WO2008083451A1 - Composition de polymères, vulcanisat moussé, de type caoutchouc, microporeux, et semelle de chaussure moussée, de type caoutchouc, microporeuse - Google Patents

Composition de polymères, vulcanisat moussé, de type caoutchouc, microporeux, et semelle de chaussure moussée, de type caoutchouc, microporeuse Download PDF

Info

Publication number
WO2008083451A1
WO2008083451A1 PCT/BR2007/000168 BR2007000168W WO2008083451A1 WO 2008083451 A1 WO2008083451 A1 WO 2008083451A1 BR 2007000168 W BR2007000168 W BR 2007000168W WO 2008083451 A1 WO2008083451 A1 WO 2008083451A1
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
rubber
polymer composition
mixtures
block copolymer
Prior art date
Application number
PCT/BR2007/000168
Other languages
English (en)
Inventor
Martins Gomes Júnior JARBAS
Original Assignee
Dupé S/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 Dupé S/A filed Critical Dupé S/A
Publication of WO2008083451A1 publication Critical patent/WO2008083451A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with 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
    • 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
    • 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 more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • TITLE "POLYMER COMPOSITION, MICROPOROUS RUBBER-LIKE FOAMED VULCANIZATE, AND MICROPOROUS RUBBER-LIKE FOAMED SHOE SOLE"
  • the present invention relates to footwear, and more particularly to a sole which has improved softness properties while maintaining a desirable wear-resistance. More specifically, the present invention relates to shoe soles made from polymer materials for affording minimal fatigue and ease of wearing by effectively absorbing shocks during walking, and cumulatively without losses in wear- resistance.
  • a preferred footwear sole is an entire sandal sole manufactured from a polymer composition based on rubber-like materials imparting a gel quality to said sole.
  • Soles with special characteristics are well known in the footwear industry. Soles can be either made as an integral body, or can be made up from two or more layers of different materials imparting different properties to the sole as a whole. Exemplary shoe soles consisting of two layers is described in U.S. Patent 3,698,108. In addition, soles including outsoles and insoles can be formed as a sheet with openings for inserting components having improved softness characteristics corresponding to sensitive foot parts, e.g., foot heel.
  • Gels of prior art are generally either pre-set to fit the contours of a foot, or as soft liquid gels which must be placed in a bladder, or even environmentally-responsive gels.
  • a conforming medium containing gels for customized fitting components to be used in a shoe is disclosed.
  • Such a shoe sole components are environmentally-responsive gels, i.e., they are temperature-responsive gels so that they react to body heat to transition from a liquid to a gel and vice versa.
  • the disclosed gel composition has a viscosity of less than 5000 cps at a first temperature and a viscosity of greater than 500,000 cps at a second temperature.
  • U.S. Patent 5,695,850 describes performance enhancing athletic shoe components which provide energy return and shock absorption useful for athletes shoes, said components being produced from a cured mix of high-cis 1 ,4-polybutadiene and a rubber selected from natural rubber, synthetic rubber, synthetic isoprene rubber, polyisoprene, butadiene acrylonitrile rubber and ethylenepropylene diene modified rubber.
  • a gel texture should not make possible an adequate energy return, e.g., to make possible jumping or running abilities.
  • U.S. Patent Nos 5,755,045 and 5,681 ,649 describe footwear sole members comprising a cushioning material for obtaining improved shock absorbing properties and light weight from a polymer composition
  • a polymer composition comprising (A) a composite material in which a low molecular weight material is retained in a medium material, and (B) a high molecular weight or polymer material.
  • the polymer material is composed mainly of a thermosetting material.
  • medium materials are cited: thermoplastic elastomers, such as styrene elastomers; and thermoplastic resins.
  • a limitation in choosing (A) and (B) materials is that the difference in solubility parameter between the low molecular weight material and the polymer material is up to 4.0.
  • the footwear member is to be used in insoles, midsoles or outsoles of a shoe aiming to improve shock absorbing properties and hardness.
  • the disclosed footwear sole member is only used as inserts into soles (in-, mid- or outsoles), i.e., the member could not be used as an entire sole because of a lack of suitable wear-resistance.
  • Another example of the use of gel compositions as portions inserted into the sole is disclosed in the U.S.
  • Patent 6,598,319 in which an insole construction made from a sheet of polymeric foam material with openings in the arch and/or heel areas that are filled with a polymeric gel is described.
  • the foam is substantially closed cell polymeric foam, such as neoprene, and the gel may be of any polymeric material which is substantially free of air bubbles and voids and exhibits gel properties of being deformable, such as polyurethane elastomeric gel.
  • U.S. Patent 5,728,744 an olefin thermoplastic elastomer foamed product is described, said product having several uses, including shoe soles and sandals.
  • the olefin thermoplastic elastomer foamed product is obtained by heating a foamable composition comprising: (i) a partially crosslinked thermoplastic elastomer composition (A) obtained by heating, in the presence of an organic peroxide, a mixture of a peroxide-crosslinkable olefin copolymer rubber, e.g.
