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EP3781616A1 - Mousses à base d'élastomères thermoplastiques - Google Patents

Mousses à base d'élastomères thermoplastiques

Info

Publication number
EP3781616A1
EP3781616A1 EP19717942.7A EP19717942A EP3781616A1 EP 3781616 A1 EP3781616 A1 EP 3781616A1 EP 19717942 A EP19717942 A EP 19717942A EP 3781616 A1 EP3781616 A1 EP 3781616A1
Authority
EP
European Patent Office
Prior art keywords
shoe
shaped body
particle
weight
components
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Withdrawn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
EP19717942.7A
Other languages
German (de)
English (en)
Inventor
Elmar Poeselt
Peter Gutmann
Florian Tobias RAPP
Frank Prissok
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP3781616A1 publication Critical patent/EP3781616A1/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Withdrawn legal-status Critical Current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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08G2350/00—Acoustic or vibration damping material
    • 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
    • C08G2410/00—Soles
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • 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
    • C08J2207/00—Foams characterised by their intended use
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene

Definitions

  • Particle foams or particle foams, particle foam
  • shaped articles based thereon on the basis of thermoplastic polyurethane or other elastomers are known (for example WO 94/20568, WO 2007/082838 A1, WO2017030835, WO 2013/153190 A1
  • Particle foam or particle foam in the sense of the present invention denotes a foam in the form of a particle, wherein the average diameter of the particle foam is between 0.2 to 20, preferably 0.5 to 15 and in particular between 1 to 12 mm.
  • non-spherical, e.g. elongated or cylindrical particle foam is meant by diameter the longest dimension.
  • Sufficient bonding or welding of the particle foams is essential in order to obtain advantageous mechanical properties of the molded part produced from the particle foam.
  • its properties can not be used to their full extent, as a result of which the overall mechanical properties of the molded part obtained are adversely affected.
  • the mechanical properties at the weakened sites are unfavorable with the same result as mentioned above.
  • the application which is of primary importance for the subject of the present invention is the use in the shoe sector, wherein the particle foams can be used for shaped bodies for components of the shoe in which cushioning and / or padding is relevant, such as e.g. Midsoles and inserts.
  • a shaped particle of foam with low compression properties fundamentally a higher density and thus more material than a molded body of foam particles with high compression properties in order to genrieren at the end similar properties.
  • the applicability of a particle foam for specific applications is also given by this connection.
  • particle foams are advantageous in which the compression properties of the molded articles produced from the particle foams are rather low with little force, and in the region in which the shoe is worn have a deformation which is sufficient for the wearer.
  • a further problem is that in the case of large-scale production of particle foam via extrusion, the highest possible throughput of material is desirable in order to produce the required quantities in as short a time as possible.
  • too fast processing of the material into inferior material leads to instability and / or collapse of the obtained particle foams. Accordingly, there is still a need to provide particle foams in which the production time is as low as possible.
  • thermoplastic polyurethane as component I.
  • thermoplastic polyurethanes used as component I are well known.
  • the preparation is carried out by reacting (a) isocyanates with (b) isocyanate-reactive compounds, for example polyols, having a number-average molecular weight of 500 g / mol to 100,000 g / mol (b1) and optionally chain extenders having a molecular weight of 50 g / mol to 499 g / mol (b2), if appropriate in the presence of (c) catalysts and / or (d) customary auxiliaries and / or additives.
  • isocyanates for example polyols, having a number-average molecular weight of 500 g / mol to 100,000 g / mol (b1) and optionally chain extenders having a molecular weight of 50 g / mol to 499 g / mol (b2)
  • thermoplastic polyurethanes are obtainable by reacting (a) isocyanates with (b) compounds which are reactive towards isocyanates, for example polyols (b1) having a number-average molecular weight of from 500 g / mol to 100,000 g / mol and one Chain extender (b2) having a molecular weight of from 50 g / mol to 499 g / mol, if appropriate in the presence of (c) catalysts and / or (d) customary auxiliaries and / or additives.
