WO2001025331A1 - Article chaussant realise a partir d'une composition elastomere thermoplastique d'aspect mat - Google Patents

Article chaussant realise a partir d'une composition elastomere thermoplastique d'aspect mat Download PDF

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Publication number
WO2001025331A1
WO2001025331A1 PCT/EP2000/009764 EP0009764W WO0125331A1 WO 2001025331 A1 WO2001025331 A1 WO 2001025331A1 EP 0009764 W EP0009764 W EP 0009764W WO 0125331 A1 WO0125331 A1 WO 0125331A1
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WO
WIPO (PCT)
Prior art keywords
footwear
component
metallocene
density
stabilisers
Prior art date
Application number
PCT/EP2000/009764
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English (en)
Inventor
Alan Michael Batt
Caroline Rita Nicole Maes
Eddy Verheyden
Philippe Vosters
Original Assignee
Kraton Polymers Research B.V.
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 Kraton Polymers Research B.V. filed Critical Kraton Polymers Research B.V.
Priority to AU11335/01A priority Critical patent/AU1133501A/en
Publication of WO2001025331A1 publication Critical patent/WO2001025331A1/fr

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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the invention relates to footwear made from a thermoplastic elastomer composition having a dull look. More in particular, the invention relates to footwear, such as in soles and heels. Background of the invention
  • Thermoplastic elastomer compositions are based on materials which behave like elastomeric rubbers at room temperature, but when heated can be processed like plastics. They are used in the manufacture of casual shoes and sport shoes.
  • the thermoplastic elastomers (TPEs) most frequently used in the production of shoe soles are styrenic block copolymers such as poly (styrene- butadiene-styrene) or SBS copolymers (market share of about 15%) .
  • TPEs thermoplastic elastomers
  • Such compositions have advantages over natural rubber and PVC (e.g. easy and cheap to process; good low temperature crack resistance and excellent grip in wet conditions) .
  • Shell Chemicals published a bulletin on the formulation of TPE compositions for footwear applications based on an SBS copolymer sold as "KRATON” D (KRATON is a trademark) .
  • KRATON is a trademark
  • This bulletin, TPE 4.2.2 issued December 1994 provides a typical formulation comprising oils, styrenic resins, ethene-vinyl acetate (EVA), polyolefins, fillers, antioxidants, UV stabilisers and other ingredients in addition to the "KRATON” D TPE.
  • EVA ethene-vinyl acetate
  • This bulletin also provides general information regarding the compounding equipment and mixing schemes and conditions.
  • a later fact sheet also available from Shell Chemicals, K0002FS-99e, "Starting Formulations for KRATON D Footwear Compounds” provides even more detailed formulations for use in e.g., general purpose solid soling, high hardness thin fashion soling, hiking/mountain boots, and sneakers/slippers.
  • mouldings based on such TPE compositions can have a surface appearance which is less desirable in a range of sole/footwear applications. In particular, they lack the uniform ⁇ dull look' typical of vulcanised natural rubber. This problem may be solved by the addition of a small amount of partially crystalline syndiotactic 1, 2-polybutadiene (e.g., "RB830" sold by JSR) to the TPE composition.
  • RB830 is expensive and not broadly available. It would therefore be desirable to find an alternative TPE composition for footwear applications having a uniform dull look.
  • the new composition should at least retain important footwear properties such as Din Abrasion. Summary of the invention
  • the invention provides footwear made from a thermoplastic elastomer composition comprising
  • Styrenic block copolymers are thermoplastic elastomers having two or more distinguishable polymer blocks, of which at least one is glassy at service temperature but fluid at higher temperatures, and at least one of which is elastomeric (rubbery) at service temperature.
  • a comprehensive review on such polymers is provided by Messrs. Legge, Holden and Schroeder, in "Thermoplastic Elastomers", published by Hanser Publishers in 1987 (ISBN 3-446-14827-2) .
  • block copolymers come in the form of linear diblocks, triblocks and multiblocks (produced with sequential polymerization techniques or difunctional coupling agents), or branched block copolymers (using multifunctional coupling agents and/or re-initiation techniques) .
  • component (a) may be mixture of a triblock or multiblock copolymer with the diblock copolymer that has been used in the preparation of such triblock or multiblock copolymers.
