WO2006090221A1 - Melange granule de materiaux thermoplastique a base de polyurethanne pour la formation de produits fabriques legers et expanses, notamment des pieces d'article chaussant - Google Patents

Melange granule de materiaux thermoplastique a base de polyurethanne pour la formation de produits fabriques legers et expanses, notamment des pieces d'article chaussant Download PDF

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Publication number
WO2006090221A1
WO2006090221A1 PCT/IB2006/000174 IB2006000174W WO2006090221A1 WO 2006090221 A1 WO2006090221 A1 WO 2006090221A1 IB 2006000174 W IB2006000174 W IB 2006000174W WO 2006090221 A1 WO2006090221 A1 WO 2006090221A1
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WO
WIPO (PCT)
Prior art keywords
mixture
micro
blowing agent
total weight
thermoplastic
Prior art date
Application number
PCT/IB2006/000174
Other languages
English (en)
Inventor
Gianni Perozzi
Original Assignee
Goldenplast S.P.A.
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 Goldenplast S.P.A. filed Critical Goldenplast S.P.A.
Publication of WO2006090221A1 publication Critical patent/WO2006090221A1/fr

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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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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

Definitions

  • the present invention relates to the preparation of thermoplastic mixtures for the production of lightened manufactured products and relates to a foamable thermoplastic polyurethane-based granulated mixture which can be used to form manufactured products, in particular for the production of parts of footwear such as soles .
  • thermosetting polyurethane-based plastic mixtures are widely used for the production of soles for footwear in place of other similar materials used for the same purpose, for example rubber or conventional thermosetting polyurethane .
  • thermoplastic mixtures are characterised by their capacity to give the finished product made from them high level mechanical properties, plus an external appearance very similar to that of rubber, particularly suitable for winter footwear.
  • thermoplastic mixtures as such have a fundamental disadvantage which is an intolerably greater weight, all other properties being equal .
  • polyurethane-based thermoplastic mixtures are also foamed so that they also have a reduced density, significantly less than 1 kg/dm 3 .
  • thermoplastic polyurethane or polyurethane-based thermoplastic mixtures in the granulated state, are combined with blowing agents encapsulated and contained in special micro-cells of powdered solid substances .
  • thermoplastic polyurethane granules are significantly greater than the dimensions of the granules of solid substances which contain the blowing agents (granules with a diameter of approximately 1 ⁇ m, which therefore have the appearance of a very fine powder)
  • the above-mentioned combination of the thermoplastic polyurethane and powdered substances containing the blowing agent is achieved using operating methods which for the sake of simplicity may be broadly divided into three different types .
  • the choice of the method most suited to the various circumstances is guided by the greater or lesser relative weight ratio of the powdered substances containing the blowing agent to the granulated thermoplastic polyurethane.
  • the blowing agent when the percentage weight of the powdered substances containing the blowing agent is relatively low compared with the weight of the polyurethane, the blowing agent is dispersed in the solid state in the form of a master, that is to say, it is first agglomerated into larger granules and then mechanically mixed with the thermoplastic polyurethane granules.
  • the combination is achieved by mechanical mixing in the solid state of the powdered substance containing the blowing agent and the mass of polyurethane granules.
  • the powdered substance is made to adhere to the outer surface of the individual thermoplastic polyurethane granules with the insertion of a mild adhesive agent between them, consisting of a sort of semi-fluid sticky mastic which anchors the powders to the thermoplastic material granules .
  • a mild adhesive agent between them, consisting of a sort of semi-fluid sticky mastic which anchors the powders to the thermoplastic material granules .
  • the semi-finished material obtained by mechanical mixing of such solid components has a great lack of homogeneity in the distribution of the granules of powdered substance agglomerated in the granulated mass of thermoplastic polymer to be foamed.
  • the thermoplastic manufactured product formed with that material has a consequent uneven density- distribution, also corresponding to extreme variability of the mechanical properties from one zone to the next of the manufactured product . This is accompanied by random variations in colour due to the alternation of zones in which the material is more compact and zones in which the material is more foamed.
  • the aim of the present invention is therefore to overcome the above-mentioned problems with a mixture of polyurethane-based granulated thermoplastic materials and of powders containing the blowing agent, in which the combination of said components is achieved with a strictly even distribution of the components and with absolute irreversibility of their mixing.
  • thermoplastic materials intended to constitute the semi-finished material, which can be thermally recast, for forming light manufactured products, in particular for forming soles for footwear made of foamed material with a micro-honeycomb structure .
  • the mixture comprises at least one first component consisting of a polyurethane-based thermoplastic material, and at least one second component consisting of micro-cells encapsulating a blowing agent, which are contained in the polymeric mass of the first component .
  • the first component may consist of pure thermoplastic polyurethane, or of a mixture of thermoplastic materials, in which in any case the polyurethane is the basic material, whose percentage presence in the mixture is greater than the presence of the added materials .
