EP1937777A4 - Formules pulvérulentes thermoplastiques de polyuréthane et applications - Google Patents

Formules pulvérulentes thermoplastiques de polyuréthane et applications

Info

Publication number
EP1937777A4
EP1937777A4 EP06849147A EP06849147A EP1937777A4 EP 1937777 A4 EP1937777 A4 EP 1937777A4 EP 06849147 A EP06849147 A EP 06849147A EP 06849147 A EP06849147 A EP 06849147A EP 1937777 A4 EP1937777 A4 EP 1937777A4
Authority
EP
European Patent Office
Prior art keywords
powder composition
composition
thermoplastic
article
thermoplastic polyurethane
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Withdrawn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
EP06849147A
Other languages
German (de)
English (en)
Other versions
EP1937777A2 (fr
Inventor
Stephen Horton
Brent Cassata
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.)
Avient Corp
Original Assignee
Polyone Corp
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 Polyone Corp filed Critical Polyone Corp
Publication of EP1937777A2 publication Critical patent/EP1937777A2/fr
Publication of EP1937777A4 publication Critical patent/EP1937777A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2140/00—Compositions for moulding powders

Definitions

  • the present invention relates to thermoplastic polyurethane powder compositions and uses thereof.
  • thermoplastic plastics thermoplastic elastomers
  • thermoset plastics thermoset plastics
  • thermoset elastomers thermoset plastics
  • PVC polyvinyl chloride
  • one application where ductile failure modes are preferred involves manufacture of articles for passenger compartments of vehicles such as automobiles, airplanes, trucks, farm equipment, construction equipment, et cetera.
  • Polymeric materials are used to manufacture many parts and subassemblies within such passenger compartments.
  • instrument panels, door panels, armrests, headrests, center consoles, and air bags, et cetera can be made from one or more polymeric materials.
  • a subcomponent of such articles often takes the form of a "polymeric skin.”
  • Polymeric skins can provide the outer surface of larger articles, being filled with molded foam or other cushiony materials to provide body and a sculpted appearance to the overall article.
  • padded or cushioned articles within passenger compartments such as instrument panels, door panels, and the like, have been made by providing a powdered PVC slush-molded skin. The skin is held in place over a substrate and then back-filled with a foam (e.g., urethane foam) material in an injection process in which the edges of the skin are sealed in order to provide a finished product.
  • foam e.g., urethane foam
  • the finished product includes the skin with the padded foam backing bonded to the substrate, which may include the edges of a door panel, the edges of an instrument panel, or the like.
  • Reference to the use of polymeric skins in this manner can be found in, e.g., U.S. Patent Publication No. US 2002/0125734 Al.
  • materials exhibiting brittle failure modes at some or all temperatures of intended use are used in making polymeric skins for such applications, however, they pose a risk for the passenger in the event of impact, or other event leading to an article's failure. This risk is heightened by using brittle materials due to the tendency of brittle materials to shatter upon failure and fragment into many tiny pieces, oftentimes having jagged or sharp edges.
  • HVIF high velocity impact fusion
  • HVIF has been used to impart polymeric coatings onto articles in order to protect underlying surfaces or materials coming into contact with the underlying surface from damage (e.g., contamination).
  • the polymeric coating provides a relatively clean, non-toxic surface and is made from a relatively inert material.
  • polyethylene is coated on the inside of steel railroad cars using HVIF in order to prevent foodstuff transported by the railroad car from becoming contaminated.
  • the invention provides a thermoplastic powder composition suitable for formation into an article using high velocity impact fusion.
  • Such powder compositions have a uni-modal particle size distribution and comprise at least one thermoplastic polyurethane having a melt flow index of at least about 8 g/10 min when tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg; at least one internal lubricant in an amount of up to about 5 weight % based on total weight of the composition; and, optionally, at least one flow agent or other components (e.g., heat stabilizers, light stabilizers, pigments, antioxidants, plasticizers, fillers, and mattening agents).
  • at least one flow agent or other components e.g., heat stabilizers, light stabilizers, pigments, antioxidants, plasticizers, fillers, and mattening agents.
  • thermoplastic powder compositions are also facilitated by the present invention.
  • the powder composition can have a uni-modal particle size distribution or a bi-modal particle size distribution.
  • the invention provides a thermoplastic powder composition suitable for formation into an article using slush molding.
  • Such powder compositions have a bi-modal particle size distribution and comprise at least one thermoplastic polyurethane having a melt flow index of at least about 8 g/10 min when tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg; at least one internal lubricant in an amount of up to about 5 weight % based on total weight of the composition; and, optionally, at least one flow agent or other components (e.g., heat stabilizers, light stabilizers, pigments, antioxidants, plasticizers, fillers, and mattening agents).