  • the block copolymer to be used in the compound of the present invention may be prepared by any method known in the art including the well known full sequential polymerisation method, optionally in combination with re-initiation, and the coupling method, as illustrated in e.g. US Patents Nos . 3,231,635; 3,251,905; 3,390,207; 3,598,887 and 4,219,627, in European patent application Nos. 413,294, 387,671, 636,654 and International application No. 94/22931.
  • the or each glassy polymer block of the block copolymer is made of polymerized vinylaromatic monomer, such as styrene, in an amount of at least 80 mole% on the total monomer content of the polymer block.
  • Styrene is the preferred vinylaromatic monomer, but other suitable vinylaromatic monomers include ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, and various other alkyl-substituted styrenes, alkoxy-substituted styrenes, vinylnaphthalene and vinyl xylene.
  • alkyl and alkoxy groups may contain from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms.
  • Comonomers if present, may be selected from (di)olefins and other compounds copolymerizable with styrene.
  • Preferred styrenic block copolymers are those wherein the or each elastomeric block of the block copolymer is made of polymerized conjugated diene, such as butadiene or isoprene, in an amount of at least 60 mole% on the total monomer content of the elastomeric block.
  • polymerized conjugated diene such as butadiene or isoprene
  • butadiene and isoprene are the preferred dienes
  • other suitable conjugated dienes include dienes with from 4 to 8 carbon atoms per monomer, for example, 2-ethyl-l, 3-butadiene, 2, 3-dimethyl-l, 3-butadiene, 1, 3-butadiene,
  • 1, 3-pentadiene, 2 -hexadiene, 3-ethyl-l, 3-pentadiene, and mixtures thereof.
  • These conjugated dienes may be copolymerized in either a 1,2- or 1,4-fashion, leading to a vinyl content in the range of 5-80%.
  • Comonomers, if present, may be selected from vinylaromatic monomers and other compounds copolymerizable with the diene.
  • Preferred block copolymers are those that are based on styrene (“S") and butadiene (“B”) or isoprene (“I”) and are conventionally referred to as (SB) n X, (SI) n X, SB, SI, SBS and SIS, wherein “X” refers to the residue of a coupling agent, and "n” has a value of at least 2, preferably more than 2.
  • styrenic block copolymers may also be fully or partially hydrogenated.
  • Preferred hydrogenated styrenic block copolymers are those wherein only the elastomeric block is selectively hydrogenated (more than 80%, preferably more than 99% on total unsaturation) .
  • Such hydrogenated block copolymers provide improved properties in respect of durability, sensitivity to oil and chemicals and floor marking (i.e., leaves less markings in indoor sports) .
  • the content of the vinyl aromatic monomer of the final block copolymer is preferably in the range of from 15 to 75% by weight, and more preferably 20 to 60% by weight, based on the total block copolymer.
  • the total apparent molecular weight of the block copolymer is preferably in the range from 100,000 to 500,000 g/mol, more preferably in the range from 150,000 to 400,000 g/mol.
  • apparent molecular weight as used throughout the specification is meant the molecular weight of a polymer as measured with gel permeation chromatography (GPC) using polystyrene calibration standards (according to ASTM D 3536) .
  • Suitable block copolymers include, amongst others, those sold by Shell under the trademark "KRATON".
  • metallocene polyolefins are polyolefins produced with a metallocene catalyst such as those described in United States Patents Nos . 4,871,705, 5,322,728 and 5,272,236 which are hereby incorporated by reference.
  • metallocene polyolefins are available from Dow Chemical Company under the trademark “AFFINITY” or “ENGAGE” (ethene/octene copolymers) and from Exxon Chemical Company under the trademark “EXACT” (ethene/butene copolymers) .
  • the metallocene polyolefins have low crystallinity when ethene is copolymerised with from 8% to 40% by weight of an alpha-olefin comonomer having from 3 to 20 carbon atoms, preferably from 4 to 12 carbon atoms.
  • Such polyolefins have a good distribution of ethene and the comonomer (as further explained in the references ) .
  • the metallocene polyolefins have a Melt
  • metallocene polyolefins have an MFI in the range of 1.0 to 30 g/10 min.
  • the density of suitable metallocene polyolefins varies from 0.86 to 0.95 kg/1, preferably from 0.88 to 0.92 kg/1.
  • Metallocene polyolefins having a density in the range of 0.89 to 0.90 kg/1 are preferred.
