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    • 专利摘要:
    process for producing a shoe sole, and shoe sole. the present invention relates to a process for the production of a shoe sole, which comprises a hybrid material, produced from polyurethane foam as a matrix material and foamed thermoplastic polyurethane particles, by preparing an insert united expanded particles (c ") of thermoplastic polyurethane and the placement of the expanded particles thermoplastic polyurethane units in a mold and by inserting the insert with a reaction mixture, capable of being obtained by mixing (a) polyisocyanates and with (b) compounds having hydrogen atoms reactive with isocyanates and, if appropriate, with (d) chain extenders and / or cross-linking agents, and with (e) catalysts, and with (f) blowing agents, and with ( g) other additives, and reacting the reaction mixture, so that the sole of the shoe is provided, the present invention also relates to shoe soles, obtainable through such a proc this.
    公开号:BR112013011437B1
    申请号:R112013011437
    申请日:2011-11-14
    公开日:2020-02-04
    发明作者:Kamm Andre；Chen Bin-Eric；Prissok Frank；Khim Raymond Toh Yoke
    申请人:Basf Se；
    IPC主号:
    专利说明:

    “PROCESS TO PRODUCE A SHOE SOLE, AND, SHOE SOLE”
    Description [001] The present invention relates to a process for the production of a shoe sole, which comprises a hybrid material, produced from a polyurethane foam as a matrix material and foamed thermoplastic polyurethane particles, by preparing of an insertion of joined expanded particles (c ”) of thermoplastic polyurethane and placement of the joined expanded particles of thermoplastic polyurethane in a mold, and by embedding the insert with a reaction mixture, capable of being obtained by mixing (a) isocyanates with (b) compounds having hydrogen atoms reactive to isocyanates and, if appropriate, with (d) chain extenders and / or cross-linking agents, and with (e) catalysts, and (f) blowing agents, and with (g) other additives, and reacting the reaction mixture, so that the sole of the shoe is provided. The present invention also relates to shoe soles, obtainable through such a process.
    [002] Molded parts made of elastic polyurethane with a compact surface and a cell core, known as flexible integral polyurethane foams, have been known for a long time and are used in various sectors. A typical use is to use as a shoe sole, for example as shoes for outdoor areas, sports shoes, sandals, and boots. Even more particularly, flexible integral polyurethane foams can be used in the production of outer soles, midsoles and molded soles.
    [003] There are also flexible integral polyurethane foams, which comprise foamed thermoplastic polyurethane particles. These are described, by way of example, in WO 2008087078. The production process described in WO 2008087078 allows homogeneous distribution of the foamed polyurethane particles within the matrix material. The advantages of such
    Petition 870190113853, dated 11/06/2019, p. 9/40 / 28 hybrid materials are very good adhesion between the matrix material and the foamed polyurethane particles, providing the hybrid material with good mechanical properties.
    [004] In order for comfort to be increased, the cushioning elements are introduced inside the shoe soles, particularly in the heel region. These are intended to reduce the load on muscles and joints, and also on the skeleton, during the impact of walking. Typical cushioning elements are air bags, also known as "air bags". The region of the sphere and fingers is not cushioned by means of an air cushion. The relatively rigid sole material in that region minimizes energy dissipation when lifting feet from the ground, and the sole provides the shoe user with good adhesion.
    [005] A known disadvantage of air cushions is that they stiffen the sole of the shoe, inhibiting the natural rolling motion of the feet.
    [006] It was an object of the present invention to provide a shoe sole, which has excellent cushioning properties, but which, however, is highly flexible, and thus allows the natural rolling motion of the feet.
    [007] This object is achieved by means of a shoe sole, which comprises a hybrid material, produced from a polyurethane foam as a matrix material, and foamed particles of thermoplastic polyurethane, which is capable of being obtained through preparing an insert of expanded expanded particles (c ”) of thermoplastic polyurethane and placing the expanded particles of thermoplastic polyurethane units in a mold and inserting the insert with a reaction mixture, capable of being obtained by mixing (a ) polyisocyanates with (b) compounds having hydrogen atoms reactive to isocyanates and, if appropriate, with (d) chain extenders and / or agents
    Petition 870190113853, dated 11/06/2019, p. 10/40 / 28 cross-linking, and with (e) catalysts, and (f) blowing agents, and (g) other additives, and reaction of the reaction mixture, so that the sole of the shoe is provided.
    [008] Another possible process for obtaining said shoe sole, which comprises a hybrid material, produced from a polyurethane foam as a matrix material and particles of thermoplastic polyurethane foams, is by preparing a insertion of joined particles (c ') of thermoplastic polyurethane, which comprises a blowing agent, and by placing the expanded particles thermoplastic polyurethane units in a mold and by inlaying the insert with a reaction mixture, capable of being obtained by mixing (a) polyisocyanates with (b) compounds having hydrogen atoms reactive to isocyanates, and with (d) chain extenders and / or crosslinking agents, and with (e) catalysts, and with (f) blowing agents , and (g) other additives, and through the reaction of the reaction mixture, in such a way that a shoe sole is provided, in which the expandable particles are foamed, in a s ncrono with the heat produced by the reaction of the reaction mixture in a manner that is formed particles (c ') of thermoplastic polyurethane.
    [009] For the purposes of the invention, the mixture of components a) to d) and, moreover, if appropriate, e) to g) is here called the reaction mixture in conversions less than 90%, based on the isocyanate groups.
    [0010] Organic and / or modified polyisocyanates (a), used to produce the composite polyurethane materials of the invention, comprise the aliphatic, cycloaliphatic and aromatic difunctional or polyfunctional isocyanates known from the prior art (constituent a-1) , and also any desired mixtures thereof. Examples are diphenyl methane 4,4'-diisocyanate, diphenyl methane 2,4'-diisocyanate, mixtures of monomeric diphenyl methane diisocyanates with diphenyl methane diisocyanate homologues having a relatively large number of rings (polymer
    Petition 870190113853, dated 11/06/2019, p. 11/40 / 28
    MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and tolylene 2,4 or 2,6-diisocyanate (TDI), and mixtures of the mentioned isocyanates.