  • olefin plastic a homopolymer or copolymer containing 50 to 100% by mol of an ⁇ -olefin
  • B an olefin plastic
  • C a foaming agent
  • the term "partially crosslinked thermoplastic elastomer composition” means a composition having a gel content of not less than 10% by weight, preferably 20 to 97% by weight.
  • the resulting foamed products are soft to the touch and has heat resistance and weathering resistance. Specifically, such a foamed product does not exhibit a proper friction resistance, and consequently it is unsuitable in view of wear-resistance.
  • Gel-containing rubber mixtures are also known as appropriate for using in other articles such as tire manufacturing.
  • EPDM ethylene/propylene/diene terpolymer
  • SBR styrene/butadiene copolymers
  • polymer gel compositions used in tire manufacturing is described in U.S. Patent 6,127,488, in which rubber mixtures are used in making a tire tread.
  • the styrene/butadiene rubber gel (A) component are microgels obtained by crosslinking styrene/butadiene copolymers containing from 1 to 80 wt.
  • the at least one rubber (B) component is selected from a group containing polybutadiene, styrene/butadiene copolymers, styrene/butadiene copolymers and graft polymers; and ethylene/propylene/diene terpolymer.
  • Patent 6,127,4808 the disclosed rubber mixtures are suitable for the preparation of vulcanizates having unusually high damping at temperatures of from -20 to +20 0 C as well as unusually low damping at temperatures of from 40 to 80 0 C that are desirable properties in manufacturing vehicle tires which need to grip in the wet and to have low rolling resistance. Clearly, these are not characteristics to impart feet comfort and wear-resistance to a shoe sole.
  • an outsole having high gripping force to obtain superior slip prevention performance to be used, in particular, in trekking shoes is disclosed.
  • Such a shoe outsoles are produced from a molded vulcanized rubber material containing 70-100 wt. % of styrene-butadiene rubber whose glass transition temperature (Tg) is higher than -33°C and less than -10 0 C. It is mentioned that by using a styrene-butadiene rubber having a styrene content ranging from 15 to 25 wt. % and a butadiene content ranging from 35 to 70 wt. %, the vulcanized rubber has high tensile strength, wear resistance and stability.
  • an outsole made with such a rubber has a durable, high degree of ground-gripping performance.
  • an outsole is wear-resistant, it is not suitable for using as a comfortable sole, particularly in case of a sandal. Accordingly, the outsole of U.S. Patent 6,335,392 needs to present rather a high stability than a soft texture.
  • the present invention is characterized in that an improved sole has softness properties which result from a microporous, vulcanizing polymer composition based on rubber-like materials imparting a gel quality to said sole; and in that said rubber-like materials are present in said composition in a such proportions that desirable physical properties, e.g., wear resistance are the same as compared with soles in which the gel quality is absent.
  • the rubber-like materials are styrene-based copolymers having different styrene content as well as different monomer units arrangements in the polymer chain and combined in a way for obtaining said desirable properties.
  • the present invention relates to a polymer composition
  • a polymer composition comprising: (A) at least one styrene block copolymer selected from the group consisting of SIS (styrene-isoprene- styrene) block copolymer, SBS (styrene-butadiene-styrene) block copolymer, SEBS (styrene- ethylene-butylene-styrene) block copolymer, SEPS (styrene-ethylene-propylene-styrene) block copolymer, and mixtures thereof; (B) at least one rubber-like material containing double bonds selected from the group consisting of styrene-butadiene copolymer with high styrene content, styrene-butadiene copolymer with mean styrene content, polybutadiene rubber, polyisoprene rubber, natural rubber and mixtures thereof; (C
  • the polymer composition of the invention comprises: (A) a styrene- butadiene block copolymer; (B) at least two rubber-like materials containing double bonds selected from the group consisting of styrene-butadiene copolymer having a high styrene content, styrene- butadiene copolymer having a mean styrene content, polybutadiene rubber, and mixtures thereof; (C) a softness enhancer polymer selected from ethylene-propylene copolymer, ethylene- propylene-diene terpolymer, and mixtures thereof; and (D) optionally fillers and rubber auxiliary substances, wherein the components (A), (B), and (C) are in a proportion such that the (A):(B) ratio ranges from 1:7 to 2:1 , and the (A):(C) ratio ranges from 1:3 to 9:1.
  • a second embodiment of the present invention relates to a microporous rubber-like foamed vulcanizate produced from a polymer composition
  • a polymer composition comprising: (A) at least one styrene block copolymer selected from the group consisting of (styrene-isoprene-styrene) block copolymer, (styrene-butadiene-styrene) block copolymer, (styrene-ethylene-butylene-styrene) block copolymer, (styrene-ethylene-propylene-styrene) block copolymer, and mixtures thereof; (B) at least one rubber-like material containing double bonds selected from the group consisting of styrene-butadiene copolymer with high styrene content, styrene-butadiene copolymer with mean styrene content, polybutadiene rubber, polyisopren
  • the present invention refers to a microporous rubber-like foamed shoe sole obtained from a polymer composition
