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EP2220159A1 - Compositions thermoplastiques pour chaussures sans caractéristiques de marquage - Google Patents

Compositions thermoplastiques pour chaussures sans caractéristiques de marquage

Info

Publication number
EP2220159A1
EP2220159A1 EP08856769A EP08856769A EP2220159A1 EP 2220159 A1 EP2220159 A1 EP 2220159A1 EP 08856769 A EP08856769 A EP 08856769A EP 08856769 A EP08856769 A EP 08856769A EP 2220159 A1 EP2220159 A1 EP 2220159A1
Authority
EP
European Patent Office
Prior art keywords
composition
component
tpe
thermoplastic elastomer
dark pigmented
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Withdrawn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
EP08856769A
Other languages
German (de)
English (en)
Inventor
Antonio Batistini
Gianni Perozzi
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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
Priority claimed from ITMI20072294 external-priority patent/ITMI20072294A1/it
Priority claimed from ITMI20072332 external-priority patent/ITMI20072332A1/it
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP2220159A1 publication Critical patent/EP2220159A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the invention relates to a dark pigmented thermoplastic elastomer composition for, in particular, use in footwear components.
  • Preferably such components have low marking, and more preferably no marking, characteristics from wear friction .
  • Thermoplastic elastomer (TPE) compositions are based on materials which behave like elastomeric rubbers at room temperature, but when heated can be processed like plastics. These materials have a look and touch comparable to vulcanized rubber, although their technology, workability, and recyclability are typical of thermoplastic products.
  • the TPE most frequently used in the production of shoe soles are styrenic block copolymers such as poly styrene-butadiene- styrene (SBS) copolymers.
  • SBS poly styrene-butadiene- styrene
  • TPEs compositions based on SBS and/or thermoplastic polyurethane (TPU) have been used in the footwear industry for several years; formulations comprising SBS, ethene-vinyl acetate (EVA) , oils, polyolefins, TPU, fillers, anti-oxidants, pigments and other ingredients are well known in the industry. Improvements of such formulations have been described in the prior art, e.g. the "dull look" obtained via addition of metallocene polyolefins (WO 01/25331);
  • Thermoplastic materials based on polyurethane components for forming light foamed products, in particular, for forming soles for footwear are described in WO 2006/090221.
  • the invention relates to a dark pigmented thermoplastic elastomer composition suitable, for production of articles, in particular, footwear components.
  • Such composition comprises:
  • SBS styrene butadiene styrene block copolymers
  • a black pigment composition which is carbon black free (d) a black pigment composition which is carbon black free; (e) optionally, polydimethylsiloxane (PDMS);
  • PDMS polydimethylsiloxane
  • ingredients selected from extender oils, fillers, hardness regulators, flow improvers, flex crack resistance improvers, stabilizers, UV stabilizers, pigments, blowing agents, and anti- blocking agents.
  • TPE compositions described above can be used in particular, to produce dark colored footwear components such as shoe soles and heels.
  • the TPE compositions according to this invention may find other industrial applications in the fields where TPE compositions are used and low or no marking effects under friction are desired.
  • TPE compositions according to this invention allow production of manufactured articles, in particular shoe soles which do not exhibit the marking of the contact surface from wear friction typically associated with the current dark pigmented thermoplastic elastomer compounds.
  • dark pigmented thermoplastic composition or “dark pigmented thermoplastic elastomer (TPE) composition” means a thermoplastic elastomer composition which contains one or more coloring pigment (s) wherein at least 40 per cent by weight of the total coloring pigment (s) in the thermoplastic elastomer composition is a black color pigment” .
  • the component (d) constitutes a specific and distinguishing feature of this invention and is always present in the TPE compositions of this invention.
  • the components (e) and (f) are optionally present in the TPE compositions. According to a preferred embodiment of the invention, one, or more ingredients listed under (f) is/are usually comprised by these TPE compositions.