  • at least one thermoplastic polyurethane having a melt flow index of at least about 8 g/10 min when tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg
  • at least one internal lubricant in an amount of up to about 5 weight % based on total weight of the composition
  • at least one flow agent or other components e.g., heat stabilizers, light stabilizers, pigments, antioxidants, plasticizers, fill
  • the thermoplastic polyurethane comprises aliphatic thermoplastic polyurethane or aromatic thermoplastic polyurethane.
  • the thermoplastic polyurethane comprises polyether-based thermoplastic polyurethane (e.g., an aromatic polyether- based thermoplastic polyurethane) or polyester-based thermoplastic polyurethane (e.g., an aliphatic polyester-based thermoplastic polyurethane).
  • thermoplastic powder composition comprises about 0.01 to about 1.0 weight % of an internal lubricant such as, for example, mono- and di-stearyl acid phosphate.
  • an internal lubricant such as, for example, mono- and di-stearyl acid phosphate.
  • the composition is essentially free of components prone to blooming migration in articles prepared therefrom.
  • the powder composition can be a powder composition blend.
  • Powder composition blends of the invention comprise at least one thermoplastic polyurethane and at least one other polymer (e.g., polyvinyl chloride).
  • the other polymer comprises greater than about 10 weight % of the total composition.
  • the other polymer can be polyvinyl chloride in an amount up to about 90 weight % of the total composition.
  • the composition comprises about 5 to about 50 weight %, about 10 to about 30 weight %, or still further about 15 to about 25 weight % of the thermoplastic polyurethane based on total weight of the composition.
  • Other components can also be present, including for example melt- processible rubber.
  • thermoplastic powder compositions of the invention A variety of articles can be prepared from thermoplastic powder compositions of the invention.
  • polymeric skin subcomponents of further articles for passenger compartments of a vehicle can be formed from the thermoplastic powder compositions.
  • Such further articles include instrument panels, door panels, armrests, headrests, center consoles, and air bags for a passenger compartment of a vehicle.
  • Compositions of the invention advantageously provide alternatives to and advantages as compared to conventional materials used for such purposes.
  • Processes of the invention include those for preparing the thermoplastic powder compositions. Such processes include steps of providing a thermoplastic polyurethane, mixing the thermoplastic polyurethane with one or more optional components, and transforming the thermoplastic polyurethane and optional components into a powder having a uni-modal or otherwise predetermined particle size distribution. In an exemplary embodiment, the composition is transformed into a powder using cryogenic grinding, screening, and recycling steps. [00021] Processes for preparing articles from the thermoplastic powder composition include those using a high velocity impact fusion, fluidized bed powder coating, electrostatic spray, thermal spray, slush molding, or rotational molding technique. According to exemplary embodiments of the invention, an external mold release agent is not necessary or utilized to form such articles.
  • FIGURE 1 is a uni-modal particle size distribution associated with powder compositions useful for formation of articles according to a high velocity impact fusion technique according to the invention.
  • FIGURE 2 is a bi-modal particle size distribution associated with powder compositions useful for formation of articles according to a slush molding technique according to the invention.
  • FIGURE 3 is a schematic flow diagram of an exemplary process for formation of powder compositions of the invention.
  • Thermoplastic polyurethane (TPU) powder compositions of the invention comprise at least one base TPU and one or more optional components, selected according to the intended use of the composition.
  • TPU is a desirable thermoplastic elastomer as it exhibits high tensile and tear strength, high flexibility at low temperatures, and extremely good abrasion and scratch resistance. TPU is also relatively stable against oil, fats and many solvents, as well as ultraviolet radiation. Because of these desirable features, TPU can be beneficially used for a number of end use applications, such as those in automotive and the footwear industries.
  • polyurethane as used herein includes polymers containing urethane (also known as carbamate) linkages, urea linkages, or combinations thereof (i.e., in the case of poly(urethane-urea)s).
  • urethane also known as carbamate
  • urea linkages or combinations thereof (i.e., in the case of poly(urethane-urea)s).
  • thermoplastic polyurethanes of the invention contain at least urethane linkages and, optionally, urea linkages.
  • TPU chemistries are suitable for use as the base TPU in the invention.
  • a number of aliphatic and aromatic chemistries can be used.
  • One or more TPU chemistries can be used to form the base TPU for compositions of the invention.
  • aromatic refers to TPUs derived from mononuclear aromatic hydrocarbon groups or polynuclear aromatic hydrocarbon groups.
  • the term includes those TPUs derived from arylene groups.