  • polyols b1 having a number-average molecular weight of from 500 g / mol to 100,000 g / mol
  • Chain extender (b2) having a molecular weight of from 50 g / mol to 499 g / mol
  • the components (a) isocyanate, (b) compounds which are reactive toward isocyanates, for example polyols (b1), and optionally chain extenders (b2) are also mentioned individually or together as synthesis components.
  • the synthesis components, including the catalyst and / or the customary auxiliaries and / or additives, are also called starting materials.
  • the amounts used of the synthesis components (b) can be varied in their molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender in the component (b), while Melt index decreases with a constant molecular weight of the TPU.
  • thermoplastic polyurethanes To prepare the thermoplastic polyurethanes, the synthesis components (a), (b), where (b) in a preferred embodiment also contains chain extenders, in the presence of a catalyst (c) and optionally auxiliaries and / or additives in such quantities Reaction brought that the equivalence ratio of NCO groups of the diisocyanates (a) to the sum of the hydroxyl groups of component b) in the range of 1 to 0.8 to 1 to 1.3.
  • a catalyst c
  • auxiliaries and / or additives in such quantities Reaction brought that the equivalence ratio of NCO groups of the diisocyanates (a) to the sum of the hydroxyl groups of component b) in the range of 1 to 0.8 to 1 to 1.3.
  • the index is defined by the ratio of the total of the isocyanate groups used in the reaction to the isocyanate-reactive groups, ie in particular the reactive groups of the polyol component and the chain extender. With a figure of 1000, an isocyanate group has an active hydrogen atom. For ratios above 1000, more isocyanate groups exist than isocyanate-reactive groups.
  • the ratio in the reaction of the abovementioned components is in the range from 965 to 1110, preferably in the range from 970 to 110, more preferably in the range from 980 to 1030 and very particularly preferably in the range from 985 to 1010 particularly preferred.
  • thermoplastic polyurethanes are preferably prepared in which the thermoplastic polyurethane has a weight-average molecular weight (M w ) of at least 60,000 g / mol, preferably of at least 80,000 g / mol and in particular greater than 100,000 g / mol.
  • M w weight-average molecular weight
  • the upper limit for the weight-average molecular weight of the thermoplastic polyurethanes is generally determined by the processability as well as the desired property spectrum.
  • the number-average molecular weight of the thermoplastic polyurethanes is preferably between 80,000 and 300,000 g / mol.
  • thermoplastic polyurethane as well as for the synthesis components (a) and (b) are the weight average determined by means of gel permeation chromatography (eg according to DIN 55672-1, March 2016 or analogous).
  • organic isocyanates (a) it is possible to use aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates.
  • the aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethyltetramethylene 1, 4-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohe
  • Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisoyanate (EDI), methylene diphenyl diisocyanate (MDI), where the term MDI denotes 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate.
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • TODI 3,3'-dimethyl-4,4'-diisocyanato-diphenyl
  • PDI
  • mixtures can also be used.
  • examples of mixtures are mixtures which contain, in addition to 4,4'-methylene diphenyl diisocyanate and at least one further methylene diphenyl diisocyanate.
  • methylene diphenyl diisocyanate denotes 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers.
  • the polyisocyanate composition may also contain further, the above-mentioned polyisocyanates.
  • mixtures are containing polyisocyanate compositions
  • the polyisocyanate composition contains 4,4'-MDI in an amount of 2 to 50% based on the total polyisocyanate composition and the other isocyanate in an amount of 3 to 20% based on the total polyisocyanate composition.
  • crosslinkers for example the above-mentioned higher-functional polyisocyanates or polyols, or also other higher-functional molecules having a plurality of isocyanate-reactive functional groups.
  • crosslinkers for example the above-mentioned higher-functional polyisocyanates or polyols, or also other higher-functional molecules having a plurality of isocyanate-reactive functional groups.
  • a cross-linking of the products by an excess of used isocyanate groups relative to the hydroxyl groups are triisocyanates, e.g. B.
  • triphenylmethane-4,4 ', 4 "-triisocyant and isocyanurates furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the abovementioned diisocyanates, furthermore oligomers obtained by targeted implementation of semiblocked diisocyanates with polyols having an average of more than two and preferably three or more hydroxy groups are available.
  • the polyisocyanate composition may also contain one or more solvents.
