EP2572019A2 - Produit polymère extrudé et son procédé de fabrication - Google Patents

Produit polymère extrudé et son procédé de fabrication

Info

Publication number
EP2572019A2
EP2572019A2 EP11721298A EP11721298A EP2572019A2 EP 2572019 A2 EP2572019 A2 EP 2572019A2 EP 11721298 A EP11721298 A EP 11721298A EP 11721298 A EP11721298 A EP 11721298A EP 2572019 A2 EP2572019 A2 EP 2572019A2
Authority
EP
European Patent Office
Prior art keywords
polymer product
extruded polymer
rice hulls
cellulose
cellulose material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11721298A
Other languages
German (de)
English (en)
Inventor
Thomas Burkhart
Carsten Günter HELDMANN
Volker JÖRRES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fiberweb Holdings Ltd
Original Assignee
Fiberweb Corovin GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fiberweb Corovin GmbH filed Critical Fiberweb Corovin GmbH
Priority to EP11721298A priority Critical patent/EP2572019A2/fr
Publication of EP2572019A2 publication Critical patent/EP2572019A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/286—Raw material dosing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2886—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules of fibrous, filamentary or filling materials, e.g. thin fibrous reinforcements or fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/06—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers

Definitions

  • the invention relates to a product using a polymer material and a percentage of cellulose material, as well as a method and a device for manufacturing this product.
  • cellulose materials have been known for many years. Frequently used cellulose materials include wood dust or wood chips. Also known is the manufacturing of textile fabrics, which are formed from spunbond, melt- blown nonwovens or needle punched nonwovens. In addition, laminates of combinations of one or more layers of a nonwoven and a film are known.
  • thermoplastic polymer The application of film layers of a thermoplastic polymer on textile fabrics is also known.
  • multi-layer fabrics produced using thermobonding are described in WO 95/1 1803.
  • the object of the present invention consists of making available a polymer product using a polymer material and a cellulose material, which can be manufactured with reasonable financial expense.
  • the extruded polymer product has the advantage that relatively thin-walled polymer prod- ucts or polymer products with very small diameters can be manufactured, which have a wood-like character and can be manufactured on the usual plastic processing systems.
  • An extruded polymer product comprising at least one polyolefin and wherein cellulose material obtained from rice hulls is embedded in the polymer material is suggested.
  • the cellulose material is embedded as a filler material in the polymer material, which acts as a matrix component in the composite that occurs.
  • the polymer material has at least one polyolefin, preferably a polyethylene or a polypropylene.
  • the extruded polymer product is formed as a film.
  • This film can be designed with one or more layers and be created by means of an extrusion process.
  • the extruded polymer product is a spun fiber.
  • Nonwovens that contain these types of fibers can be produced in various ways. Ad- vantageously, the nonwoven is produced according to a spun bond method. A method of this type is described, for example in DE 10322460 and DE 10240191. However, in addition, embodiments are possible for this nonwoven, in which, e.g., a melt-blown process has been used for manufacturing the nonwoven, as is described in DE 19923344.
  • the polymer product can have as matrix-forming components, in addition to a polyolefin or its copolymers, other film-forming or spinnable plastics, for example polyam- ides, polyesters, polyurethanes, acrylate-based polymers and similar polymers.
  • other additives in the form of processing aids, other fillers, especially of an inorganic nature, like, e.g., calcium carbonate, dyes, pigments or functional additives, for example antioxidants, UV stabilizers, flame inhibitors or antistatics are provided.
  • the polymer products in the following can have a surface treatment, which is carried out during the manufacturing process for the polymer product or can be carried out in a subsequent process step. For example, they can be provided with a hydrophilic coating, which is preferably sprayed on or applied to the polymer product in an immersion process.
  • a polyethylene with an MFI between 15 and 35 g/10 min, and preferably between 15 and 20 g/10 min. according to ISO 1 133 and a density of 0.935 to 0.965 g/cm 3 according to ASTM D-792 can be used.