  • Component (a) This component consists of one or more styrene butadiene styrene (SBS) block copolymers having two or more distinct polymer blocks, at least one of which is glassy (i.e., below glass transition point, therefore brittle and stiff) at service temperature but fluid at higher temperatures, and at least one of which is elastomeric (i.e., above glass transition point, therefore flexible or elastic) at service temperature .
  • SBS styrene butadiene styrene
  • the styrene (S) and butadiene (B) monomers can be replaced by, respectively, other vinylaromatic and 1 , 3-conjugated diene monomers.
  • the terms "butadiene-styrene-butadiene block copolymers" or "SBS block copolymers” include also those block copolymers where the styrene and butadiene monomers are replaced by the other vinylaromatic and 1, 3-conjugated diene that are hereafter defined in more detail.
  • the SBS block copolymers can be in the form of linear diblock, triblocks and multiblock SBS copolymers or in the form of radial SBS block copolymers.
  • a mixture of linear SBS block copolymer and of radial SBS block copolymer can also be used, according to this invention.
  • the methods for producing these SBS block copolymers for use according to this invention are well known in the art. See for instance US 3,251,905, US 3,231,635, US 3,598,887 and US 4,219,627.
  • the glassy block (s) of the SBS block copolymers is/are made of a vinylaromatic monomer, such as styrene.
  • a vinylaromatic monomer such as styrene
  • styrene is the preferred monomer
  • other vinylaromatic monomers can be employed such as ⁇ -methylstyrene, other styrene derivatives where the benzene ring is substituted by one to three (Ci- C 4 )alkyls, preferably methyl or ethyl group (s), or vinylnaphthalene optionally substituted by one or two methyl or ethyl groups.
  • Each styrene glassy polymer block contains a total styrene monomer amount of at least 80 mole percent, the remaining portion, if any, consisting of other vinylaromatic monomer (s), e.g. CC-methyl styrene.
  • s vinylaromatic monomer
  • the elastomeric block (s) of the SBS block copolymers used as component (a) of the TPE compositions according to this invention are made of polymerized conjugated 1,3-diene, such as butadiene.
  • 1, 3-butadiene is the preferred monomer
  • other conjugated diene of 5-6 carbon atoms can be employed, such as isoprene, 1, 3-pentadiene, 2, 3-dimethyl-l, 3-butadiene, and 2 , 4-hexadiene .
  • These conjugated dienes may be polymerized in either 1,2 or 1,4-fashion to a vinyl content in the range of 5 to 80% (mole%) .
  • Each elastomeric block of the SBS block copolymer contains a total conjugated diene monomer, such as butadiene or isoprene, which is more than 50%, preferably at least 70% (mole%) , the remaining portion, if any, consisting of other co- polymerizable monomers such as vinylaromatic monomers.
  • the SBS block copolymers employed as component (a) according to this invention may also be partially or fully hydrogenated.
  • Preferred hydrogenated SBS block copolymers for use as component (a) are those wherein only the elastomeric block is selectively hydrogenated (usually more than 80%, preferably more than 99% (mole%) on total unsaturation) .
  • the ratio between the 1, 3-conjugated diene preferably butadiene, and the vinylaromatic monomer, preferably styrene, in the SBS block copolymer is from 90 to 10, preferably from 80 to 20, more preferably is 70 to 30 (molar%) .
  • the total weight average molecular weight of the SBS block copolymer preferably ranges from 100.000 to 500.000, more preferably from 150.000 to 400.000 (g/mole) .
  • the SBS block copolymers can be extended with hydrocarbon extender oils such as paraffin and or naphthenic oils which are hereinafter described in more detail, in an amount that ranges from 0 to 40 part by weight of the total extended SBS block copolymer.
  • the extender oils may be already included in the SBS block copolymers which are commercially available.
  • the amount of component (a) in the TPE composition in general ranges from 0 to 80 per cent by weight, preferably from 0 to 70, more preferably from 0 and 60 by weight, based on total weight of the composition.
