Method of making fibrous material

ES 2 397 791 T3

DESCRIPTION

Fibrous material manufacturing method

TECHNICAL FIELD

[0001] This invention relates to methods of manufacturing fibrous materials.

BACKGROUND

[0002] Fibrous materials, for example cellulosic and ligno-cellulosic materials, are produced, processed, and used in large quantities in a number of applications. Often such fibrous materials are used once, and then disposed of as waste.

[0003] US 4,244,847 describes a process for preparing: (1) a generally dry fiber blend; (2) a composite master batch or a full fiber / elastomer powder composite charge; or (3) a composite master batch or a full load of fiber / elastomer composite

[0004] EP 0801168 A1 discloses a method and apparatus for individually picking up layers of a laminated film containing many layers made of different materials by peeling or separating the layers from each other.

[0005] GB 1 503 103 describes a method of removing foreign material from the surfaces of plastic materials.

ABSTRACT

The invention relates to the subject of the appended claims 1 to 12.

[0007] Methods of manufacturing fibrous materials are disclosed that include cutting a fiber source to provide a first fibrous material, and passing the first fibrous material through a first screen having an average aperture size of 1.59 mm or minus (1/16 inch, 0.0625 inch) to provide a second fibrous material.

[0008] In some embodiments, the mean opening size of the first screen is less than about 0.79 mm (1/32 inches, 0.03125 inches), for example less than about 0.40 mm (1/64 inches, 0.015625 inches), less than about 0.20 mm (1/128 inches, 0.0078125 inches), or even less than about 0.10 mm (1/256 inches, 0.00390625 inches).

[0009] In specific applications, cutting is done with a rotating blade.

The second fibrous material can, for example, be collected in a hopper with a pressure below nominal atmospheric pressure, for example, at least 10 percent below nominal atmospheric pressure or at least 75 percent per below nominal atmospheric pressure.

The second fibrous material can, for example, be cut once or numerous times, for example twice, three times or even more, for example ten times.

The second fibrous material can, for example, be cut and the resulting fibrous material passed through the first screen.

The second fibrous material can be cut, and the resulting fibrous material passed through a second screen with an average aperture size smaller than the first screen, providing a third fibrous material.

[0014] A ratio of a half length / diameter ratio of the second fibrous material to a half length / diameter ratio of the third fibrous material may be, for example, less than about 1.5, less than about 1.4, less than about 1.25, or even less than about 1.1.

The second fibrous material can, for example, be passed through a second screen with a smaller average aperture size than the first screen.

[0016] Cutting and passing can, for example, be carried out at the same time.

The second fibrous material may have a mean length / diameter ratio, eg, greater than about 10/1, greater than about 25/1, or even greater than about 50/1.

[0018] An average length of the second fibrous material can be, for example, between about 0.5 mm and about 2.5 mm, for example, between about 0.75 mm and about 1.0 mm. An average width of the second fibrous material may be, for example, between about 5 pm and about 50 pm, for example between about 10 pm and about 30 pm.

[0019] A standard deviation of a length of the second fibrous material may be less than 60 percent of an average length of the second fibrous material, for example, less than 50 percent of an average length of the

ES 2 397 791 T3 second fibrous material.

[0020] In some embodiments, a BET surface area of ​​the second fibrous material is greater than about 0.5 µm²/ g, for example, greater than about 1.0 m2 / g, greater than about 1.5 m²/ g, greater than about 1.75 m²/ g, or even greater than about 0.5 m²/ g.

In some embodiments, a porosity of the second fibrous material is greater than 70 percent, eg, greater than 85 percent, or greater than 90 percent.

[0022] In some applications, a ratio of a mean length / diameter ratio of the first fibrous material to a mean length / diameter ratio of the second fibrous material is less than about 1.5, eg, less than about 1.4, less of about 1.25, or less than about 1.1.

[0023] In specific embodiments, the screen is formed by weaving monofilaments.

The fiber source can include, for example, a cellulosic material, a lignocellulosic material. For example, the fiber source can be sawdust.

[0025] In some embodiments, the fiber source includes a blend of fibers, eg, fibers derived from a paper source and fibers derived from a textile source, eg, cotton.

Fibrous materials can be produced having an average length / diameter ratio of more than about 5, and with a standard deviation of a fiber length of less than sixty percent of an average fiber length.

For example, the mean length / diameter ratio may be greater than about 10/1, for example, greater than about 15/1, greater than about 25/1, greater than about 35/1, greater than about 45 / 1, or even greater than about 50/1.

[0028] For example, the average length can be between 0.5mm and about 2.5mm.

[0029] Compounds are disclosed that include a fibrous material produced by the method of the invention, a resin, and a dye. For example, tinting can aid in masking the fibrous material in the composite.

[0030] For example, the fibrous material may have a mean length to diameter ratio of more than about 5, and a standard deviation of a fiber length of less than sixty percent of a mean fiber length.

[0031] In some embodiments, the compound additionally includes a pigment.

In some applications, the dyeing is done by soaking or on the surface of the fibers.

[0033] The compounds can include a perfume or a fragrance.

[0034] Composite manufacturing methods are also disclosed that include dyeing a fibrous material; combining fibrous material with a resin; and forming a compound of the combination.

[0035] Compounding methods are disclosed which include adding a dye to a resin to provide a dye / resin combination with a fibrous material; and forming a composite from the dye / resin combination and fibrous material.

Any compound can be, for example, in the form of a stepped footstool, pipes, panels, floor materials, boards, covers, sheets, blocks, bricks, posts, fences, elements, doors, shutters, awnings, blinds, signs, racks, window boxes, boards, floors, tiles, railroad ties, trays, tool handles, stalls, films, wrappers, boxes, baskets, shelves, covers, folders, dividers, walls, mats, frames, shelves, sculptures, chairs, tables, desks, toys, games, pallets, docks, piers, boats, masts, septic tanks, automotive panels, computer covers, overhead and underground electrical boxes, furniture, picnic tables, benches , shelters, trays, hangers, trays, chests, book covers, canes and crutches.

The first aspect and / or embodiments of the first aspect may have any of or combinations of the following advantages. Fibrous materials are easy to disperse, for example, in a molten thermoplastic resin. Fibrous materials can have, for example, a relatively narrow length and / or length / diameter distribution, such that their properties are constantly defined. For example, when mixed with a molten resin, the fibers of fibrous materials can modify the rheology of the molten resin in a consistent and predictable way, resulting in resin / fibrous material combinations that are, for example, easier to cast. and extrude. For example, fibrous materials can easily be passed through small openings or channels, such as those found in or associated with injection molds, eg, locks or hot channels. The molded parts of such fibrous materials can have a good surface finish, for example with small visible specks of large particles and / or agglomerated particles, when so desired.

ES 2 397 791 T3

[0038] Generally, a comparative aspect shows densified fibrous materials, methods of making densified fibrous materials, and composites made from the densified fibrous materials.

[0039] Fibrous material densification methods are disclosed which include adding, to a fibrous material, a water soluble binder, a water swellable binder, and / or a binder with a glass transition temperature of less than about 25 ° C. , to provide a combination of the binder with the fibrous material. The combination of the binder with the fibrous material is densified to provide a densified fibrous material having a bulk density that is at least two times the bulk density of the fibrous material, for example, three times, four times, five times, six times. , eight times, ten times, twelve times, twenty times or more, for example, forty times greater. Preferably, the bulk density of the densified material is at least about five times or about four times the bulk density of the fibrous material.

[0040] Fibrous material densification methods are also disclosed that include a fibrous material derived at least in part from polycoated paper to provide a densified fibrous material having a bulk density that is at least about two times the bulk density of the material. fibrous, for example, three times, four times, five times, six times, eight times, ten times, twelve times, twenty times or more, for example, forty times greater. Densification includes heating the fibrous material to a temperature of at least about 50 ° C.

[0041] Fibrous material densification methods are disclosed which include moving a fibrous material beyond a binder application area where a binder is applied to provide a combination of the binder with the fibrous material. The combination of the binder with the fibrous material is densified to provide a densified fibrous material having a bulk density of at least about two times the bulk density of the fibrous material, for example, three times, four times, five times, six times, eight times, ten times, twelve times, twenty times or more, for example, forty times greater.

[0042] Methods of densifying fibrous material are disclosed which include evacuating air from the fibrous material to increase the bulk density of the fibrous material at least about two times. For example, the method may include enclosing the fibrous material in a container and evacuating the air from the container.

[0043] Granules or chips that include a densified fibrous material are developed. The granules or chips have a bulk density of at least 0.3 g / cm³ The densified fibrous material includes a cellulosic or lignocellulosic material and a water soluble binder, a water swellable binder, and / or binders having a glass transition temperature of less than about 25 ° C. The granules or chips have, for example, an average thickness between about 2 mm and about 20 mm, an average width of between about 2 mm and about 40 mm and an average length of between about 5 mm and about 40 mm. In some embodiments, the granules define a hollow internal portion, or a multi-lobal structure.

[0044] Plate-like densified fibrous materials are disclosed having a bulk density of at least 0.3 g / cm³. The densified fibrous material materials include a cellulosic or lignocellulosic material. The densified fibrous materials have, for example, an average thickness between about 2 mm and about 20 mm, an average width between about 2 mm and about 40 mm and an average length between about 5 mm and about 40 mm.

[0045] Fibrous material densification methods are also disclosed which include adding, to a fibrous material, a water soluble binder, a water swellable binder and / or binders having a glass transition temperature of less than about 25 ° C, to provide a fibrous-binder material combination. The fibrous material-binder combination includes less than 25 weight percent binder, eg, 15 weight percent, 10 weight percent, 5 weight percent, or less than 1 weight percent. The fibrous material-binder combination is densified to provide a densified fibrous material having a bulk density that is at least about two times the bulk density of the fibrous material, for example, three times, four times, five times, six times. , eight times, ten times, twelve times, twenty times or more, for example, about forty times greater.

[0046] Methods of compressing fibrous materials are disclosed that characterize positioning a fibrous material including a binder relative to an element, for example, between a first element and a second element, to provide an uncompressed composite, and compressing the uncompressed composite to provide a compressed compound.

[0047] In some embodiments, compression is performed using a single element and a support.

[0048] Any densified fibrous material can be used to form any particle disclosed herein.

[0049] The densified fibrous materials can include a flavor or a fragrance.

The densified fibrous material can, for example, be used to make composites, or they can be used alone or together with additives, for example, as controlled release matrices.

[0051] Fibrous material densification methods are also disclosed, e.g. eg, a cellulosic or lignocellulosic material that does not use a binder.

[0052] Granules or chips of the densified fibrous material are developed having a bulk density of at least about 0.3g / cm3. Densified fibrous materials include fibrous material other than cellulosic or material

ES 2 397 791 T3 cellulosic and a binder. The granules or chips have an average thickness between about 2 mm and about 20 mm, an average width of between about 2 mm and about 40 mm, and an average length between about 5 mm and about 40 mm.

[0053] Plate-like densified fibrous materials are disclosed having a bulk density of at least about 0.3g / cm3. Densified fibrous materials include a fibrous material other than cellulosic or lignocellulosic and a binder. Plate-type densified fibrous materials have an average thickness of between about 2mm and about 20mm, an average width of between about 2mm and about 40mm, and an average length of between about 5mm and about 40mm.

The second aspect and / or embodiments of the second aspect may have any of, or combinations of, the following advantages. Densified fibrous materials, eg, in the form of granules or chips, are easier to handle, machine feed, transport, and mix with other materials, eg, resins. for example, thermoplastic resin.

[0055] Generally, a comparative aspect shows characteristics of cross-linked composites, and composites that include fillers at the nanometer scale. Compounds including the nano-scale fillers are optionally cross-linked when desired.

[0056] Composite manufacturing methods are disclosed which include combining a fibrous material with a radiation crosslinkable resin, eg, a thermoplastic resin, to provide a fibrous material / crosslinkable resin combination. The fibrous material has an average length / diameter ratio of about 5, and a standard deviation of a fiber length is less than eighty-five percent of an average fiber length. Fibrous material / crosslinkable resin is irradiated, for example with ionizing radiation, to at least partially crosslink the crosslinkable resin. In some embodiments, prior to the irradiation step, the crosslinkable resin / fibrous material combination is formed into a desired shape.

The radiation crosslinkable resin can be, for example, thermoplastic or thermoset, for example a thermoset casting. For example, the radiation crosslinkable resin can be a polyolefin, for example, a polyethylene (for example, a polyethylene copolymer), a polypropylene (for example, a polypropylene copolymer), a polyester (for example, polyethylene terephthalate), a polyamide (for example, nylon 6, 6/12 or 6/10), a polyethyleneimine, elastomeric styrenic copolymers (for example, styrene-ethylene butylene-styrene copolymers), a polyamide elastomer (for example, polyether-polyamide copolymer), ethylene vinyl acetate copolymer, or compatible mixtures of these resins.

