EP3846655B1 - Schuh mit einer sohle aus einem thermoplastischen material und verfahren zur verwendung bei der herstellung solch eines schuhs - Google Patents

Schuh mit einer sohle aus einem thermoplastischen material und verfahren zur verwendung bei der herstellung solch eines schuhs Download PDF

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EP3846655B1
EP3846655B1 EP19759626.5A EP19759626A EP3846655B1 EP 3846655 B1 EP3846655 B1 EP 3846655B1 EP 19759626 A EP19759626 A EP 19759626A EP 3846655 B1 EP3846655 B1 EP 3846655B1
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EP
European Patent Office
Prior art keywords
hot melt
sole
shoe
melt adhesive
chosen
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EP19759626.5A
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English (en)
French (fr)
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EP3846655A1 (de
EP3846655C0 (de
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Alwin PAPEGAAIJ
Roman STEPANYAN
Jan Henderikus Udding
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Covestro Netherlands BV
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Covestro Netherlands BV
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    • 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
    • A43B9/00—Footwear characterised by the assembling of the individual parts
    • A43B9/12—Stuck or cemented footwear
    • 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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D25/00—Devices for gluing shoe parts
    • A43D25/20—Arrangements for activating or for accelerating setting of adhesives, e.g. by using heat
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/121—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyesters, polycarbonates, alkyds
    • D06N3/123—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyesters, polycarbonates, alkyds with polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/04—Foam
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/06—Melt
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2738—Coating or impregnation intended to function as an adhesive to solid surfaces subsequently associated therewith
    • Y10T442/2746—Heat-activatable adhesive