  • SBS block copolymers which are suitable for the TPE compositions of this invention include EUROPRENE SOl T172 SBS block copolymer (Polimeri Europa of San Donato Milanese, Milan, Italy), KRATON (Texas Pacific, Fort Worth, Texas, USA), STEREON (Fireston, Akorn, Ohio, USA), FINAPRENE (Total Petrochemicals Elastomers, Brussels, Belgium) , TUFPRENE (Asahi Kasei Corp., Tokyo, Japan) and others.
  • the SBS block copolymer material of component (a) can be partially substituted up to 40% by weight, based on total weight of the composition, by a polybutadiene polymer (see, for instance "Component J” in TABLE 1), a polyolefin elastomer such as ethylene/propylene copolymers, e.g. EPDM copolymers, or by styrene-butadiene (SBR) copolymers.
  • a polybutadiene polymer see, for instance "Component J” in TABLE 1
  • a polyolefin elastomer such as ethylene/propylene copolymers, e.g. EPDM copolymers
  • SBR styrene-butadiene
  • This component consists of one or more polyolefin elastomers.
  • the olefin copolymer of component (b) for use in the TPE composition of the present invention is an olefin copolymer that has a density from 0.86 to 0.92 g/cm 3 and is obtained through copolymerization of ethylene with an ⁇ -olefin, or the copolymerization of propylene with ethylene or an ⁇ -olefin having 4 to 12 carbon atoms.
  • the olefin copolymer is obtained through copolymerization of ethylene with an ⁇ -olefin, including, but not limited to, propylene and an ⁇ -olefin having 4 to 12 carbon atoms, and more preferably the copolymerization of ethylene with 1-butene, 1- hexene or 1-octene.
  • an ⁇ -olefin including, but not limited to, propylene and an ⁇ -olefin having 4 to 12 carbon atoms, and more preferably the copolymerization of ethylene with 1-butene, 1- hexene or 1-octene.
  • Examples of the ⁇ -olefin having 4 to 12 carbon atoms used to form the ethylene or propylene and ⁇ -olefin copolymer of component (b) include 1-butene, 2-methyl-l-butene, 3-methyl-l- butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1- decene and 1-dodecene. These ⁇ -olefins may be used individually or in combinations of two or more to provide the structural units of the olefin copolymer (b) .
  • the olefin copolymer of component (b) may be any of the known materials.
  • those that have a density of 0.86 to 0.92 g/cm 3 are selected from the products including ENGAGE (product name) available from The Dow Chemical Company, EXACT series (product name) manufactured by ExxonMobil Chemical Co., Ltd., TAFMER series (product name) manufactured by Mitsui Petrochemical Industries Ltd., and N-series of ESPREN SPO (product name) manufactured by Sumitomo Chemical Industry Co., Ltd.
  • metallocene based polyolefin elastomers elastomers prepared in the presence of a metallocene catalyst, including, for example, bis-metallocene catalysts and contained geometry catalysts
  • metallocene polyolefins produced by copolymerizing ethylene with from 8% to 40% (mole%) of an alpha-olefin of 3 to 20 carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from 6 to 10 carbon atoms, with a good distribution of ethene and comonomers are suitably employed as component (b) .
  • it is preferred that such polyolefins have a low crystallinity degree .
  • these metallocene polyolefins have a Melt Flow Index ("MFI" at 190°C/5kg, determined in accordance with ISO 1133) ranging from 0.5 to 40 g/min, preferably from 1.0 to 30 g/10 min, and their density is in the range from 0.86 to 0.89 kg/1, and preferably from 0.86 to 0.885 kg/1.
  • MFI Melt Flow Index
  • component (b) of the TPE compositions of this invention are, for instance, the ethene (or ethylene) -octene copolymers marketed under the trademarks AFFINITY, and ENGAGE (by The Dow Chemical Company) , EXACT (by ExxonMobil Chemical Co.) and TAMFER (from Mitsui Petrochemical Industries Ltd.) .
  • the amount of component (b) in the TPE composition of this invention may range from 0 to 99 per cent by weight, preferably from 0 and 80, more preferably from 0 and 60, based on total weight of the composition.