  • Suitable solvents are known to the person skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.
  • Preferred isocyanate-reactive compounds (b1) are those having a molecular weight between 500 g / mol and 8000 g / mol, more preferably 500 g / mol to 5000 g / mol, in particular 500 g / mol to 3000 g / mol.
  • the isocyanate-reactive compound (b) has on statistical average at least 1, 8 and at most 2.2, preferably 2, Zerewitinow active hydrogen atoms, this number is also referred to as functionality of the isocyanate-reactive compound (b) and gives the amount of a substance theoretically reduced to a molecule amount of the isocyanate-reactive groups of the molecule.
  • the isocyanate-reactive compound is preferably substantially linear and is an isocyanate-reactive substance or a mixture of various substances, in which case the mixture satisfies the said requirement.
  • the ratio of components b1) and b2) is varied so that the desired hard segment content is obtained, which can be calculated according to the formula disclosed in PCT / EP2017 / 079049.
  • a hard segment content of less than 60%, preferably less than 40%, particularly preferably less than 25% is suitable.
  • the isocyanate-reactive compound (b1) preferably has a reactive group selected from the hydroxyl group, the amino group, the mercapto group or the carboxylic acid group. It is preferably the hydroxyl group and very particularly preferably primary hydroxyl groups.
  • the isocyanate-reactive compound (b) is particularly preferably selected from the group of the polyester oil, the polyether oil or the polycarbonate diols, which are also combined under the term "polyols".
  • homopolymers such as, for example, polyether oil are suitable, polyester oxide, polycarbonate (diol) s, polysiloxane diols, polybutadiene diols, but also block copolymers and hybrid polyols such as poly (ester / amide).
  • preferred polyetheroils are polyethylene glycols, polypropylene glycols, polytetramethylene glycol (PTHF), polytrimethylene glycol.
  • Preferred polyester polyols are polyadipates, polysuccinic acid esters and polycaprolactones.
  • the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol composition contains a polyol selected from the group consisting of polyether oils, polyester oils, polycaprolactones and polycarbonates.
  • Suitable block copolymers are, for example, those which have ethers and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks.
  • Polyetheroic preferred are polyethyleneglycols according to the invention, polypropylene glycols, polytetramethylene glycol (PTHF) and Polytri methylenglykol. Further preferred is polycaprolactone.
  • the polyol used has a molecular weight Mn in the range from 500 g / mol to 4000 g / mol, preferably in the range from 500 g / mol to 3000 g / mol.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 4000 g / mol.
  • At least one polyol composition containing at least polytetrahydrofuran is used to prepare the thermoplastic polyurethane.
  • the polyol composition in addition to polytetrahydrofuran also contain other polyols.
  • polyethers are suitable as further polyols, but also polyesters, block copolymers and hybrid polyols, such as, for example, polyesters.
  • Suitable block copolymers are, for example, those which have ethers and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or also polyethers with polycaprolactone end blocks.
  • Preferred polyetheroie are according to the invention polyethylene eneglycols, polypropylene glycols. Further preferred polycaprolactone is another polyol.
  • Suitable polyols are, for example, polyethers, such as polytrimethylene oxide or polytetramethylene oxide. Accordingly, the present invention according to another embodiment relates to a thermoplastic polyurethane as described above, wherein the polyol composition at least one polytetrahydrofuran and at least one further polyol selected from the group consisting of a further polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and Contains polycaprolactone.
  • PTHF polytetramethylene oxide
  • the polytetrahydrofuran has a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol, more preferably in the range of 550 to 2500 g / mol, particularly preferably in the range of 650 to 2000 g / mol and most preferably in the range of 650 to 1400 g / mol.
  • the composition of the polyol composition can vary widely within the scope of the present invention.
  • the content of the first polyol, preferably polytetrahydrofuran can be in the range of 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.
  • the polyol composition may also contain a solvent. Suitable solvents are known per se to the person skilled in the art.
  • the number average molecular weight Mn of the polytetrahydrofuran is, for example, in the range from 500 g / mol to 5000 g / mol, preferably in the range from 500 to 3000 g / mol. More preferably, the number average molecular weight Mn of the polytetrahydrofuran is in the range of 500 to 1400 g / mol.