  • Preferred metallocene polyolefins are grades 8150 (density 0.868 kg/1; MFI 2 g/10 min); 8585 (density 0.885 kg/1; MFI 8 g/10 min); and 8440 (density 0.897 kg/1; MFI 6 g/10 min). The latter is particularly preferred.
  • Hydrocarbon extender oils are generally known as paraffinic and/or naphthenic oils . They usually are fractions of products deriving from petroleum refining having less than about 30% by weight of aromatics, measured by clay-gel analysis, and have usually a viscosity comprised between about 100 and about 500 SSU at 37.8 °C (100 °C) . These hydrocarbon extender oils are commercially known, for instance with the trademark "CATENEX SM 925" or "PROCESS KD28", produced and sold by Shell.
  • the amount of extender oils used in the composition of the present invention can range from 0 to 100, preferably from 5 to 30 phr. Higher amounts than 100 phr, however, may be used for some thermoplastic elastomer compositions.
  • the extender oil may be included in the TPE, e.g., as in the oil-extended KRATON D4123, D4270, D4271, KX224, D4272 and/or VECTOR 7400D.
  • the thermoplastic elastomer composition may comprise other components .
  • Such components include inorganic fillers, such as clay, talc, silica, alumina, titanium dioxide, carbon black, calcium carbonate, sawdust and the like, and other pigments.
  • the preferred fillers comprise silica, calcium carbonate and the like and mixtures thereof.
  • the particle sizes may vary from 1 to 50 micrometers, but are usually smaller (e.g., less than 10 micrometers) .
  • the amount of filler employed can range for each of these additional components independently from 0 to 100 phr, preferably from 5 to 50 phr.
  • thermoplastic polymers such as (toughened) polystyrene, polypropene, ethene-vinyl acetate and others.
  • Polystyrene in particular is a common additive to increase the hardness, albeit at the detriment of the appearance.
  • TPE compositions defined above are already known.
  • European patent application No. 712,892 describes compositions comprising I) one or more block copolymers having at least two monoalkenyl arene blocks (i.e., glassy blocks) separated by a saturated conjugated diene block and II) a metallocene polyolefin having a density from 0.86 to 0.91, and a molecular weight distribution of less than 3.
  • TPE compositions comprising block copolymers wherein the conjugated diene block still contains residual unsaturation are believed to be novel.
  • novel TPE compositions that comprise: (a) one or more styrenic block copolymers; (b) -optionally- one or more ingredients selected from extender oils, fillers, hardness regulators, flow improvers, flex crack resistance improvers, stabilisers, UV stabilisers, pigments, blowing agents, and antiblocking agents; and (c) one or more metallocene-based polyolefins of ethene and from 8% to 30% by weight of an alpha-olefin comonomer having from 3 to 20 carbon atoms, having a density from 0.86 to 0.91 and a molecular weight distribution (Mw/Mn) less than 3, with the proviso that component (a) is not a block copolymer having at least two glassy blocks separated by a saturated conjugated diene block.
  • Mw/Mn molecular weight distribution
  • component (a) which excludes the hydrogenated block copolymer known from European patent application No. 712,892.
  • the TPE compositions for footwear applications may be made by compounding the TPE with the other components, for instance using high-shear compounding equipment. On an industrial scale, this is carried out on either a batch mixer or continuous extrusion equipment . Use of co- rotating twin screw extruders have proved to be particularly suitable. Some typical mixing schemes and conditions for the various types of mixing equipment used in KRATON D compounding is disclosed in the aforementioned Bulletin TPE 4.2.2, herewith incorporated by reference. Footwear in accordance with the present invention may find use as soling material (outer, mid or in soles), as clasps (ski-boots), heel counters and toe puffs. However, the TPE composition may also be used in adhesives or other applications that require a uniform dull look. Experimental
  • compositions 1 to 8 are made in accordance with the present invention, whereas compositions A to D are not.
  • Table 1 illustrates the suitability of metallocene polyolefins (e.g., "ENGAGE” 8440) as replacement of
  • Compound D may have the best DIN Abrasion score, but it also has the worst dull look. This is the result of the presence of 20 phr hardener, instead of either metallocene polyolefin of RB 830. If the hardener is replaced by a metallocene polyolefin, then best results are achieved with "ENGAGE" 8440.
  • VD Very Dull
  • D Dull
  • S/S Semi Shiny
  • S Shiny
  • VD Very Dull
  • D Dull
  • S/S Semi Shiny
  • S Shiny