    [0011] It is preferable to use 4,4'-MDI. The 4,4'-MDI can preferably comprise from 0 to 20% by weight of 2,4'-MDI and small amounts of up to 10% by weight of allophanate modified polyisocyanates or uretonimine. It is also possible to use small amounts of polyphenylene polymethylene polyisocinate (polymer-MDI). The total quantity of these highly functional polyisocyanates must not exceed 5% by weight of the isocyanate used.
    [0012] The polyisocyanate component (a) is preferably used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers are obtainable by reacting the polyisocyanates (a-1) described above with polyols (a-2), so that the prepolymer is provided, for example, at temperatures from 30 to 100 ° C, and preferably about 80 ° C.
    [0013] Polyols (a-2) are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch [Plastics Handbook], Volume 7, Polyurethane (Polyurethenes]." Carl Hanser Verlag, 3rd Edition, chapter 3.1.
    [0014] The polyols (a-2) used herein preferably comprise the high molecular weight compounds described under b), which have isocyanate-reactive hydrogen atoms.
    [0015] Conventional chain extenders or crosslinking agents are, if appropriate, added to the mentioned polyols during the production of the isocyanate prepolymers. These substances are described under e) below. [0016] Conventional chain extenders or crosslinking agents are, if appropriate, added to the mentioned polyols during the production of the isocyanate prepolymers. These substances are described under e) below.
    Petition 870190113853, dated 11/06/2019, p. 12/40 / 28 [0017] The chain extenders or crosslinking agents used preferably comprise dipropylene glycol or tripropylene glycol.
    [0018] For example, compounds of relatively high molecular hair b) having at least two H atoms in relation to isocyanate groups, can be polyetherols or polyesterols.
    [0019] Polyetherols are prepared through known processes, for example, through anionic polymerization, using, as catalysts, alkali metal hydroxides or alkali metal alcoholates, and with the addition of at least one initiator molecule, which comprises of 2 to 3 reactive hydrogen atoms, or through cationic polymerization using Lewis acids, such as antimony pentachloride or boron fluoride etherate, from one or more alkylene oxides, having 2 to 4 atoms of carbon in the alkylene radical. Examples of suitable alkylene oxides are tetrahydrofuran, propylene 1,3-oxide, butylene 1,2-oxide, butylene 2,3-oxide, and preferably ethylene oxide and 1,2-oxide. propylene. Other catalysts that can be used are multimetal cyanide compounds, known as DMC catalysts. Alkylene oxides can be used individually, in alternating succession, or in the form of a mixture. It is still preferable to use mixtures composed of 1,2-propylene oxide and ethylene oxide, in which the amounts of ethylene oxide, used as ethylene oxide and block (EO capping) are from 10 to 50%, providing the resulting polyols in more than 70% of primary OH end groups.
    [0020] The initiator molecule may further comprise water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2- and 1,3-propane diol, diethylene glycol, dipropylene glycol, 1,4-butane diol, glycerol or trimethylol propane.
    [0021] The functionality of polyether polyols, preferably polyoxypropylene polyols, is from 2 to 3 and their molar masses are from a
    Petition 870190113853, dated 11/06/2019, p. 13/40 / 28 from 1000 to 8000 g / mol, and preferably from 2000 to 6000 g / mol. [0022] As an example, polyester polyols can be prepared from organic dicarboxylic acids, having from 2 to 12 carbon atoms, preferably from aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and from polyhydric alcohols, preferably from diols, having from 2 to 12 carbon atoms, and preferably from 2 to 6 carbon atoms. Examples of dicarboxylic acids, which can be used, are: succinic acid, glutaric acid, adipic acid, submeric acid, azelaic acid, sebacic acid, dicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. In this case, dicarboxylic acids can be used either individually or in a mixture with each other. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, for example, the dicarboxylic esters of alcohols having 1 to 4 carbon atoms, the dicarboxylic anhydrides. It is preferable to use mixtures of dicarboxylic acid composed of succinic, glutaric, and adipic acid in quantitative proportions, for example, from 20 to 34; from 35 to 50; from 20 to 32 parts by weight, and more particularly adipic acid. Examples of dihydric and polyhydric alcohols, in particular diols, are: ethane diol, diethylene glycol, 1,2- or 1,3-propane diol, dipropylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,10decane diol, glycerol, and trimethylol propane. It is preferable to use ethane diol, diethylene glycol, 1,4-butane diol, 1,5-pentane diol, and 1,6-hexane diol. It is also possible to use polyester polyols derived from lactones, for example, ε-caprolactone, or hydroxycarboxylic acids, for example, ωhydroxycaproic acid.
    [0023] For the preparation of polyester polyols, organic polycarboxylic acids, for example, aromatic, and preferably aliphatic and / or their derivatives and polyhydric alcohols can be polycondensed without
    Petition 870190113853, dated 11/06/2019, p. 14/40 / 28 a catalyst, or preferably, in the presence of esterification catalysts, and advantageously in an atmosphere composed of inert gas, for example, nitrogen, carbon monoxide, helium, argon, etc., at melting temperatures, which are from 150 to 250 ° C, preferably from 180 to 220 ° C, and if appropriate under reduced pressure, until the desired acid number has been reached, this preferably less than 10, and particularly preferably less than 2. According to a preferred embodiment, the esterification mixture is polycondensed at the above-mentioned temperatures, until the acid number is a from 80 to 30, and preferably from 40 to 30, at atmospheric pressure, and then at a pressure, which is less than 500 mbar, and preferably from 50 to 150 mbar. Examples of esterification catalysts, which can be used, are iron catalysts, cadmium catalysts, cobalt catalysts, lead catalysts, zinc catalysts, antimony catalysts, magnesium catalysts, titanium catalysts, and tin catalysts , and in the form of metals, metal oxides, or metal salts. However, the polycondensation process can also be carried out in a liquid phase, in the presence of diluents and / or entraining agents, for example, benzene, toluene, xylene, or chlorobenzene, for the azeotropic removal of condensation water, through distillation Polyester polyols are advantageously produced by the polycondensation of organic polycarboxylic acids and / or polycarboxylic acid derivatives and polyhydric alcohols, in a molar ratio of 1: 1 to 1, 8, and preferably from 1: 1.05 to 1.2.
    [0024] The functionality of the resulting polyester polyols is preferably from 2 to 4, and more particularly from 2 to 3, their molar mass being from 480 to 3000 g / mol, and preferably from 1000 to 3000 g / mol.