  • an LLDPE with a density between 0.85 and 0.90 g/cm 3 according to ASTM D-762 is possible.
  • a polymer mixture consisting of polyethylene homopolymers and/or polyethylene copolymers can be used.
  • a polymer mixture of a polyethylene manufactured by the Dow company under the manufacturer designation "ASPUN 6834" can be used as polymer matrix.
  • This material is suitable for purchase by the manufacturer for the manufacturing of nonwoven fibers and/or polymer fibers.
  • Another polymer that can be used as matrix is the polyethylene sold by the Dow company under the manufacturer designation "ASPUN 6834A.” This has a density of 0.955 g/cm 3 according to ASTM D.792, a MFI of 30 according to ASTM D-1238 and a DSC melting point of 131 °C.
  • cellulose material is understood to mean organic filler or reinforcement materials, which in addition to other constituents, e.g., lignin, also have a portion of cellulose or hemi-cellulose.
  • the cellulose material is obtained from a renewable plant material.
  • Polymer products in the sense of this invention are not restricted to cellulose materials of rice hulls.
  • rice hulls exhibit about 50 weight-% cellulose and hemi- cellulose and 26 weight-% lignin, and thus belong to the so-called lignocellulose- containing materials and with respect to the composition are related to other natural fibers, e.g., wood fibers.
  • the cellulose material can also be obtained from wood in the form of sawing or planing chips, peat, kenaf, flax, linen, hulls from seed shells, especially grain hulls, grass seed, bran, compost of rinds, coconut fibers or substances with low or no fiber content, especially rinds or nut shells or mixtures of natural materials containing fiber, with low fiber or free of fiber.
  • the average raw density of the cellulose fibers, especially the percentage of cell wall substance and the degree of fiber inclusion is between 0.3 to 1.3 g/cm 3 , preferably between 0.4 to 0.8 g/cm 3 and more preferably between 0.4 to 0.6 g/ g/cm 3 .
  • the apparent density of the cellulose fibers lies between 90 and 500 kg/m 3 , preferably between 130 to 330 kg/m 3 , measured according to DIN EN 12580.
  • filler or reinforcement materials for example rice hulls or other materials containing cellulose in a suitable way in a polymer and process it to a polymer product
  • an elastic component is created in a visco-elastic component.
  • microcracks and cracks develop at the boundary surface of the multi-phase system, which can lead to failure of the system.
  • One embodiment of the invention provides that the filler or reinforcement materials for example the cellulose material such as rice hulls are crushed and coated. Since the materials containing cellulose provided in the scope of this invention have a ductile behavior, impact and centrifugal mills are required for their crushing process. Versions of these crushing devices, which have milling elements resting on a rotor that rotate at high speed like impact bars, hammers, arms, pins or tabs, which crush the material in flight by impact and bouncing, but not by cutting or by pressure against a base, are known, for example, from a book by Vauck and Mijller "Basic operations of chemical process technology" 10th Edition (1994) Deutscher Verlag fur die Grundstoffindustrie Stuttgart Stuttgart pp. 324-328.
  • a cooling compound can be used during the crushing process.
  • One embodiment of the invention provides for a method in which the rice hulls are cryo- genically crushed to a specified average size before they are mixed with the polymer material.
  • the rice hulls are crushed in a cryogenic crushing system in which the crushing mill itself is chilled.
  • a coolant will then especially be preferred if a material containing cellulose used in the sense of this invention requires increased crushing force in order to be brought to the necessary milled fineness or in order to be able to adequately fibrillate the cellulose material.
  • the named crushing options supply very different particle shapes, particle sizes, particle size distributions and a different morpho- logical fine structure. These factors have an effect on the pore percentage, the pore size and their distribution, as well as the absorption and swelling behavior of the cellulose material.
  • the milled material obtained can have fibers with a length of up to 200 ⁇ and a diameter up to 20 ⁇ .
  • a uniformity of the material containing cellulose is necessary in order to obtain uniform product qualities.
  • the use of rice hulls is planned, whereby the rice hulls are crushed and added to the polymer material having a polyolefin to form a mixture and extruding a polymer product from the mixture.
  • the rice hulls are crushed to a size that can be specified.