In some specific embodiments, the resin is a polyolefin having a polydispersity of more than about 2, for example, more than about 3, more than about 3.5, more than about 4.0, more than about 4, 5, more than about 5.0, more than about 7.5, or even more than about 10. High polydispersity can improve impact resistance in the crosslinked compound. In some embodiments, the polyolefin has a melt flow index greater than about 10, for example, greater than 15, greater than 20, greater than 25, greater than 30, or even greater than about 50. High melt flow can assist compound production, for example by reducing shear heating during compound formation.

[0059] In specific embodiments, the fibrous material is provided by shearing a fiber source, eg, sawdust from a soft or hard wood mill (eg, oak, cedar, or redwood).

The average length / diameter ratio of the fibers of fibrous materials can be, for example, greater than about 10/1, for example, greater than 15/1, greater than 25/1, or even greater than about 50 / 1. A high L / D can improve the mechanical properties, for example, tensile strength and flexural modulus of the composite. In some embodiments, the standard deviation of the fiber length is less than 75 percent of the average fiber length, for example, less than fifty percent, less than 35 percent, less than 25 percent, less 15 percent, less than 10 percent, less than 5 percent, or even less than 2.5 percent. A low standard deviation can, for example, improve the processibility of the fibrous material / resin mixture. An average length of the fibrous material may be, for example, between about 0.5mm and about 2.5mm, for example, between about 0.75mm and about 1.0mm. An average width of the fibrous material is between about 5 mm and about 50 mm, for example, between about 10 mm and about 30 mm.

The fibrous material can, for example, be derived from a tissue, for example cotton waste or remnants, a paper source, a plant or a tree. In some embodiments, the fibrous material includes a mixture of fibers, eg, fibers derived from a paper source and fibers derived from a textile source, eg, cotton.

[0062] In specific embodiments, the radiation of the crosslinkable fiber / resin combination is done with gamma rays or an electron beam.

[0063] In some embodiments, the composite is in the form of a structure, ornamental products or articles, a footstool, pipes, panels, deck / decking material, boards, shells, sheets, blocks, bricks, posts, fences, elements , doors, shutters, awnings, blinds, signs, racks, window covering, boards, floors, tiles, railway sleepers, trays, tool handles, lockers, films, containers, boxes, baskets, shelves, covers, folders, dividers, walls, mats, frames, shelves, sculptures, chairs, tables,

ES 2 397 791 T3 desks, toys, games, pallets, docks, piers, boats, masts, septic tanks, automotive panels, computer cases, overhead and underground electrical boxes, furniture, picnic tables, benches, shelters, trays, hangers, fountains, chests, book covers, canes and crutches.

The fibrous material is prepared by cutting a fiber source to provide a first fibrous material, and passing the first fibrous material through a first screen having an average aperture size of about 1.59 mm or less (1 / 16 inches, 0.0625 inches) to provide a second material. In some embodiments, the average opening size of the first screen is less than 0.79 mm (1/32 inch, 0.03125 inch), for example, less than about 0.40 mm (1/64 inch, 0.015625 inches).

[0065] In some embodiments, the radiation is made with electromagnetic radiation that has an energy per photon (in electron volts) of more than about 102 eV / photon, for example, more than 103, 104, 105, 106, or even more than about 107 eV / photon. In some embodiments, the electromagnetic radiation has an energy per photon of between about 104 and about 107, for example, between about 105 and about 106 eV / photon.

In some embodiments, the radiation is done with electromagnetic radiation that has a frequency of more than about 10 Hz, greater than about 10 Hz, 10, 10, 10, or even greater than about 10 Hz. In some embodiments, the electromagnetic radiation has a frequency between about 10¹⁸and about 10²², for example, between about 10¹⁹up to about 10²¹ hz.

In some embodiments, radiation is performed until the crosslinkable fiber / resin combination receives a dose of at least about 0.25 Mrad, eg, at least 1.0 Mrad, at least 2.5 Mrad, at least 5.0 Mrad, or at least about 10 Mrad. In some embodiments, radiation is performed until the crosslinkable resin / fibrous material combination receives a dose of between about 1.0 Mrad and about 6.0 Mrad, eg, between about 1.5 Mrad and about 4.0 Mrad.

In some embodiments, the radiation is performed at a dose rate of between about 5 and about 1500 kiilorads / hour, for example, between about 10 and about 750 kiilorads / hour or between about 50 and about 350 kiilorads / hour.

60069] In some embodiments, the radiation is made with electromagnetic radiation generated from a source ⁶⁰Co.

Composites are disclosed that include a cross-linked resin and a fibrous material that has a mean length / diameter ratio of more than about 5 and a standard deviation of a fiber length is less than 75 percent of a mean length. fiber.

In some embodiments, the mean length / diameter ratio is greater than about 10/1, eg, greater than about 15/1, greater than about 25/1, or even greater than about 50/1.

In some embodiments, the standard deviation of the fiber length is less than 75 percent of the average fiber length, eg, less than fifty percent, less than 35 percent, less than 25 percent, less than 15 percent, less than 10 percent, less than 5 percent, or even less than about 2.5 percent. In some embodiments, an average length of the fibrous material is between about 5 mm and about

2.5mm, for example, between about 5mm and about 50mm.

Comparative composite manufacturing methods are also disclosed which include cutting a fiber source to provide a fibrous material; combining the fibrous material with a crosslinkable resin to provide a fibrous material / resin combination; and irradiating with gamma radiation to at least partially crosslink the crosslinkable resin.

[0074] In some embodiments, the cutting is done with a rotary blade cutter.

Comparative composite manufacturing methods are also disclosed which include combining a fibrous material with a radiation crosslinkable resin to provide a crosslinkable resin / fibrous material combination. Fibrous material has a mean length / diameter ratio of less than about 5, and a standard deviation of a fiber length is less than 75 percent of a mean fiber length. The crosslinkable resin / fibrous material is formed into a desired shape and irradiated to at least partially crosslink the crosslinkable resin.

Comparative composite manufacturing methods are also disclosed which include combining a filler, eg, a fibrous material, with a radiation crosslinkable resin to provide a filler / crosslinkable resin combination and irradiating the filler combination combination. / crosslinkable resin to at least partially crosslink the crosslinkable resin.

[0077] Methods of reducing biological overgrowth, eg, of yeast and / or bacteria, in compounds are disclosed which include irradiating a compound with ionizing radiation prior to use. In some embodiments, the composite is in the form of a board, eg, flooring material.

ES 2 397 791 T3

[0078] Composites are disclosed that include a resin, a filler having a transverse dimension of less than about 1000 nm, and a fibrous material. In some applications, the transverse dimension is less than 500 nm.

[0079] In some embodiments, the resin is crosslinked, for example, using a chemical crosslinking agent or radiation.

[0080] In some embodiments, the fibrous material includes a cellulosic or lignocellulosic material.

In specific embodiments, the fibrous material has a mean length / diameter ratio of more than about 5 and a standard deviation of a fiber length is less than 75 percent of an average fiber length.

[0082] Methods of making composites are disclosed which include combining a filler having a transverse dimension of less than about 1000 nm and a fibrous material with a resin. The methods may further comprise forming the filler / fibrous material / resin combination into a desired shape. The desired shape can be, for example, irradiated to at least partially crosslink the resin.

Methods of making composites are disclosed which include combining a filler having a cross-sectional dimension of less than about 1000 nm and a fibrous material with a radiation crosslinkable resin to provide a filler / fibrous material / crosslinkable resin combination; and irradiating the filler / fibrous material / crosslinkable resin combination to at least partially crosslink the crosslinkable resin.

Composites including a resin and sawdust having fibers that have a mean length / diameter ratio of more than about 5 and a standard deviation of a fiber length is less than 75 percent of a length are also disclosed. fiber media dispersed in it. In some embodiments, the sawdust is derived from a hardwood, eg, oak, or a softwood, eg, cedar, redwood, or pine.

[0085] Also disclosed are methods of making composites that include sawdust to provide a fibrous material, and combining the fibrous material with a resin to provide a combination of resin with the fibrous material. In some embodiments, the methods may further include irradiating the fibrous material / resin combination with gamma radiation to at least partially crosslink the resin.

The comparative aspect and / or embodiments of the comparative aspect may have any of, or combinations of, the following advantages. The composites can have excellent mechanical properties, for example, abrasion resistance, compressive strength, breaking strength, impact strength, flexural strength, modulus of elasticity, and elongation at break. The compounds can have excellent low temperature performance, for example, having a reduced tendency to break and / or crack at low temperatures, for example temperatures below 0 ° C, for example below -10 ° C, - 20 ° C, -40 ° C, -50 ° C, -60 ° C or even below -100 ° C. Furthermore, the compound may have advantageous mechanical properties at relatively high temperatures, for example at temperatures above 100 ° C, for example above 125 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C. , 400 ° C, or even above 500 ° C. The compounds can have excellent chemical resistance, for example, resistance to swelling in a solvent, for example, a hydrocarbon solvent, resistance to chemical attack, for example, by strong acids, strong bases, strong oxidizing agents (eg, chlorine or bleach) or reducers (for example, active metals such as sodium and potassium). The compounds may have a reduced tendency to rot and decompose since treating the compounds with radiation tends to kill any microbes, eg, fungi, bacteria or insects.

[0087] Generally, a comparative aspect is characterized by perfumed compounds, and methods of making them. The perfumed compounds can be cross-linked if desired.

[0088] Sources of fibers, fibrous materials or fibrous densified materials are disclosed in combination with a fragrance. Examples of fragrances include cedarwood, evergreen, or redwood. In some embodiments, the fiber source, fibrous material, or densified fibrous material in combination with the fragrance includes a colorant and / or a biocide. In some embodiments, the fragrance includes a tree fragrance, eg, natural redwood fragrance, and the color, eg, red, matches the tree from which the fragrance is derived.

[0089] Sources of fibers, fibrous materials or fibrous densified materials in combination with a fragrance and a resin, for example a thermoplastic resin, are also disclosed. In some embodiments, a colorant and / or a biocide is used. In some embodiments, the fragrance includes a tree fragrance, eg, natural redwood fragrance, and the color, eg, red, matches the tree from which the fragrance is derived.

[0090] Compounding methods are disclosed which include adding a fragrance to a fibrous material to provide a combination of the perfume with the fibrous material, and compressing the combination of the fragrance with the fibrous material to provide a composite. The fragrance can be, for example, in a resin that is added to the fibrous material.

[0091] Compounds including a fibrous material and a fragrance are also disclosed. In some embodiments, the composites also include a resin, for example, a thermoplastic or thermoset resin. The fibers of the material

Fibrous ES 2 397 791 T3 may have, for example, a length / diameter ratio of more than about 5, eg, greater than 10, greater than 25, greater than 50, or greater than about 100.

The comparative aspect and / or embodiments of the comparative aspect may have any of, or combinations of, the following advantages. Developed flavored compounds, for example wood substitutes and densified fibrous materials, can spark interest at the point of sale, and can allow unusual marketing and branding opportunities.

[0093] Composites are disclosed which include a resin and a fibrous material, and which have an outer surface. Some of the fibrous material is visible.

The fibrous material may be visible on the outer surface, on the outer surface, or under the outer surface, for example, under the surface at a distance of less than about 2.54 mm (0.100 inches) for example, less 1.27 mm (0.050 inches), less than 0.635 mm (0.025 inches), less than 0.254 mm (0.010 inches), or less than about 0.127 mm (0.005 inches).

[0095] Composites including a transparent resin, eg, clear nylon or clarified polypropylene, and a fibrous material are also disclosed.

[0096] Methods of making composites are also disclosed that include combining a resin and fibrous material to provide a resin / fibrous material combination; and compressing the resin / fibrous material combination to provide a composite having an outer surface in which part of the fibrous material is visible.

[0097] Methods of making composites are disclosed that include combining a clear resin and a fibrous material to provide a clear resin / fibrous material combination; and compressing the clear resin / fibrous material combination to provide a composite.

The comparative aspect and / or embodiments of the comparative aspect may have any of, or combinations of, the following advantages. The composites can have unique, pleasant or surprising visual properties and at the same time they can have desirable mechanical properties, for example abrasion resistance, compressive strength, breaking strength, impact resistance, flexural strength, modulus of elasticity and elongation to break. Such compounds can, for example, increase brand recognition and brand loyalty.