  • thermoplastic polyurethanes i.e., substances obtained by reaction of a diisocyanate composition with at least one difunctional compound capable of reacting with an isocyanate group, preferably, at least one difunctional polyhydroxy compound, and optionally a chain extender.
  • difunctional means that the average functionality of the isocyanate composition or the polyhydroxy compound is about 2.
  • the diisocyanate reactant may be aromatic or aliphatic.
  • Aromatic diisocyanates include, for example, 4,4'- and 2, 2 ' -diphenyl-methanediisocyanate (MDI) and the corresponding isomeric mixtures.
  • MDI 4,4'- and 2, 2 ' -diphenyl-methanediisocyanate
  • the diisocyanate component may also be an MDI variant.
  • MDI variants are well known in the art, and particularly include liquid products obtained by introducing carbodiimide groups into said diisocyanate composition.
  • aliphatic and cycloaliphatic isocyanate compounds include 1, 6-hexamethylene-diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4'-, 2,2'- and 2,4'- dicyclohexylmethanediisocyanate (H12MDI), the isomeric mixtures thereof; 1, 3-tetramethylene xylene diisocyanate; norbane diisocyanate; and 1,3- and 1,4- bis (isocyanatomethyl) cyclohexane can also be used with the present invention.
  • Mixtures of the aromatic, aliphatic and cycloaliphatic isocyanates may also be used.
  • isocyanate compositions comprising aromatic diisocyanate and more preferably MDI.
  • the difunctional compound preferably a difunctional polyhydroxy compound, has a molecular weight of between 500 and 20000, and may be selected from derivatives of polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes and especially, polyesters, polyethers, polycaprolactone or mixtures thereof.
  • Polyesters include hydroxy-polyesters reaction products of dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 2- methylpropanediol, 3-methylpentane-l, 5-diol, 1, 6-hexanediol, or cyclohexane dimethanol or mixtures thereof, and dicarboxilic acids or their esters, such as adipic, glutaric, succinic, sebacic, and terephthalic acid, phthalic anhydride, tetrachlorophthalic anhydride or mixture thereof.
  • dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 2- methylpropanediol, 3-methylpentane-l, 5-diol, 1, 6-hexanediol, or cycl
  • Polyethers include products obtained by the polymerization of a cyclic oxide, e.g. ethylene, propylene, butylene oxide or tetrahydrofuran in the presence, where necessary, of difunctional initiators.
  • Suitable initiator compounds include water, ethylene glycol, propylene glycol, di-ethylene glycol, tri-ethylene glycol, di-propylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1,6- hexanediol and the like. Mixtures of initiators and/or cyclic oxides may be used.
  • Polyolefin diols include hydroxyl-terminated butadiene homo- and copolymers.
  • Suitable chain extender include aliphatic diols, such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1,5- pentanediol, 1, 6-hexanediol, 1, 2-propanediol, 2- methylpropanediol, 1, 3-butanediol, 2, 3-butanediol, 1,3- pentanediol 1, 2-hexanediol, 3-methylpentane-l, 5-diol, neopentyl glycol, diethylene glycol, di-propylene glycol and tri-propylene glycol, and aminoalcohols such as ethanolamine, N-methyldiethanolamine and the like; 1, 4-butanediol is preferred.
  • the TPU employed as component (c) of the TPE compositions of this invention may optionally contain additives, stabilizers, surface active agents and foam stabilizers, plasticizers, and the like.
  • Additives that can be mixed with the TPU are, for instance, poly-vinyl chloride or ethylvinylacetate, paraffin or naphthenic oil, fillers of mineral origin, and the like.
  • Stabilizers which may be added to the TPU include anti-static and anti-oxidant and anti-UV.
  • TPU surface active agents and foam stabilizers which may be added to the TPU include for example, siloxane-oxyalkylene copolymers .
  • Plasticizers of the TPU component include, for instance, alkyl phthalates and alkyl-benzoates .