    [0025] Other suitable polyols are polyols modified with
    Petition 870190113853, dated 11/06/2019, p. 15/40 / 28 polymer, and preferably polymer modified polyesterols or polyetherols, and particularly preferably graft polyetherols or graft polyesterols, and even more particularly, polyetherols. These are what is known as a polyol polymer. In the usual way, having from 5 to 60% by weight, preferably from 10 to 55% by weight, particularly preferably from 30 to 55% by weight, and even more particularly from 40 to 50% by weight of polymer content, preferably thermoplastic. These polymer polyesterols are described, for example, in WO 05/098763 and EP-A 250 351, and are prepared, in the usual way, by free radical polymerization of suitable olefinic monomers, such as styrene, acrylonitrile , (meth) acrylates, (meth) acrylic acid and / or acrylamide. In a polyester, which serves as the graft base. Side chains are produced, in general, by transferring free radicals from growing polymer chains to polyesterols or polyetherols. The polyol polymer comprises, together with the graft copolymer, mainly the homopolymers of the olefins, dispersed in polyester or unchanged polyetherol.
    [0026] In still a preferred embodiment, the monomers used comprise acrylonitrile, styrene, or acrylonitrile and styrene, and particularly preferably, exclusively styrene. The monomers are, if appropriate, polymerized in the presence of other monomers, a macromer, and a moderate, and with the use of a free radical initiator, mainly azo compounds or peroxide compounds, in a polyester or polyetherol as the continuous phase. This process is described, by way of example, in DE 111 394, US 3 304 273, US 3 383 351, US 3 523 093, DE 1 152 536 and in DE 1 152 537.
    [0027] During the free radical polymerization process, macromers are incorporated, concurrently, in the copolymer chain. This provides the block copolymers having a polyester or
    Petition 870190113853, dated 11/06/2019, p. 16/40 / 28 also, respectively, a polyether block and a polyacrylonitrile styrene block, in which these act as compatibilizers at the interface of the continuous phase and the dispersed phase and suppress the agglomeration of the polyester particles of the polymer. The proportion of macromers is usually 1 to 20% by weight, based on the total weight of the monomers used to produce the polyol polymer.
    [0028] If the relatively high molecular weight compound b) comprises polyol polymer, it is preferably comprised together with other polyols, for example, polyetherols, polyesterols, or a mixture of polyetherols and depolyesterols. The proportion of polymer polyol is preferably preferably greater than 5% by weight, based on the total weight of component (b). The amount of polyol polymer present can, by way of example, be from 7 to 90% by weight, or from 11 to 80% by weight, based on the total weight of component (b). It is particularly preferred that the polyol polymer is a polyester polymer or a polyetherol polymer.
    [0029] Examples of expandable thermoplastic polyurethane particles (c '), which can be used, comprising blowing agents in one were dispersed or dissolved, are particles impregnated with a thermoplastic polyurethane blowing agent. Particles of this type and their production are described, for example, in WO 94/20568, WO 2007/082838 and WO 2008/087078.
    [0030] For the production of expandable particles (c '), it is particularly preferred to use thermoplastic polyurethanes, for which the melting range is initiated below 130 ° C, and particularly preferably below 120 ° C , when measuring DSC, using a heating rate of 20 K / minute, and where the melting flow rate (MFR) of the thermoplastic polyurethane (also called TPU) at 190 ° C and with an applied weight of 21, 6 kg according to DIN EN ISO 1133, is at most
    Petition 870190113853, dated 11/06/2019, p. 17/40 / 28 of 2450 g / 10 minutes, and particularly preferably being less than 200 g / 10 minutes. The average diameter of the thermoplastic polyurethane, which comprises the blowing agent, is preferably 0.1 to 10 mm. [0031] This type of thermoplastic polyurethane is preferably based on a polyalcohol, and particularly preferably on a polyether diol. Polytetrahydrofuran can be used, in this case, in a particularly preferred way. It is particularly preferred that the TPU is based on a polytetrahydrofuran with a molar mass of from 600 g / mol to 2500 g / mol. Polyalcohols can be used either individually or in a mixture with one another.
    [0032] As an alternative, good results can be achieved with a TPU based on an alcohol polyester, preferably on a polyester diol, and even more preferably based on an adipic acid and 1,4butane diol, with a molecular mass from 500 to 2500 g / mol, and even more particularly preferred from 600 g / mol to 900 g / mol.
    [0033] The thermoplastic polyurethane of the invention is produced, by way of example, by the reaction of isocinates (c1) with reactive compounds to isocyanates, with a molecular weight of from 500 to 10,000 (c2) and, if appropriate, with chain extenders with a molecular weight from 50 to 499 (c3), and if appropriate, in the presence of catalysts (c4) and / or conventional auxiliaries and / or additives (c5).
    [0034] The starting materials (c1) to (c5) and the processes for producing the expandable particles (c ') are known and are described, by way of example, in WO 94/20568, WO 2007/082838, and in WO 2008/087078. It is preferable that the foamed particles are based on a thermoplastic polyurethane, produced through the use of polytetrahydrofuran as the component (c2). The molar mass of the polytetrahydrofuran used is preferably from 600 to 2500 g / mol. In yet another preferred embodiment, a polyalcohol polyester, with a molar mass from
    Petition 870190113853, dated 11/06/2019, p. 18/40 / 28 from 500 to 2500 g / mol, and preferably from 600 to 900 g / mol, is used as the component (c2).
    [0035] If the process of the invention for producing the hybrid material of the invention uses the previously expanded particles (c ') of the thermoplastic polyurethane, instead of the expandable particles (c') of the thermoplastic polyurethane, they are preferably obtained by expanding the expansion particles (c '), for example, when the impregnated pellets are depressurized at temperatures above the softening point of the thermoplastic polyurethane, during the suspension process, or when the discharge from the extruder occurs in a atmospheric pressure during the extrusion process.
    [0036] The foamed particles (c ") preferably comprise a diameter from from 0.1 mm to 10 cm, preferably from 0.5 mm to 5 cm, and preferably particularly from 1 mm to 2 cm, and they are preferably spherical or ellipsoid. In the case of non-spherical particles, for example, elliptical particles, the diameter means the longest axis. The density of the foamed thermoplastic polyurethane particles is in this case preferably from 10 to 300 g / l, and particularly preferably from 20 to 200 g / l, and even more preferably from 40 to 150 g / l.