[0099] The term fibrous material, as used herein, is a material that includes numerous loose, discrete and separable fibers. For example, a fibrous material can be prepared from a polycoated paper or a bleached Kraft paper fiber source by cutting, for example, with a rotary blade cutter.

[0100] The term "sieve", as used herein, means an element capable of sieving material according to size, for example, a perforated plate, cylinder or the like, or a metallic or cloth fabric.

[0101] A nanoscale filler is one that has a transverse dimension of minus about 1000 nm. The transverse dimension of a nano-scale filler is its diameter if it is a spherical particle or a relatively long thin fiber, or a maximum size of an irregularly shaped particle.

[0102] A fibrous material is visible on or in a composite if the fibrous material can be seen by a medium-sighted human under daylight conditions when the composite is held at a distance of three feet from the human.

[0103] Other features and advantages of the invention will be apparent from the following detailed description, and from the Claims.

DESCRIPTION OF THE DRAWINGS

[0104]

Fig. 1 is a block diagram illustrating fiber source conversion into a first and second fibrous material.

Fig. 2 is a cross-sectional view of a rotary blade cutter.

Figs. 3-8 are top views of a variety of sieves made of monofilaments.

Fig. 9 is a block diagram illustrating the conversion of a fiber source to a first, second, and third fibrous material.

Figs. 10A and 10B are photographs of fiber sources; Fig. 10A which is a photograph of a polycoated paper container, and Fig. 10B which is a photograph of unbleached Kraft paper rolls.

Figs. 11 and 12 are scanning electron micrographs of a fibrous material produced from polycoated paper

ES 2 397 791 T3 with 25 X magnification and 1000 X magnification, respectively. The fibrous material was produced on a rotary knife cutter using a 1/8 inch aperture screen.

Figs. 13 and 14 are scanning electron micrographs of fibrous material produced from bleached Kraft cardboard at 25X magnification and 1000X magnification, respectively. The fibrous material was produced on a rotary knife cutter using a screen with 1/8 inch openings.

Figs. 15 and 16 are scanning electron micrographs of fibrous material produced from bleached Kraft paperboard at 25X magnification and 1000X magnification, respectively. The fibrous material was cut twice on a rotary knife cutter using a screen with 1.59 mm (1/16 inch) openings during each cut.

Figs. 17 and 18 are scanning electron micrographs of fibrous material produced from bleached Kraft cardboard at 25X magnification and 1000X magnification, respectively. The fibrous material was cut three times on a rotary knife cutter. During the first cut, a 3.175 mm (1/8 inch) screen was used; during the second cut, a 1.59 mm (1/16 inch) screen was used, and during the third cut a 0.79 mm (1/32 inch) screen was used.

Fig. 19 is a block diagram illustrating the conversion of a fiber source to a fibrous material, and then densification of the fibrous material.

Fig. 20 is a densified fibrous material in the form of a granule.

Fig. 20A is a cross section of a hollow granule in which a center of the hollow is in line with a center of the granule.

Fig. 20B is a cross section of a hollow granule in which a center of the hollow is out of line with the center of the granule.

Fig. 20C is a cross section of a three lobed granule.

Fig. 21 is a block diagram illustrating reversible bulk densification.

Fig. 22 is a schematic side view of a process for coating a fibrous material with a binder and / or adding additives to the fibrous material

Fig. 23 is a schematic side view of a process for forming a densified fibrous material.

Fig. 24 is a cross-sectional perspective view of a granule mill.

Fig. 25 is a schematic side view of a densified fibrous material manufacturing process.

Fig. 25A is an enlarged view of area 25A of Fig. 25.

Fig. 26 is a block diagram illustrating converting a crosslinkable fibrous material / resin combination into a desirable shape, and irradiating the desired shape to form a crosslinked composite.

Fig. 27 is a perspective sectional view of a gamma irradiator.

Fig. 28 is an enlarged view of region 28 of Fig. 27.

Fig 29 is a photograph of a resin / fibrous material composite in the form of a stool in which part of the fibrous material of the composite is visible.

Fig. 30 is an enlarged view of the box region of Fig. 29.

Figs. 31A, 31B and 31C schematically illustrate the manufacture of a composite from a mold having a mold surface.

Fig. 32 is a sectional view of a resin / fibrous material composition having an inner portion that has no fibrous material and an outer portion surrounding the inner portion that includes fibrous material.

FIG. 33 is a sectional view of a transparent resin / fibrous material composite having an inner portion having substantially all of the fibrous material and an outer portion having substantially no fibrous material surrounding the inner portion.

DETAILED DESCRIPTION

[0105] In general, comparative fibrous materials, densified fibrous materials and composites made of these materials and combinations of these materials are disclosed.

ES 2 397 791 T3

[0106] Some of the fibrous materials disclosed herein are easy to disperse in a resin, such as thermoplastic resin, and can advantageously modify the rheology of the resin in a consistent and predictable way, resulting in resin / fibrous material combinations that can be, for example, easier to mold and extrude. Many of the fibrous densified materials disclosed herein, such as in granule or chip form, can be easier to handle, machine feed, transport, and mix with other materials. Many of these compounds disclosed herein have excellent mechanical properties, such as abrasion resistance, compressive strength, breaking strength, impact strength, flexural strength, modulus of elasticity, and elongation at break. Many of the compounds, and especially many of the crosslinked compounds, have a reduced tendency to break and / or crack at low temperatures and have improved high temperature stability and chemical resistance. Some of the scented compounds, such as wood substitute compounds, can spark interest at a point of sale, and can allow unusual branding and marketing opportunities. Many disclosed compounds have unique, pleasing, or even surprising visual properties.

FIBROUS MATERIALS

[0107] Fibrous material is derived from one or more fiber sources, eg by cutting a fiber source to release fibrous material.

[0108] Referring to Fig. 1, a fiber source 10 is cut, for example, in a rotary blade cutter, to provide a first fibrous material 12. This fibrous material can thus be used, for example, to make densified fibrous materials and / or composites in comparative embodiments, or according to the invention the first fibrous material 12 is passed through a first screen 16 having an average aperture size of 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material 14. If desired, the fiber source 10 can be cut prior to being cut, for example, with a shredder. For example, when using a paper as the fiber source 10, the paper may first be cut into strips that are, for example, 6.35mm to 12.7mm wide (1 / 4- to 1/2 inch), using a crusher, for example, a counter-rotating screw crusher, such as those manufactured by Munson (Utica, NY).

[0109] In some embodiments, the cutting of the fiber source 10 and the passage of the resulting first fibrous material 12 through the first screen 16 are performed at the same time. Cutting and passing can also be done in a batch process.

[0110] For example, a rotary knife cutter can be used to simultaneously cut the fiber source 10 and screen the first fibrous material 12. Referring to Fig. 2, a rotary knife cutter 20 includes a hopper 22 that It can be loaded with a source of shredded fiber 10 'prepared by shredding the source of fiber 10. The source of shredded fiber 10' is shredded between fixed knives 24 and rotating knives 26 to provide a first fibrous material 12. The first fibrous material 12 passes through the screen 16 having the dimensions described above, and the second fibrous material 14 is captured in the hopper 30. To aid in the collection of the second fibrous material 14, the hopper 30 may have a pressure below nominal atmospheric pressure, for example, at least 10 percent below nominal atmospheric pressure, for example, at least 25 percent below nominal atmospheric pressure, at least 50 percent below nominal atmospheric pressure, or at least 75 percent below nominal atmospheric pressure. In some embodiments, a vacuum source 50 is used to keep the hopper below nominal atmospheric pressure.

[0111] With reference to Figs. 3-8, in some embodiments, the average opening size of the first screen 16 is less than 0.79 mm (1/32 inches, 0.03125 inches), for example, less than 0.51 mm (1/50 inches , 0.02000 inch), less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.23 mm (0.009 inch), less than 0.20 mm (1/128 inch, 0, 0078125 inches), less than 0.18 mm (0.007 inches), less than 0.13 mm (0.005 inches), or even less than less than 0.10 mm (1/256 inches, 0.00390625 inches). Screen 16 is prepared by braiding monofilaments 52 having an appropriate diameter to give the desired aperture size. For example, monofilaments can be made of a metal, for example stainless steel. As the size of the openings becomes smaller, the structural demands on monofilaments become greater. For example, for aperture sizes less than 0.40mm, it may be advantageous to manufacture the monofilament sieves made of a material other than stainless steel, for example, titanium, titanium alloys, amorphous metals, nickel, tungsten, rhodium, rhenium. , ceramic, or glass. In some embodiments, the screen is made of a plate, eg, a metal plate, that has openings, eg, cut into the plate using a laser.

[0112] In some embodiments, the second fibrous material 14 is cut and passed through the first screen 16, or a different size screen. In some embodiments, the second fibrous material 14 is passed through a second screen having an average aperture size equal to or less than that of the first screen 16.

[0113] Referring to Fig. 9, a third fibrous material 62 can be prepared from the second fibrous material 14 by cutting the second fibrous material 14 and passing the resulting material through the second screen 60 having a smaller average aperture size. that of the first sieve 16.

[0114] Suitable fiber sources include cellulosic fiber sources, including paper and paper products as shown in Figs. 10A (polycoated paper) and 10B (Kraft paper), and source of lignocellulosic fibers, including

ES 2 397 791 T3 wood, and wood-related materials, eg particle board. Other suitable fiber sources include natural fiber sources, eg herbs, rice pods, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corncobs, rice pods, coconut hair; source of fibers high in α-cellulose content, for example, cotton; source of synthetic fibers, extruded yarn (oriented or non-oriented yarn) or source of carbon fibers; inorganic fiber sources; and source of metal fibers. Synthetic or natural fiber sources can be obtained from virgin textile scrap materials, eg scraps or they can be post-consumer residues, eg rags. When paper products are used as a source of fibers, they can be virgin materials, for example virgin scrap materials, or they can be post-consumer waste. Additional fiber sources have been described in US Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035, and 5,952,105.

[0115] In specific embodiments, the fiber source includes sawdust, for example, from the grinding, machining or sanding of hard or soft woods. Examples of hardwoods include oak, maple, cherry (for example, Brazilian cherry), walnut, Brazilian cherry), walnut, mahogany, cypress, or rosewood. Examples of softwoods include cedar (eg, red and white cedar), pine, spruce, fir (eg, Douglas fir), and redwood. In some embodiments it is advantageous to use aromatic wood, such as cedar or redwood, because it can impart a fragrance to the compound. In some embodiments, the fragrance is added to the sawdust. In some embodiments, it is advantageous to cut the sawdust, for example, using a rotating blade, to deagglomerate the sawdust.

[0116] Mixtures of any of the above sources of fibers or fibrous materials can be used, for example, to make composites or densified fibrous materials.

[0117] Generally, the fibers in fibrous materials can have a relatively large mean length / diameter ratio (eg, greater than 20/1), even if they have been cut more than once. Furthermore, the fibers of the fibrous materials described herein may have a relatively narrow length and / or length / diameter distribution ratio. Without wishing to be bound by any particular theory, it is currently believed that the relatively large mean length / diameter ratio and the relatively narrow length and / or length / diameter ratio distribution are, at least in part, responsible for the ease with which Fibrous materials are dispersed in a resin, for example a liquid thermoplastic resin. It is also believed that the relatively large mean length / diameter ratio and the relatively narrow length / diameter ratio distribution and / or length are, at least in part, responsible for the constant properties of fibrous materials, the predictable change in rheology that fibrous materials convey onto a resin, the ease with which combinations of fibrous materials and resins are cast, extruded and injection molded, the ease with which fibrous materials pass through small, often tortuous channels and openings and the excellent surface finishes possible with molded parts, eg glossy finishes and / or finishes substantially free of visible specks.

[0118] As used herein, mean fiber widths (ie, diameters) are those determined optically randomly by selecting approximately 5,000 fibers. Average fiber lengths are length-weighted corrected lengths. BET surface areas (Brunauer, Emmet and Teller) are multipoint area surfaces, and the porosities are those determined by mercury porosimetry.

[0119] The mean length / diameter ratio of the second fibrous material 14 can be, for example greater than 10/1, for example greater than 25/1 or greater than 50/1. An average length of the second fibrous material 14 may be, for example, between about 0.5mm and 2.5mm, for example, between about 0.75mm and 1.0mm, and a mean width (i.e., diameter ) of the second fibrous material 14 may be, for example, between about 5mm and 50mm, for example, between about 10mm and 30mm.