  • a preferred further development of the invention provides an extruded polymer product, wherein the cellulose material,for instance the rice hulls have a fiftieth percentile (D 50 ) from 1 to 2 ⁇ .
  • the 90th percentile (D 90 ) of the cellulose material is preferably less than 10 ⁇ .
  • the diameter of the forming tool for example a spinning nozzle, should be about three times the diameter of the cellulose fiber.
  • the thickness of the slot of a wide slit dye is three times the diameter of the cellulose fiber.
  • cellulose materials contain a compensating moisture of about 8% to 12%.
  • a compensating moisture of about 8% to 12%.
  • a further development of the invention provides a method in which the rice hulls are dried after they have been crushed.
  • the effort required for the drying process for the cellulose materials after a crushing process can be very different, depending on the quality of the cell structure and the surface geometry.
  • moisture contents of the cellulose materials after the drying process that lie between 3 weight% to 6 weight-% have proved to be advantageous.
  • a surface treatment of the cellulose materials is provided, which makes it possible to achieve an adequate bonding strength between a non-polar matrix that is present in the case of the polyolefins and a natural fiber, which tends to high water absorption.
  • this process it is necessary to disperse the cellulose particles, preferably in the polymer matrix in order to prevent agglomeration of the particles.
  • a further development of the invention provides an extruded polymer product wherein the cellulose material is treated with an additional material and wherein the additional material is embedded in the polymer material.
  • Variations of the adhesion increase of the composite partners polymer matrix and cellulose material consist, for example, in equipping the cellulose material with silanes or substances with hydrophobizing effects or coating with a functionalized polymer material, for example a functionalized polyolefin material or a functionalizing of the polymer matrix cou- pled with a silanized cellulose material.
  • silanes can involve radical reactions with the polymer matrix. Silanes can contribute to an improvement to an improvement of the adhesion between the cellulose fibers and the polymer matrix, but also to better dispersion of the fibers in the matrix.
  • stearic acids and salts thereof can be used.
  • substances with hydrophobizing action are provided to treat the cellulose fibers.
  • fatty acid derivatives are used as coating materials for the crushed rice hulls.
  • the addition of the materials with hydrophobizing action for treating the cellulose fibers can be between 0.05 and 10 weight-% related to the portion of the cellulose fibers.
  • Usual additives, which are added to the polymer as compatibility promoter can lie between 0.05 - 5 weight-% related to the polymer.
  • the addition of the compatibility promoter preferably lies between 0.05 - 5 weight-% related to the portion of cellulose fibers.
  • the extruded polymer product can have a cellu- lose material wherein the percentage of the cellulose material of the total weight of the extruded polymer product is larger than or equal to 2 weight-% or 20 weight-% and smaller than or equal to 90 weight-% or 45 weight-%.
  • the percentage of the cellulose material is between 20 to 90 weight-%, related to the total weight of the polymer product.
  • the polymer product has a percentage of the second portion of the total weight of the polymer product between 2 weight-% and 45 weight-%.
  • the cellulose material is added to the extruded polymer product as a master batch from polymer material and the cellulose material.
  • the percentage of the cellulose material of the master batch can be between 4 weight-% to 90 weight-%, related to the total weight of the master batch.
  • filler contents can be ad- justed as desired.
  • the cellulose material can have different arrangements in this product by the selection of the process parameters during manufacturing of the polymer product.
  • the extruded polymer product is characterized in that a distribution of the cellulose materials over a cross section of the extruded polymer products is not uniform, whereby a first area that is adjustable by the manufacturing of the extruded polymer product has a higher percentage of cellulose material than a second area.
  • a polymer product designed as a spun fiber can be present as a fiber-filled one- or multiple-component fiber.
  • the components of a multi- component fiber can be present in a mixture or as separate components.
  • bi-component or multi-component fibers with different structures and distributions of the components over the fiber cross section can be formed.