  • the number-average molecular weight Mn can be determined via gel permeation chromatography as mentioned above.
  • the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol composition selected from the group consisting of polytetrahydrofurans having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / contains mol.
  • the chain extenders (b2) used are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of from 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive compounds, which are also referred to as functional groups.
  • Preferred chain extenders are diamines and / or alkanediols, more preferably alkanediols having 2 to 10 carbon atoms, preferably 3 to
  • chain extenders (c) are used, these are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive groups, which are also functional groups be designated.
  • the chain extender is preferably at least one chain extender selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol , 1, 6-hexanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-dimethanolcyclohexane, neopentyl glycol and hydroquinone bis (beta-hydroxyethyl) ether (HQEE).
  • HQEE hydroquinone bis (beta-hydroxyethyl) ether
  • chain extenders selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol and mixtures of the above-mentioned chain extenders.
  • Examples of specific chain extenders and mixtures are disclosed, inter alia, in PCT / EP2017 / 079049
  • catalysts (c) are used with the synthesis components. These are in particular catalysts which accelerate the reaction between the NCO groups of the isocyanates (a) and the hydroxyl groups of the isocyanate-reactive compound (b) and, when used, the chain extender.
  • Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron organyls, such as tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyltin or tin organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth-alkyl compounds or the like, or iron compounds, preferably iron (MI) acetylacetonate or the metal salts of the carboxylic acids such as Tin isooctoate, tin dioctoate, titanic acid ester or bismuth (III) neodecanoate.
  • organyls such as tin organyl compounds, preferably tin dialkyls such as di
  • catalysts are tin dioctoate, bismuth decanoate and titanic acid esters.
  • the catalyst (d) is preferably used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound (b).
  • conventional auxiliaries (d) can also be added to the synthesis components (a) to (b). Mention may be made, for example, of surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, optionally stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or plasticizer.
  • Suitable dyes and pigments are listed below.
  • Stabilizers in the context of the present invention are additives which protect a plastic or a plastic mixture against harmful environmental influences.
  • examples include primary and secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, quenchers and flame retardants.
  • examples of commercial stabilizers are given in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), p.98-S136.
  • the preparation of the thermoplastic polyurethanes can be carried out according to the known methods dis- continuously or continuously, for example with reaction extruders or the tape method according to the "one-shot" - or the prepolymer process, preferably by the "one-shot” - method.
  • the TPU can then be directly granulated or convoluted by extrusion into lens granules. In this step, it is possible to include further additives or other polymers.
  • the synthesis components (a), (b) and, in preferred embodiments, also (c), (d) and / or (e) are introduced into the extruder individually or as a mixture and, preferably, at temperatures of from 100.degree 280 ° C, preferably 140 ° C to 250 ° C, reacted.
  • the resulting polyurethane is extruded, cooled and granulated or granulated directly via an underwater granulation as lens granules.
  • thermoplastic polyurethane is prepared in a first step from the synthesis components isocanate (a), isocyanate-reactive compound (b) including chain extenders and in preferred embodiments the other starting materials (c) and / or (d) and in a second Extrusion step incorporated the additives or excipients.
  • a twin-screw extruder is used, since the twin-screw extruder works positively conveying and so a more precise adjustment of the temperature and discharge rate is possible on the extruder.
  • the production and expansion of a TPU can be carried out in a reaction extruder in one step or via a tandem extruder according to methods known to the person skilled in the art.
  • polystylene By the polyolefins mentioned as component II is meant homopolypropylene.
  • the crystallite melting point (DIN EN ISO 1 1357-1 / 3, February 2017 / April 2013, W peak melting temperature) of the polyolefins which can be used according to the invention is generally between 90 and 170.degree.
  • composition comprises Z
  • the composition comprises Z
  • thermoplastic polyurethane as component I
  • composition comprises Z
  • thermoplastic polyurethane as component I
  • the non-expanded starting material, the composition Z, required for the production of the particle foam is prepared in a manner known per se from the individual thermoplastic elastomers (TPE-1) and (TPE-2) and optionally further components. Suitable methods are, for example, customary mixing methods in a kneader or an extruder.