[0120] In some embodiments, a standard deviation of the length of the second fibrous material 14 is less than 60 percent of an average length of the second fibrous material 14, eg, less than 50 percent of the average length, less than 40 percent of the average length, less than 25 percent of the average length, less than 10 percent of the average length, less than 5 percent of the average length, or even less than 1 percent of the average length.

[0121] In some embodiments, a BET surface area of ​​the second fibrous material 14 is greater than 0.5 µm²/ g, for example, greater than 1.0 m²/ g, greater than 1.5 m²/ g, greater than 1.75 m²/ g or even greater than 5.0 m²/ g. A porosity of the second fibrous material 14 may be, for example, greater than 70 percent, eg, greater than 80 percent, greater than 85 percent, or greater than 90 percent.

[0122] In some embodiments, a ratio of the mean length / diameter ratio of the first fibrous material 12 to the mean length / diameter ratio of the second fibrous material 14 is, for example, less than 1.5, for example, less than 1 , 4, less than 1.25, or even less than 1.1.

[0123] In particular embodiments, the second fibrous material 14 is cut again and the resulting fibrous material is passed through a second screen having a smaller average aperture size than the first screen to provide a third fibrous material 62. In In such situations, a ratio of the mean length / diameter ratio of the second fibrous material 14 to the mean length / diameter ratio of the third fibrous material 62 may be, for example, less than 1.5. for example, less than 1.4, less than 1.25, or even less than 1.1.

ES 2 397 791 T3

[0124] In some embodiments, the third fibrous material 62 is passed through a third screen to produce a fourth fibrous material. The fourth fibrous material can, for example, be passed through a fourth screen to produce a fifth material. Similar screening processes can be repeated as many times as desired to produce the desired fibrous material having the desired properties.

[0125] In some embodiments, the desired fibrous material includes fibers that have a mean length / diameter ratio of more than 5 and that have a standard deviation of fiber length that is less than sixty percent of the mean length. For example, the average length to diameter ratio may be greater than 10/1, for example greater than 25/1, or greater than 50/1, and the average length may be between about 0.5mm and 2.5mm. , for example, between about 0.75mm and 1.0mm. An average width of the fibrous material can be between about 5mm and 50mm, for example, between about 10mm and 30mm. For example, the standard deviation may be less than 50 percent of the mean length, for example, less than 40 percent, less than 30 percent, less than 25 percent, less than 20 percent, less than 10 percent. , less than 5 percent, or even less than 1 percent of the average length. A desired fibrous material may have, for example, a BET surface area of ​​more than 0.5 m2 / g, for example, more than 1.0 m2 / g, more than 1.5 m2 / g, more than 1.75 m2. / g., more than 5 m2 / g, or even more than 10 m2 / g. A desired material can have, for example, a porosity of more than 70 percent, for example, more than 80 percent, more than 87.5 percent, more than 90 percent, or even more than 95 percent.

Examples of Fibrous Materials

[0126] Scanning electron micrographs were obtained on a JEOL 65000 field scanning electron microscope. Fiber lengths and widths (ie, diameters) were determined by Integrated Paper Services, Inc., Appleton, WI, using an automated analyzer ( TAPPI T271). BET area surfaces were determined by Micromeritics Analytical Services, as well as porosity and apparent density.

Comparative Example 1 - Preparation of Fibrous Material from Polycoated Paper

[0127] A 680 kg (1500 pound) skid of half gallon cartons of virgin juice, made of unprinted polycoated Kraft white paperboard with a bulk density of 0.32 g / cm³ (20 Ib / ft³) was obtained from International Paper. Each carton was folded, and then put into a 3 hp Flinch Baugh shredder at a rate of approximately 6.8 kg to 9.1 kg (15 to 20 pounds) per hour. The shredder was equipped with two 12-inch (304.8 mm) rotating blades, two fixed blades, and a 0.30-inch (7.62 mm) discharge screen. The space between the rotating and fixed blades was adjusted to 2.54 mm (0.10 inches). Shredder output resembled confetti with width between 2.54mm (0.1 inch) and 12.7mm (0.5 inch), length between 6.35mm (0.25 inch) and 25.4 mm (1 inch) and a thickness equivalent to that of the starting material (about 1.9 mm (0.075 inch)). The confetti-like material was fed to a Munson rotary blade cutter, Model SC30. The Model SC30 is equipped with four rotating knives, four fixed knives, and a screen that has 1/8 inch (3,175 mm) openings. The space between the rotating and fixed blades was set at approximately 0.51mm (0.020 inches). The rotating blade cut the confetti-like pieces along the edges of the blade, crushing the pieces and releasing a fibrous material at a rate of about one pound per hour. The fibrous material had a BET surface area of ​​0.9748 µm²/ g +/- 0.0167 m²/ g, a porosity of 89.0437 percent, and a bulk density (@ 0.53 psia) of 0.1260 g / mL. A mean fiber length was 1.141mm and a mean fiber width was 0.027mm, giving a mean L / D of 42: 1. Scanning electron micrographs of the fibrous material are shown in Figs. 11 and 12 with 25X magnification and 1000X magnification, respectively.

Comparative Example 2 - Preparation of Fibrous Material from Bleached Kraft Cardboard

[0128] A 680 kg (1500 lb) skid of bleached white Kraft virgin cardboard having a bulk density of 0.48 g / cm³ (30 lb / ft³) was obtained from International Paper. The material was flattened and then fed into a 3 hp Flinch Baugh crusher at a rate of approximately 6.8 to 9.1 kg (15 to 20 pounds) per hour. The shredder was equipped with two 12 inch (304.8 mm) rotating blades, two fixed blades, and a 0.30 inch (7.62 mm) discharge screen. The gap between the rotating and fixed blades was adjusted to 2.54 mm (0.10 inches). The outlet from the shredder resembled confetti with a width of between 2.54 mm (0.1 inches) and 12.7 mm (0.5 inches), a length between 6.35 mm (0.25 inches) and 25.4 mm (1 inch) and a thickness equivalent to that of the starting material (about 1.9 mm (0.075 inch). The confetti-like material was fed to a Munson rotary knife cutter, Model SC30. The discharge screen had openings 3.175 mm (1/8 inch). The space between the rotating and fixed blades was set at approximately 0.51mm (0.020 inches). The rotating blade cut the confetti-like pieces, releasing a fibrous material at a rate of approximately one pound per hour. The fibrous material has a BET surface area of ​​1.1316 µm²/ g +/- 0.0103 m²/ g, a porosity of 88.3285 percent, and a bulk density (@ 0.53 psia) of 0.1497 g / mL. An average fiber length was 1.063mm and an average fiber width was 0.0245mm, giving an average L / D of 43: 1. Scanning electron micrographs of the fibrous material are shown in Figs. 13 and 14 with 25X magnification and 1000X magnification, respectively

Example 3 - Preparation of Fibrous Material Cut Twice From Bleached Kraft Cardboard

[0129] A 680 kg (1500 pound) skid of bleached white Kraft virgin cardboard having a bulk density of 0.48 g / cm³ (30 Ib / ft³) was obtained from International Paper. The material was flattened and then fed into a 3 hp Flinch Baugh crusher at a rate of approximately 6.8 to 9.1 kg (15 to 20 pounds) per hour. The shredder was

ES 2 397 791 T3 equipped with two 12 inch (304.8 mm) rotating knives, two fixed knives and a 0.30 inch (7.62 mm) discharge screen. The space between the rotating and fixed blades was adjusted to 2.54 mm (0.10 inches). The shredder's output resembled confetti (as above). The confetti-like material was fed to a Munson Model SC30 rotary blade cutter. The discharge screen had 1.59 mm (1/16 inch) openings. The space between the rotating and fixed blades was set at approximately 0.51 mm (0.020 inches). The rotating blade cut the confetti-like pieces, releasing a fibrous material at a rate of approximately one pound per hour. The material resulting from the first cut was fed again in the same configuration described above and cut again. The resulting fibrous material had a BET surface area of ​​1.4408 µm²/ g +/- 0.0156 m²/ g, a porosity of 90.8998 percent, and a bulk density (@ 0.53 psia) of 0.1298 g / mL. A mean fiber length was 0.891 mm and a mean fiber width was 0.026 mm, giving a mean L / D of 34: 1. Scanning electron micrographs of fibrous material are shown in Figs. 15 and 16 with 25X magnification and 1000X magnification, respectively.

Example 4 - Preparation of Fibrous Material Cut Three Times From Bleached Kraft Cardboard

[0130] A 680 kg (1500 lb) skid of bleached white Kraft virgin cardboard with a bulk density of 0.48 g / cm³(30 Ib / ft³) was obtained from International Paper. The material was flattened and then fed into a 3 hp Flinch Baugh crusher at a rate of approximately 6.8 kg to 9.1 kg (15 to 20 pounds) per hour. The shredder was equipped with two 12 inch (304.8 mm) rotating knives, two fixed knives, and a 0.30 inch (7.62 mm) discharge screen. The space between the rotating and fixed blades was adjusted to 2.54 mm (0.10 inches). The shredder's output resembled confetti (as above). The confetti-like material was fed to a Munson Rotary Blade Cutter, Model SC30. The discharge screen had 1/8 inch openings. The gap between the rotating and fixed blades was set at approximately 0.51mm (0.020 inches). The rotating blade cut the confetti-like pieces along the edges of the blade. The material resulting from the first cut was fed again in the same configuration described above and the screen was replaced with a 1.59 mm (1/16 inch) screen. This material was cut. The material resulting from the second cut was put back into the same configuration and the screen was replaced with a 0.79 mm (1/32 inch) screen. This material was cut. The fibrous material had a BET surface area of ​​1.6897 μm²/ g +/- 0.0155 m²/ g, a porosity of 87.7163 percent, and a bulk density (@ 0.53 psia) of 0.1448 g / mL. A mean fiber length was 0.824 mm and a mean fiber width was 0.0262 mm, giving a mean L / D of 32: 1. Scanning electron micrographs of the fibrous material are shown in Figs. 17 and 18 with 25X magnification and 1000X magnification, respectively.

COMPARATIVE DENSIFICATION OF FIBROUS MATERIALS

[0131] Referring to Fig. 19, a fiber source is converted to a fibrous material. The fibrous material is subsequently densified. A binder and optionally other additives, such as fillers and antistatic materials, are added to the fibrous material prior to densification. The fibrous material with binders and any desired additives or fillers are densified by application of pressure, for example, by passing the fibrous material through a defined nip between counter-rotating pressure rollers by passing the fibrous material through a granule mill, or by composing the fibrous material and binder in an extruder (eg, a single screw or twin screw extruder). During the application of pressure, heat can optionally be applied to aid in the densification of the fibrous material.

[0132] The fiber source can be transformed into the fibrous material, eg by mechanical means, eg by cutting or shearing the fiber source, as discussed above.

[0133] Any of the fibrous materials discussed above and others can be densified. For example, the fibers of the fibrous material may have, for example, a mean length / diameter (L / D) ratio of more than 3, for example, 5. 6, 7, 8, 10, 10, 25, 50, or plus, for example, 100. In some embodiments, the fibers of the fibrous material have an average length of, for example, 0.25mm or more, for example, 0.3mm, 0.5mm, 0.75mm, 1mm, 2mm, 3 mm, 4mm, 5mm or more, for example 10mm, and a transverse dimension of more than 0.05mm, for example 0.075mm, 0.1mm, 0.2mm, 0.3mm, 0 , 4mm, 0.5mm or more, for example 1mm. If desired, the fibers can be separated from the fibrous material, for example, by sieving into fractions having different L / D ratios.

[0134] In some embodiments, the fibrous material prior to densification has a bulk density of less than 0.25 g / cm³eg 0.20 g / cm³0.15 g / cm³0.10 g / cm³0.05 g / cm³or less, for example 0.025 g / cm³. Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a measuring cylinder of known volume with a sample and obtaining a sample weight. Bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters.

[0135] The fibrous material may optionally be treated, eg, chemically treated or steam treated, to make the fibers of the fibrous material lyophilic, lyophobic, more adherent, and / or more dispersible or processable. For example, the fibrous material can be plasma treated or chemically treated with, for example, silanes.

[0136] Preferred binders include binders that are water-soluble, water-swellable, or have a glass transition temperature of less than 25 ° C, as determined by differential scanning calorimetry. By water soluble binders, we mean binders having a solubility of at least 0.05 weight percent in water. By water-swellable binders, we mean binders that increase in volume more than 0.5 percent at the

ES 2 397 791 T3 exposure to water.