    [0037] It is preferable that the foamed particles have a compact outer film. A compact film in this case means that the foam cells are smaller in the outer region of the foamed particles than in their interior. It is still particularly preferable that the outer region of the foamed particles does not comprise pores.
    [0038] In accordance with the present invention, the expandable particles (c ') or the expanded particles (c ") are joined together so that they can form an insert. The connection can, for example, be achieved by introducing the particles (c ') or (c ”) into a
    Petition 870190113853, dated 11/06/2019, p. 19/40 / 28 bag, preferably produced from a material, that is impermeable to the constituents of the resulting matrix material, where the material is impermeable to expandable particles (c ') or expanded particles (c ”) , an example being a network. It is still preferable that the expandable particles (c ') and, respectively, the expanded particles (c ”) are attached to each other, by way of example, by means of an adhesive bond. For adhesive bonding, all types of adhesives can be used. Preferably, polyurethane-based adhesives, such that those known as one-component or two-component polyurethane binders, can be used. The appropriate binders and a method for bonding the particles are set out, for example, in DE 102008054962. In a thermal adhesive bond or in a thermal adhesive bond process or in a melt bonding process, in this case, the outer region of the foamed thermoplastic polyurethane particles are heated to an extent, where the foamed particle can be adhered to one another after they have been brought into contact, and then cooled again. This process can, for example, be placed in a mold, if appropriate during the foaming of the expandable particles (c '), so that the expanded particles (c ”) are supplied.
    [0039] In the case of large particles here, for example, those having a diameter greater than 3 cm, for example, from 4 to 6 cm, it is also possible to use only one particle as the insert. The configuration of this particle can, for example, correspond to that of a conventional airbag. Under these circumstances, an insertion of expanded expanded particles (c ") also includes an insertion of an expanded particle (c").
    [0040] In a preferred embodiment, the expanded particles are bonded together to form an insert, preferably through adhesive bonding.
    [0041] Inserts are produced, or by joining the particles
    Petition 870190113853, dated 11/06/2019, p. 20/40 / 28 expandable (c ') or expanded particles (c ”) in an amount and size of the desired insert, for example, by placing it inside a mole of the desired size, and then by joining it inside of the mold, or by joining them in larger quantities, so that large aggregates are formed, for example, in the form of leaves. These large aggregates can be cut into inserts of the desired size. [0042] The blowing agents (d) are also present as a matrix material, during the production of polyurethane foams. These blowing agents comprise water, where appropriate. The blowing agents (d), which can be used, are not only water, but also known compounds, having a chemical and / or physical action. Chemical blowing agents are compounds, which form gaseous products through reaction with isocyanate, an example being formic acid. Physical blowing agents are compounds, which have been dissolved or emulsified within the starting materials for the production of polyurethane, and which are vaporized under the conditions of formation of polyurethane. As an example, these are hydrocarbons, halogenated hydrocarbons, and still other compounds, for example, perfluorinated alkanes, such as perfluoroexane, fluorochlorocarbons, and ethers, esters, ketones and / or acetals, examples being the aliphatic hydrocarbons (cycle) having from 4 to 8 carbon atoms, or fluorocarbons, such as Solkane® 365 mfc. In still a preferred embodiment, the blowing agent used comprises a mixture of said blowing agents, which comprise water, and in particular water is the only blowing agent. If water is not used as the blowing agent, it is preferable to use only physical blowing agents.
    [0043] The water content in a preferred embodiment is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight, and even more particularly from 0.4 to 1% by weight, based on the total weight of components (a) to
    Petition 870190113853, dated 11/06/2019, p. 21/40 / 28 (g) · [0044] In yet another preferred embodiment, hollow microcounts, which comprise a physical blowing agent, are added as an additional blowing agent to the reaction components (a), (b) and, if appropriate, (d) · Hollow microcounts can also be used in a mixture with the aforementioned blowing agents · [0045] The hybrid materials of the invention can be produced with or without the concomitant use of (e) extenders of chain and / or crosslinking agent · However, the extension of chain extenders, crosslinking agents or, if appropriate, still a mixture of them, can prove to be advantageous for the modification of the mechanical properties, for example, of hardness · These chain extenders and / or crosslinking agents are substances with a molar mass, which is preferably less than 400 g / mol, and particularly preferably 60 to 400 g / mol, and chain, in this case, have 2 hydrogen atoms ions reactive to isocyanates, while crosslinking agents have 3 hydrogen atoms reactive to isocyanates · These can be used individually or as a mixture · It is preferable to use diols and / or triols with molecular weights less than 400, particularly preferably 60 to 300, and most particularly preferred 60 to 150 · Examples of those that can be used are aliphatic, cycloaliphatic and / or araliphatic diols, having 2 to 1 4, and a preferably from 2 to 10, carbon atoms, for example, ethylene glycol, 1,2propane diol, 1,3-propane diol, 1,3-butane diol, 1,10-decane diol, o-, m-, or p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, and preferably 1,4-butane diol, 1,6-hexane diol, and bis (2-hydroxyethyl) hydroquinone, triols, such as 1,2, 4- or 1,3,5-trihydroxycyclohexane, glycerol, and trimethylol propane, and low molecular weight polyalkylene oxides, which comprise a group hydroxy and which are based on ethylene oxide and / or
    Petition 870190113853, dated 11/06/2019, p. 22/40 / 28
    Propylene 1,2-oxide and the aforementioned diols and / or triols as initiator molecules.
    [0046] To the extent that chain extenders, crosslinking agents, or a mixture thereof is used, their amounts advantageously used are 1 to 60% by weight, preferably 1.5 to 50%, in weight, and in particular from 2 to 40% by weight, based on the weight of components (b) and (e).