  • Suitable TPUs are commercially available, and include, among others, those sold under the name EPAMOULD (Epaflex Polyurethane S.r.l., Milan, Italy), LARIPUR (Coim S. p. A., Settimo Milanese (Milan), Italy), APILON (Api Plastic S. p. A., Mussolente (Vicenza) , Italy), AVALON (Huntsman Poyurethanes, Salt Lake City, Utah, USA) and ELASTOLLAN (Elastogran GmbH, Lamfoerde, Germany), PELLETHANE (The Dow Chemical Co., Midland, Michigan USA) .
  • EPAMOULD Epaflex Polyurethane S.r.l., Milan, Italy
  • LARIPUR Coim S. p. A., Settimo Milanese (Milan), Italy
  • APILON Api Plastic S. p. A., Mussolente (Vicenza) , Italy
  • AVALON Haunt
  • the amount of component (c) in the TPE composition in general may range from 0 to 80, preferably from 0 to 60 more preferably 0 to 40 per cent by weight, based on total weight of the composition.
  • Component (d) This component constitutes an essential feature of the TPE composition of this invention since it gives the dark color to the footwear produced with the TPE composition without involving any marking effect.
  • a black pigment is a pigment, which when blended into a thermoplastic polymer or polymer composition, at a level of 0.1 to 3 per cent by weight %, based on the total weight of the final composition, leads to a reflectance (of this blend) of less than 15 % over the wavelength from 400 to 700 nm, as measured by a spectrophotometer equipped with an integrating sphere and using a setting such that the specular component of the light reflectance is included
  • the reflectance is less than 12 %. More preferable the reflectance is less than 9%. In one embodiment the reflectance of the pigmented polymer over this wavelength pattern is less than 7 %.
  • black pigment composition refers to a composition comprising a black pigment, as discussed above .
  • the TPE composition of this invention may contain other pigments, which are not black pigments, besides the black pigment of component (d) hereabove defined.
  • the black pigment component (d) generally comprises at least 40 wt% of the total pigment used in the dark pigmented thermoplastic composition. If desired, the black pigment can comprise greater than 60 wt%, or even greater than 70 wt% of the total pigment used in the dark pigmented thermoplastic composition. If desired, the black pigment may comprise 100 wt% of the pigment added to the dark thermoplastic composition. This component is characterized in that it is carbon black free.
  • black pigments or combination of pigments for use in the present invention include, for example, those commercialized by Clariant Masterbatches S. p. A., Milan, Italy under the trademarks RENOL PV90050120 - BN/GUM and RENOL PC GUM NERO CBF.
  • the amount of component (d) in the TPE composition may range from 0.1 to 3 per cent by weight, based on total weight of the composition .
  • Component (e) This component is a polydiorganosiloxane, having a viscosity of at least one million centistokes at 25 0 C. Such an additive can be added to further increase wear resistance of developed formulations, as well as act as internal lubricating and demoulding agent .
  • the amount of component (e) in the TPE composition may range from 0 to 4% by weight, based on total weight of the composition .
  • compositions may comprise extender oils which may be added to the whole composition blend in addition to the amount which may be originally included into the SBS block copolymer (component (a) ) , as described above.
  • extender oils are products deriving from petroleum refining having less than 30 per cent by weight of aromatic hydrocarbons .
  • the amount of extender oil which may be added to the whole composition blend besides the amount that may be included into the component (a) , when present in the composition blend, ranges from 0 to 40 by weight, based on total weight of the composition .
  • extender oils include, for example, CELTIS 902 from ENI S. p. A., Stagno (Livorno) Italy .
  • Other ingredients which may be optionally present in the TPE composition of this invention include, for instance, fillers of mineral origin such as clay, silica, talc, calcium carbonate, alumina and the like, hardness regulators such as polystyrene crystals, other (not black) pigments, and chemical or physical blowing agents. Blowing agents are usually added to the other components of the TPE composition when it is desired to reduce the density of the TPE up to 0.5 kg/1. Any known blowing agent used for the preparation of foamed thermoplastic products may be used in the present invention.
  • blowing agents are usually added according to a known method such as the one described in WO 00/44821, wherein the blowing agent is encapsulated and contained in special microspheres added to the granulated TPE blend mixture, or according to the method disclosed in WO 2006/090221.