  • a polymer composition comprising (A) at least one styrene block copolymer selected from the group consisting of (styrene-isoprene-styrene) block copolymer, (styrene-butadiene- styrene) block copolymer, (styrene-ethylene-butylene-styrene) block copolymer, (styrene-ethylene- propylene-styrene) block copolymer, and mixtures thereof; (B) at least one rubber-like material containing double bonds selected from the group consisting of styrene-butadiene copolymer with high styrene content, styrene-butadiene copolymer with mean styrene content, polybutadiene rubber, polyisoprene rubber, natural rubber and
  • thermoplastic-thermosetting polymers relationships for balancing the desirable properties of both types of polymers.
  • the inventors have surprisingly found polymer combinations based on the best possible compromise between (i) elastomeric-like performance properties of styrene block copolymers, (ii) suitable Mooney viscosities to handle the polymer mass into the processing (compression/injection-vulcanization) equipment, (iii) good mechanical properties, e.g. high wear resistance, (iv) thermo-oxidative stability, (v) improved hardness with no significant losses in mechanical and gel-like softness properties, and (vi) improved gel-like softness texture with no significant losses in wear resistance.
  • the polymer composition comprises (A) at least one styrene block copolymer; (B) at least one rubber-like material containing double bonds; (C) a softness enhancer polymer; and (D) optionally fillers and rubber auxiliary substances in specific proportions to impart to a microporous, vulcanized foamed product made from said composition both softness and wear resistance qualities.
  • the polymer components (A) + (B) + (C) are present in the composition in a proportion ranging from about 20 wt.% to about 70 wt.%, and more preferably from about 30 wt.% to about 65 wt.%.
  • fillers and rubber auxiliary substances (D) are preferably present in the composition of the invention in a proportion from about 30 wt.% to about 80 wt.%, and more preferably from about 35 wt.% to about 70 wt.%.
  • styrene block copolymer means thermoplastic rubber-like materials which differ in chemical and physical properties from the conventional random SBR/SIR/SEBR/SEPR copolymers. Its molecular configuration consists of polystyrene end blocks and elastomeric mid blocks, or domains. Block copolymers covering a range of molecular weights and containing various end block/mid block copolymer ratios are commercially available.
  • the elastomeric mid blocks can be butadiene, isoprene, ethylene, butylene, or propylene based.
  • SBS is a block copolymer of styrene-butadiene-styrene
  • SIS is a styrene-isoprene- styrene block copolymer
  • SEBS is a styrene-ethylene-butylene-styrene block copolymer
  • SEPS ia a styrene-ethylene-propylene-styrene block copolymer.
  • the block copolymer to be used in the composition is selected from SBS, SIS, SEBS, SEPS or mixtures thereof.
  • the styrene block copolymer to be used in the composition of the invention is a styrene-butadiene-styrene block copolymer (SBS) having a bound styrene content of about 48 wt.%, and a block styrene content of about 30 wt.%, e.g. SSBR B30-4548, a Coperflex SSBR® copolymer available from Petroflex, Rio de Janeiro, Brazil.
  • SBS styrene-butadiene-styrene block copolymer
  • (A) component is present in the composition of the invention in a proportion of from about 2% to about 30 wt.% related to the total composition weight, more preferentially in a proportion of from about 6% to about 20 wt. %.
  • the term "rubber containing double bonds" means a foamable, olefin thermoplastic elastomer having a relatively low Tg to impart high resilience, good abrasion resistance to the molded article, and compatibility with the other polymer components to confer a uniform microporous gel-like softness texture.
  • the rubber-like material containing double bonds can be one ore more copolymers selected from styrene-butadiene copolymer with high styrene content, styrene-butadiene copolymer with mean styrene content, polybutadiene rubber, polyisoprene rubber, natural rubber and mixtures thereof.
  • component(s) (B) are present in the composition of the present invention as a combination of styrene-butadiene copolymers (SBR) having different styrene contents, more preferably they are a combination of a styrene-butadiene copolymer having a high styrene content and at least one styrene-butadiene copolymer having a mean styrene content.
  • SBR styrene-butadiene copolymers
  • styrene-butadiene copolymer having a high styrene content is intended to mean a SBR having a styrene content ranging from about 80 wt.% to about 95 wt.%, preferably from about 80 wt. % to about 85 wt.%, and even more preferably a SBR having a styrene content of about 80 wt.% to about 83 wt.%.
  • styrene-butadiene copolymer having a mean styrene content is intended to mean a SBR having a styrene content ranging from about 10 wt.% to about 40 wt.%, preferably from about 15 wt.% to about 30 wt.%, and even more preferably a SBR having a styrene content of about 18 wt.% to about 25 wt.%.
  • styrene-butadiene copolymers having a mean styrene content preferred to be used in the composition of the invention can be cited, for example, a styrene-butadiene copolymer with a bound styrene content of about 25% (e.g., SSBR 4525, a Coperflex SSBR® copolymer available from Petroflex, Rio de Janeiro, Brazil), a styrene-butadiene copolymer with a bound styrene content of about 18% (e.g., SSBR 4518 A, a Coperflex SSBR® copolymer available from Petroflex, Rio de Janeiro, Brazil), a styrene- butadiene copolymer with a bound styrene content of about 22,95% (e.g., SBR 1502, a Coperflex SSBR® copolymer obtained from an emulsion polymerization process, available from Petroflex