  • arylene group means a divalent aromatic group.
  • aliphatic refers to TPUs derived from saturated or unsaturated, linear, branched, or cyclic hydrocarbon groups. This term is used to encompass those TPUs derived from alkylene (e.g., oxyalkylene), aralkylene, and cycloalkylene (e.g., oxycyclo alkylene) groups, for example.
  • alkylene group means a saturated, linear or branched, divalent hydrocarbon group.
  • alkylene groups are oxyalkylene groups.
  • oxyalkylene group means a saturated, linear or branched, divalent hydrocarbon group with a terminal oxygen atom.
  • aralkylene group means a saturated, linear or branched, divalent hydrocarbon group containing at least one aromatic group.
  • cycloalkylene group means a saturated, linear or branched, divalent hydrocarbon group containing at least one cyclic group.
  • oxycycloalkylene group means a saturated, linear or branched, divalent hydrocarbon group containing at least one cyclic group and a terminal oxygen atom.
  • a TPU is obtained by reacting a difunctional isocyanate composition with at least one difunctional polyhydroxy compound and optionally a chain extender in such amounts that the isocyanate index is between about 90 and about 110, preferably between about 95 and about 105, and most preferably between about 98 and about 102.
  • difunctional as used herein means that the average functionality of the isocyanate composition and the polyhydroxy compound is about 2
  • isocyanate index is the ratio of isocyanate groups over isocyanate-reactive hydrogen atoms present in a composition, given as a percentage.
  • the isocyanate index expresses the percentage of isocyanate actually used in a composition with respect to the amount of isocyanate theoretically required for reacting with the amount of isocyanate-reactive hydrogen used in a composition. It should be observed that the isocyanate index as used herein is considered from the point of view of the actual polymer forming process involving the isocyanate ingredient and the isocyanate-reactive ingredients.
  • the difunctional polyhydroxy compound has a weight average molecular weight of between about 500 and about 20,000, and is selected from diols such as polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes, polybutadienes and, preferably, polyesters and polyethers, or mixtures thereof.
  • diols such as polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes, polybutadienes and, preferably, polyesters and polyethers, or mixtures thereof.
  • Other dihydroxy compounds such as hydroxyl-ended styrene block copolymers like known SBS, SIS, SEBS, or SIBS block copolymers may be used as well.
  • Suitable initiator compounds contain two active hydrogen atoms and include water; butanediol; ethylene glycol; propylene glycol; diethylene glycol; Methylene glycol; dipropylene glycol; 1,3-propane diol; neopentyl glycol; 1,4- butanediol; 1,5-pentanediol; 1,6-pentanediol; and the like. Mixtures of initiators and/or cyclic oxides may be used.
  • Especially useful polyether diols include polyoxypropylene diols and poly(oxyethylene-oxypropylene) diols obtained by the simultaneous or sequential addition of ethylene or propylene oxides to difunctional initiators.
  • polyether diols include polytetramethylene diols obtained by the polymerization of tetrahydrofuran. Also suitable are polyether diols containing low unsaturation levels (i.e. less than about 0.1 milliequivalents per gram diol).
  • modified diols often referred to as "polymer diols” include products obtained by the in-situ polymerization of one or more vinyl monomers, for example styrene and acrylonitrile, in polymeric diols, for example polyether diols, or by the in-situ reaction between a polyisocyanate and an amino- and/or hydroxyfunctional compound, such as triethanolamine, in a polymeric diol.
  • Polyoxyalkylene diols containing from about 5-50 weight % of dispersed polymer are useful as well. Particle sizes of the dispersed polymer of less than 50 microns are preferred.
  • Polyester diols that may be used include hydroxyl-terminated reaction products of dihydric alcohols such as ethylene glycol; propylene glycol; diethylene glycol; 1,4-butanediol; neopentyl glycol; 2-methylpropanediol;
  • dihydric alcohols and dicarboxylic acids or their ester-forming derivatives e.g., succinic, glutaric, and adipic acids or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, dimethyl terephthalate and mixtures thereof.
  • Polyesteramides may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
  • Polythioether diols that may be used include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols, or aminocarboxylic acids.
  • Polycarbonate diols that may be used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol, or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerizing cyclic acetals.
  • Suitable polyolefin diols include hydroxy-terminated butadiene homo- and co-polymers.
  • Suitable polysiloxane diols include polydimethylsiloxane diols.
  • Suitable difunctional chain extenders include aliphatic diols, such as ethylene glycol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol;
  • 2,3-butanediol 1,3-pentanediol; 1,2-hexanediol; 3-methylpentane-l,5-diol; diethylene glycol; dipropylene glycol; and tripropylene glycol, and aminoalcohols such as ethanolamine, N-methyldiethanolamine, and the like. Of these, 1,4-butanediol is preferred.