  • the unexpanded polymer mixture of composition Z required for the preparation of the particle foam is prepared in a known manner from the individual components and, if appropriate, other components such as processing aids, stabilizers, compatibilizers or pigments.
  • Suitable processes are, for example, customary mixing processes with the aid of a kneader, continuous or discontinuous, or an extruder, such as a co-rotating twin-screw extruder.
  • compatibilizers or auxiliaries such as stabilizers
  • these can also be incorporated in the preparation of the components in this already.
  • the individual components are combined before the mixing process or metered into the apparatus which takes over the mixing.
  • the components are all dosed into the feeder and conveyed together into the extruder or individual components added via a side dosing (usually not for foams as this part of the extruder is not tight).
  • Processing takes place at a temperature at which the components are in a plasticized state.
  • the temperature depends on the softening or melting ranges of the components, but must be below the decomposition temperature of each component.
  • Additives such as pigments or fillers or further of the abovementioned customary auxiliaries (d) are not melted, but incorporated in the solid state.
  • the particle foams according to the invention generally have a bulk density of from 50 g / l to 200 g / l, preferably from 60 g / l to 180 g / l, particularly preferably from 80 g / l to 150 g / l.
  • the bulk density is measured analogously to DIN ISO 697, whereby a vessel with 10 l volume is used instead of a vessel with 0.5 l volume in the determination of the above values, in contrast to the standard, since especially for the foam particles with lower Dense and large mass a measurement with only 0.5 l volume is too inaccurate.
  • the diameter of the particle foams is between 0.5 to 30; preferably 1 to 15 and especially between 3 to 12 mm.
  • diameter the longest dimension:
  • the amount of blowing agent is preferably 0.1 to 40, in particular 0.5 to 35 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the amount of the composition (Z) used.
  • composition (Z) according to the invention in the form of a granule
  • Another embodiment of the above method comprises a further step: i. Providing a composition (Z) according to the invention in the form of a granule;
  • the granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, for example via dynamic image analysis with the use of an optical measuring apparatus named PartAn 3D from Microtrac).
  • the individual granules generally have an average mass in the range from 0.1 to 50 mg, preferably in the range from 4 to 40 mg and more preferably in the range from 7 to 32 mg.
  • This average mass of the granules is determined as an arithmetic mean by weighing 3 times each of 10 granular particles.
  • An embodiment of the above method comprises impregnating the granules with a propellant under pressure and then expanding the granules in step (ii) and (iii): ii. Impregnation of the granules in the presence of a propellant under pressure at elevated temperatures in a suitable closed reaction vessel (for example autoclave)
  • a suitable closed reaction vessel for example autoclave
  • the impregnation in step ii) can be carried out in the presence in the presence of water and optional suspension aids or only in the presence of the blowing agent and the absence of water.
  • Suitable suspension aids are e.g. water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants such as sodium dodecylarylsulfonate. They are usually used in amounts of 0.05 to 10 wt .-%, based on the composition of the invention.
  • the impregnation temperatures are in the range of 100-200 ° C., depending on the selected pressure, the pressure in the reaction vessel being between 2 and 150 bar, preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar, the duration of impregnation. generally takes 0.5 to 10 hours.
  • Suitable propellants for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases which are in a gaseous state in the processing conditions, such as hydrocarbons or inorganic gases, or mixtures of organic liquids or gases and inorganic gases, which may also be combined.
  • Suitable hydrocarbons are, for example, halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.
  • Preferred organic blowing agents are saturated, aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane or pentane.
  • Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the abovementioned gases.
  • the impregnation of the granules with a blowing agent under pressure comprises processes and subsequent expansion of the granules in step (ii) and (iii):
  • Suitable blowing agents in this process variant are volatile organic compounds having a boiling point at atmospheric pressure of 1013 mbar 35 from -25 to 150, in particular -10 to 125 ° C.
  • Very suitable are hydrocarbons (preferably halogen-free), in particular C 4 -C 10 -alkanes, for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably iso-pentane.
  • Further possible blowing agents are also sterically more demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates.
  • the composition in step (ii) is melt-blended in an extruder with the blowing agent under pressure, which is fed to the extruder.
