izod (ft-lb/in) 1.39 (ASTM D256-97) A fifth composition contains the following ingredients: Composition No. Ingredient Amount (parts) SUPERFLEX CaCO 3 22 Fibre2, 4 67 HDPE compatibilizer)"' 3 100 The properties of Composition No. 5 are as follows: Flexural strength (105 psi) 8.38 (ASTM D790) 15 Ultimate elongation <5 (ASTM D638) Flexural modulus (105 psi) 9.86 (ASTM D790) Notch Izod (ft-lb/in) 1.37 (ASTM D256-97) A sixth composition contains the following ingredients: Composition No. 6 .20 Ingredient Amount (parts) ULTRAFLEX CaCO 3 33 Fibre2, 4 67 o S* HDPE/compatibilizer"' 3 100 The properties of Composition No. 6 are as follows: I 25 Flexural strength (10 5 psi) 7.43 (ASTM D790) Ultimate elongation <5 (ASTM D638) Flexural modulus (105 psi) 11.6 (ASTM D790) Notch Izod (ft-lb/in) 1.27 (astm D256-97) A seventh composition contains the following ingredients: Composition No. 7 Ingredient Amount (pbw) HDPE compatibilizer) 3 Kraftboard 2 5 HDPE with melt-flow index <1 [1:\DAYLIB\1ibaa109339.doc:sak The properties of Composition No. 7 are as follows: Flexural Strength (105 psi) 7.79 (ASTM D790) Ultimate elongation <5 (ASTM D638) Flexural Modulus (105 psi) 7.19 (ASTM D790) Example 3 Foamed epoxies are used in thermal insulation applications where superior water resistance and elevated temperature properties are desired. Such epoxies can be reinforced with texturised fibre prepared according to the procedure in Example 1. Fillers such as calcium carbonate may optionally be used to obtain some cost reductions.

However, overloading with filler can weaken the strength of the foam cell walls, particularly when the foam densities are in the range of five pounds per cubic foot or less, since such low foam density can result in thin, fragile walls within the foam. Filler loadings are generally in the four to five pounds/hundred weight (phr) of resin.

Reinforcing with texturised fibre can also provide for reduced weight and cost. In addition, improved strength can be realized because of the high length-to-diameter (L/D) ratios of the texturised fibre. It is not unreasonable to employ up to 30 phr of the fibre. A typical formulation includes: Ingredient Parts DGEBA (diglycidyl ether, ofbisphenol A) 100 20 MPDA (m-phenylenediamine) Celogen® (p,p -oxybis-benzenesulfonylhydrazide) (Uniroyal Chemical Company) Surfactant 0.15 Styrene Oxide 25 Texturised Fibre This formulation is mixed using standard epoxy mixing techniques. It produces a very high exotherm at the curing temperature of 120oC and a foam density of about seven pounds per cubic foot.

Other embodiments are within the claims.

[I:\DAYLB\ibaa]09339.doc:sak

Claims (56)

1. A composite comprising a resin and fibre, wherein the fibre is cellulosic or lignocellulosic fibre that has been sheared.

2. The composite of claim 1, comprising at least about 5% by weight sheared fibre.

3. The composite of claim 1, wherein the fibre is newsprint.

4. The composite of claim 1, wherein the fibre is jute. The composite of claim 1, wherein the fibre is kenaf.

6. The composite of claim 1, wherein the fibre is magazine paper.

7. The composite of claim 1, wherein the fibre is bleached kraft board.

8. The composite of claim 1, wherein the fibre is poly-coated paper.

9. The composite of claim 1, wherein the resin is a thermoplastic resin. The composite of claim 9, wherein the resin is selected from the group consisting of polystyrene, polycarbonate, polybutylene, thermoplastic polyesters, polyethers, thermoplastic polyurethane, PVC, and Nylon.

11. The composite of claim 9, wherein the thermoplastic resin is polyethylene. S* 12. The composite of claim 9, wherein the thermoplastic resin is polypropylene.

13. The composite of claim 1, wherein the composite comprises about 30% to about 70% by weight resin and about 30% to about 70% by weight fibre. 20 14. A composite comprising polyethylene and fibre, wherein the fibre is cellulosic *c or lignocellulosic fibre that has been sheared. A composite comprising a resin and fibre, wherein the composite has a flexural strength of at least 3,000 psi, wherein the fibre is cellulosic or lignocellulosic fibre that has been sheared. 25 16. The composite of claim 15, wherein the composite has a flexural strength of at least 6,000 psi.

17. The composite of claim 15, wherein the composite has a flexural strength of at least 10,000 psi.

18. A process for manufacturing a composite, the process comprising shearing cellulosic or lignocellulosic fibre, and combining the sheared cellulosic or lignocellulosic fibre with a resin.