[0137] In some embodiments, binders that are water soluble or swellable include a functional group that is capable of forming a bond, eg, a hydrogen bond, with the fibers of the fibrous material, eg, cellulosic fibrous material. For example, the functional group can be a carboxylic acid group, a carboxylate group, a carbonyl group, for example, from an aldehyde or ketone, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a group phosphate, an amide group, an amine group, a hydroxyl group, for example, of an alcohol, and combinations of these groups, for example, a carboxylic acid group and a hydroxyl group. Specific monomeric examples include glycerin, glyoxal, ascorbic acid, urea, glycine, pentaerythritol, a monosaccharide or a disaccharide, citric acid, and tartaric acid. Suitable saccharides include glucose, sucrose, lactose, fructose, mannose, arabinose, and erythrose. Polymeric examples include polyglycols, polyethylene oxide, polycarboxylic acids, polyamides, polyamines, polysulfonic acid polysulfonates. Specific polymeric examples include polypropylene glycol (PPG), polyethylene glycol (PEG), polyethylene oxide, for example POLYOX®, copolymers of ethylene oxide and propylene oxide, polyacrylic acid (PAA), polyacrylamide, polypeptides, polyethyleneimine, polyvinylpyridine, polyvinylpyridine, poly (sodium-4-styrene sulfonate) and poly (2-acrylamide-methyl-1-propanesulfonic acid).

[0138] In some embodiments, the binder includes a polymer that has a glass transition temperature of less than 25 ° C. Examples of such polymers include thermoplastic elastomers (TPEs). Examples of TPEs include polyether block amide, such as those available under the trademark PEBAX®, polyester elastomers, such as those available under the trademark HYTREL®, and styrenic block copolymers, such as those available under the trademark KRATON®. Other suitable polymers having a glass transition temperature of less than 25 ° C include ethylene vinyl acetate (EVA) copolymer, polyolefins, for example, polyethylene, polypropylene, ethylene-propylene copolymers, and copolymers of ethylene and alpha olefins, for example. , 1-octane, such as those available under the ENGAGE® brand. In some embodiments, for example when the fiber source used to make the fibrous material includes polycoated paper, the fibrous material is densified without the addition of a different low glass transition temperature polymer. For example, fibrous material made from polycoated paper can be densified by heating to above about 50 ° C, for example, 75 ° C, 80 ° C, 90 ° C, 100 ° C or higher, for example, 125 °. C, and applying pressure during heating, for example, pressure greater than about 345 kPa (50 lb / in²), for example 689 kPa (100 lb / in²), 1724 kPa (250 Ib / in²), 3447 kPa (500 lb / in²), 6895 kPa (100 Ib / in²) or higher, for example 17237 kPa (2500 lb / in²).

[0139] In a particular embodiment, the binder is a lignin, for example a natural or synthetically modified lignin.

[0140] In some embodiments, the fiber source used to make the fibrous material already includes a binder so that no additional binder needs to be added to effect densification.

[0141] The binder can offer other functions in addition to binding to fibrous material. For example, when densified fibrous material is used to make composites, the binder can act as a compatibility or coupling aid, helping to reconcile the composite resin and fibrous material. Specific examples of such binders include modified polymers that have been functionalized, for example, with maleic anhydride. Maleic anhydride graft polymers are available from DuPont ™ under the trademark FUSABOND®. Other specific examples include carbon monoxide terpolymers of modified ethylene acrylate and ethylene vinyl acetate (EVAs), also available from DuPont ™. If desired, the binder can include a fragrance or an essence.

[0142] A suitable amount of the binder added to the fibrous material, calculated on a dry weight basis, is, for example, from 0.01 percent to 50 percent, for example, 0.03 percent, 0, 05 percent, 0.1 percent, 0.25 percent, 0.5 percent, 1.0 percent, 5 percent, 10 percent or more, for example, 25 percent, based on a total weight of the fibrous densified material. The binder can be added to the fibrous material as a clean, pure liquid, as a liquid having the binder dissolved in it, as a dry powder of the binder, or as granules of binder.

[0143] In other embodiments, the amount of binder added to the fibrous material is greater than 50 percent (calculated on a dry weight basis), eg, greater than 55 percent, greater than 60 percent, greater than 65 percent, greater than 75 percent, or even greater than 85 percent. These embodiments can have, for example, less than 90 percent polymers (eg, a thermoplastic polymer).

[0144] The fibrous material, after densification, may be in the form of granules (Fig. 20) or chips having a variety of shapes, the desired shape being, in part, application dependent. For example, when the granules or chips have to be dry mixed with a resin, and then the mixture plasticized and molded to form composite parts, it is often desirable that the granules or chips are cylindrical in shape, for example having a maximum transverse dimension of, for example, 1mm or more, for example, 2mm, 3mm, 5mm, 8mm, 10mm, 15mm or more, for example, 25mm. Another convenient way to make composites includes granules or chips that are plate-like in shape, for example having a thickness of 1mm or more, for example 2mm, 3mm, 5mm, 8mm, 10mm or more, for example, 25mm; a width of, for example, 5mm or more, for example 10mm, 15mm, 25mm, 30mm or more, for example 50mm; and a length of 5mm or more, eg 10mm, 15mm, 25mm, 30mm or more, eg 50mm.

[0145] Now referring to Figs. 20A and 20B, the granules can be made by extrusion through a die that

ES 2 397 791 T3 has a solid central portion so that the corresponding granule has an internal hollow. As shown, the gap may be generally in line with the center of the granule (Fig. 20A), or out of line with the center of the granule (Fig. 20B). Making the granule hollow on the inside can decrease the cooling time needed to fully configure the granule, and can therefore increase the rate of formation of the granule. Each granule can have the same or different cross section.

[0146] Referring to Fig. 20C, the granule may have, for example, a cross-sectional shape that is multilobular, eg, three-lobed as shown, or four-lobed, five-lobed, six-lobed, or ten-lobed. lobes. Manufacturing the granules in such cross-sectional shapes can decrease the cooling time.

[0147] As discussed above, granules can be used, for example, to form compounds. The granules or chips can also be used by themselves, for example, as absorbents or controlled release matrices. As controlled release matrices, granules or chips can be used, for example, to fertilize lawns, release drugs or biocides, or to release fragrances. As absorbents, granules or chips can be used, for example, as animal litter, packaging material or in contamination control systems. In embodiments where granules or chips are used as controlled release matrices, the granules or chips can include a polymer, eg, a degradable material. Representative degradable polymers include polyhydroxy acids, eg, polylactides, polyglycolides and copolymers of lactic acid and glycolic acid, poly (hydroxybutyric acid), poly (hydroxyvaleric acid), poly [lactido-co- (s-caprolactone)], poly [glycolide -co- (s-caprolactone)], polycarbonates, poly (amine acids), poly (hydroxyalkanoates) s, polyanhydrides, polyorthoesters and mixtures of these polymers.

[0148] The fibrous densified material, together with a resin, can be used to form articles such as pipes, panels, roofing / decking material, boards, housings, sheets, blocks, bricks, posts, fences, elements, doors, shutters , awnings, blinds, signs, racks, window covering, boards, floors, tiles, railway sleepers, trays, tool handles, lockers, films, containers, boxes, baskets, shelves, covers, folders, dividers, walls, mats, frames, shelves, sculptures, chairs, tables, desks, toys, games, pallets, docks, piers, boats, masts, septic tanks, automotive panels, computer cases, overhead and underground electrical boxes, furniture , picnic tables, benches, shelters, trays, hangers, fountains, chests, book covers, canes, and crutches.

[0149] The granules or chips have a variety of densities, the desired density, in part, depending on the application. For example, when granules or chips are to be used in the manufacture of composites, the granules or chips can have, for example, a density of about 0.11 g / cm³0.15 g / cm³, 0.20 g / cm³, 0.25 g / cm³, 0.3 g / cm³0.4 g / cm³, 0.5 g / cm³, 0.6 g / cm³, or more, for example 0.8 g / cm³. When used to make composites, it is often advantageous to select a density such that the granules are cut and / or heat separated to release the fibrous material from which the granule or chip is formed. For many applications, the densified fibrous material can be substituted for fibrous material since the densified fibrous material is converted back to a fibrous material within a processing device, for example, an extruder or an injection molding machine.

[0150] Referring to Fig. 21, a fibrous material having a low bulk density can be reversibly densified without using a binder for a fibrous material q₃which has a higher bulk density. For example, a fibrous material that has a bulk density of 0.05 g / cm³It can be densified by sealing the fibrous material in an airtight bag, and then evacuating air from the bag. After evacuation of the air from the bag, the fibrous material can have, for example, a bulk density of more than 0.3 g / cm³for example 0.5 g / cm³, 0.6 g / cm³, 0.7 g / cm³or more, for example 0.85 g / cm³. This can be advantageous when it is desired to transport fibrous material to another location, for example a remote manufacturing plant, prior to densification of the fibrous material with a binder. After piercing the impermeable air pocket, the densified fibrous material returns to almost its initial bulk density, for example, more than 60 percent of its initial bulk density, for example, 70 percent, 80 percent, 85 percent or greater, for example, 95 percent of its initial bulk density. To reduce static electricity in the fibrous material, an antistatic agent can be added to the fibrous material. For example, an antistatic chemical compound, eg, a cationic compound, eg, quaternary ammonium compound, can be added to the fibrous material. Static in fibrous material can also be reduced, for example, by induction, grounding or ionization.

[0151] Fig. 22 explains the operation of a device 70 that generates and processes the fibrous material. Sheet of paper 73, eg, bleached sheet of Kraft paper, is supplied from the roll 72 and distributed to a fibering apparatus 74, such as a rotary cutter. Sheet 73 is converted to fibrous material 12 'and carried to fiber loading zone 80 by conveyor 78. If desired, the fibers of the fibrous material can be separated, for example, by sieving into fractions having different L / D ratios. In some embodiments, the fibrous material 12 'is delivered continuously to zone 80, and in other embodiments, the fibrous material is supplied in batches. A loop blower 82 84 is positioned adjacent the fiber loading zone 80 and is capable of moving a gaseous medium, for example air, at a speed and volume sufficient to circulate the fibrous material 12 'in a direction indicated by the arrow 88 through loop 84.

[0152] In some embodiments, the velocity of air traveling in the loop is sufficient to evenly disperse and

ES 2 397 791 T3 convey the fibrous material around the entire loop 84. In some embodiments the flow velocity is greater than 12.7 m / s (2,500 ft / minute) eg 25.4 m / s (5,000 ft / minute) 30.5 m / s (6,000 ft / minute) or more, for example 38.1 m / s (7,500 ft / minute).

[0153] The entrained fibrous material 12 'passing through the loop passes a binder application zone 90, which forms part of the loop 84, when the binder is applied. In operation, the binder application zone 90 applies a liquid solution of binder 96 to the circulating fibrous material through nozzles 98, 99, and 100. The nozzles produce an atomized spray or mist of the binder material, which impacts and coats fibers as they the fibers pass close to the nozzles. Valve 102 is operated to control the flow of liquid binder material to respective nozzles 98, 99, and 100. After a desired amount of binder material is applied, valve 102 closes.

[0154] In some embodiments, the binder application zone 90 is 0.61m (two) to 30.5m (one hundred feet) long or longer, eg, 38.1m (125 feet), 45, 8 m (150 ft), 76.2 m (250 ft) long or more, for example 152.4 m (500 ft) long. Larger binder application zones allow binder application for a longer period of time during the passage of fibrous material 12 'through application zone 90. In some embodiments, the nozzles are spaced about three to four feet along the length of the loop 84.

[0155] In some embodiments, the binder provides a coating over a substantial majority of the surface area of ​​each fiber of the fibrous material 12 ', eg, fifty percent or more, eg, sixty percent, seventy percent, seventy percent. five percent or more, for example, eighty percent. In some embodiments, the binder forms a coating that is about 1 micron thick or less, eg 0.5, 0.3 microns or less, eg 0.1 microns.

[0156] Any of the additives and / or fillers described herein may optionally be added to loop 84 from a supply 106 during the flow of fibrous material 12 'to form a mixture of fibers and additives.

[0157] In some embodiments, after application of the liquid binder material to fibrous material 12 ', coated fibrous material 110 is removed from loop 84 by spacer 112, which is selectively connected to loop 84 at section 114 and the gate valve 116. When valve 116 is opened, another valve 120 also opens to allow air to enter loop 84 to compensate for air exiting through separator 112. With separator 112 in the loop, the coated fibrous material is collected in separator 112, and is then removed from the separator via outlet 122.

[0158] In some embodiments, the fibrous material is dried with an optional heater 130 before the material is removed from the loop 84. For example, the heated air can be mixed with the air flowing through the conduit to accelerate the drying of the liquid, water, in which the binder is incorporated.