  • the propellant-containing mixture is squeezed out under pressure, preferably with moderately controlled back pressure (for example, underwater granulation) and granulated.
  • moderately controlled back pressure for example, underwater granulation
  • the melt strand foams and granules give the particle foams.
  • Suitable extruders are all conventional screw machines, in particular single-screw and twin-screw extruders (eg type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders, as they eg in Saechtling (ed.), plastic paperback, 27th edition, Hanser-Verlag Kunststoff 1998, chap. 3.2.1 and 3.2.4 are described.
  • the extruder is usually operated at a temperature at which the composition (Z1) is in the form of a melt, for example at 120 ° C. to 250 ° C., in particular 150 to 210 ° C. and a pressure after the addition of the blowing agent of 40 to 200 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar to ensure homogenization of the blowing agent with the melt.
  • the implementation can be carried out in an extruder or an arrangement of one or more extruders.
  • a first extruder the components can be melted and blended, and a propellant injected.
  • the impregnated melt is homogenized and the temperature and / or the pressure are adjusted.
  • the see the components and the injection of the propellant are divided into two different process parts. If, as preferred, only one extruder is used, then all process steps, melting, mixing, injection of the blowing agent, homogenization and adjustment of the temperature and / or the pressure in an extruder are carried out.
  • the corresponding, possibly even already colored, particle foam can be produced directly by impregnating the corresponding granulate with a supercritical fluid, from which the supercritical fluid is removed from
  • Suitable supercritical fluids are e.g. those described in WO2014150122 or described e.g. Carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.
  • the supercritical fluid may also contain a polar fluid having a Hildebrand solubility parameter equal to or greater than 9 MPa-1/2.
  • the supercritical fluid or the heated fluid may also contain a dye, whereby a dyed, foamed article is obtained.
  • Another object of the present invention is a molded article produced from the particle foams according to the invention.
  • the corresponding shaped bodies can be produced by methods known to the person skilled in the art.
  • a preferred method for producing a foam molding comprises the following steps:
  • step (ii) fusing the particle foams of step (i) according to the invention.
  • the fusion in step (ii) is preferably carried out in a closed form, wherein the fusion can be effected by steam, hot air (as described for example in EP1979401 B1) or energetic radiation (microwaves or radio waves).
  • the temperature at the fusing of the particle foam is preferably below or close to the melting temperature of the polymer from which the particle foam was made. Accordingly, the temperature for fusing the particle foam is between 100 ° C. and 180 ° C., preferably between 120 and 150 ° C., for the customary polymers. In this case, temperature profiles / residence times can be determined individually, for example in analogy to the methods described in US20150337102 or EP2872309B1.
  • the welding via energetic radiation generally takes place in the frequency range of microwaves or radio waves, if appropriate in the presence of water or other polar liquids, such as e.g. polar group-containing microwave-absorbing hydrocarbons (such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene eneglycols) and can be carried out in analogy to the processes described in EP3053732A or WO16146537.
  • polar group-containing microwave-absorbing hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene eneglycols
  • the particle foams can preferably be wetted with a polar liquid which is suitable for absorbing the radiation, for example in proportions of from 0.1 to 10% by weight, preferably in fractions of from 1 to 6 wt .-%, based on the particle foams used.
  • the welding with high-frequency electromagnetic radiation of the particle foams can also be achieved in the context of the present invention without the use of a polar liquid.
  • the thermal bonding of the foam particles takes place, for example, in a mold by means of high-frequency electromagnetic radiation, in particular by means of microwaves.
  • High-frequency is understood to mean electromagnetic radiation with frequencies of at least 20 MHz, for example of at least 100 MHz.
  • electromagnetic radiation is used in the frequency range between 20 MHz and 300 GHz, for example between 100 MHz and 300 GHz.
  • microwaves in the frequency range between 0.5 and 100 GHz, more preferably 0.8 to 10 GHz, and irradiation times of between 0.1 to 15 minutes.
  • the frequency range of the microwave is adapted to the absorption behavior of the polar liquid or, conversely, the polar liquid is selected on the basis of the absorption behavior in accordance with the frequency range of the microwave device used. Suitable methods are described, for example, in WO 2016 / 146537A1.