  • polybutadiene preferably a polybutadiene of low viscosity, e.g., a polybutadiene having a viscosity of up to 55 Mooney viscosity.
  • Preferred polybutadiene materials are those having, e.g., 35 Mooney viscosity, 45 Mooney viscosity, 55 Mooney viscosity, as Coperflex BR® products available from Petroflex, Rio de Janeiro, Brazil.
  • the styrene-butadiene copolymers can be selected from a solution-polymerized random SBR (S-SBR) and an emulsion-polymerized random SBR (E-SBR).
  • composition of the invention is to combine good qualities of similar polymers aiming to use them in soles manufacture.
  • S-SBR polymers have poor processability properties but have superior mechanical properties, particularly tensile strength
  • E-SBR polymers have good processability properties, such as good dimensional stability, but have poorer mechanical properties as compared with S-SBR, such as lower resilience.
  • the (C) component of the composition of the invention i.e., a polymer selected from ethylene- propylene copolymer (EPM) and ethylene-propylene-diene terpolymer (EPDM), is an important ingredient to impart a gel-like softness to the resulting vulcanizate and/or sole of the present invention.
  • EPM ethylene- propylene copolymer
  • EPDM ethylene-propylene-diene terpolymer
  • the (C) component is present in the composition in a proportion of from about 2% to about 30 wt.% related to the total composition weight, more preferably in a proportion of from about 6% to about 16 wt,%.
  • gel-like is intended to mean a quality imparted to a polymer material which results in highly viscoelastic, excellent shock absorption and damping characteristics.
  • rubber-like material is intended to mean polymers and copolymers which exhibit qualities similar to those characteristics of rubber matter, such as flexibility, elasticity, toughness, impermeability, electrical resistance.
  • Exemplary rubber-like materials are styrene copolymers and polybutadiene used in the compositions of the invention.
  • the composition of the invention may contain fillers and rubber auxiliary substances.
  • fillers to adjust the viscoelasticity of the vulcanized rubber-like material may be used, e.g., recycled crumb rubber, silica, kaolin, calcium carbonate, clay, metal silicates, such as calcium silicates, zinc silicate.
  • rubber auxiliary substances which can be used in the composition of the invention are selected from, e.g., cross-linking agents, reaction accelerators, vulcanizing agents, foaming agents, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing auxiliary substances, plasticizers, softeners, tachifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids retardants, metal oxides, and other processability auxiliary substances.
  • cross-linking agents e.g., cross-linking agents, reaction accelerators, vulcanizing agents, foaming agents, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing auxiliary substances, plasticizers, softeners, tachifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids retardants, metal oxides, and other processability auxiliary substances.
  • vulcanizing agents for vulcanizing the rubber base of the inventive composition are used, for instance, suphur, organic sulphur-containing compounds, organic peroxide, and the like.
  • the polymer mixtures according to the invention may contain vulcanization accelerators, such as, for example, mercaptobenzothiazoles, guanidines, thiurans, thiocarbonates, dithiocarbamates, zinc oxide, dicumyl peroxide, polyethylene glycol.
  • Vulcanizing agents and/or vulcanizing accelerators are used in the composition in amounts ranging from 0 to about 6 wt. %, preferably from about 0.1 % to about 3 wt. % related to the total weight composition.
  • plasticizers for adjusting softness properties of the vulcanized products.
  • plasticizers such as, for instance, mineral oil materials including processing of aromatic, naphtene and paraffin systems; vegetal oil materials including castor oil, soybean oil, palm oil, coconut oil; pitch materials including bitumen, coal tar pitch; polyester solution; hydrocarbon resins; hydrazine thiosulfate.
  • Softeners and/or plasticizers are used in the inventive compositions in amounts ranging from 0 to about 20 wt. %, preferentially from about 0.1% to about 10 wt. % related to the total weight composition.
  • Lubricants to be used in the composition of the present invention it may be cited: hydrocarbon lubricants, such as paraffin and wax; fatty acid lubricants, e.g. higher fatty acids and oxyfatty acids; alcohol lubricants such as aliphatic alcohols, polyhydric alcohols, polyglycols, and polyglycerols, polyethylene glycol.
  • Lubricants are used in the inventive compositions in amounts ranging from 0 to about 20 wt. %, preferentially from about 0.1 to about 10 wt. % related to the total weight composition.
  • processability auxiliary substances are properly used in the polymer compositions of the invention, e.g., fluxing agents, such as carboxylic acid, abietic acid, citric acid, 2-furoic acid, malic acid and polyacrylic acid; and solvents, such as sulfonane.
  • fluxing agents such as carboxylic acid, abietic acid, citric acid, 2-furoic acid, malic acid and polyacrylic acid
  • solvents such as sulfonane.
  • the other processability auxiliary substances are used in the inventive composition in quantities ranging from 0 to about 3 wt. %, preferentially from about 0.1% to about 2 wt. % related to the total weight composition.