  • Any thermally expandable microspheres can be used in the present invention.
  • microspheres containing hydrocarbons, in particular aliphatic or cycloaliphatic hydrocarbons are preferred.
  • the micro-cells or microspheres containing the blowing agent which are incorporated into the TPE blend mixture according to the above mentioned methods consist of a copolymer of the acrylic/methacrylonitrile or acrylonitrile/acrylic or ester/olefin group encapsulating the blowing agent.
  • suitable physical blowing agents include volatile liquids such as chlorofluorocarbons, partially halogenated hydrocarbons or non-halogenated hydrocarbons like propane, n- butane, isobutane, n-pentane, isopentane and/or neopentane.
  • Microspheres containing aliphatic or cycloaliphatic hydrocarbons are commercially available, for instance, under the trademark EXPANCELL, (AKZO Nobel Industries, Amsterdam, Holland) or MICROPEARL (Matsumoto Yushi Seiyaku, Osaka Japan) . Both endothermic and exothermic chemical blowing agents can be used. Examples of suitable chemical blowing agents include gaseous compounds such as nitrogen or carbon dioxide, gas (e.g. CO 2 ) forming compounds such as azodicarbonamides, carbonates, bicarbonates, citrates, nitrates, borohydrides, carbides such as alkaline earth and alkali metal carbonates and bicarbonates e.g.
  • Preferred endothermic blowing agents comprise bicarbonates or citrates .
  • Azodicarbonamide type blowing agents are preferred as exothermic blowing agents.
  • the amount of the optional ingredients, other than the extender oils, which are collectively designated hereinabove as component (f ) , as a whole, may range from 0 to 4 per cent by weight .
  • the amount of blowing agent (s), when employed, may range from 1 to 3 per cent by weight.
  • the TPE compositions suitable for the production of shoe soles with no marking effect, have no or low polystyrene and mineral filler content, and have no or low level of plasticizer.
  • the total per cent amount of the various components (a) to (f) of the TPE of this invention must sum up to 100 per cent and that the total amount of component (s) (a) and/or at least one of one of (b) and (c) in the TPE composition must be at least 55 per cent, preferably at least 70 percent, more preferably at least 80 percent by weight, based on total weight of the composition.
  • Compounding and Injection moulding The formulations for the TPE compositions of this invention are prepared according to compounding procedures known to the skilled in the art. In practice, all components are mixed by using a tumble mixer at variable speed and then fed to a co- rotating twin screw extruder at 140-220 0 C.
  • the extruded strands are water cooled and granulated.
  • the granules are molded using a injection moulding machine with the injection unit set at 12O 0 C to 16O 0 C to obtain plates and soles prototypes.
  • Testing Plates and soles prototypes are tested for abrasion resistance, tensile strength, elongation, tear and strength. The tests are carried out on plates according to the DIN methods indicated in TABLE 2. The marking effect is evaluated by visual inspection, after manually fractioning the molded plates sample on a surface, e.g. the tiles, hardwood, vinyl flooring.
  • Component A EUROPRENE Sol T 172 SBS block copolymer, 70% (mole%) butadiene, 30% styrene, extended with paraffinic oil (50 pbw for 100 of polymer); from Polimeri Europa, San Donato Milanese, Milan (Italy)
  • Component B ENGAGE 8200, ethene/octene copolymer, from Dow Chemical Company, Midland, Michigan - (USA)
  • Component C EPAMOULD 8OA, polyester based thermoplastic polyurethane; from Epaflex Polyurethane SrI - Milan (Italy)
  • Component D RENOL PV 90050120-BN/GUM, black master batch from carbon black free pigment composition into PE-EVA from Clariant Masterbatches SpA - Milan (Italy)
  • Component E Polydimethylsiloxane (MP50 from Dow Corning Co) having a viscosity of 20 million centistokes at 25 0 C
  • Component F CELTIS 902, paraffinic oil; from ENI SpA - Stagno
  • Component G SARMAPRENE Nero tech; from Clariant Masterbatches
  • Component H Mineral filler calcium carbonate, from Omya SpA -
  • Component I Polystyrene crystal, melt flow index 25 at 19O 0 C,
  • Component J JSR RB 840/830, syndiotactic polybutadiene polymer; from JSR Corporation - Tokio (Japan)
  • pellets or granules obtained therefrom are injection moulded into plates which are submitted to testing as described above.