  • the particle foam may also contain dyes.
  • the addition of dyes can take place via different routes.
  • the produced particle foams can be colored after production.
  • the corresponding particle foams are contacted with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity which is suitable for sorption of the carrier liquid into the particle foam.
  • TF carrier liquid
  • Suitable dyes are, for example, inorganic or organic pigments.
  • Suitable natural or synthetic inorganic pigments are, for example, carbon black, graphite, titanium oxides, iron oxides, zirconium oxides, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds.
  • Suitable organic pigments are, for example, azo pigments and polycyclic pigments.
  • the color may be added in the production of the particle foam.
  • the dye may be added to the extruder via extrusion.
  • already dyed material can be used as the starting material for the production of the particle foam, which is extruded or expanded in a closed vessel according to the above-mentioned method.
  • the supercritical fluid or the heated fluid may contain a dye.
  • the molded parts according to the invention have advantageous properties for the abovementioned applications in the shoe or sports shoe sector.
  • the tensile and compression properties of the moldings produced from the particle foams are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798, April 2008), the elongation at break is above 100% (DIN EN ISO 1798, April 2008 ) and the compressive stress is above 15 kPa at 10% compression (analogous to DIN EN ISO 844, November 2014, the deviation from the standard is the height of the sample at 20 mm instead of 50 mm and thus the adaptation of the test speed to 2 mm / min).
  • the rebound resilience of the moldings produced from the particle foams is above 55% (analogous to DIN 53512, April 2000, the deviation from the standard is the test piece height, which should be 12 mm, but in this test is carried out at 20 mm). beat "the sample and avoid measuring the ground).
  • the density and compression properties of the molded bodies produced are related.
  • the density of the molded parts produced is between 75 and 375 kg / m 3 , preferably between 100 and 300 kg / m 3 , particularly preferably between 150 and 200 kg / m 3 (DIN EN ISO 845, October 2009).
  • the ratio of the density of the molding to the bulk density of the particle foams of the invention is generally between 1, 5 and 2.5, preferably from 1.8 to 2.0.
  • the invention furthermore relates to the use of a particle foam according to the invention for the production of a shaped body for shoe midsoles, shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components in the automotive interior and exterior, in balls and sports equipment or as a floor covering, in particular for sports surfaces, athletics tracks, sports halls, children's playgrounds and sidewalks.
  • a particle foam according to the invention for the production of a shaped body for shoe midsoles, shoe insoles, shoe combination soles or upholstery element for shoes.
  • the shoe is preferably a street shoe, sports shoe, sandal, boots or safety shoe, particularly preferably a sports shoe.
  • a further subject matter of the present invention is therefore also a molded article, wherein the molded article is a shoe combination sole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • Another object of the present invention is therefore also a molded article, wherein the molded article is a midsole for shoes, preferably for street shoes, sports shoes, sandal, boots or safety shoes, particularly preferably sports shoes.
  • a further subject matter of the present invention is also a shaped body, wherein the shaped body is an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • a further subject matter of the present invention is also a shaped body, wherein the shaped body is a padding element for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.
  • the cushioning element may be e.g. Heel area or forefoot area can be used.
  • a further subject of the present invention is therefore also a shoe in which the shaped article according to the invention is used as midsole, midsole or padding in the e.g. Heel area, forefoot area is used, wherein the shoe is preferably a street shoe, sports shoe, sandal, boots or safety shoe, particularly preferably a sports shoe.
  • Particle foam comprising a composition (Z) comprising
  • thermoplastic polyurethane as component I.
  • thermoplastic polyurethane as component I
  • Particle foam according to embodiment 1, comprising a) 70-80% by weight of thermoplastic polyurethane as component I b) 20-30% by weight of polypropylene as component II,
  • Shaped body according to embodiment 8, 9 or 10 characterized in that the
  • Shaped body according to one of the embodiments 8 to 14 characterized in that the rebound resilience of the shaped body is above 55%.
  • Shaped body according to one of the embodiments 8 to 15 characterized in that the ratio of the density of the molded part to the bulk density of the particle showers is between 1, 5 and 2.5.