  • the fibers formed in this way can be present as conjugated fibers.
  • the extruded polymer product is a spun fiber with a core-sheath structure, whereby in the core a higher percentage of cellulose material is arranged than in the sheath.
  • the extruded polymer product is designed as a spinnable material.
  • the extruded polymer product comprises a spun fiber manufactured from a single polymer material, wherein the concentration of the cellulose material, preferably of the crushed rice hull material, is larger at its surface than inside the fiber.
  • spun fibers are formed with a content of cellulose fibers between 10 weight-% and 30 weight-% related to the total weight of the spun fibers.
  • the fibers were manufactured under the following spinning conditions:
  • the formed spun fibers or polymer fibers with the use of a polypropylene of the type Moplen HP462R and cellulose fiber content between 10 - 20 weight-% exhibit the following properties:
  • the extruded polymer product can be formed as a coextruded film, comprising coex- trusion layers having different weight percentages of cellulose material. Preferably weight parts between 20 weight-% and 45 weight-% are provided in these film.
  • the drying of the cellulose materials can occur in one or several steps.
  • a preferred version of the invention provides that a system with an extruder is used, whereby the extruder has a degassing system. This has the advantage that a complicated upstream drying step for the cellulose material that is present with an enlarged surface due to the milling process is not necessary. On the other hand, the liquid particles that still adhere in spite of a drying process can be eliminated during the processing method in order to obtain a polymer product free of bubbles.
  • a system for manufacturing a polymer product has a drying unit for the cellulose material that is connected to the extrusion device of the system, whereby the drying unit makes possible the use of waste heat from the drying of the cellulose material.
  • the drying unit makes possible the use of waste heat from the drying of the cellulose material.
  • hot air resulting from the processing step can be used.
  • a preferred version of the invention provides a system, wherein an extrusion device and a drying unit for drying the crushed rice hulls are connected by heat transport means arranged to transport waste heat of the extrusion device to the drying unit and wherein the drying unit is arranged to dry the crushed rice hulls using the waste heat.
  • the incorporation of the cellulose material into the polymer matrix can occur in different ways.
  • the crushed and possibly fractionated cellulose materials can be processed together with one or more polymers, which can also be present in a finely divided form, in a mixer, for example, in a heating-cooling mixer combination to an agglomerate.
  • other additives e.g., processing aids, can be measured in.
  • These agglomerates are formed, for example, in a subsequent extrusion process to a polymer product in the form of a fiber or film.
  • the incorporation of the cellulose material into the polymer material can, for example, also take place in a stream of gas, in which mixing and possibly milling of cellulose particles occurs, as well as a batch coating of the cellulose particles with polymer material in the gas stream.
  • a polymer material can result by a direct pro- cessing of the polymer and cellulose fiber components on a double screw extruder with screw shafts running in the same direction or opposite directions.
  • a preferred version of the invention provides that a system with a double screw extruder is used, whereby the double screw extruder has a degassing system.
  • Preferable here is a system for manufacturing an extruded polymer product comprising a polymer material comprising at least a polyolefin and a cellulose material obtained from rice hulls, whereby a double screw extruder is used to mix polymer material and dried crush rice hulls.
  • the double screw extruder comprises mixing zones for mixing the poly- mer material and the dried crushed rice hulls.
  • a polymer mixture can be measured into the extruder and the cellulose material can be supplied by way of a separate hopper, which opens into the supply line to the extruder.
  • a preferred embodiment of the method provides that a master batch to be extruded is prepared.
  • a master batch is understood to mean a material produced in granulate form, which has a polymer component and a portion of cellulose material. If necessary, other additive can also be used in the form of processing aids, dyes, pigments or functional additives, for example, flame retardants or antistatics.