  • the TPU powder composition comprises an aromatic, polyether-based TPU.
  • the TPU powder composition comprises an aliphatic, polyester-based TPU.
  • the latter TPU chemistry is particularly desirable due to the ability to more precisely and accurately control melt flow properties (e.g., melt flow index (MFI)) thereof as compared to the former chemistry.
  • MFI melt flow index
  • TPU compositions are commercially available.
  • a TPU it is desirable for a TPU to have a MFI of at least about 8 g/10 min when tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg. In further embodiments, it is desirable for a TPU to have a MFI of at least about 10 g/10 min when tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg. In still further embodiments, it is desirable for a TPU to have a MFI of at least about 12 g/10 min when tested according to ASTM D 1238 at 19O 0 C and a weight of 2.16 kg.
  • TPUs having a MFI in the preferred range are available from BASF Corp. under the ELASTOLLAN trade designation.
  • TPUs having a lower MFI may also be used as the base TPU.
  • small amounts of water may be injected into an extruder containing the molten TPU. Addition of water in this way causes the molten TPU polymer backbone to undergo chain scission, which reduces molecular weight and increases the MFI of the TPU.
  • the prepared or supplied base TPU will be provided in a non-powdery form (e.g., as pellets or granules).
  • the base TPU and other optional components described below are transformed into a powder after mixing and prior to use. The powder formation process is also described further below.
  • compositions of the invention can be included in compositions of the invention to improve or obtain certain properties of the composition or components therein, such as the desired MFI of the base TPU. It is to be understood that, depending on the manufacturing method for the base TPU or commercial source thereof, one or more additional components may already be present in the base TPU. If other desired components are not present, however, they may be added to the base TPU when preparing compositions of the invention.
  • These components include, for example, internal and other lubricants, flow agents, heat stabilizers, light stabilizers, pigments (e.g., carbon black), antioxidants, plasticizers, fillers (e.g., talc and CaCO 3 ), and mattening agents (e.g., polyurea powders and various silicas).
  • lubricants for example, internal and other lubricants, flow agents, heat stabilizers, light stabilizers, pigments (e.g., carbon black), antioxidants, plasticizers, fillers (e.g., talc and CaCO 3 ), and mattening agents (e.g., polyurea powders and various silicas).
  • materials that reduce porosity of a molten film of the composition during formation of articles therefrom are beneficially added when the MFI of the composition does not alone sufficiently minimize entrapment of air between the molten film and surface on which it is being formed. If too much air becomes entrapped, porosity will be apparent on the outer surface of the article formed. In many applications, particularly those involving parts for consumer applications, little porosity can be tolerated before the article is rejected for aesthetic reasons.
  • plasticizers may be added for this purpose, it is desired to minimize their use in certain applications due to their tendency to migrate from the material's surface (e.g., often referred to as "blooming," a phenomenon that causes fogging of windshields when used in vehicle instrument panels) and negatively impact resultant physical properties of articles prepared therefrom.
  • compositions of the invention comprise up to about 5 weight % based on total weight of the composition of at least one internal lubricant.
  • a composition comprising about 0.01 to about 1.0 weight % mono- and di-stearyl acid phosphate (e.g., AX-71, available from Asahi Denka Kogyo K.K., Tokyo, Japan, under the ADK STAB trade designation) based on total weight of the composition was found useful according to the invention.
  • AX-71 is not marketed as an internal lubricant, it has been discovered that it is useful for this purpose.
  • the TPU comprises an aliphatic chemistry, generally less lubricant is needed to obtain the same results as when lubricant is used in conjunction with TPUs comprising aromatic chemistries.
  • At least one flow agent is incorporated into the composition in order to decrease porosity in resulting articles without the disadvantages associated with effecting lower porosity by way of increasing the TPU' s MFI alone.
  • a composition comprising precipitated amorphous silica (e.g., PS-200, available from Glassven C. A., a Venezuelan company, under the PIROSIL trade designation) can beneficially be used according to the invention.
  • compositions containing one or more of these optional components are capable of eliminating the blooming phenomenon referenced above with respect to plasticizers.
  • plasticizers and other components prone to such migration are excluded from or minimized in compositions of the invention.
  • Such other components include certain antioxidants, hindered amine light stabilizers, UV-stabilizers, and other compounds known to promote undesirable blooming.