[0159] The coated fibrous material is transferred from the outlet 122 freely onto a conveyor 132 where it is transferred to the densification station 150 shown in Fig. 23 or the densification station 200 shown in Fig. 24.

[0160] Referring to Fig. 23, the coated fibrous material 110 from above is distributed from a joint box 152 through a slit 154 and over a screen 156, eg, a Fourdrinier screen. Excess water is removed from the coated fibrous material 110 deposited on the screen 156 by a conventional under-screen vacuum system (not shown), leaving a densified fibrous material 160 that includes the binder. The non-densified fibrous material 160 is then transferred to two sets of roll rolls 162, 164, each defining a groove through which the fibrous material passes. After passing through the grooves, the densified undried material 170 enters a drying section 180 where it is dried, and then chopped into granule or chip form.

[0161] In an alternative embodiment, the densified fibrous material can be manufactured in a granule mill. Referring to Fig. 24, a pellet mill 200 has a hopper 201 to hold the fibrous material without densifying 110. The hopper 201 communicates with a feeder 204 which is driven by the variable speed motor 206 so that the non-densified fibrous material 110 can be conveyed to a conditioner 210 that agitates the non-densified material 110 with paddles 212 that are rotated by the conditioner motor 214. Other ingredients, for example, any of the additives and / or fillers described herein, can be added to inlet 220. If desired, heat can be added while the fibrous material is in conditioner 210.

[0162] After conditioning, the fibrous material passes from conditioner 210 through a discharge channel 222, and onto another conveyor 224. The discharge channel 222, controlled by actuator 223, allows the unobstructed passage of fibrous material from the conditioner 210 to conveyor 224. Conveyor 224 is rotated by motor 230, and controls the feeding of fibrous material to nozzle and roller assembly 232. Specifically, the fibrous material is introduced into a hollow cylindrical nozzle 240 which rotates about a horizontal axis and has radially extending nozzle holes 250. The die 240 is rotated about the axis by the motor 242, which includes a gauge of power, indicating the total energy consumed by motor 242.

[0163] A set of rollers 256 rolls around the inner circumference of cylinder 240, around axes parallel to that of nozzle 240, to press fibrous material through the holes of cylinder 250, forming granules 300,

ES 2 397 791 T3 that fall from the spill chute 301 and are captured and packed into boxes.

[0164] The fibrous material treated above can be densified using other methods. For example, referring to Figs. 25 and 25A, an apparatus 310 may be used to form a densified fibrous material 311, eg, a composite, eg, pressboard. As shown, the densified fibrous material 311 is formed from a combination of fibrous material-binder 313 by rolling the combination of fibrous material-binder 313 between elements 312 and 314. Lamination is accomplished, for example, by applying pressure alone or by applying heat and pressure to an uncompressed composite 322. The fibrous-binder material combination 313 may optionally include any of the additives discussed above.

[0165] Apparatus 310 includes first and second elements 312 and 314 provided from rollers 321 and 323, respectively, and a hopper 320 for storing fibrous material, binder, and any additives. The fibrous material, binder, and any additives are distributed between elements 312 and 314 to form an uncompressed composite 322. Uncompressed composite 322 is then passed through a series of heated rolls 330, 332, 334, 336, 338, 340, and 342 defining an s-shaped track, and then lamination rolls 350, 352, and 354, 356 to produce compound 311. Agitators may be provided within hopper 320 to ensure that fibrous material, binder, and any additives do not clog or obstruct the feeding operation. The uncompressed compound 322 is partially densified after passing through the s-shaped pathway defined by heated rollers 330, 332, 334, 336, 338, and 340, and then fully densified to form compound 311 by passing through the heating rollers. lamination 350, 352 and 354, 356.

[0166] In some embodiments, the fiber source used to make the fibrous material already includes a binder. In that case, no binder needs to be added to effect densification. For example, when the fiber source used to make the fibrous material includes polycoated paper, the fibrous material is densified without the addition of a different binder, eg, a low glass transition temperature polymer.

[0167] The laminating rolls 354, 356 can be rotated such that each has a higher surface speed than each laminating roll 350, 352. In such a configuration, the densified fibrous material is stretched between the laminating rolls 350, 352 and laminating rolls 354, 356. In some applications, stretching the densified fibrous material is desirable because stretching can improve many mechanical properties of the composite, eg, flexural modulus, flexural strength, and tensile strength.

[0168] The elements, for example bands, can be made of, for example, polycoated paper, plastic film, plastic material or a textile fabric material, for example a woven or non-woven textile mesh material. Where desirable to minimize the amount of element material in the fibrous densified material, a thickness T1 and T2 of elements 312 and 314, respectively, may be, for example, less than 1.27 mm (0.050 inches), for example , 1.0 mm (0.040 inches), 0.64 mm (0.025 inches), 0.51 mm (0.020 inches), 0.25 mm (0.010 inches), 0.127 mm (0.005 inches) or less, for example 0.064 mm (0.0025 inch). When it is desired to maximize the mechanical properties of the fibrous densified material, the thickness T1 and T2 of the elements 312 and 314, respectively, can be greater than 1.27 mm (0.050 inches), for example, 1.52 mm (0.060 inches) , 1.65 mm (0.065 inches), 1.90 mm (0.075 inches), 2.16 mm (0.085 inches), 2.54 mm (0.100 inches), 3.81 mm (0.150 inches), 6.35 mm (0.250 inches), 19.05 mm (0.75 inches) or larger, for example, than 50.8 mm (2.00 inches).

[0169] In some applications, rollers 330, 332, 334, 336, 338 and 340 are heated to between 149 ° C (300 ° F) to about 260 ° C (500 ° F). In embodiments where the plastic film is used as an element material, these temperatures act to rapidly soften the polymeric material in the film.

[0170] In some applications, hot rollers 330, 332, 334, 336, 338 and 340 are between about 127mm (5 inches) in diameter to about 1067mm (42 inches) in diameter, for example 254mm (10 inches). ), 381 mm (15 inches), 508 mm (20 inches), 635 mm (25 inches), or larger, for example, 914.4 mm (36 inches).

[0171] The element feed speed can be, for example, from about 0.018 m / s (3.5 feet per minute) to about 1.27 m / s (250 feet per minute), for example 0.13 m 25 ft / s (25 feet per minute), 0.25 m / s (50 feet per minute), 0.51 m / s (100 feet per minute) or greater, for example, 0.89 m / s (175 feet per minute) minute)

[0172] Lamination rolls 350, 352 and 354, 356 may or may not heat up. When heated, they are typically heated to a lower temperature than heated rolls 330, 332, 334, 336, 338, and 340 to allow the materials that will form the densified fibrous material to begin to cool and set. For example, laminating rolls 350, 352 and 354, 356 are heated from 38 ° C (100 ° F) to about 149 ° C (300 ° F). The pressure between the laminating rollers is, for example, at least about 8930 kg / m (500 pounds per linear inch) e.g. 17,860 kg / m (1,000 pounds per linear inch), 44,650 kg / m (2,500 pounds per linear inch) linear), 89,300 kg / m (5,000 pounds per linear inch) or more 446,500 kg / m (for example, 25,000 pounds per linear inch).

[0173] In some applications, a thickness T 'of the densified fibrous material 311 is at least about two times less than a thickness T of the uncompressed composite 322, for example, three times, four times, five times or less, for example, ten times less. Consequently, the bulk density of the densified fibrous material is higher than the uncompressed composite. For example, the density of the uncompressed composite can be, for example, less than 0.25

ES 2 397 791 T3

3 3 3 3 3 g / cm, for example 0.20 g / cm, 0.15 g / cm, 0.10 g / cm, 0.05 g / cm or less, for example 0.025 g / cm, and the bulk density of the densified fibrous material may, for example, be greater than about 0.3 g / cm³for example 0.4 g / cm³, 0.5 g / cm³, 0.6 g / cm³, or more, for example 0.8 g / cm³.

[0174] The cooled densified fibrous material 311 can be rolled or cut into sheets. Densifying a fibrous material between elements can be advantageous when it is desirable to transport the fibrous material to another location, for example, a remote manufacturing plant. After reaching the other location, the densified fibrous material can be reconverted to fibrous material by any of the methods discussed herein.

[0175] Alternatively, the cooled densified fibrous material can be used in a variety of applications. For example, it can be used for soundproofing, insulation, structural elements, heavy-duty boxes, and partitions.

[0176] While embodiments have been described in which a binder is applied to a fibrous material by vaporizing a binder solution, eg, a binder solution containing the binder dissolved in water, onto the fibrous material, in some embodiments, the binder is applied to fibrous material as liquid only from the binder or as a dry powder. The binder can also be applied as a gaseous material.

[0177] While embodiments have been described in which a fibrous material is converted into a densified fibrous web, and then the densified fibrous material is cut into granules or chips, in some embodiments, the densified fibrous material is first collected on a roll. The densified fibrous web can be used, for example, as an absorbent mat material, or it can be transported to a remote manufacturing site where it is made into granules or chips. The densified fibrous web material may have a convenient shape in which to transport the fibrous material because of its high bulk density.

[0178] While embodiments in which single-layer elements 312 and 314 are used to form a densified fibrous material 311, eg, a composite, have been described, in some embodiments, multi-layer elements are used. For example, the elements can each have, for example, two layers, three layers, five layers or more, for example, seven layers. Furthermore, while fibrous densified materials have been described in which the fibrous material sandwiched between two elements, in some embodiments, a densified fibrous material is made by compressing a fibrous material that is under a single element.

Examples of Densified Fibrous Materials

Example 5 - Preparation of Densified Fibrous Material from Bleached Kraft Cardboard without Added Binder

[0179] Fibrous material is prepared according to Example 2. About 0.45 kg (1 lb) of water is sprayed on every 4.5 kg (10 lb) of fibrous material. The fibrous material is densified using a California Pellat Mill 1100 operating at 75 ° C. Granules were obtained with an apparent density from about 0.11 g / cm³ (7 lb / ft³) up to about 0.24 g / cm³ (15 lb / ft³).

Example 6- Preparation of Densified Fibrous Material From White Kraft Cardboard Bleached with D'gante

[0180] Fibrous material is prepared according to Example 2.

[0181] A 2 weight percent stock solution of POLYOX ™ WSR N10 (polyethylene oxide) in water is prepared.

[0182] About 0.45 kg (1 lb) of the stock solution was sprayed onto each 4.5 kg (10 lb) of the fibrous material. The fibrous material was densified using a California Pellet Mill 1100 operating at 75 ° C. Granules are obtained that have an apparent density going about 0.24 g / cm³ (15 lb / ft³) up to about 0.64 g / cm³ (40 lb / ft³).

COMPARATIVE FIBROUS MATERIAL / RESIN COMPOUNDS

[0183] Composites can be prepared including any of the fibrous materials discussed above (including the densified fibrous materials) or mixtures of any of the above fibrous materials, eg, first 12 or second fibrous material 14, and a resin, eg, a thermoplastic resin or a thermosetting resin, combining the desired fibrous material and the desired resin. The desired fibrous material can be combined with the desired resin, for example, by mixing the fibrous material and resin in an extruder or other mixer. To form the composite, the fibrous material can be combined with the resin as the fibrous material itself or as a densified fibrous material that can be reopened during the combination.

[0184] Examples of thermoplastic resins include rigid and elastomeric thermoplastics. Rigid thermoplastics include polyolefins (eg, polyethylene, polypropylene, or polyolefin copolymers), polyesters (eg, polyethylene terphthalate), polyamides (eg, nylon 6, 6/12, or 6/10), and polyethyleneimines. Examples of elastomeric thermoplastic resins include elastomeric styrenic copolymers (eg, styrene-ethylene-butylene-styrene copolymers), polyamide elastomers (eg, polyamide-polyether copolymers), and ethylene-vinyl acetate copolymer.

[0185] In some embodiments, the thermoplastic resin has a melt flow index of between 10 g / 10 minutes to 60

ES 2 397 791 T3 g / 10 minutes, for example, between 20 g / 10 minutes to 50 g / 10 minutes, or between 30 g / 10 minutes to 45 g / 10 minutes, measured using ASTM 1238.

[0186] In some embodiments, compatible blends of any of the above thermoplastic resins can be used.

[0187] In some embodiments, the thermoplastic resin has a polydispersity index (PDI), that is, a weight average molecular weight ratio, of more than 1.5, eg, more than 2.0, more than 2 , 5, more than 5.0, more than 7.5, or even more than 10.0.

[0188] In specific embodiments, polyolefins or polyolefin blends are used as the thermoplastic resin.