19. The process of claim 18, wherein the resin is a thermoplastic resin. The process of claim 18, wherein the step of shearing the cellulosic or lignocellulosic fibre comprises shearing with a rotary knife cutter. [I:\DAYLIBIibaa]09339.doc:sak S21. A process for preparing a texturised fibrous material, the process comprising: shearing a cellulosic or lignocellulosic material having internal fibres.

22. The process of claim 21, wherein said cellulosic or lignocellulosic material is selected from the group consisting of flax, hemp, cotton, jute, rags, paper, paper products, and byproducts of paper manufacturing.

23. The process of claim 21, wherein the cellulosic or lignocellulosic material is pulp board.

24. The process of claim 21, wherein the cellulosic or lignocellulosic material is a synthetic material.

25. The process of claim 21, wherein the cellulosic or lignocellulosic material is a non-woven material.

26. The process of claim 21, wherein the cellulosic or lignocellulosic material is poly-coated paper.

27. The process of claim 21, wherein at least about 50% of the fibres have a length/diameter ratio of at least about

28. The process of claim 21, wherein at least about 50% of the fibres have a length/diameter ratio of at least about

29. The process of claim 21, wherein at least about 50% of the fibres have a length/diameter ratio of at least about 20 30. A fibrous material comprising a cellulosic or lignocellulosic material, wherein said cellulosic or lignocellulosic material is sheared to the extent that it has a bulk density less than about 0.5 g/cm 3 "31. The fibrous material of claim 30, wherein said material is incorporated into a structure or carrier. :25 32. The fibrous material of claim 31, wherein the structure or carrier also comprises a fibrous material having a bulk density less than about 0.5 g/cm 3

33. The fibrous material of claim 30, wherein said texturised fibrous material has a bulk density less than about 0.2 grams per cubic centimeter.

34. The fibrous material of claim 30, wherein said texturised fibrous material has a bulk density on the order of about 0.1 grams per cubic centimeter. The fibrous material of claim 30, wherein said cellulosic or lignocellulosic material comprises paper or paper products.

36. A composition comprising the fibrous material of claim 30 and a chemical or chemical formulation. [I:\DAYLIB\fibaa]09339.doc:sak

37. The composition of claim 36, wherein the chemical formulation comprises a pharmaceutical.

38. The composition of claim 36, wherein the chemical formulation an agricultural compound.

39. The composition of claim 36, wherein the chemical formulation comprises an enzyme. A composition comprising the fibrous material of claim 30 and a liquid.

41. A composition comprising the fibrous material of claim 30 and particulate, powdered, or granulated solid.

42. The composition of claim 41, wherein the solid comprises plant seed.

43. The composition of claim 41, wherein the solid comprises a foodstuff.

44. The composition of claim 41, wherein the solid comprises bacteria. The composite of claim 1, further comprising an inorganic additive.

46. The composite of claim 45, wherein the inorganic additive is selected from the 15 group consisting of calcium carbonate, graphite, asbestos, wollastonite, mica, glass, fibre glass, chalk, talc, silica, ceramic, ground construction waste, tire rubber powder, carbon fibres, and metal fibres.

47. The composite of claim 46, wherein the inorganic additive comprises from about 0.5% to about 20% of the total weight of the composite. •20 48. The composite of claim 1, wherein said composite is in the form of a pallet.

49. The composite of claim 48, wherein said pallet is injection molded. The composite of claim 1, wherein said composite is in the form of an article selected from the group consisting of panels, pipes, decking materials, boards, housings, sheets, poles, straps, fencing, members, doors, shutters, awnings, shades, signs, frames, S. 25 window casings, backboards, wallboards, flooring, tiles, railroad ties, forms, trays, tool handles, stalls, bedding, dispensers, staves, films, wraps, totes, barrels, boxes, packing materials, baskets, straps, slips, racks, casings, binders, dividers, walls, indoor and outdoor carpets, rugs, wovens, and mats, frames, bookcases, sculptures, chairs, tables, desks, art, toys, games, wharves, piers, boats, masts, pollution control products, septic tanks, automotive panels, substrates, computer housings, above- and below-ground electrical casings, furniture, picnic tables, tents, playgrounds, benches, shelters, sporting goods, beds, bedpans, thread, filament, cloth, plaques, trays, hangers, servers, pools, insulation, caskets, bookcovers, clothes, canes, crutches, and other construction, agricultural, material handling, transportation, automotive, industrial, environmental, naval, electrical, electronic, recreational, medical, textile, and consumer products. [1:\DAYLIB\libaa]09339.doc:sak

51. The composite of claim 1, wherein said composite is in the form of a fibre, filament, or film.

52. A composite comprising a resin and fibrous reinforcement, wherein the fibrous reinforcement has a bulk density less than about 0.5 g/cm 3

53. The composite of claim 52, wherein the fibrous reinforcement has a bulk density less than about 0.2 g/cm 3

54. A composition comprising a matrix reinforced with at least about 2% fibre, wherein the fibre is a lignocellulosic or cellulosic material that has been sheared to the extent that the internal fibres are substantially exposed.