  • compositions of the invention include powder composition blends comprising at least one base TPU and at least one other polymer. Such blends are provided in a powdered form to facilitate their use in a variety of article-forming processes providing substantial benefits as discussed throughout. For example, one preferred use involves formation of an article therefrom using the unique HVIF technique.
  • Optional components described above can also be included within powder composition blends of the invention to obtain desired properties and facilitate efficient processing of the compositions as desired.
  • the ultimate blend can also be referred to as an "alloy" when a single phase is obtained.
  • powder composition blends of the invention include at least about 10 weight % based on total weight of the composition of at least one polymer other than the TPU. It has been found, for example, that a powder composition blend comprising about 10 weight % TPU and up to about 90 weight % polyvinyl chloride (PVC) based on total weight of the composition is useful in providing materials with improved properties.
  • PVC polyvinyl chloride
  • the use of PVC in powder composition blends of the invention provides a relatively cost-effective material with improved properties over PVC alone.
  • the base TPU component is present in an amount of about 5 to about 50 weight % based on total weight of the composition. In progressively preferred embodiments, the base TPU component is present in amounts of about 10 to about 30 weight % or about 15 to about 25 weight % based on total weight of the composition.
  • the remaining components include PVC and other optional components.
  • melt-processible rubber available from Advanced Polymer Alloys division of Ferro Corp. (Wilmington, DE) under the ALCRYN trade designation.
  • melt-processible rubbers can be present in the compositions in an amount of about 5 to about 50 weight % based on total weight of the composition.
  • melt-processible rubber can be present in the compositions in an amount of about 10 to about 40 weight % based on total weight of the composition.
  • melt-processible rubber can be present in the compositions in an amount of about 15 to about 30 weight % based on total weight of the composition.
  • Powder composition blends of the invention offer such improved materials. Compositions of the invention are capable of successfully passing rigorous tests imposed by vehicle manufacturers with respect to air bag materials. [00068] Formation Of Powder [00069] Powder compositions of the invention are prepared such that they have an average particle size and particle size distribution according to the desired use and processing method for articles prepared therefrom. A variety of particle sizes may be prepared. In one exemplary embodiment, powder compositions of the invention have an average particle size of about 80 ⁇ m to about 300 ⁇ m. In a further embodiment, the average particle size is at least about lOO ⁇ m, or even at least about 200 ⁇ m in still further embodiments.
  • the particle size distribution is preferably uni-modal, such as that distribution illustrated in FIGURE 1.
  • 50% of the particles screened had a size of about 128 ⁇ m or less and 95% of the particles screened had a size of about 253 ⁇ m or less.
  • the particle size distribution is preferably bi-modal, such as that distribution illustrated in FIGURE 2.
  • 50% of the particles screened had a size of about 230 ⁇ m or less and 95% of the particles screened had a size of about 423 ⁇ m or less.
  • compositions are first mixed in proportional amounts selected according to the desired overall formulation and intended use. It is during the mixing of the base TPU that water may be optionally injected into the mixture in a minor amount sufficient (e.g., usually a trace amount of water will suffice for this purpose) to increase the MFI of the TPU when desired.
  • water may be optionally injected into the mixture in a minor amount sufficient (e.g., usually a trace amount of water will suffice for this purpose) to increase the MFI of the TPU when desired.
  • water may be optionally injected into the mixture in a minor amount sufficient (e.g., usually a trace amount of water will suffice for this purpose) to increase the MFI of the TPU when desired.
  • a minor amount sufficient (e.g., usually a trace amount of water will suffice for this purpose) to increase the MFI of the TPU when desired.
  • the composition can be formed by multiple mixing and powder-forming steps.
  • mixing may occur in the presence of heat and/or pressure.
  • the components may be mixed in an extruder, exiting the extruder via a pelletizer. Once processed in this manner, the pellets so formed can be transformed into a powder of the desired particle size and distribution.
  • any suitable powder- forming technique can be used.
  • a powder can be prepared from the mixed composition using mechanical techniques such as cryogenic grinding or hammer milling.
  • FIGURE 3 illustrates an exemplary embodiment of a process for preparation of powder compositions of the invention. Details and variations with respect to the steps and equipment illustrated therein are within the knowledge of those skilled in the art.
  • a high intensity mixer 10 e.g. , a mixer for a high intensity mixer.
  • a high intensity mixer 10 e.g. , a mixer for a high intensity mixer.
  • Henschel-type variable speed mixer such as those available from the Japanese company, Mitsui Mike operating at a temperature of about 12O 0 C to about 14O 0 C is provided for the initial mixing steps.
  • the high intensity mixer 10 is loaded with a mixture 12 of base TPU and other components desired for the particular application (e.g., lubricants, flow agents, stabilizers, pigments, and the like) desired.