  • a method for producing a shaped article according to one of the embodiments 8 to 17 comprising
  • step (ii) fusing the particle foams from step (i).
  • step (ii) takes place in a closed form.
  • step (ii) takes place by means of steam, hot air or energy radiation.
  • Shoe comprising a shaped body according to one of the embodiments 8 to 17.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne des mousses particulaires constituées d'un polyuréthane et d'un polypropylène thermoplastiques, des pièces moulées produites à partir de ces dernières, un procédé de production des mousses particulaires et des pièces moulées ainsi que l'utilisation des pièces moulées pour des semelles intermédiaires de chaussure, des semelles intérieures de chaussure, des semelles combinées de chaussure, des éléments de rembourrage pour des chaussures, des selles de bicyclette, des pneus de bicyclette, des éléments d'amortissement, des rembourrages, des matelas, des supports, des poignées, des films protecteurs, dans des pièces dans la zone de l'intérieur et de l'extérieur des automobiles, dans des balles et des articles de sport ou en tant que revêtement de sol.
EP19717942.7A 2018-04-20 2019-04-18 Mousses à base d'élastomères thermoplastiques Withdrawn EP3781616A1 (fr)

Applications Claiming Priority (2)

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EP18168478 2018-04-20
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022090222A1 (fr) * 2020-10-28 2022-05-05 Basf Se Dispositif de sport pour sports de raquette
KR20220092707A (ko) 2020-12-24 2022-07-04 현대자동차주식회사 자동차 내장재 및 자동차 내장재를 성형하는 방법

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4883837A (en) * 1988-06-24 1989-11-28 The Dow Chemical Company Compatible blends of polyolefins with thermoplastic polyurethanes
DE4307648A1 (de) 1993-03-11 1994-09-15 Basf Ag Schaumstoffe auf Basis thermoplastischer Polyurethane sowie expandierbare, partikelförmige, thermoplastische Polyurethane, insbesondere geeignet zur Herstellung von Schaumstoff-Formkörpern
DE502007005193D1 (en) 2006-01-18 2010-11-11 Basf Se Schaumstoffe auf basis thermoplastischer polyurethane
SI2109637T1 (sl) * 2007-01-16 2018-09-28 Basf Se Hibridni sistemi iz penjenih termoplastičnih elastomerov in poliuretanov
WO2010010010A1 (fr) * 2008-07-25 2010-01-28 Basf Se Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants
DE102011108744B4 (de) * 2011-07-28 2014-03-13 Puma SE Verfahren zur Herstellung einer Sohle oder eines Sohlenteils eines Schuhs
ES2873897T3 (es) 2012-04-13 2021-11-04 Basf Se Procedimiento para la producción de granulado expandido
US8961844B2 (en) 2012-07-10 2015-02-24 Nike, Inc. Bead foam compression molding method for low density product
US9144956B2 (en) 2013-02-12 2015-09-29 Nike, Inc. Bead foam compression molding method with in situ steam generation for low density product
US9498927B2 (en) 2013-03-15 2016-11-22 Nike, Inc. Decorative foam and method
US9375866B2 (en) 2013-03-15 2016-06-28 Nike, Inc. Process for foaming thermoplastic elastomers
EP3540012B1 (fr) * 2014-01-17 2025-01-08 Lubrizol Advanced Materials, Inc. Procédés d'utilisation de polyuréthanes thermoplastiques dans la modélisation par dépôt fondu, systèmes et articles correspondants
DE102015202013B4 (de) 2015-02-05 2019-05-09 Adidas Ag Verfahren zur Herstellung eines Kunststoffformteils, Kunststoffformteil und Schuh
EP3268422B1 (fr) 2015-03-13 2020-08-19 Basf Se Procédé de fabrication de mousses à particule à base d'élastomères thermoplastiques par liage thermique à l'aide de micro-ondes
WO2017030835A1 (fr) 2015-08-19 2017-02-23 Nike Innovate C.V. Procédé de préparation de mousse élastomère thermoplastique et article en mousse
CN106336523A (zh) * 2016-08-31 2017-01-18 杭州博适特新材料科技有限公司 一种制备热塑性聚合物发泡珠粒的方法

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