  • thermoplastic polyurethane refers to thermoplastic substances with characteristics and properties well known to experts in the field, that is to say, substances for example belonging to the aromatic and aliphatic thermoplastics families, to esters, isocyanates, mixtures of polycarbonates, polybutadienes, glycols, etc. with the addition of additives, stabilisers, surfactants, plasticisers, etc.
  • the weight content of the thermoplastic polyurethane present in the mixture may vary from a minimum of 55% to a maximum of 98% of the total weight of the mixture, the remaining 2% being the minimum weight of the component containing the blowing agent .
  • thermoplastic materials to be mixed as additives with the basic material may include thermoplastic elastomers such as thermoplastic rubbers of the styrene-butadiene-styrene type; or styrene-isoprene-styrene thermoplastic rubbers or even styrene- ethylene-butadiene-styrene thermoplastic rubbers.
  • Other possible additives may belong to the polyvinyl chloride or ethylvinylacetate families, supplied both individually or combined.
  • thermoplastic materials may contain various types of additives, such as paraffin or naphthenic oil, fillers of mineral origin, thermoplastic polybutadiene, styrenated resins, ethylvinylacetate, etc.
  • the component containing the blowing agent preferably consists of micro-cells, incorporated in the polyurethane polymer material and/or in the material of the polymers which with it constitute the mixture, consisting of a copolymer of the acrylic/methacrylonitrile or acrylonitrile/acrylic or ester/olefin group encapsulating the blowing agent which is, for example, a hydrocarbon such as an alkane C ⁇ -C. Both endothermic and exothermic agents can be used.
  • Blowing substances already known and available for purchase consist for example of the families of EXPANCELL ® from EXPANCELL NOBEL INDUSTRIES SWEDEN ® or for example of the families of blowing agents marketed under the name "MICROPEARL” ® from MATSUMOTO YUSHI
  • the mixture is prepared with the following steps:
  • the screw extruder comprises two parallel screws rotating in opposite directions, having several zones, separated from one another along the screw axis, in which the screw pitch is noticeably reduced compared with the pitch of the other parts of the screws.
  • compositions of the mixture are as follows :
  • Example 1 Polyurethane-based thermoplastic mixture for the production of soles for footwear comprising, as a percentage of the total weight of the composition:
  • thermoplastic polyurethane present in the mixture in a weight ratio varying between 60 and 98% of the total weight of the mixture
  • thermoplastic rubber present in the mixture in a weight ratio of between 0 and 40% of the total weight of the mixture
  • Polyurethane-based thermoplastic mixture for the production of soles for footwear comprising, as a percentage of the total weight of the composition:
  • thermoplastic polyurethane present in the mixture in a weight ratio of 96% of the total weight of the mixture
  • a first, exothermic micro-cellular blowing agent present in the mixture in a weight ratio substantially close to 2% of the total weight of the mixture for example EXPANCELL 0.92 MB120
  • a second, endothermic micro-cellular blowing agent for example IMC 7175 ACR from TRAMACO ® , present in the mixture in a weight ratio substantially close to 2% of the total weight of the mixture. Whilst the first blowing agent is contained in the polymeric mass of the thermoplastic material, the second blowing agent is outside of the polymeric mass of the previous components, allowing the formation of a film coating.
  • Polyurethane-based thermoplastic mixture for the production of soles for footwear comprising, as a percentage of the total weight of the composition: - thermoplastic polyurethane present in the mixture in a weight ratio of 95% of the total weight of the mixture;
  • a first, exothermic micro-cellular blowing agent present in the mixture in a weight ratio substantially close to 5% of the total weight of the mixture (for example EXPANCELL 092MB120) contained in the polymeric mass of the previous components.
  • the characteristics of such a mixture are good workability, fairly good resistance to abrasion (close to 120 mm 3 ) and fairly even density (0.6 +0.03).
  • Example 4 Polyurethane-based thermoplastic mixture for the production of soles for footwear comprising, as a percentage of the total weight of the composition:
  • thermoplastic polyurethane present in the mixture in a weight ratio close to 65% of the total weight of the mixture
  • thermoplastic rubber present in the mixture in a weight ratio close to 30% of the total weight of the mixture
  • Example 5 thermoplastic polyurethane and thermoplastic rubber present in the mixture in an overall weight ratio of 95% of the total weight of the mixture; - micro-cellular blowing agent, present in the mixture in a weight ratio of 5% of the total weight of the mixture (EXPANCELL ® 092 MB 120) , contained in the polymeric mass of the previous components .
  • the characteristics of such a mixture are excellent workability, fairly good resistance to abrasion (close to 125 mm 3 ) and excellent evenness of density (0.6 ⁇ 0.01).
  • the mixtures disclosed have many advantages.
  • the main advantages may be summarised as follows : - optimum workability which allows the following to be obtained: foaming conditions strictly repeatable from one part to another with minimised rejects; with the widest freedom of choice of the technology for forming manufactured products, since for example it is possible to process the mixture in machines with open channels or in extrusion machines, without the need for volumetric machines operating with a closed chamber,- total absence of volatilization of powders in the environment and/or of sedimentation and build up of the component containing the blowing agent on the physical parts of the machines, treatment equipment and in the environments used for processing the materials; even density of products on the surface, with the possibility of obtaining a strong, even skin, giving improved resistance to abrasion and giving the manufactured products even strength at all points of their mass, whether inside or outside;