  • This master batch can preferably be equipped with a very high content of cellulose materials and manufactured on a double screw extruder with screw shafts running in the same direction, a so-called compounder. This master batch can then be used directly for manufacturing a polymer product or portions can be added to a polymer in order to be able to process it to a polymer product.
  • the invention provides a master batch, which is preferably used for manufacturing spun fibers, but also films, whereby in the master batch a polyolefin is provided that contains rice hulls that have been crushed to a maximum size that can be specified.
  • the manufactured polymer product can be designed alone or as a composite with other nonwovens or materials, for example, with another polymer product in the form of a film or several films. In particular it can be connected with the other material to form a layered material.
  • the resulting flat monolayer or multilayer fabric can also be embossed, bonded, laminated and/or mechanically treated, especially connected with another material. For example, this can occur physically, chemically and/or with form fitting.
  • thermal and/or ultrasonic connection possibilities can be used in order to connect the individual layers to each other.
  • embossing surfaces can be provided with a percentage of 10%-50%, related to the entire surface of the flat fabric.
  • Manufacturing of a laminate of several layers of a nonwoven from spunbond or melt-blown fibers or combinations thereof can be manufactured according to the tech- nical teaching disclosed, for example, in US5178931 , US3704198, US3849241 and
  • an adhesive for example a spray adhesive or a so-called hot-melt adhesive, latex-based adhesive or other adhesive can be used.
  • a laminate can also be formed in which at least one film is combined with at least one nonwoven.
  • calendering step For laminate formation, different types of processing are possible. For example, individual layers can be manufactured as nonwoven or film in separate processing steps, which are joined in another processing step, for example a calendering step, to form a laminate, whereby different calender roller arrangements can be provided that cause a thermal compacting of the laminate.
  • a calendering method such as this is described, for example, in US 3,855,046.
  • smooth or profiled calender rollers are used, which can be combined with each other according to the planned usage purpose and required characteristics profile for the laminate.
  • embossing rollers discrete embossed bonds can be formed in the laminate. Methods for manufacturing separate layers and lam- inate produced from them are described, for example, in DE 431 1867.
  • a nonwoven is formed and this nonwoven is coated in-line with a film.
  • a film can be extruded first, which, for example, is placed on a holding line, whereby a created nonwoven is deposited in-line on this film.
  • the composite formation can also occur here using a calendering arrangement.
  • other types of composite formation are also possible, for example by needling or water stream compacting. Special variations for the formation of this flat fabric can be seen, for example, in DE10360845A1 , US 4,021 ,284 and US 4,024,612.
  • the manufactured polymer product in the form of a nonwoven fabric is characterized, for example, by the following characteristic values:
  • - Filament surface is hydrophilized and has values for penetration times, measured according to EDANA ERT 150, of less than 5 s.
  • a polymer product created in the form of a film can have densities between 0.60 to 0.9 g/cm 3 .
  • the polymer product manufactured from it for example, in the form of a film, has densities from 0.9 to 1 .2 g/cm 3 .
  • these can be used in all dif- ferent types of application areas, for example, for:

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

L'invention porte sur un produit polymère extrudé comprenant une matière polymère comprenant au moins une polyoléfine, une matière cellulosique obtenue à partir de balles de riz étant incorporée dans la matière polymère. L'invention porte aussi sur un procédé par lequel le polymère extrudé pourrait être fabriqué.
EP11721298A 2010-05-21 2011-05-20 Produit polymère extrudé et son procédé de fabrication Withdrawn EP2572019A2 (fr)

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EP11721298A EP2572019A2 (fr) 2010-05-21 2011-05-20 Produit polymère extrudé et son procédé de fabrication
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CN107987545A (zh) * 2017-11-24 2018-05-04 壳氏（黑龙江）新材料科技有限公司 一种稻壳粉母料及其制备方法

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