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un article chaussant réalisé à partir d'une composition élastomère thermoplastique contenant (a) un ou plusieurs copolymères séquencés styréniques, (b) éventuellement un ou plusieurs ingrédients sélectionnés parmi des huiles d'extension, des charges, des régulateurs de dureté, des améliorateurs d'écoulement, des améliorateurs de la résistance à la craquelure par flexion, des stabilisateurs, des stabilisateurs d'UV, des pigments, des agents d'expansion, et des agents anti-adhérents, et (c) une ou plusieurs polyoléfines d'éthylène, à base de métallocènes, et de 8 % à 40 % en poids d'un comonomère d'alpha-oléfine ayant 3 à 20 atomes de carbone, présentant une densité de 0,86 à 0,95 kg/l, et une distribution de la masse molaire (Mw/Mn) inférieure à 3.
PCT/EP2000/009764 1999-10-06 2000-10-04 Article chaussant realise a partir d'une composition elastomere thermoplastique d'aspect mat WO2001025331A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11335/01A AU1133501A (en) 1999-10-06 2000-10-04 Footwear made from a thermoplastic elastomer composition having a dull look

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99307867.4 1999-10-06
EP99307867 1999-10-06

Publications (1)

Publication Number Publication Date
WO2001025331A1 true WO2001025331A1 (fr) 2001-04-12

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072429A2 (fr) * 2004-12-30 2006-07-13 Braun Gmbh Composition d'elastomere thermoplastique
FR2904632A1 (fr) * 2006-08-07 2008-02-08 Plymouth Francaise Sa Composition et procede pour la realisation notamment d'une laminette ou d'un bracelet elastique.
FR2904631A1 (fr) * 2006-08-07 2008-02-08 Plymouth Francaise Sa Soc Composition et procede pour la realisation notamment d'une laminette ou d'un bracelet elastique
US7442742B1 (en) 2007-04-04 2008-10-28 Carolina Color Corporation Masterbatch composition
WO2009071549A1 (fr) * 2007-12-06 2009-06-11 Dow Global Technologies Inc. Compositions thermoplastiques pour chaussures sans caractéristiques de marquage
CN104974458A (zh) * 2015-07-23 2015-10-14 温州市宜和鞋材有限公司 一种新型高耐磨、免喷漆鞋底材料及其制备方法
US9969881B2 (en) 2014-07-18 2018-05-15 Carolina Color Corporation Process and composition for well-dispersed, highly loaded color masterbatch
US10428189B2 (en) 2014-07-18 2019-10-01 Chroma Color Corporation Process and composition for well dispersed, highly loaded color masterbatch