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention a trait à un mélange granulé de matériaux thermoplastiques pour la formation de produits fabriqués légers, notamment pour la formation de semelles pour article chaussant, comportant au moins un premier constituant composé d'un matériau thermoplastique à base de polyuréthanne, et au moins un deuxième constituant composé de microcellules renfermant un agent de gonflement. Le deuxième constituant est contenu dans la masse du premier constituant ou chacun des premiers constituants. Le moussage thermique du mélange est possible lors d'un traitement de formage destiné à procurer aux produits fabriqués réalisés à partir de celui-ci une structure en nid d'abeilles sensiblement isotrope en termes de densité et de propriétés mécaniques et technologiques.
PCT/IB2006/000174 2005-02-22 2006-01-23 Melange granule de materiaux thermoplastique a base de polyurethanne pour la formation de produits fabriques legers et expanses, notamment des pieces d'article chaussant WO2006090221A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRN2005A000006 2005-02-22
ITRN20050006 ITRN20050006A1 (it) 2005-02-22 2005-02-22 Miscela granulare di materiali termoplastici a base poliuretanica per la formatura di manufatti leggeri,espansi, in particolare parti di calzature

Publications (1)

Publication Number Publication Date
WO2006090221A1 true WO2006090221A1 (fr) 2006-08-31

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IT (1) ITRN20050006A1 (fr)
WO (1) WO2006090221A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071549A1 (fr) * 2007-12-06 2009-06-11 Dow Global Technologies Inc. Compositions thermoplastiques pour chaussures sans caractéristiques de marquage
US9781970B2 (en) 2013-02-13 2017-10-10 Adidas Ag Cushioning element for sports apparel
US9781974B2 (en) 2012-04-13 2017-10-10 Adidas Ag Soles for sports shoes
US9930928B2 (en) 2013-02-13 2018-04-03 Adidas Ag Sole for a shoe
US10039342B2 (en) 2014-08-13 2018-08-07 Adidas Ag Co-molded 3D elements
DE102017216814A1 (de) 2017-09-22 2019-03-28 Adidas Ag Verfahren zum Herstellen eines Formteils und Formteil
USD906648S1 (en) 2013-04-12 2021-01-05 Adidas Ag Shoe
US10905919B2 (en) 2015-05-28 2021-02-02 Adidas Ag Ball and method for its manufacture
US10925347B2 (en) 2014-08-11 2021-02-23 Adidas Ag Shoe sole
US10952489B2 (en) 2015-04-16 2021-03-23 Adidas Ag Sports shoes and methods for manufacturing and recycling of sports shoes
CN112795062A (zh) * 2021-01-15 2021-05-14 商丘京威体育用品有限公司 一种耐磨橡胶发泡运动鞋材及其制备方法
US11291268B2 (en) 2015-04-10 2022-04-05 Adidas Ag Sports shoe and method for the manufacture thereof
US11957206B2 (en) 2015-03-23 2024-04-16 Adidas Ag Sole and shoe