[0189] Examples of thermosetting resins include natural rubber, butadiene rubber, and polyurethanes.

[0190] Generally, the fibers in fibrous materials can have a relatively large mean length / diameter ratio (eg, greater than 20-to-1), even if they have been cut more than once. Furthermore, the fibers of the fibrous materials described herein may have a relatively narrow length distribution and / or length / diameter ratio distribution. Without wishing to be bound by any particular theory, it is presently believed that the relatively large mean length / diameter ratio and the relatively narrow length distribution and / or length / diameter ratio distribution are, at least in part, responsible for the ease in which the fibrous materials are dispersed in a resin, for example a liquid thermoplastic resin. It is also believed that the relatively large mean length / diameter ratio and the relatively narrow length and / or length / diameter ratio distribution are, at least in part, responsible for the constant properties of fibrous materials, the predictable rheology modification that fibrous materials impart on a resin, the ease in which combinations of fibrous materials and resins are cast, extruded and injection molded, the ease with which fibrous materials pass through small, often tortuous openings and channels, and the excellent surface finishes possible with molded parts, for example glossy finishes and / or finishes substantially devoid of visible specks, when desired .

[0191] During compounding, a chemical foaming agent, eg, an exothermic or endothermic foaming agent, can be used, and / or a gas, eg, nitrogen or carbon dioxide, can be injected into the mixture. It may be advantageous to form articles of large cross section, for example to avoid sagging, to reduce the density of the parts and / or reduce the cooling time. Chemical blowing agents are available from Clariant Corporation, for example, under the brand name HYDROCEROL®.

Additives

[0192] Any of the following additives can be added to the fibrous materials, fibrous densified materials and composites described herein. Additives can be added, for example in the form of a solid, a liquid or a gas, for example, to the combination of a fibrous material and resin. Additives include fillers such as calcium carbonate, graphite, wollastonite, mica, glass, fiberglass, silica, and talc; inorganic flame retardants such as alumina trihydrate or magnesium hydroxide; organic flame retardants such as chlorinated or brominated organic compounds; construction waste; chopped tire rubber; carbon fibers; or metal fibers or powders (eg aluminum, stainless steel). These additives can strengthen, extend, or change compatibility, mechanical, or electrical properties. Other additives include lignin, fragrances, coupling agents, compatibilizers, eg, maleated polypropylene, processing aids, lubricants, eg, fluorinated polyethylene, plasticizers, antioxidants, opacifiers, heat stabilizers, colorants, blowing agents, impact modifiers, polymers, eg, degradable polymers, light stabilizers, biocides, antistatic agents, eg, stearates or amino acids from ethoxylated fat. Suitable antistatic compounds include carbon blacks, carbon fibers, metal fillers, cationic compounds, for example quaternary ammonium compounds, for example, N- (3-chloro-2-hydroxypropyl) -trimethylammonium chloride, alkanolamides, and amines. . Representative degradable polymers include polyhydroxy acids, eg, polylactides, polyglycolides and copolymers of lactic acid and glycolic acid, poly (hydroxybutyric acid), poly (hydroxyvaleric acid), poly [lactido-co- (e-caprolactone)], poly [glycolide -co- (ecaprolactone)], polycarbonates, poly (amine acids), poly (hydroxyalkanoates) s, polyanhydrides, polyorthoesters and mixtures of these polymers.

[0193] When the disclosed additives are included, they may be present in amounts, calculated on a dry weight basis, of from less than 1 percent to as much as 80 percent, based on a total weight of the fibrous material. More typically, the amounts range from 0.5 percent to 50 percent by weight, for example 5 percent, 10 percent, 20 percent, 30 percent or more, for example 40 percent. .

[0194] Any additive described herein can be encapsulated, eg, atomized or microencapsulated, eg, to protect the additives from heat or moisture during handling.

[0195] Fibrous materials, fibrous densified materials, resins or additives can be dyed. For example, the fibrous material can be dyed prior to combining with the resin and composition to form composites. In some embodiments, this staining can be useful to mask or hide fibrous material, especially large

ES 2 397 791 T3 agglomerations of fibrous material, in molded or extruded parts, when this is desired. Such large agglomerations, when present in relatively high concentrations, can appear as spots on the surfaces of molded or extruded parts.

[0196] For example, the desired fibrous material can be dyed using an acid dye, direct dye, or reactive dye. Such dyes are available from Spectra Dyes, Kearny, NJ or Keystone Aniline Corporation, Chicago, IL. Specific examples of stains include SPECTRA ™ LIGHT YELLOW 2G, SPECTRACID ™ YELLOW 4GL CONC 200, SPECTRANYL ™ RHODAMINE 8, SPECTRANYL ™ NEUTRAL RED B, SPECTRAMINE ™ BENZOPER GREPURINE, SPECTRADIAZO ™ BLACK OB, SPECTRAMINE ™ TURQUOISELAMINE 200, and SPECTRAMINE ™ TURQUOISE 200%. , each being available from Spectra Dyes.

[0197] In some embodiments, pigment-containing resin color concentrates are mixed with the dyes. When such blends are then compounded with the desired fibrous material, the fibrous material can be dyed on-site during compounding. Color concentrates are available from Clariant.

[0198] It may be advantageous to add a scent or fragrance to fibrous, densified fibrous or composite materials. For example, it may be advantageous for composites to smell and / or resemble natural wood, eg, cedar wood. For example, the fragrance, eg, natural wood fragrance, can be compounded into the resin used to make the composite. In some applications, the fragrance is compounded directly into the resin as an oil. For example, the oil can be compounded into the resin using a roll mill, for example a mixer or a Banbury® extruder, for example a twin screw extruder with counter rotating screws. An example of a Banbury® mixer is the F-Series Banbury® mixer, manufactured by Farrel. An example of a twin screw extruder is the WP ZSK 50 MEGAcompunder ™, manufactured by Krupp Werner & Pfleiderer. After compounding, the flavored resin can be added to the fibrous material and extruded or molded. Alternatively, masterbatches of fragrance-filled resins are commercially available from International Flavors and Fragrances, under the PolyIff ™ trademark or from the RTP Company. In some embodiments, the amount of fragrance in the compound is between 0.005% by weight and 10% by weight, for example, between 0.1% and 5% or 0.25% and 2.5%. .

[0199] Other natural wood fragrances include evergreen or redwood. Other fragrances include peppermint, cherry, strawberry, peach, lime, spearmint, cinnamon, anise, basil, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus, pine, fir, geranium, ginger, grapefruit, jasmine, juniper cone , lavender, lemon, tangerine, myrrh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, or blends of these fragrances. In some embodiments, the amount of fragrance in the fibrosofragrance material blend is between 0.005% by weight and 20% by weight, for example, between 0.1% and 5% or 0.25% and 2, 5 %.

[0200] While fibrous materials, such as cellulosic and lignocellulosic fibrous materials, have been described, other fillers can be used to make the composites. For example, inorganic fillers such as calcium carbonate (for example, precipitated calcium carbonate or natural calcium carbonate), aragonite clay, orthorhombic clays, calcite clay, rhombohedral clays, kaolia, clay, bentonite plaster, phosphate of calcium, tricalcium phosphate, calcium pyrophosphate, insoluble sodium metaphosphate, precipitated calcium carbonate, trimagnesium orthophosphate, trimagnesium phosphate, hydroxyapatites, synthetic apatites, alumina, silica xerogel, metal aluminosilicate complexes, sodium aluminum silicate, zirconium silicate, silicone dioxide or combinations of the additives. Fillers may, for example, have a particle size greater than 1 micron, eg greater than 2 microns, 5 microns, 10 microns, 25 microns, or even greater than 35 microns.

[0201] Nanoscale fillers can be used alone, or in combination with fibrous materials. The fillers can be in the form of, for example, a particle, a plate or a fiber. For example, clays, carbon and silicone nanotubes, carbon nanowires and silicone measured with nanometers can be used. The filler may have a transverse dimension less than 1000nm, for example, less than 900nm, 800nm, 750nm, 600nm, 500nm, 350nm, 300nm, 250nm, 200nm, less than 100nm, or even less than 50 nm.

[0202] In some embodiments, the nano-clay is a montmorillonite. Such clays are available from Nanocor, Inc. and Southern Clay products, and have been described in US Patents 6,849,680 and 6,737,464. Clays can be pretreated before mixing into, for example, a resin or fibrous material. For example, clay can be surface treated such that its surface is ionic in nature, eg, cationic or anionic.

[0203] Nanoscale aggregated or agglomerated fillers, or nano-scale fillers that assemble into supramolecular structures, eg, self-assembled supramolecular structures, can also be used. Aggregate or supramolecular fillers can open or close in the structure, and can have a variety of shapes, eg, cage, tube, or spherical.

STRUCTURES

[0204] Any compound described herein can be in the form of items such as pipes, panels, flooring materials, boards, covers, sheets, blocks, bricks, posts, fences, elements, doors, shutters, awnings, blinds, signs, racks, window boxes, boards, floors, tiles, railroad ties, trays, tool handles, stalls, films, wrappers, boxes, baskets, shelves, covers, folders, dividers, walls,

ES 2 397 791 T3 mats, frames, shelves, sculptures, chairs, tables, desks, toys, games, pallets, docks, piers, boats, masts, septic tanks, automotive panels, computer covers, overhead and underground electrical boxes, furniture, picnic tables, benches, shelters, trays, hangers, trays, chests, book covers, canes and crutches, household items and structures ..

RADIATION CROSSLINK COMPOUNDS

[0205] Referring to Fig. 26, radiation crosslinked composites can be made, for example, by combining a fibrous material including different fibers with a radiation crosslinkable resin, for example, a thermoplastic resin (eg, a polypropylene of high melt flow index) to provide a crosslinkable fibrous material / resin combination. The fibrous material can have, for example, an average length / diameter ratio of more than 5, and a standard deviation of a fiber length that is, for example, less than eighty-five percent of an average fiber length. The crosslinkable fibrous material / resin is formed, for example, using injection molding or extrusion, into a desired shape, for example, a floor board, and is irradiated, for example, with ionizing radiation (for example, a beam of electrons, x-ray radiation or gamma radiation) to at least partially cross-link the cross-linkable resin.

[0206] In specific embodiments, gamma radiation is used to crosslink the crosslinkable resin. With reference to Figs. 27 and 28, a gamma irradiator 400 includes sources of gamma radiation 408, for example, granules⁶⁰Co, a worktable 410 for putting the compound to irradiate and reservoir 412, for example, made of a plurality of iron plates, all of which are housed in a cement containment chamber 402 that includes a labyrinth entrance door 404 past a 406 lead lined door. Store 412 includes a plurality of channels 420, eg, sixteen or more channels, that allow gamma radiation source 408 to pass through reservoir 412 on its way near worktable 410.

[0207] In operation, the compound to be irradiated is placed on the worktable 410. The irradiator is configured to deliver the desired dose and the control equipment is connected to the experimental block 440. The operator then leaves the containment chamber 402, passing through the maze entrance door 404 and through the lead lined door 406. The operator attends to a control panel 442, ordering a computer to raise the radiation sources 408 to the working position using cylinder 441 attached to a hydraulic pump 444.

[0208] In embodiments where the irradiation is performed with electromagnetic radiation (eg, as above), the electromagnetic radiation may have, for example, energy per photon (in electron volts) of more than 102 eV, for example, more than 10³, 10⁴, 10⁵, 10⁶, or even more than 10⁷ eV. In some embodiments, electromagnetic radiation has energy per photon between 10⁴ and 10⁷, for example, enter 10⁵ and 10⁶ eV. Electromagnetic radiation can have a frequency of, for example, greater than 1016 Hz, greater than 10¹⁷ hz, 10¹⁸, 10¹⁹, 10²1⁰₈, or even greater than 10²¹ hz. In some embodiments, the electromagnetic radiation has a frequency between 10¹⁸ and 10²² hz, for example, between 10¹⁹ to 10²¹ hz.

[0209] In some embodiments, an electron beam is used as the radiation source. Electron beams can be generated, for example, by means of electrostatic generators, cascade generators, transformer generators, low-energy accelerators with a sweep system, low-energy accelerators with a linear cathode, linear accelerators, and pulsed accelerators. Electrons can be useful as a source of ionizing radiation, for example for compounds having relatively thin sections, for example less than 0.5 inches, for example less than 0.4 inches, 0.3 inches, 0.2 inches, or less than 0.1 inches. In some embodiments, the energy of each electron in the electron beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), for example, from about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.