  • Foaming agents are included as important rubber auxiliary substances where expanded, foamed rubber products are required.
  • one or more of the following substances can be used as foaming agents: azodicarbonamide, azobutyronitrile, dlazoamino benzene, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, urea, benzene sulfonyl hydrazide, benzene disulfonyl hydrazide.
  • Foaming agents are used in the inventive composition in quantities ranging from 0 to about 4 wt. %, preferentially from about 0.1% to about 2 wt. % related to the total weight composition.
  • the vulcanizing agent and various compounding agents including fillers are added to the base rubber-like material
  • the kneading is conducted at a temperature enough to appropriately homogenize the softened rubber-like mass, e.g., at a temperature ranging from 100 0 C to 200 0 C, and for a period of time which is known in the art, such as 3-8 minutes.
  • various apparatuses can be used, such as, Bambury mixer, kneader, single-screw or twin-screw extruder, or a continuous mixer of closed type.
  • a Bambury mixer is used to knead the mentioned components.
  • the resulting homogenized mixture is subjected to a lamination step aiming to obtain a crude sheet-like material.
  • the resulting crude sheet-like material is put in a forming die in order to simultaneously mold and vulcanize it to thereby form the inventive vulcanizate and/or sole, at a suitable temperature, e.g., at a temperature ranging from 100 0 C to 200°C, preferably from 140°C to 160 0 C, and for a period of time which is known in the art, such as, 280-400 seconds.
  • a suitable temperature e.g., at a temperature ranging from 100 0 C to 200°C, preferably from 140°C to 160 0 C, and for a period of time which is known in the art, such as, 280-400 seconds.
  • the resulting crude sheet-like material is cut in strips to be used in preparing the required sized shoe soles.
  • injection molding or press molding or the like can be used.
  • a compression strength e.g., 110-190 kgf/cm2, preferentially 160-180 kgf/cm2, and more preferentially 170 kgf/cm2 is applied to the forming die in order to obtain the desired properties in the resulting article, such as gel-like softness and a good wear-resistance.
  • a suitable closure die pressure e.g., 70-180 kgf/cm2
  • a suitable injection pressure e.g. 170-270 bar are applied to the forming die in order to obtain said desired properties in said resulting articles.
  • the shoe sole e.g. sandal sole
  • the shoe sole produced from the polymer composition of the invention by a press molding or an injection molding process as described before, has a higher thickness in the portion corresponding to the heel area.
  • This effect is obtained by means of a modified die to provide different heights, in a gradual- or in a step-fashion, from the toe area to the heel area, to such sandal sole.
  • Example 1 Vulcanizate and/or shoe sole having gel-like softness and wear-resistance obtained by a press molding process.
  • a microporous, foamed article e.g., a sheet-like material, a shoe sole and the like
  • inventive styrene-based copolymer composition first of all it is necessary to seek a proportion of components which can satisfy a frequently antagonist requirements, i.e., a gel-like softness and a good wear-resistance.
  • Table 1 below presents compositions that satisfy both characteristics.
  • Table 1 Exemplary styrene-based copolymer compositions according to the invention tp be used in a press molding process
  • the ingredients according to the inventive compositions that are defined and quantified in Table 1 were mixed and knead as described hereinbefore. Then, the resulting mixture was laminated as a crude sheet-like material which was subjected to a press molding process to produce a microporous, foamed sheet-like material having gel-like softness and wear-resistance properties.
  • the conditions of the press molding step are as follows: (a) vulcanizing/die temperature: 145- 165°C; (b) compression force: 170 kgf/cm2; (c) molding time: 280-400 seconds.
  • the resulting vulcanizate, i.e. the microporous, foamed sheet-like material having gel-like softness and wear- resistance properties so obtained may be used to produce articles for which these qualities are required, such as a seat.
  • the crude sheet-like material is cut in strips before being subjected to the press molding process.
  • Sandal soles manufactured in such a way have the following properties: sandal expansion: about 25% (cold); density: from 0.35 g/cm3 to 0.45 g/cm3; hardness: from 15 to 25 Shore A; softness: a gel-like texture; wear resistance: similar as compared with soles in which the gel-like texture is absent.
  • Example 2 Vulcanizate and/or shoe sole having gel-like softness and wear-resistance obtained by an injection molding process.
  • Example 2 As in the case of the press molding process of Example 1 , the components of compositions defined in Table 2 were mixed and knead as described hereinbefore. Then, the resulting mixture was laminated as a crude sheet-like material which was subjected to an injection molding process to produce a microporous, foamed sheet-like material having gel-like softness and wear-resistance properties.
  • the conditions of the injection molding step are as follows: (a) vulcanizing/die temperature: 145-165°C; (b) closure die pressure: 70-180 kgf/cm2; (c) molding time: 250-400 seconds; (d) injection pressure: 170-270 bar; (e) injection pulse time: 28-50 seconds; (f) satured steam pressure: 4.5-6.5 kgf/cm2.
  • the resulting vulcanizate and/or shoe sole present similar qualities as compared with products obtained by applying the press molding process.