    [0047] If catalysts (f) are used to produce the hybrid materials of the invention, it is preferable to use compounds, which greatly accelerate the reaction of the compounds of component (b) and, if appropriate, (d) comprising hydroxy groups with modified organic polyisocyanates, if appropriate. Examples, which can be mentioned, are amidines, such as 2,3-dimethyl-3,4,5,6tetrahydropyrimidine, tertiary amines, such as triethyl amine, tributyl amine, dimethylbenzyl amine, N-methyl-, N-ethyl- , or N-cyclohexylmorpholine, N, N, N ', N'tetramethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'tetramethylexanediamine, pentamethyldiethylene triamine, tetramethyl diamino ether, bis ( dimethylaminopropyl) urea, dimethyl piperazine, 1,2-dimethyl imidazole, 1-azabicyclo [3.3.0] octane, and preferably 1,4-diazabicyclo {2.2.2] octane, and amine alkanol compounds, such as triethanol amine triisopropanol amine, N-methyl and N-ethyl diethanolamine, and dimethylethanol amine. The organo-metallic compounds can also be used, preferably the organo-tin compounds, such as the stannous salts of organic carboxylic acids, for example, stannous acetate, stannous octoate, stannous ethyl hexoate, and stannous laurate, and the dialkyl salts tin (IV) of organic carboxylic acids, for example, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate, tin dioctyl diacetate, and also bismuth carboxylates, such as bismuth (III) neodecanoate, 2- ethyl bismuth hexanoate, and bismuth octanoate, or a
    Petition 870190113853, dated 11/06/2019, p. 23/40 / 28 mixture of them. Organometallic compounds can be used in isolation or, preferably, in combination with strongly basic amines. If component (b) involves an ester, it is preferable to use only amine catalysts.
    [0048] It is preferable to use from 0.001 to 5% by weight, in particular from 0.05 to 2% by weight, of catalyst or a combination of catalysts, based on the weight of component (b).
    [0049] The auxiliaries and / or additives (g) can, if appropriate, also be added to the reaction mixture for the production of the hybrid materials of the invention. Examples, which can be mentioned, are surfactants, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis stabilizers, odor-absorbing substances, and fungistatic and bacteriostatic substances.
    [0050] Examples of surfactants, which can be used, are compounds, which serve to promote the homogenization of starting materials and, if appropriate, are also capable of regulating cell structure. Examples that can be mentioned are emulsifiers, such as the sodium salts of castor oil sulfates or fatty acids, and also the fatty acid salts with amines, for example, diethyl amine oleate, diethanol amine stearate , diethanolamine ricinoleate, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecyl benzene or dinafty methane disulfonic acid and ricinoleic acid; foam stabilizers, for example, siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkyl phenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters of ricinoleic esters, red Turkey oil and peanut oil, and cell regulators , such as paraffins, fatty alcohols, and dimethyl polysiloxanes. Oligomeric acrylates having, as pendant groups, polyoxyalkylene radicals and fluoroalkane radicals are, moreover, suitable for improving the emulsifying action and
    Petition 870190113853, dated 11/06/2019, p. 24/40 / 28 the cell structure, and / or for foam stabilization. The usual amounts used in surfactants are 0.01 to 5 parts by weight, based on 100 parts by weight of component (b).
    [0051] Examples, which may be mentioned, of suitable release agents are: the products of the reaction of fatty esters with polyisocyanates, salts derived from polysiloxanes comprising amino groups and fatty acids, salts derived from carboxylic acids saturated or unsaturated aliphatic (cycle) having at least 8 carbon atoms and tertiary amines, and also, in particular, internal lubricants, for example, carboxylic esters and / or carboxamides, produced through esterification or amidation of a mixture composed of montanic acid and at least one aliphatic carboxylic acid having at least 10 carbon atoms with at least alkanol dibasic amines, polyols, and / or polyamides, whose molar masses are from 60 to 400 g / mol, as exposed , by way of example, in EP-A 153 639, or with a mixture composed of organic amines, metal stearates, and monocarboxylic acids and / or dicarboxyl organic compounds or their anhydrides, as set out, for example, in DE-A 36 07 447, or a mixture composed of an imino compound, a metal carboxylate, and, if appropriate, a carboxylic acid, such as set forth, by way of example, in US 4764 537.
    [0052] The fillers, in particular the reinforcing fillers, are the usual organic and inorganic fillers, reinforcing agents, weight forming agents, agents for improving the paint abrasion compound, coating agents, etc. ., which are known in themselves. The individual fillers, which can be mentioned by way of example, are: inorganic fillers, such as silicate materials, such as phyllosilicates, for example, antigorite, bentonite, serpentine, Hornblendas, amphiboles, chrysotile, and talc, metal oxides , for example, kaolin, aluminum oxides, oxides
    Petition 870190113853, dated 11/06/2019, p. 25/40 / 28 of titanium, oxide of five, and oxides of iron, metallic salts, for example, plaster and barite, and inorganic pigments, for example cadmium sulfide and zinc sulfide, and also glass, etc. It is preferable to use kaolin (Chinese clay), aluminum silicate, and coprecipitates produced from barium sulfate and aluminum silicate, or natural or synthetic fibrous mineral materials, for example, volastonite, metallic fibers, and in particular glass fibers, of variable length, which may, if appropriate, have been treated with a sizing material. Examples of organic fillers that can be used are: carbon black, melamine, rosin, cyclopentadienyl resins, and graft polymers, as well as cellulosic fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, and polyester fibers, in which they are based on aromatic and / or aliphatic dicarboxyl esters, and in particular carbon fibers.
    [0053] The organic and inorganic fillers can be used individually or in the form of a mixture, and the amounts of these added, advantageously, to the reaction mixture, are from 0.5 to 50% , by weight, preferably from 1 to 40% by weight, based on the weight of components (a) to (c), in which the content of mats, nonwoven and textile materials, produced from natural and synthetic fibers can, however, reach values of up to 80% by weight.
    [0054] The hybrid materials according to the invention are produced through a known process. For this, the polyisocyanates (a) are reacted with the compounds (b) having hydrogen atoms reactive to isocyanates, and with blowing agents (d), and with the expandable particles of thermoplastic polyurethane (c '), which comprises blowing agents in a dispersed or dissolved form, or with expanded thermoplastic polyurethane particles (c ”), blowing agent (d), and also, if appropriate, with chain extenders and / or crosslinking agents (e), and with catalysts
    Petition 870190113853, dated 11/06/2019, p. 26/40 / 28 (f), and with additional additives (g), in such quantities that the equivalent ratio of NCO groups of the polyisocyanates (a) to the total reactive hydrogen atoms of components (b) and, if present, (d) and (f), it is 1: 0, 8 to 1: 1, 25, preferably 1: 0.9 to 1: 1.15. It is also possible, in this case, to use components (c ') or, respectively, (c ”) as the initial filler in a mold and add the reaction mixture comprising components a), b), d) and, if appropriate , (e) to (g) to the mold.