  • Examples 1, 2, 5 and 7 are comparative examples which are carried out according to the teachings of the state of the art.
  • TPE compositions of this invention allow production of dark pigmented articles, in particular, footwear such as shoe soles and heels that maintain the functional characteristic required for their use (i.e., abrasion resistance, tear and tensile strength, etc.), and do not show any undesired marking effect.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition élastomère thermoplastique pigmentée noire pour la production d'articles, en particulier de composants de chaussures, et qui comprend les composants principaux suivants : (a) un ou plusieurs copolymères séquencés de styrène-butadiène-styrène (SBS), et/ou au moins l'un de (b) et (c) où : (b) est un ou plusieurs élastomères de polyoléfine et (c) est un ou plusieurs polyuréthanes thermoplastiques (TPU) ; et (d) une composition de pigment noir qui est exempte de noir de carbone ; et qui contient facultativement d'autres composants auxiliaires tels que des huiles de charge, des régulateurs de dureté, des charges, des plastifiants, des pigments, des agents gonflants et similaires.
EP08856769A 2007-12-06 2008-12-02 Compositions thermoplastiques pour chaussures sans caractéristiques de marquage Withdrawn EP2220159A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI20072294 ITMI20072294A1 (it) 2007-12-06 2007-12-06 Composizioni termoplastiche contenenti pigmento scuro per calzature prive di effetti di segnatura
ITMI20072332 ITMI20072332A1 (it) 2007-12-13 2007-12-13 Composizioni termoplastiche contenenti pigmento scuro per calzature prive di effetti di segnatura
PCT/EP2008/066643 WO2009071549A1 (fr) 2007-12-06 2008-12-02 Compositions thermoplastiques pour chaussures sans caractéristiques de marquage

Publications (1)

Publication Number Publication Date
EP2220159A1 true EP2220159A1 (fr) 2010-08-25

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EP08856769A Withdrawn EP2220159A1 (fr) 2007-12-06 2008-12-02 Compositions thermoplastiques pour chaussures sans caractéristiques de marquage

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Country Link
EP (1) EP2220159A1 (fr)
BR (1) BRPI0819054A2 (fr)
TW (1) TW200936681A (fr)
WO (1) WO2009071549A1 (fr)

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RU2017141610A (ru) * 2015-04-30 2019-05-31 Басф Се Полимерная композиция, содержащая термопластичный полиуретан и полиолефин
US20180291229A1 (en) * 2015-05-18 2018-10-11 Tarkett Gdl Halogen-Free Decorative Homogeneous Surface Coverings
CN110903629A (zh) * 2019-12-21 2020-03-24 惠安伟盛鞋业有限公司 一种高弹性耐磨聚氨酯发泡鞋材及其制备方法

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Publication number Priority date Publication date Assignee Title
DE69725619T2 (de) * 1996-11-29 2004-08-19 Riken Technos Corp. Thermoplastische Elastomerzusammensetzung
WO2001025331A1 (fr) * 1999-10-06 2001-04-12 Kraton Polymers Research B.V. Article chaussant realise a partir d'une composition elastomere thermoplastique d'aspect mat
ITRN20050006A1 (it) * 2005-02-22 2006-08-23 Goldenplast Spa Miscela granulare di materiali termoplastici a base poliuretanica per la formatura di manufatti leggeri,espansi, in particolare parti di calzature

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Title
See references of WO2009071549A1 *

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TW200936681A (en) 2009-09-01
WO2009071549A1 (fr) 2009-06-11
BRPI0819054A2 (pt) 2015-05-05

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