[0210] In some embodiments, irradiation (with any radiation source) is performed until the crosslinkable fiber / resin combination receives a dose of less than 0.25 Mrad, eg, at least 1.0 Mrad, at minus 2.5 Mrad, at least 5.0 Mrad, or at least 10.0 Mrad. In some embodiments, irradiation is performed until the crosslinkable fiber / resin combination receives a dose of between 1.0 Mrad and 6.0 Mrad, for example, between

1.5 Mrad and 4.0 Mrad.

[0211] In some embodiments, irradiation is performed at doses between 5.0 and 1500.0 kiilorads / hour, for example, between 10.0 and 750.0 kiilorads / hour or between 50.0 and 350.0 kiilorads / hour.

[0212] The radiation crosslinkable resin can be, for example, a thermoplastic or a thermoset (eg, a cast thermoset). For example, the radiation crosslinkable resin can be a polyolefin, for example, a polyethylene (for example, a polyethylene copolymer), a polypropylene (for example, a polypropylene copolymer), a polyester (for example, polyethylene terephthalate). , a polyamide (for example, nylon 6, 6/12 or 6/10), to polyethyleneimine, styrenic elastomeric copolymers (for example, styrene-ethylene-butylene-styrene copolymers), a polyamide elastomer (for example, polyamide-polyether copolymer), vinyl acetate-ethylene copolymer, cast polyurethane, cast silicone, or compatible blends of these resins.

[0213] In some specific embodiments, the resin is a polyolefin having a polydispersity of greater than 2.0, eg, greater than 3.0, greater than 3.5, greater than 4.0, greater 4.5, more than 5.0, more than 7.5 or even more

ES 2 397 791 T3 of 10.0 (measured using high temperature gel permeation chromatography against polystyrene standards; see, for example, ASTM D6474-99). High polydispersity can improve impact resistance in crosslinked composites. In some embodiments, the polyolefin has a flow rate of greater than 10.0 g / 10 minutes, for example, greater than 15.0, greater than 20.0, greater than 25.0, greater than 30.0, or even greater than 50.0 g / 10 minutes (measured using ASTM D1238, 230 ° C / 2.16 kg). A melt flow can aid compound production, for example by reducing shear heating during compound formation.

[0214] In a specific embodiment, the resin is a 50:50 weight percent melt flow index (IFF) mixture of polypropylene and 50 IFF polypropylene. Polypropylenes are also available from Sunoco Chemical.

[0215] Crosslinked compounds can include any or any combination of the fillers and / or additives disclosed herein.

[0216] While the embodiment of Fig. 27 illustrates a "dry" containment system, water containment systems are possible. While the embodiment of Fig. 27 illustrates irradiation of a compound under ambient conditions, the compound can be cooled during irradiation. While the embodiment of Fig. 27 illustrates irradiation in atmospheric normal air, the irradiation can take place in an inert atmosphere, eg, nitrogen or argon atmosphere.

[0217] Radiation chemistry is described by Ivanov in Polymer Radiation Chemistry (Russian translation), VSP Press BV, Ultrech, The Netherlands, (ISBN 90-6764-137-5), 1992.

COMPOUNDS WITH CERTAIN VISUAL ATTRIBUTES

[0218] With reference to Figs. 29 and 30, a composite 500, for example, in the form of a stool (as shown), includes a resin and a fibrous material 504 and has an outer surface 505. Some of the fibrous material is visible on, in, or just above below the outer surface of the compound. Such compounds can have unique, pleasant or even surprising visual properties, and at the same time they can have desirable mechanical properties, for example flexural strength and impact resistance.

[0219] The composite can be made, for example, by combining a resin and fibrous material 14 to provide a resin / fibrous material combination, and compressing the resin / fibrous material combination to provide the composite with the outer surface. Generally, the resin, fibrous material, and conditions for forming the composite are chosen such that the fibrous material is visible on, above, or just below the external surface, rather than being deeply buried below the surface where it is not. it would be visible. For example, for a translucent or opaque material, the fibrous material is visible under the outer surface of the composite when the fibrous material is below the outer surface, for example, at a distance less than 2.54 mm (0.100 inches), for example , less than 1.27 mm (0.050 inches) less than 0.635 mm (0.025 inches) less than 0.254 mm (0.010 inches), less than 0.127 mm (0.005 inches), less than 0.064 mm (0.0025 inches), or a distance of less than 0.0254 mm (0.001 inches).

[0220] The composites can be made using any plastic processing machinery, eg injection molding equipment and compression molding equipment or extrusion equipment.

[0221] The resin can be a thermoplastic or a thermoset. When the resin is a thermoplastic, it can be, for example, a polyolefin, such as a polyethylene (for example, a polyethylene copolymer), or a polypropylene (for example, a polypropylene copolymer); a polyester, such as polyethylene terephthalate (PET); a polyamide, such as nylon 6, 6/12, or 6/10; an elastomeric styrenic copolymer, such as a styrene-ethylene-butylene-styrene copolymer; a polyamide elastomer, such as a polyether-polyamide copolymer; a copolymer of ethylene and vinyl acetate, or mixtures of this resin.

[0222] To provide the unique composites, it is often desirable to use a relatively viscous resin, which can increase fiber visibility by preventing the fibrous material from slipping below the outer surface where it would be hidden.

[0223] In some applications, the resin is a polyolefin, eg a polypropylene, which has a melt flow index of less than 50 g / 10 minutes, eg less than 25 grams / 10 minutes, less than 20 grams / 10 minutes, less than 17 g / 10 minutes, less than 15 grams / 10 minutes, less than 10 g / 10 minutes, less than 7.5 grams / 10 minutes, less than 5 g / 10 minutes, less than 2 , 5 grams / 10 minutes, or even less than 1 g / 10 minutes. The low limit of melt flow will depend on the processing technique used to compound, for example injection molding or extrusion. For injection molding, it may be desirable for the melt flow index to be greater than 0.5 grams / 10 minutes. For compression molding and extrusion, it may be desirable for the melt flow rate to be 0.1 grams / 10 minutes. Melt flow index is measured using ASTM D1238 at 230 ° C and 2.16 kg, the disclosure of which is incorporated herein by reference in its entirety.

[0224] The fibrous material used can be, for example, a densified fibrous material manufactured by applying pressure to a fibrous material (optionally with a binder), for example by passing the fibrous material through a

ES 2 397 791 T3 slot defined between counter-rotating pressure rollers or passing fibrous material through a granule mill, as discussed above. The densified fibrous material can be, for example, in the form of granules or chips or other geometries having a variety of shapes. The density of the densified fibrous material can be, for example, greater than 0.11 g / cm³, for example, greater than 0.15 g / cm³, greater than 0.20 g / cm³, greater than 0.25 g / cm³, greater than 0.3 g / cm³, greater than 0.4 g / cm³, greater than 0.5 g / cm³, or even greater than 0.6 g / cm³. It is desirable to select a density such that the densified material is disintegrated by cutting and / or heat to release the fibrous material or agglomerated fibrous material. Generally, it is desirable that the densified fibrous material have a density of less than 0.9 g / cm³.

[0225] Fibers in fibrous materials can have a relatively large mean length / diameter ratio (eg, greater than 20/1). The mean length / diameter ratio of the second fibrous material 14 may be, for example greater than 10/1, for example greater than 25/1 or greater than 50/1. An average length of the second fibrous material 14 may be, for example, between about 0.5mm and 2.5mm, for example, between about 0.75mm and 1.0mm, and a mean width (i.e., diameter ) of the second fibrous material 14 may be, for example, between about 5mm and 50mm, for example, between about 10mm and 30mm.

[0226] To improve the speckled appearance of composites, it is often desirable for fibrous materials to have a relatively large percentage of fibers greater than 2.5mm in length. For example, at least 2.5 percent by weight of the fibrous material are fibers that are greater than 2.5 mm in length, for example, at least 5.0 percent by weight of the fibrous material are fibers that have a greater length. that 2.5 mm, at least 7.5 percent by weight of the fibrous material are fibers that have a length greater than 2.5 mm, or at least 10.0 percent by weight of the fibrous are fibers that have a greater length than 2.5 mm. In any of these situations, for example, in order not to adversely affect processing, less than 25 weight percent of the fibrous material is fibers that are greater than 2.5mm in length.

[0227] For a translucent or opaque resin material, the composite may have, for example, more than 20 percent by weight of fibrous material, for example, more than 30 percent, more than 40 percent, more than 50 percent, more than 55 percent, or even more than 60 percent by weight of fibrous material. For any of the applications in this paragraph, the composites generally have less than 70 weight percent fibrous material.

[0228] If desired, the fibrous material can be dyed, for example, to enhance the strength of the visual effect. The fibrous material can be dyed, for example by dyeing, before combining with the resin and to form the composites. In some applications, this tinting can, for example, increase the visibility of the fibrous material on the external surface, especially large clumps of the fibrous material.

[0229] In some applications, the resin may be tinted, for example, with a pigment or dye, to increase the contrast between the fibrous material (colored or natural) and the resin, for example, to increase the overall strength of the visual effect. Color concentrates are available from Clariant.

[0230] Any of these compounds having certain visual attributes can include any of the additives described herein, including fragrances.

[0231] The compound can be shaped in a variety of ways, such as those described above.

[0232] When composites are injection molded, it is often desirable to quickly "freeze" the molten resin, for example by shaping the composite against a liquid surface, so that the fibers do not have time to sink below the surface of the resin. where they would hide. With reference to Figs. 31A-31C, speckled composites can be prepared by forming a composite 600 by compressing a liquid resin against a mold 602 having a cooled surface 604, and then releasing the formed composite 600. In some applications, compression is performed against a surface of the mold having a temperature less than 100 ° C, for example, less than 75 ° C, less than 50 ° C, less than 25 ° C, or less than 15 ° C.

[0233] Still other compounds that have unique, pleasing or even surprising visual properties and desirable mechanical properties include a transparent resin and a fibrous material. In some applications, fibrous material can be seen within the composite. Generally, to make such composites a transparent resin and fibrous material are combined to provide a transparent resin / fibrous material combination and the transparent resin / fibrous material combination is compressed, for example, in an extruder or in a mold, to provide the compound.

[0234] The resin can be a thermoplastic or a thermoset. When the resin is a thermoplastic, it can be, for example, a clarified polyolefin, such as a clarified polypropylene (eg, a polypropylene copolymer); a polyester, such as polyethylene terephthalate (PET); an amorphous polyamide; a polycarbonate; a styrenic polymer, such as styrene-acrylonitrile-copolymer (SAN); a polyacrylate, such as polymethylmethacrylate (PMMA).

[0235] Clarifying agents are available from Milliken Chemical under the trademark MILLAD®, eg MILLAD® 3988. Clarified polyolefin colorants are also available from Milliken Chemical under the trademark CLEARTINT®.

ES 2 397 791 T3

[0236] To enhance the effect with a transparent resin, it is often desirable that the resin has a spectral transmission greater than 60 percent, for example, greater than 65 percent, greater than 70 percent, greater than 75 percent, greater than 80 percent, greater than 85 percent, or even greater than 90 percent. In addition, it is also often desirable for the resin to have a haze of less than 40 percent, for example, less than 35 percent, less than 30 percent, less than 25 percent, less than 20 percent, less than 15 percent. percent, or even less than 10 percent. Both spectral transmission and haze are measured using ASTM D1003-92, which is incorporated herein in its entirety by reference.

[0237] To enhance the effect with a transparent resin, it is desirable that the composite has a relatively low content of fibrous material, for example, less than 20 percent by weight of fibrous material, less than 17.5 percent, less than 15 percent, less than 12.5 percent, less than 10 percent, less than 7.5 percent, less than 5 percent, less than 2.5 percent, or even less than 1 percent by weight of the fibrous material. A relatively low fiber content allows light to pass through the composite so that masses of fibrous material within the composite can be seen.

[0238] Referring to Fig. 32, a resin / fibrous material composite may have an inner portion 610 that includes a first resin that has substantially no fibrous material and an outer portion 612 that includes a second resin that surrounds the portion. internal and includes substantially all fibrous material. Said compound can be made, for example, by co-molding or coextrusion. Any of the fibrous materials or additives described above can be used in the preparation of said compound. Said compounds can be formed in any of the ways described above. The first and second materials can be the same or different, and can be, for example, any of the resins described above.

[0239] Referring to Fig. 33, a transparent resin / fibrous material composite may have an inner portion 620 having a first resin and substantially all of the fibrous material and an outer portion 622 surrounding the inner portion having a second resin. and is substantially free of fibrous material. Any of the fibrous materials or additives mentioned above can be used in the preparation of said compound. Said compounds can be formed in any of the ways described above. The first and second materials can be the same or different, and can be, for example, any of the resins described above.