  • further other components 14 desired for the particular application are then added to high intensity mixer 10 after being pre-heated (e.g., in certain embodiments, plasticizer can be added after being pre-heated to a temperature of about 8O 0 C to about 9O 0 C).
  • the mixture is then transferred from the high intensity mixer 10 to a low intensity mixer 16 (e.g., a Henschel-type cooler mixer operating at a speed of about 110 rpm) that simultaneously cools the mixture.
  • a powder composition blend is being formed, the other polymer 18 (e.g., polyvinyl chloride) can be added to the mixture while being processed in the low intensity mixer 16.
  • the mixture reaches a temperature of about 5O 0 C it can be discharged to a hopper 20 for further processing to complete the dry blending operations 22.
  • a screener 24 e.g., a vibratory screener having a 10-mesh screen, such as a Sweco-type screener. Any oversize components 26 are discarded with the remaining components being then transferred to a receptacle 28 where they remain in the form of a dry powder until being transferred to an extruder 30 (e.g., a twin-screw extruder such as a Leistritz 27- millimeter co-rotating extruder having the designation MIC 27 GL/40D) for melt compounding (e.g., at a temperature of about 18O 0 C and a speed of about 350 rpm) followed by the remaining extrusion operations 32.
  • an extruder 30 e.g., a twin-screw extruder such as a Leistritz 27- millimeter co-rotating extruder having the designation MIC 27 GL/40D
  • melt compounding e.g., at a temperature of about 18O 0 C and a speed of about 350
  • water can be injected into the extruder to help control MFI of the material as desired.
  • a water cooler 34 e.g., a strand pelletizer equipped with a trough, such as those available from the Conair Group Inc. of Pittsburgh, PA.
  • the material exits the pelletizer 36 in the form of pellets 38.
  • the pellets 38 are then subjected to cryogenic grinding operations 40.
  • the pellets 38 are cooled in liquid nitrogen 42 and then transferred to an attrition mill 44 (e.g., such as cryogenic attrition mills available from Midwest Elastomers, Inc. of Wapakoneta, OH). From the attrition mill 44, the pellets are then run through a first cyclone separator 46 to a screener 48, which allows for transfer of particles of a desired dimension to a second cyclone separator 50. Oversize particles 52 are returned to the liquid nitrogen 42 for further milling. En route to the second cyclone separator 50 the screened composition can be heated using, for example, dry forced air. Finally, the resulting powder composition 54 exits the second cyclone separator 50 where it is stored until it is packaged or used for formation of an article prepared from the powder composition 54. [00081] Uses
  • TPU compositions of the invention can be used to form a variety of articles.
  • compositions of the invention are capable of providing improved surface finishes on many articles prepared therefrom.
  • polymeric skins formed therefrom often have few surface imperfections as compared to those prepared from other compositions.
  • a first exemplary use of compositions of the invention involves high velocity impact fusion (HVIF). This technique facilitates formation of polymeric skins using formulations of the invention.
  • the TPU powder composition preferably has an average particle size corresponding to the particle size distribution of FIGURE 1.
  • the composition is heated and then sprayed onto a mold surface to form an article.
  • the composition is heated to the point of melting using a hot nitrogen or oxygen environment. Once fluidized in this manner, the composition is directed toward a substrate (e.g., nickel- plated steel) maintained at approximately room temperature. Once the composition comes to rest upon the substrate, it cools to form the article.
  • a substrate e.g., nickel- plated steel
  • the article is a continuous, solid film (e.g., a polymeric skin).
  • the mold surface is textured in order to impart a desired surface finish to an article.
  • the mold surface may be textured to appear leathery when preparing articles such as instrument panels, armrests, headrests, door panels, and other items in passenger compartments of vehicles.
  • HVIF high velocity oxygen fuel
  • a fuel gas such as propylene or hydrazine and oxygen under high pressure at approximately 0.4 - 0.6 MPa (60 to 90 psi) is burned in an internal combustion chamber.
  • Hot exhaust gases discharge from the combustion chamber through exhaust ports and expand into an extended nozzle where it meets with the powdered composition, which is fed into the nozzle with an inert carrier gas such as nitrogen and confined by the exhaust gas stream.
  • the powdered composition melts therein and exits the nozzle in a high speed jet stream having a length of about 9 decimeters (36 inches) and a stream diameter of about 1.2 centimeters (1/2 inch). Utilizing this technique, a sufficiently dense coating of the composition is capable of being produced with properties superior to those obtained using other techniques.
  • compositions of the invention for formation of articles involve conventional powder coating techniques including fluidized bed, electrostatic spray, and thermal spray techniques.