    [0055] The particles of the expanded thermoplastic polyurethane (c ") bonded together, in order to form an insertion, can then be inserted, for example, into the heel region or to the inside of the toe region , preferably within the heel region of a mold for producing shoe soles. The procedure for this is analogous to the conventional process, which uses the known “airbag”.
    [0056] The hybrid materials of the invention are preferably produced through a single loading process, with the aid of low or high pressure technology, advantageously in temperature-controlled molds. Molds are usually composed of metal, for example, aluminum or steel. These procedures are described, by way of example, by Plechota and Rohr in “Integralschaumstoff” [integral foam], Carl-Hanser-Verlag, Munich, Vienna, 1975, or in “Kunststoffhandbuch”, Volume 7, Polyurethane [Plastics Handbook, volume 7, Polyurethanes], 3rd Edition, 1993, chapter 7.
    [0057] For this, the starting components are mixed at a temperature of from 15 to 90 ° C, preferably from 20 to 35 ° C, and, if appropriate, introduced, at high temperature, to the interior of a closed mold. Mixing can be performed mechanically, using a stirrer or a stirring screw, or at high pressure, by what is known as the countercurrent injection process. The temperature of the mold is advantageously 20 to 90 ° C, and preferably 30 to
    Petition 870190113853, dated 11/06/2019, p. 27/40 / 28
    60 ° C.
    [0058] The amount of the reaction mixture introduced into the molded parts is judged in such a way that the density of the resulting integral foam molded parts is from 0.08 to 0.70 g / cm 3 , and particularly from 0.12 to 0.60 g / cm3. The degrees of compaction for the production of molded parts with an extreme compacted zone and cell core are in the range of 1.1 to 8.5, and preferably 2.1 to 7.0.
    [0059] The matrix material used, in this case, preferably comprises a polyurethane material, which is conveniently used in shoe soles. Even more particularly, this is a flexible integral polyurethane foam. Flexible integral polyurethane foams are polyurethane foams according to DIN 7726 with a cell core and a compact surface, where the molding process provides the extreme zone at a higher density than the core. The foamed particles of thermoplastic polyurethane may, in this case, more particularly on the upper and lower side of the shoe sole, extend as far as the surface of the flexible integral polyurethane foam. The tensile strengths of a polyurethane shoe sole of the invention are preferably 0.5 to 10 N / mm 2 , and particularly preferably 1 to 5 n / mm 2, measured according to DIN 53504 The elongation of the shoe sole according to the invention is, in addition, from 100 to 800%, and preferably from 180 to 500%, measured according to DIN 53504. The bounce resilience of the shoe sole of the invention according to DIN 53512 is furthermore preferably from 0.5 to 10 N / mm, and preferably from 1.0 to 4 N / mm, measured according to ASTM D3574. In the region of foamed particles of thermoplastic polyurethane (c ”), the elasticity of the shoe sole according to the invention is higher, and its rebound value is better, than in the rest of
    Petition 870190113853, dated 11/06/2019, p. 28/40 / 28 sole.
    [0060] The density of the matrix material is preferably from 100 to 800 g / l, and particularly preferably from 150 to 600 g / l, and even more particularly from 200 to 500 g / l, where the density of the foamed particles of thermoplastic material is preferably less than the density of the matrix material.
    [0061] Preferably, the region of the ball and toe of the shoe sole of the invention is, in essence, free of foamed thermoplastic polyurethane particles or portions of foamed thermoplastic polyurethane particles. The shoe sole is, in this case, divided into two halves of equal length, along a line between the rear end (heel) and the front end (toes) of the sole. For the purposes of the invention, everything within the rear portion of the sole is referred to as the heel region, and everything within the front portion of the sole is referred to as the ball zone and the toe zone. The heel region preferably comprises the rear third of the sole, and the region of the ball and toes preferably comprises the front third of the sole, in each case based on the length of the sole.
    [0062] Furthermore, preferably, the outer end of the heel region is also, in essence, free of foamed particles of thermoplastic material or portions of foamed particles of thermoplastic polyurethane in a region of at least 0.2 cm , preferably from 0.3 to a maximum of 5.0 cm, and particularly preferably from at least 0.5 to a maximum of 3.0 cm, based in each case , in the distance from the outer edge of the sole. “Outer end of the sole”, in this case, does not comprise the upper or lower side of the sole.
    [0063] "Essentially free" means, in this case, that the amount of foamed particles of thermoplastic polyurethane, comprised in said region of the sole, is less than 5%, by weight, preferably of
    Petition 870190113853, dated 11/06/2019, p. 29/40 / 28 less than 2% by weight, and particularly preferably less than 1% by weight, and even more particularly less than 0.5% by weight.
    [0064] The height of that region of the sole, in which the foamed particles of thermoplastic polyurethane are found, depends on the height of the sole in that region. It is preferable that the matrix material completely surrounds the foamed TPU particles, but that this can extend as far as the surface.
    [0065] The foamed particles, in this case, are composed of a foamed thermoplastic polyurethane material. The diameter of said foamed particles is preferably 0.1 mm to 10 cm, and preferably 0.5 mm to 5 cm, and particularly preferably 1 mm to 2 cm, and they are , preferably, spherical or ellipsoid. In the case of non-spherical particles, for example, elliptical particles, the diameter means the longest axis. The density of the foamed thermoplastic polyurethane particles, in this case, is preferably from 10 to 300 g / l, and particularly preferably from 20 to 200 g / l, and even more so from 40 to 150 g / l. In the case of large particles, in this case, for example, those having a diameter greater than 3 cm, for example 4 to 6 cm, it is also possible to use only one particle. Its configuration can, for example, correspond to that of a conventional airbag.
    [0066] It is preferable that the foamed particles have a compact outer film. A compact film in this case means that the foam cells are smaller in the outer region of the foamed particles than in their interior. It is particularly preferable that the outer region of the foamed particles does not comprise pores.