Landscapes

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

Abstract

La présente invention porte sur une composition de polymères comprenant : (A) au moins un copolymère à blocs du styrène, choisi dans le groupe constitué par les copolymères à blocs styrène-isoprène-styrène, les copolymères à blocs styrène-butadiène-styrène, les copolymères à blocs styrène-éthylène-butylène-styrène, les copolymères à blocs styrène-éthylène-propylène-styrène, et leurs mélanges ; (B) au moins une matière de type caoutchouc contenant des doubles liaisons, choisie dans le groupe constitué par les copolymères styrène-butadiène ayant une teneur élevée en styrène, les copolymères styrène-butadiène ayant une teneur moyenne en styrène, le caoutchouc polybutadiène, le caoutchouc polyisoprène, le caoutchouc naturel et leurs mélanges; (C) un polymère augmentant la souplesse, choisi parmi les copolymères éthylène-propylène et les terpolymères éthylène-propylène-diène, et leurs mélanges ; et (D) facultativement des charges et des substances auxiliaires de caoutchouc, les composants (A), (B), et (C) étant présents dans une proportion telle que le rapport (A):(B) se situe dans la plage de 1 :30 à 3:1 , et le rapport (A):(C) se situe dans la plage de 1:15 à 15:1. D'autres modes de réalisation de l'invention comprennent un vulcanisat moussé, de type caoutchouc, microporeux, et une semelle de chaussure moussée, de type caoutchouc, microporeuse, fabriqués à partir de ladite composition de polymères.
PCT/BR2007/000168 2007-01-11 2007-06-26 Composition de polymères, vulcanisat moussé, de type caoutchouc, microporeux, et semelle de chaussure moussée, de type caoutchouc, microporeuse WO2008083451A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0700089-8 2007-01-11
BRPI0700089-8A BRPI0700089B1 (pt) 2007-01-11 2007-01-11 Composição polimérica, vulcanizado espumado similar a borracha microporoso e solado de calçado espumado similar a borracha microporoso

Publications (1)

Publication Number Publication Date
WO2008083451A1 true WO2008083451A1 (fr) 2008-07-17

Family

ID=39608270

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2007/000168 WO2008083451A1 (fr) 2007-01-11 2007-06-26 Composition de polymères, vulcanisat moussé, de type caoutchouc, microporeux, et semelle de chaussure moussée, de type caoutchouc, microporeuse

Country Status (2)