  • Other such uses include conventional molding techniques such as slush molding and rotational molding.
  • a fluidized bed According to the fluidized bed technique, heated metal parts are dipped in an aerated bed of the powdered composition. The powder melts on the heated part, resulting in a smooth continuous film encapsulating the metal. This process takes place in what is referred to as a "fluidized bed.”
  • the fluidized bed has three main sections: (1) a top powder hopper where the powder is held, (2) a porous plate that allows air to pass through, and (3) a sealed bottom air chamber. When pressurized air is blown into the air chamber, it passes through the plate and causes the powder to float or "fluidize". This fluidization allows the metal part to be coated and moved through the powder with little resistance during the dipping process.
  • a cold substrate can be run over a bed of fluidized particles that are tribo-charged and, thus, cling to the substrate. The coated substrate can then be passed through a heated zone, or nip, to fuse the coating.
  • the powdered composition is dispersed in an air stream and passed through a corona discharge field.
  • the powder acquires an electrostatic charge.
  • the charged powder is attracted to and then deposited on the grounded substrate.
  • the substrate usually electrostatically coated at room temperature, is then placed in an oven where the powder melts and forms a coating.
  • Plasma flame spraying is a process whereby the deposition of a largely molten material is enabled by using a highly directional gas stream. Plasma, an ionized gas consisting of free electrons, positive ions, atoms and molecules, is used as a means of heating the powdered composition to a molten state at a high temperature (e.g., approximately 15,000 0 C) by using an electric arc.
  • a high temperature e.g., approximately 15,000 0 C
  • a selected gas such as argon or nitrogen flows between an anode and cathode. Between the anode and cathode, an arc is generated in the gas flow, which heats and propels the composition to a substrate. Upon impinging the substrate, the composition heat- fuses to form a coating.
  • the TPU powder composition preferably has a larger average particle size than that preferred for use with the HVIF technique.
  • compositions with an average particle size corresponding to the particle size distribution illustrated in FIGURE 2 can be used.
  • the particle size distribution of compositions used in this process need not be relatively uni-modal as is the case with those compositions used in the HVIF process described above. Rather, bi-modal particle size distributions can be used, such as those obtained from cryogenic grinding of the TPU.
  • Rotational molding is another technique for forming articles (e.g., armrests and headrests in passenger compartments of vehicles as well as other objects such as recreational balls).
  • the rotational molding process operates on one rotational axis using a closed-mold design.
  • a bi-modal particle size distribution can also be used when rotational molding, the distribution is typically of a larger average particle size than that used for slush molding.
  • articles are formed from TPU and TPU powder composition blends of the invention.
  • improved powder compositions of the invention with processing techniques such as the HVIF technique, superior articles are made possible.
  • Such articles are useful for not only satisfying needs of industries such as those involving manufacture of polymeric articles used in passenger compartments of vehicles.
  • a base TPU was obtained from a commercial source under the trade designation ELASTOLLAN LJ 56/187(BASF Corp. of Wyandotte, MI). When tested according to ASTM D1238 at 19O 0 C and a weight of 2.16 kg, the MFI of the base TPU was measured to be 55 g/10 min. When tested according to ASTM D1238 at the lower temperature of 17O 0 C and the same weight of 2.16 kg, the MFI of the base TPU was measured to be 27 g/10 min.
  • the base TPU was mixed with an internal lubricant (mono- and di-stearyl acid phosphate, AX-71, available from Amfine Chemical of Mie, Japan), and a pigment (carbon black, available from Cabot Corp. of Boston, MA, under the REGAL BLACK trade designation).
  • the high intensity mixer was operated at a temperature of about 12O 0 C to about 14O 0 C.
  • the mixture was then transferred from the high intensity mixer to a low intensity mixer operating at a speed of about 110 rpm to mix and simultaneously cool the mixture. When the mixture reached a temperature of about 5O 0 C, it was discharged to a hopper and then run through a screener.
  • Example 2 [000101] In a high intensity mixer, a base TPU (ELASTOLLAN LJ 56/187, available from BASF Corp.
  • Example 3 The mixture was processed to form a powder composition as described with reference to Example 1.
  • the amount of base TPU was 98.2%
  • the amount of internal lubricant was 0.2%
  • the amount of pigment was 1.6%, all weight percentages being based on total weight of the composition.
  • the process described with reference to Example 1 and FIGURE 3 was used to form a powder composition blend.
  • the powder composition blend was formed from 30.0% base TPU (ELASTOLLAN LJ 56/187, available from BASF Corp. of Wyandotte, MI), 0.1% internal lubricant (mono- and di-stearyl acid phosphate, AX-71, available from Amfine Chemical of Mie, Japan), 33.3% polyvinyl chloride resin suspension (SUSP RESIN 200F (DPK), available from Oxy vinyls Corp.