55. The composition of claim 54, wherein the matrix comprises a thermosetting resin.

56. The composition of claim 54, wherein the matrix comprises an elastomer.

57. The composition of claim 54, wherein the matrix comprises tar or asphalt.

58. The composition of claim 54, wherein the matrix comprises lignin. S• 15 59. The composition of claim 54, further comprising an additive selected from the group consisting of a pharmaceutical; an agricultural compound; an enzyme; a particulate, powdered, or granulated solid; plant seed; a foodstuff; and bacteria.

60. The composition of claim 55, wherein the thermosetting resin is selected from the group consisting of alkyds, diallyl phthalates, epoxies, melamines, phenolics, 20 silicones, ureas, and thermosetting polyesters.

61. The composition of claim 54, wherein at least about 5% by weight of the fibrous material is texturised.

62. The composition of claim 54, wherein the composition comprises about to about 90% by weight texturised fibrous material. 25 63. The composition of claim 54, wherein the composition comprises about to about 70% by weight texturised fibrous material.

64. The composition of claim 54, further comprising an additive selected from the group consisting of calcium carbonate, graphite, asbestos, wollastonite, mica, glass, fibre glass, chalk, talc, silica, ground construction waste, tire rubber powder, carbon fibres, metal fibres, plasticizers, lubricants, antioxidants, opacifiers, heat stabilizers, colorants, impact modifiers, photostabilizers, biocides, antistatic agents, organic or inorganic flame retardants, biodegradation agents, dispersants, emulsion polymers, accelerators, extenders, retardants, antifoaming agents, thixotropic agents, and waterproofing agents. The composition of claim 64, wherein the additive comprises from about 0.5% to about 20% of the total weight of the composition. [I:\DAYLIB\ibaa]09339.doc:sak S S S

66. The composition of claim 54, wherein said composition is in the form of an article selected from the group consisting of pipes, panels, decking materials, boards, housings, sheets, blocks, bricks, pebbles, stones, poles, straps, fencing, members, doors, shutters, awnings, shades, signs, frames, window casings, backboards, flooring, tiles, railroad ties, forms, trays, tool handles, stalls, bedding, dispensers, staves, films, wraps, tapes, bands, totes, barrels, boxes, packing materials, baskets, straps, slips, racks, casings, binders, dividers, walls, indoor and outdoor carpets, rugs, woven goods, mats, frames, bookcases, sculptures, chairs, tables, desks, art, toys, games, pallets and other materials handling systems, wharves, piers, boats, masts, pollution control products, gravel, paving materials, road beds, swimming pools, septic tanks, automotive panels, substrates, computer housings, above- and below-ground electrical casings, furniture, picnic tables, tents, playgrounds, benches, shelters, sporting goods, beds, bedpans, thread, filament, cloth, plaques, trays, hangers, servers, pools, insulation, caskets, book covers, clothes, canes, crutches, and other construction, agricultural, material handling, transportation, automotive, industrial, environmental, naval, electrical, electronic, recreational, medical, textile, and consumer products, rubber hoses, marine products, pipes, and polymeric foams.

67. The composition of claim 54, wherein at least about 5% of the fibres have a length/diameter ratio of at least about

68. The composition of claim 54, wherein at least about 10% of the fibres have a length/diameter ratio of at least about

69. The composition of claim 54, wherein at least about 25% of the fibres have a length/diameter ratio of at least about The composition of claim 54, wherein at least about 50% of the fibres have a length/diameter ratio of at least about

71. The composition of claim 54, wherein at least about 50% of the fibres have a length/diameter ratio of at least about

72. The composition of claim 54, wherein at least about 50% of the fibres have a length/diameter ratio of at least about

73. The composition of claim 54, wherein at least about 70% of the fibres have a length/diameter ratio of at least about

74. A composite comprising a resin and fibre, wherein the composite is substantially as hereinbefore described with reference to Example 2. A process for manufacturing a composite, wherein the process is substantially as hereinbefore described with reference to Example 1 or Example 2. [1:\DAYLIB\ibaa]09339.doc:sak

76. A composition comprising a fibrous material, wherein the composition is substantially as hereinbefore described with reference to any one of Composition Nos. 1 to 6 of Example 2.

77. A composite manufactured by the process of any one of claims 18 to 29 or Dated 12 December, 2001 Xyleco, Inc. Patent Attorneys for the Applicant/Nomninated Person SPRUSON FERGUSON 0 0: "See 55.5 [I:\DAYLIB\libaa]09339.doc:sak