    [0067] It is preferable that the foamed particles are based on a thermoplastic polyurethane, produced through the use of polytetrahydrofuran. The molar mass of the polyethrahydrofuran used is preferably that of
    Petition 870190113853, dated 11/06/2019, p. 30/40 / 28 from 600 to 2500 g / mol. In yet another preferred embodiment, a polyester polyalcohol with a molar mass of from 500 to 2500 g / mol, and preferably from 600 to 900 g / mol, is used for the foamed particles to be produced.
    [0068] A hybrid material, comprising a polyurethane matrix and the foamed particles of the thermoplastic polyurethane included herein, and the production thereof, is described, for example, in WO 2008087078. This material can, by way of example, be obtained by mixing (a) polyisocyanates with (b) compounds having isocyanate-reactive hydrogen atoms, and (c ') expandable thermoplastic polyurethane particles, which comprise blowing agents in dispersed or dissolved form, and with (d) blowing agents, and also, if appropriate, with (e) chain extenders and / or crosslinking agents, and with (f) catalysts, and (g) other additives, in a way that is provided a reaction mixture, and its reaction, so that the hybrid material is supplied, in which the reaction occurs under conditions, which lead to the expansion of the expandable particles (c ').
    [0069] In a still preferred embodiment of the invention, the hybrid material of the invention is produced by mixing (a) polyisocinates with (b) compounds having hydrogen atoms reactive to isocyanates and with (c ') expandable polyurethane particles thermoplastic, which comprise blowing agents in a dispersed or dissolved form, and with (d) blowing agents, and also, if appropriate, with (e) chain extenders and / or crosslinking agents, (f) catalysts, and ( g) other additives, in order to provide a mixture of the reaction, and its reaction, so that the hybrid material is supplied, in which this reaction occurs under conditions, which lead to the expansion of the expandable particles (c ') .
    [0070] In still a preferred embodiment of the invention, the hybrid material of the invention is produced by mixing (a) polyisocyanates
    Petition 870190113853, dated 11/06/2019, p. 31/40 / 28 with (b) compounds having isocyanate-reactive hydrogen atoms, and with (c ”) expanded thermoplastic polyurethane particles, and with (d) blowing agents, and furthermore, if appropriate, with (e) chain extenders and / or crosslinking agents and with (f) catalysts, and with (g) other additives, so that the reaction mixture is provided, and its reaction so that the hybrid material is provided.
    [0071] The hybrid materials of the invention are characterized by a very good adhesion of the matrix material to the expanded thermoplastic polyurethane particles. A hybrid material of the invention does not tear at the interface of the matrix material with the expanded thermoplastic polyurethane particles.
    [0072] The shoe soles of the invention, moreover, exhibit improved properties compared to shoe soles, which comprise conventional airbags, instead of foamed thermoplastic polyurethane particles. As an example, for an identical volume of "airbag" and foamed particles of thermoplastic polyurethane, the damping properties are comparable, while the adhesion of the insert to the matrix material has been markedly improved, in the case of foamed particles. The flexing force according to ISO 178 is also markedly less for a shoe sole according to the invention than for a conventional model with an airbag, and this is advantageous for the natural rolling motion of the feet.
    [0073] The puncture resistance of the foamed particles represents another substantial advantage compared to a conventional airbag, produced from a welded TPU film. If a pointed object, such as a nail or screw, penetrates an airbag of a conventional shoe with a welded airbag, a conventional airgbag loses its gas filling and becomes useless, because the damping properties , achieved through gas compression
    Petition 870190113853, dated 11/06/2019, p. 32/40 / 28 included, are lost. A shoe sole according to the invention, with foamed particles of thermoplastic polyurethane, has a closed cell, microcellular foam instead of a conventional airbag, and the foam does not lose its cushioning and load-bearing properties , even after damage or drilling.
    [0074] Another advantage is that no substantial changes are required in the production process, when a comparison is made with a process for the production of shoe soles with conventional "airbag".
    [0075] The invention is illustrated by the following examples: Production of expandable particles [0076] Starting from one mol of polyester polyol with an average molar mass number of 800 g / mol, based on adipic acid and 1.4 -butane diol, granules of a thermoplastic polyurethane (TPU A) with an average particle weight of 30 mg, were produced by reaction with 0.44 mol of 1,4butane diol and 1.44 mol of 4,4'-MDI . Starting from a mole of tetrahydrofuran with an average molar mass number of 1333 g / mol, granules of a thermoplastic polyurethane (TPU B) with an average particle weight of around 30 mg were produced in an analogous way, through reaction with 0.97 mol of 1,4-butane diol and 1.97 mol of 4,4'-MDI.
    [0077] The following were successively mixed, with stirring, in an autoclave: 100 parts by weight of thermoplastic polyurethane A (TPU A) and B (TPU B) with respectively 250 parts of water, 6.7 parts of phosphate tricalcium, and also 20 parts of n-butane, and heated to the temperature mentioned in Table 1. The pressure vessel contents were then discharged by means of a basal and depressurized valve, in which the pressure inside the tank was kept constant through the introduction, under pressure, of nitrogen, or, respectively, of the blowing agent used. The foam particles were released from the
    Petition 870190113853, dated 11/06/2019, p. 33/40 / 28 adherent auxiliary residues by washing with nitric acid and water, and then air dried at 50 ° C.
    [0078] Table 1 provides the conditions for impregnation and the specific masses resulting from the expanded particles.
    Table 1:
    TPU n-Butane [arts by weight] Temperature [° C] Specific mass [g / l] TPU A 20 112 300 TPU A 20 114 170 TPU B 20 119 240 TPU B 20 120 190 TPU B 20 122 140 TPU B 20 125 120
    Production of a hybrid material in the form of an integral foam (Example 1) [0079] The foamed particles, produced from thermoplastic polyurethane with a specific mass of 120 g / l, were bonded with adhesive through the use of a binder of two-component polyurethane, so that an insert measuring 8 cm x 5 cm x 1 cm, with a density of 175 g / l, was provided. For this, the foamed particles produced were placed in a mold and bonded with adhesive, with 15 parts, by weight, of a 2-component polyurethane system as the binder. The adhesive-bonded particles were placed in the heel of a temperature-controlled aluminum mold at 50 ° C, so that 29 cm shoe soles were produced. 80 g of the reaction mixture from Table 2 was then loaded into the mold. This matrix formulation consists of a conventional polyurethane blend for the production of integral medium density foams. The mold is sealed, and the molded parts are demoulded after 5 minutes. In the comparative example, the procedure was analogous, but a commercially available “airbag”, produced from a thick TPU film, produced by Nike, measuring 8 cm x 5 cm x 1 cm, was inserted into the mold, instead of the insert produced from foamed particles, bonded with adhesive.