  • Example 4 Example 4: 1.4% mixed stabilizer (CPS 507, available from Amfine Chemicals of Hopkinsville, KY), 0.1% fatty acid ester (LS-10, available from Amfine Chemicals of Mie, Japan), 0.9% phosphite stabilizer (CPL-1551 D, available from Amfine Chemical of Hopkinsville, KY), 2.8% pigment dispersion (VM6432 9779 MD GRAY MB, available from PolyOne Corp. of Avon Lake, OH), 28.1% n-octyl trimellitate plasticizer (SYNPLAST NOTM ELECTRICAL, available from Synergistics of St. Remi, Canada), and 3.3% polyvinyl chloride resin dispersion (VINNOLIT P70, available from Vinnolit of Ismaning, Germany). All weight percentages are based on total weight of the composition. [000104] Example 4
  • the process described with reference to Example 1 and FIGURE 3 was used to form a powder composition blend.
  • the powder composition blend was formed from 30.0% base TPU (ELASTOLLAN LJ 56/187, available from BASF Corp. of Wyandotte, MI), 0.1% internal lubricant (mono- and di-stearyl acid phosphate, AX-71, available from Amfine Chemical of Mie, Japan), 32.5% polyvinyl chloride resin suspension (SUSP RESIN 200F (LVL), available from Oxy vinyls Corp.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

Les formules pulvérulentes thermoplastiques et les procédés correspondants selon l'invention comprennent au moins un polyuréthane thermoplastique d'indice de fluidité à chaud d'au moins environ 8 g/10 minutes lorsqu'il est testé selon ASTM D1238 à 190 °C et une masse de 2,16 kg ; au moins un lubrifiant interne dans une quantité pouvant atteindre environ 5 % en poids par rapport au poids total de la formule ; et éventuellement, au moins un agent fluidifiant ou d'autres composants. De telles formules pulvérulentes thermoplastiques sont adaptées à la formation d'une grande diversité d'articles par l'emploi par exemple, de techniques de moulage en fusion par impact à vitesse élevée ou de moulage par embouage.
EP06849147A 2005-10-17 2006-10-16 Formules pulvérulentes thermoplastiques de polyuréthane et applications Withdrawn EP1937777A4 (fr)

Applications Claiming Priority (2)

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US72736705P 2005-10-17 2005-10-17
PCT/US2006/060005 WO2007079270A2 (fr) 2005-10-17 2006-10-16 Formules pulvérulentes thermoplastiques de polyuréthane et applications

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US10576502B2 (en) 2012-05-25 2020-03-03 Derrick Corporation Injection molded screening apparatuses and methods
US11161150B2 (en) 2012-05-25 2021-11-02 Derrick Corporation Injection molded screening apparatuses and methods
MY197340A (en) 2012-05-25 2023-06-14 Derrick Corp Injection molded screening apparatuses and methods
US9409209B2 (en) 2012-05-25 2016-08-09 Derrick Corporation Injection molded screening apparatuses and methods
CN103602004B (zh) * 2013-11-04 2015-10-14 界首市鑫豪塑胶有限公司 一种利用改性塑料制备的人造地板革
CN108025493A (zh) 2015-09-04 2018-05-11 沙特基础工业全球技术有限公司 粉末组合物、由粉末组合物制备制品和涂料的方法、以及由此制备的制品
US11505638B2 (en) 2017-04-28 2022-11-22 Derrick Corporation Thermoplastic compositions, methods, apparatus, and uses
WO2018201043A2 (fr) * 2017-04-28 2018-11-01 Derrick Corporation Compositions thermoplastiques, procédés, appareil et utilisations
CN110799274A (zh) 2017-06-06 2020-02-14 德里克公司 用于筛分的方法和装置
US11213857B2 (en) 2017-06-06 2022-01-04 Derrick Corporation Method and apparatus for screening

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EP1050549A2 (fr) * 1999-05-04 2000-11-08 Bayer Ag Compositions de moulage frittables à base de polyuréthane aliphatique thermoplastique

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EP1937777A2 (fr) 2008-07-02
CN101291992B (zh) 2011-06-08
WO2007079270A3 (fr) 2007-10-11
BRPI0617474A2 (pt) 2011-07-26
KR100960402B1 (ko) 2010-05-28
WO2007079270A2 (fr) 2007-07-12
KR20080063823A (ko) 2008-07-07
CN101291992A (zh) 2008-10-22

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