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1165674A1 (fr) * 1999-01-26 2002-01-02 Huntsman International Llc Polyurethannes thermoplastiques expansees
DE10326138A1 (de) * 2003-06-06 2004-12-23 Basf Ag Verfahren zur Herstellung von expandierbaren thermoplastischen Elastomeren

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1165674A1 (fr) * 1999-01-26 2002-01-02 Huntsman International Llc Polyurethannes thermoplastiques expansees
EP1233037A2 (fr) * 1999-01-26 2002-08-21 Huntsman International Llc Polyuréthannes thermoplastiques expansés
DE10326138A1 (de) * 2003-06-06 2004-12-23 Basf Ag Verfahren zur Herstellung von expandierbaren thermoplastischen Elastomeren

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071549A1 (fr) * 2007-12-06 2009-06-11 Dow Global Technologies Inc. Compositions thermoplastiques pour chaussures sans caractéristiques de marquage
US10716358B2 (en) 2012-04-13 2020-07-21 Adidas Ag Soles for sports shoes
US11707108B2 (en) 2012-04-13 2023-07-25 Adidas Ag Soles for sports shoes
US9781974B2 (en) 2012-04-13 2017-10-10 Adidas Ag Soles for sports shoes
US9788598B2 (en) 2012-04-13 2017-10-17 Adidas Ag Soles for sports shoes
US9788606B2 (en) 2012-04-13 2017-10-17 Adidas Ag Soles for sports shoes
US9795186B2 (en) 2012-04-13 2017-10-24 Adidas Ag Soles for sports shoes
US9820528B2 (en) 2012-04-13 2017-11-21 Adidas Ag Soles for sports shoes
US10721991B2 (en) 2013-02-13 2020-07-28 Adidas Ag Sole for a shoe
US11445783B2 (en) 2013-02-13 2022-09-20 Adidas Ag Sole for a shoe
US11986047B2 (en) 2013-02-13 2024-05-21 Adidas Ag Sole for a shoe
US9781970B2 (en) 2013-02-13 2017-10-10 Adidas Ag Cushioning element for sports apparel
US9930928B2 (en) 2013-02-13 2018-04-03 Adidas Ag Sole for a shoe
USD906648S1 (en) 2013-04-12 2021-01-05 Adidas Ag Shoe
US10925347B2 (en) 2014-08-11 2021-02-23 Adidas Ag Shoe sole
US11284669B2 (en) 2014-08-13 2022-03-29 Adidas Ag Co-molded 3D elements
US10039342B2 (en) 2014-08-13 2018-08-07 Adidas Ag Co-molded 3D elements
US10667576B2 (en) 2014-08-13 2020-06-02 Adidas Ag Co-molded 3D elements
US11957206B2 (en) 2015-03-23 2024-04-16 Adidas Ag Sole and shoe
US11291268B2 (en) 2015-04-10 2022-04-05 Adidas Ag Sports shoe and method for the manufacture thereof
US10952489B2 (en) 2015-04-16 2021-03-23 Adidas Ag Sports shoes and methods for manufacturing and recycling of sports shoes
US10905919B2 (en) 2015-05-28 2021-02-02 Adidas Ag Ball and method for its manufacture
DE102017216814A1 (de) 2017-09-22 2019-03-28 Adidas Ag Verfahren zum Herstellen eines Formteils und Formteil
CN112795062A (zh) * 2021-01-15 2021-05-14 商丘京威体育用品有限公司 一种耐磨橡胶发泡运动鞋材及其制备方法

Also Published As

Publication number Publication date
ITRN20050006A1 (it) 2006-08-23

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