Country Link
BR (1) BRPI0700089B1 (fr)
WO (1) WO2008083451A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010102432A1 (fr) * 2009-03-10 2010-09-16 Ye Sunyong Composition de caoutchouc réticulable, utilisations de cette composition, granulés de caoutchouc formés à partir de cette dernière et procédés de préparation et procédés de formage par injection desdits granulés de caoutchouc
ITAN20110150A1 (it) * 2011-11-03 2013-05-04 Tecnofilm Spa Bitume modificato e compound.
CN103865134A (zh) * 2014-03-17 2014-06-18 德州市鑫华润聚氨酯鞋材股份有限公司 一种轻质橡胶鞋底及其制备方法
US20170267847A1 (en) * 2016-03-15 2017-09-21 Nike, Inc. Foam compositions and uses thereof
IT201600127907A1 (it) * 2016-12-19 2018-06-19 Euroinga Group S P A Mescola per la produzione di suole per calzature
CN108727644A (zh) * 2017-04-18 2018-11-02 简单绿能股份有限公司 橡胶组成物
WO2020128635A2 (fr) 2018-12-20 2020-06-25 Dynasol Elastomeros, S.A. De C.V. Copolymères séquencés à deux compositions
EP3689935A1 (fr) 2019-01-30 2020-08-05 Politechnika Gdanska Composite thermoplastique polyuréthane-caoutchouc et procédé permettant d'obtenir un composite thermoplastique polyuréthane-caoutchouc
CN112694648A (zh) * 2020-12-23 2021-04-23 福建省莆田市双源鞋业有限公司 用于橡胶射出成型的鞋底组合物、鞋底及其制备方法
US11439198B2 (en) 2018-06-04 2022-09-13 Nike, Inc. Two part sole structures and uses thereof
US11523655B2 (en) 2018-12-03 2022-12-13 Nike, Inc. High energy return foam compositions having improved abrasion resistance and uses thereof
DE102021122863A1 (de) 2021-08-11 2023-02-16 Myung Gon Kim Spritzgegossenes Schuhsohlenmaterial, das Material enthaltende Schuhsohle sowie Herstellungsverfahren und Anwendung davon
WO2023138055A1 (fr) * 2022-01-21 2023-07-27 茂泰(福建)鞋材有限公司 Semelle en caoutchouc anti-fissuration légère et son procédé de préparation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55118944A (en) * 1979-03-07 1980-09-12 Aron Kasei Co Ltd Synthetic resin composition for footwear sole
US4495323A (en) * 1983-10-17 1985-01-22 Shell Oil Company Solvent resistant polymeric composition
GB2212809A (en) * 1986-10-10 1989-08-02 Boer Es Cipoeipari Kutato Fejl Process for producing shoesole material with thermoplastic character and improved features.
WO1995027756A1 (fr) * 1994-04-08 1995-10-19 Esposito Anthony S Jr Elastomere
EP0994153A1 (fr) * 1996-11-29 2000-04-19 Riken Vinyl Industry Co., Ltd. Composition de résine élastomère thermoplastique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55118944A (en) * 1979-03-07 1980-09-12 Aron Kasei Co Ltd Synthetic resin composition for footwear sole
US4495323A (en) * 1983-10-17 1985-01-22 Shell Oil Company Solvent resistant polymeric composition
GB2212809A (en) * 1986-10-10 1989-08-02 Boer Es Cipoeipari Kutato Fejl Process for producing shoesole material with thermoplastic character and improved features.
WO1995027756A1 (fr) * 1994-04-08 1995-10-19 Esposito Anthony S Jr Elastomere
EP0994153A1 (fr) * 1996-11-29 2000-04-19 Riken Vinyl Industry Co., Ltd. Composition de résine élastomère thermoplastique