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216131A (en) * 1979-05-04 1980-08-05 Shell Oil Company Smooth-look footwear composition
US4225500A (en) * 1979-04-06 1980-09-30 Usm Corporation Novel polymeric compositions for footwear tread members containing a halogenated polyethylene and a block copolymer
WO1995027756A1 (fr) * 1994-04-08 1995-10-19 Esposito Anthony S Jr Elastomere
WO1995033006A1 (fr) * 1994-06-01 1995-12-07 The Dow Chemical Company Compositions pour melanges thermoelastiques
EP0770645A2 (fr) * 1995-10-27 1997-05-02 Riken Vinyl Industry Co., Ltd. Composition thermoplastique élastomérique et procédé pour sa préparation
EP0845498A1 (fr) * 1996-11-29 1998-06-03 Riken Vinyl Industry Co., Ltd. Composition de résine élastomère thermoplastique et procédé pour sa préparation
US5847051A (en) * 1996-08-29 1998-12-08 Shell Oil Company Block copolymer composition containing polypropylene and polybutene

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225500A (en) * 1979-04-06 1980-09-30 Usm Corporation Novel polymeric compositions for footwear tread members containing a halogenated polyethylene and a block copolymer
US4216131A (en) * 1979-05-04 1980-08-05 Shell Oil Company Smooth-look footwear composition
WO1995027756A1 (fr) * 1994-04-08 1995-10-19 Esposito Anthony S Jr Elastomere
WO1995033006A1 (fr) * 1994-06-01 1995-12-07 The Dow Chemical Company Compositions pour melanges thermoelastiques
EP0770645A2 (fr) * 1995-10-27 1997-05-02 Riken Vinyl Industry Co., Ltd. Composition thermoplastique élastomérique et procédé pour sa préparation
US5847051A (en) * 1996-08-29 1998-12-08 Shell Oil Company Block copolymer composition containing polypropylene and polybutene
EP0845498A1 (fr) * 1996-11-29 1998-06-03 Riken Vinyl Industry Co., Ltd. Composition de résine élastomère thermoplastique et procédé pour sa préparation

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072429A2 (fr) * 2004-12-30 2006-07-13 Braun Gmbh Composition d'elastomere thermoplastique
WO2006072429A3 (fr) * 2004-12-30 2006-09-21 Braun Gmbh Composition d'elastomere thermoplastique
FR2904632A1 (fr) * 2006-08-07 2008-02-08 Plymouth Francaise Sa Composition et procede pour la realisation notamment d'une laminette ou d'un bracelet elastique.
FR2904631A1 (fr) * 2006-08-07 2008-02-08 Plymouth Francaise Sa Soc Composition et procede pour la realisation notamment d'une laminette ou d'un bracelet elastique
WO2008017759A2 (fr) 2006-08-07 2008-02-14 Societe Plymouth Francaise Composition et procede pour la realisation d'une laminette, d'une bande, d'une feuille ou d'un bracelet elastique
WO2008017759A3 (fr) * 2006-08-07 2008-03-27 Plymouth Francaise Sa Composition et procede pour la realisation d'une laminette, d'une bande, d'une feuille ou d'un bracelet elastique
US7442742B1 (en) 2007-04-04 2008-10-28 Carolina Color Corporation Masterbatch composition
WO2009071549A1 (fr) * 2007-12-06 2009-06-11 Dow Global Technologies Inc. Compositions thermoplastiques pour chaussures sans caractéristiques de marquage
US9969881B2 (en) 2014-07-18 2018-05-15 Carolina Color Corporation Process and composition for well-dispersed, highly loaded color masterbatch
US10428189B2 (en) 2014-07-18 2019-10-01 Chroma Color Corporation Process and composition for well dispersed, highly loaded color masterbatch
CN104974458A (zh) * 2015-07-23 2015-10-14 温州市宜和鞋材有限公司 一种新型高耐磨、免喷漆鞋底材料及其制备方法
CN104974458B (zh) * 2015-07-23 2019-05-10 温州市宜和鞋材有限公司 一种新型高耐磨、免喷漆鞋底材料及其制备方法

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