    Petition 870190113853, dated 11/06/2019, p. 34/40 / 28 [0080] Table 2 lists the composition of foams and also their mechanical properties.
    Table 2: Constitution and mechanical properties of hybrid foams (1) and conventional low density foams (comp. 1)
    Example 1 Comp. 1 Polyol 1 75.65 75.65 Polyol 2 10.0 10.0 Chain extender 10.5 10.5 Water 0.85 0.85 Amina cat. 1.0 1.0 Cell regulator 2.0 2.0 ExTPU Yes no B: that comp. That 1 119.7 119.7 Index 96 96 Mechanical properties Matrix density [g / l] 360 360 Hardness [Asker C] 59-61 59-61 Tearing in the room [N / mm] 3.2 3.2 Rebound resilience (without / with insertion) [%] 28/59 28/40 Bending force (heel part, insertion + shoe sole) [N] 94.45 142.55
    [0081] The isocyanate components used comprised isocyanate prepolymers based on MDI and mixtures of polyetherol with an NCO content of 19.0% (iso 1).
    [0082] Polyol 1 is a polyester based on adipic acid, monoethylene glycol and diethylene glycol with an OH number of 56 mg KOH / g. Polyol 2 is a polyester polymer with a solids content of 30% by weight. The chain extender is composed of a mixture of 1,4butane diol and ethylene glycol. The amine catalyst used comprised a mixture of tertiary amines in glycols. The cell regulator is a silicone surfactant polymer, sold under the trademark Elastopan® CS 7359/100.
    [0083] The tear propagation resistance (tear in the room) was determined according to ASTM D 3574F. The rebound resilience was determined according to DIN 53 512.
    [0084] As can be seen from the examples, the use of a TPU insert compared to a traditional airbag results in a
    Petition 870190113853, dated 11/06/2019, p. 35/40 / 28 decreased bending strength and higher bounce resilience.
    权利要求:
    Claims (11)
    [1]
    1. Process for producing a shoe sole, which comprises a hybrid material, produced from a polyurethane foam as a matrix material and foamed thermoplastic polyurethane particles, by preparing an insertion of joined expanded particles (c ” ) of thermoplastic polyurethane and the placement of the expanded particles joined by thermoplastic polyurethane in a mold and its inlay in the insertion with a reaction mixture, characterized by the fact that it is able to be obtained by mixing:
    a) polyisocyanates with
    b) compounds having hydrogen atoms reactive to isocyanates, and, if appropriate, with
    d) chain extenders and / or crosslinking agents, and with
    e) catalysts, and with
    f) blowing agents, and with
    g) other additives, and the reaction of the reaction mixture, so that the sole of the shoe is provided, in which the expanded particles (c ”) are joined by adhesive bonding using adhesives or thermal bonding.
    [2]
    2. Process according to claim 1, characterized by the fact that the expanded particles (c ”) were joined by means of an adhesive bond, fusion bond, through the use of a bag.
    [3]
    Process according to claim 1 or claim 2, characterized in that the shoe sole is an integral polyurethane foam.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the foamed thermoplastic polyurethane particles have a compact surface film.
    Petition 870190113853, dated 11/06/2019, p. 37/40
    2/3
    [5]
    Process according to any one of claims 1 to 4, characterized in that the density of the foamed thermoplastic polyurethane particles is 10 to 300 g / 1.
    [6]
    6. Process for producing a shoe sole, comprising a hybrid material, produced from a polyurethane foam as a matrix material and foamed thermoplastic polyurethane particles by preparing a bonded particle insert (o ') thermoplastic polyurethane comprising a blowing agent and placing the expanded particles thermoplastic polyurethane units in a mold, and embedding the insert with a reaction mixture, characterized by the fact that it is able to be obtained by mixing:
    a) polyisocyanates with
    b) compounds having hydrogen atoms reactive to isocyanates, and with
    c) expanded particles (c ”) of thermoplastic polyurethane, and also, if appropriate, with
    d) chain extenders and / or crosslinking agents, and with
    e) catalysts, and with
    f) blowing agents, and with
    g) other additives and react the reaction mixture, in order to provide the shoe sole, in which the expandable particles are foamed, in a synchronous way, until completion, through the heat of the reaction produced by the reaction mixture, in that the expanded particles (c ”) are joined by adhesive bonding.
    [7]
    7. Shoe sole, characterized in that it is capable of being obtained according to a process as defined in any one of claims 1 to 6.
    [8]
    8. Shoe sole according to claim 7,
    Petition 870190113853, dated 11/06/2019, p. 38/40
    3/3 characterized by the fact that the density of the matrix material is 100 to 800 g / l.
    [9]
    Shoe sole according to claim 7 or claim 8, characterized in that the joined expanded thermoplastic polyurethane insert has been arranged in the heel region of the shoe sole, and the ball region and the toe region of the sole shoe, are essentially free of foamed thermoplastic polyurethane particles.
    [10]
    Shoe sole according to any one of claims 7 to 9, characterized in that it does not, in essence, have foamed particles of thermoplastic polyurethane within a distance of more than 0.2 cm from the outer edge.
    [11]
    Shoe sole according to any one of claims 7 to 10, characterized in that it has foamed thermoplastic polyurethane particles in the thickness of at least 0.2 cm in the heel region.
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    同族专利:
    公开号 | 公开日
    HUE026464T2|2016-05-30|
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    EP2640760B1|2015-07-08|
    US20180103718A1|2018-04-19|
    KR20130133788A|2013-12-09|
    BR112013011437A2|2016-08-09|
    KR101923237B1|2018-11-28|
    US20130227861A1|2013-09-05|
    WO2012065926A1|2012-05-24|
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    ES2546179T3|2015-09-21|
    US9894957B2|2018-02-20|
    US10165823B2|2019-01-01|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-02-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN2010078793|2010-11-16|
    PCT/EP2011/069992|WO2012065926A1|2010-11-16|2011-11-14|Novel damping element in shoe soles|
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