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012519762A (ja) * 2009-03-10 2012-08-30 上海杜▲爾▼邦泰富▲実▼業有限公司 架橋可能ゴム組成物、その用途、その製造されたゴム粒、およびそのゴム粒を調製し射出成形する方法
WO2010102432A1 (fr) * 2009-03-10 2010-09-16 Ye Sunyong Composition de caoutchouc réticulable, utilisations de cette composition, granulés de caoutchouc formés à partir de cette dernière et procédés de préparation et procédés de formage par injection desdits granulés de caoutchouc
CN103930491B (zh) * 2011-11-03 2017-11-10 泰克诺费尔姆股份公司 用于实现柏油用改性沥青的复合物
ITAN20110150A1 (it) * 2011-11-03 2013-05-04 Tecnofilm Spa Bitume modificato e compound.
WO2013064408A1 (fr) 2011-11-03 2013-05-10 Tecnofilm S.P.A. Mélange pour la production de bitume modifié pour des asphaltes
CN103930491A (zh) * 2011-11-03 2014-07-16 泰克诺费尔姆股份公司 用于实现柏油用改性沥青的复合物
US9487633B2 (en) 2011-11-03 2016-11-08 Tecnofilm S.P.A. Compound for realization of modified bitumen for asphalts
CN103865134A (zh) * 2014-03-17 2014-06-18 德州市鑫华润聚氨酯鞋材股份有限公司 一种轻质橡胶鞋底及其制备方法
CN103865134B (zh) * 2014-03-17 2016-04-13 德州市鑫华润科技股份有限公司 一种轻质橡胶鞋底及其制备方法
US10947371B2 (en) 2016-03-15 2021-03-16 Nike, Inc. Foam compositions and uses thereof
US11149138B2 (en) 2016-03-15 2021-10-19 Nike, Inc. Foam compositions and uses thereof
US11739201B2 (en) 2016-03-15 2023-08-29 Nike, Inc. Foam compositions and uses thereof
US10344150B2 (en) 2016-03-15 2019-07-09 Nike, Inc. Foam compositions and uses thereof
US11780997B2 (en) 2016-03-15 2023-10-10 Nike, Inc. Foam compositions and uses thereof
US20170267847A1 (en) * 2016-03-15 2017-09-21 Nike, Inc. Foam compositions and uses thereof
US10927242B2 (en) 2016-03-15 2021-02-23 Nike, Inc. Foam compositions and uses thereof
US11643535B2 (en) 2016-03-15 2023-05-09 Nike, Inc. Foam compositions and uses thereof
US10947372B2 (en) 2016-03-15 2021-03-16 Nike, Inc. Foam compositions and uses thereof
WO2018116116A1 (fr) * 2016-12-19 2018-06-28 Euroinga Group S.P.A. Mélange pour la production de semelles de chaussuresa
IT201600127907A1 (it) * 2016-12-19 2018-06-19 Euroinga Group S P A Mescola per la produzione di suole per calzature
CN108727644B (zh) * 2017-04-18 2020-03-27 简单绿能股份有限公司 橡胶组成物
CN108727644A (zh) * 2017-04-18 2018-11-02 简单绿能股份有限公司 橡胶组成物
US11439198B2 (en) 2018-06-04 2022-09-13 Nike, Inc. Two part sole structures and uses thereof
US11523655B2 (en) 2018-12-03 2022-12-13 Nike, Inc. High energy return foam compositions having improved abrasion resistance and uses thereof
EP4324880A2 (fr) 2018-12-20 2024-02-21 Dynasol Elastómeros, S.A.de C.V. Copolymères séquencés à deux compositions
WO2020128635A2 (fr) 2018-12-20 2020-06-25 Dynasol Elastomeros, S.A. De C.V. Copolymères séquencés à deux compositions
EP3689935A1 (fr) 2019-01-30 2020-08-05 Politechnika Gdanska Composite thermoplastique polyuréthane-caoutchouc et procédé permettant d'obtenir un composite thermoplastique polyuréthane-caoutchouc
CN112694648B (zh) * 2020-12-23 2023-03-31 福建省莆田市双源鞋业有限公司 用于橡胶射出成型的鞋底组合物、鞋底及其制备方法
CN112694648A (zh) * 2020-12-23 2021-04-23 福建省莆田市双源鞋业有限公司 用于橡胶射出成型的鞋底组合物、鞋底及其制备方法
DE102021122863B4 (de) 2021-08-11 2023-03-16 Myung Gon Kim Spritzgegossenes Schuhsohlenmaterial, das Material enthaltende Schuhsohle sowie Herstellungsverfahren und Anwendung davon
DE102021122863A1 (de) 2021-08-11 2023-02-16 Myung Gon Kim Spritzgegossenes Schuhsohlenmaterial, das Material enthaltende Schuhsohle sowie Herstellungsverfahren und Anwendung davon
WO2023138055A1 (fr) * 2022-01-21 2023-07-27 茂泰(福建)鞋材有限公司 Semelle en caoutchouc anti-fissuration légère et son procédé de préparation

Also Published As

Publication number Publication date
BRPI0700089A (pt) 2008-08-26
BRPI0700089B1 (pt) 2018-02-06

Similar Documents

Publication Publication Date Title
WO2008083451A1 (fr) Composition de polymères, vulcanisat moussé, de type caoutchouc, microporeux, et semelle de chaussure moussée, de type caoutchouc, microporeuse
US11802189B2 (en) Foam ionomer compositions and uses thereof
EP2020879B1 (fr) Chaussure à ensemble semelle poids léger
EP1872924A1 (fr) Procédé de fabrication de mousse moulée réticulée
CN104277315B (zh) 一种含聚碳酸酯的橡塑发泡材料的制备方法
KR101203677B1 (ko) 마사이워킹 신발 중창의 소프트 감지체용 에틸렌비닐아세테이트 수지 조성물
JP7010868B2 (ja) ゴム・テルペン履物
JP4474515B2 (ja) アーチサポート及びこれを用いたインソール
US20220073739A1 (en) Composition and manufacturing methods for grips
JP2006016518A (ja) 発泡体用組成物
JPS631980B2 (fr)
JP3527855B2 (ja) 靴底用熱可塑性樹脂組成物及びそれを用いた靴
JPH0343446A (ja) ゴム組成物
TWI780526B (zh) 高功能發泡用樹脂組合物及其製備方法
JP4140794B2 (ja) 射出成形発泡性オレフィン系重合体組成物
JPS60163944A (ja) ゴム組成物
JPH0476063A (ja) 熱可塑性エラストマー組成物
JP2006028360A (ja) 発泡成形体の製造方法
WO2019204358A1 (fr) Mousse composite pour semelle intermédiaire
JPH0477018B2 (fr)
JPS6311103A (ja) 履物底材料
JPH0525255B2 (fr)
HU209136B (en) Process for producing sole material composition with improved properties
JPH0133161B2 (fr)
JPH0522730B2 (fr)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07719336

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07719336

Country of ref document: EP

Kind code of ref document: A1