Definitions

  • the present invention pertains to shoes and the manufacturing thereof. More particularly the invention pertains to shoes with a sole of a thermoplastic material and a method for making a workpiece that can be used in the manufacturing of such shoes.
  • Soles comprise the same basic parts. All shoes have a sole, which is the bottom of a shoe, in contact with the ground. Soles can be made from a variety of materials, although most modern shoes have soles made from natural rubber, polyurethane, polyvinyl chloride (PVC) or ethylene-vinyl acetate copolymer (EVA). Soles can be simple, a single material in a single layer, but most often they are more complex, with multiple structures or layers and materials. When various layers are used, soles may consist of an insole (also known as a sock liner), a midsole, and an outsole (i.e. the layer in direct contact with the ground). The midsole is the layer in between the outsole and the insole, typically there for shock absorption.
  • insole also known as a sock liner
  • midsole i.e. the layer in direct contact with the ground.
  • the midsole is the layer in between the outsole and the insole, typically there for shock absorption.
  • the upper shoe helps hold the shoe onto the foot. In the simplest cases, such as sandals or flip-flops, this may be nothing more than a few straps for holding the sole in place. Closed shoes, such as boots, trainers and most men's shoes, will have a more complex upper. This part is often decorated or is made in a certain style to look attractive.
  • the upper may be connected to the sole by a strip of leather, rubber, or plastic that is stitched between it and the sole, or it may be glued to the sole by using an adhesive.
  • the upper shoe is in most cases glued to the midsole (the latter being an important item for such shoes) using a solvent based adhesive, either using an aqueous solvent (such as water based PUD's, polyurethane adhesives) or a non-aqueous solvent (such as polychloroprene or styrene-isoprene-styrene adhesives).
  • aqueous solvent such as water based PUD's, polyurethane adhesives
  • a non-aqueous solvent such as polychloroprene or styrene-isoprene-styrene adhesives.
  • Hot melt adhesives have the advantage of being (almost) solvent free and allowing very short processing times without any foaming tendency during processing, but the adhering properties on the relatively smooth soles are relatively bad. This is in particular true when adhering an upper shoe to a sole of a thermoplastic material.
  • the latter type of material would in principle be preferred over the commonly used EVA (that is typically used for mid-soles) because of its easy recyclability when compared to EVA, the finished foam of which has thermoset properties that prevent recycling by simply melting the material and reprocessing it.
  • EVA is still the polymer of choice, using solvent based adhesives to adhere the upper shoe.
  • GB 1247855 (filed 1967 , published 1971) describes the problem of using a hot melt adhesive to bond the upper shoe to a sole of plasticised polyvinyl chloride.
  • the solution proposed in this patent is to use a polyester hot melt adhesive that includes a quantity of a nitrogen containing organic compound having a polar group, such as N-Butyl-Benzenesulphonamide or N-Ethyl-P-tolylsulphonamide.
  • a nitrogen containing organic compound having a polar group such as N-Butyl-Benzenesulphonamide or N-Ethyl-P-tolylsulphonamide.
  • N-Butyl-Benzenesulphonamide is neurotoxic and has been found to induce spastic myelopathy in rabbits.
  • N-Ethyl-P-tolylsulphonamide is toxic and highly irritating.
  • GB 2048897 (filed 1979 , published 1980) states (page 1, lines 14-16) that it is known that the receptiveness of elastomeric soling material towards adhesives and to thermoplastic materials is often unsatisfactory.
  • the solution proposed is to use aggressive primers comprising an organic halogen donor, like mixtures of isocyanuric chloride and a sulphonamide such as, for example, p-toluene sulphonamide, for promoting adhesion.
  • These primers are toxic, irritating and environmentally unfriendly.
  • JP 2003 266557 A discloses a process for preparing a shoe comprising a cover and a sole, wherein a heat sealable film is attached to the cover.
  • the heat sealable film melts during the process and adheres the sole to the cover. It is not disclosed that a hot melt is fused to a thermoplastic material which results in the absence of a borderline and/or distinct boundary between materials in Scanning Electronic Microscopy (SEM) pictures at an enlargement of 500 to 1000 times.
  • SEM Scanning Electronic Microscopy
  • JP 2017 192559 A discloses a shoe comprising an upper and a sole composed of the same thermoplastic base material. It is disclosed that the upper and sole can be connected by providing a hot melt adhesive between the sole and the upper or by heating the sole and the upper composed of the same thermoplastic base material and pressing them together. It is not disclosed that the temperatures of the hot melt adhesive and the thermoplastic base materials are chosen such that (T HM + T SUB )/2 is equal to or higher than (T M -10°C).
  • thermoplastic material per se is less receptive for adhering to another material, in particular a hot melt adhesive, it provides the option of melting an upper region of the body (i.e. a region that has a thickness beyond molecular scale, at least being at a micrometer level or beyond, i.e. 1 ⁇ m or thicker, e.g.
  • the invention also relates to a method of assembling a workpiece as defined in claim 13.
  • the total heat available is sufficient to melt the upper region of the thermoplastic body upon contact with the hot met adhesive, and fusing the two molten substances is allowed, in particular when applying pressure, e.g. when applying the upper shoe (wherein the molten hot melt adhesive may have been applied as such to the sole before applying the upper shoe, or may have been pre-applied to this upper shoe and kept at a sufficient temperature while in contact with this upper shoe alone).
  • the melting of a thin upper region of the thermoplastic body could be accomplished in various ways (using e.g. convection of hot air or a liquid, radiation, etc.) it was found that a very simple way is to use the heat capacity of the hot melt adhesive and the body themselves to provide the heat for melting the upper region of the thermoplastic body.
  • thermoplastic body by providing the fusion between the hot melt adhesive and the thermoplastic body, a very strong mechanical connection may be obtained, without the need for applying special organic molecules, primers or using complicated heating procedures and equipment.
  • a shoe is an outer covering for the human foot typically having a thick or stiff sole with an attached heel and an upper part (also denoted as the upper shoe) of lighter material, such as a textile or leather sheeting.
  • a hot melt adhesive is a thermoplastic adhesive with no (less than 1 or 2 wt%) solvent. Upon heating the adhesive softens in order to be applied to a substrate. Preferably the hot melt adhesive undergoes a first order phase transition when being heated and transformed from a solid into a liquid.
  • thermoplastic material is a material (typically a synthetic polymer material) that becomes plastic, e.g. shapeable, upon heating and hardens upon cooling to retain desired shape and is able to reversibly undergo this process repeatedly.
  • the melting temperature (T M ) of the thermoplastic material is the peak melting temperature as defined in ASTM D3418 measured during the second heating step in a Differential Scanning Calorimetry (DSC) experiment conducted at 10°C/min heating rate. If multiple peaks are present, then the first peak (e.g. lowest temperature) corresponding to the melting of the hard block of the thermoplastic elastomer should be taken.
  • a first order phase transition temperature of a material is the temperature at which the material undergoes a discontinuous change in density.
  • first order transitions are melting (solid to liquid conversion) and evaporating (liquid to gas conversion).
  • a glass-transition is a second order transition since there is no discontinuous change in density.
  • a body is a solid 3-dimensional object having predetermined dimensions.
  • To be fused means to unite to form a single entity by melting or as if by melting, in particular which results in the absence of a borderline and/or distinct boundary between materials in Scanning Electronic Microscopy (SEM) pictures at an enlargement of 500 to 1000 times.
  • SEM Scanning Electronic Microscopy
  • a textile material is a material that is consists in essence (for more than 50%, for example more than 55%, 60%, 65%, 70%, 75%, 80%, 85%, or even more than 90%) of fibrous material such as polymeric yarns.
  • a body being composed of a thermoplastic material means that the basic structure of the body consists of a thermoplastic material, the material typically containing over 50% (on a weight basis), preferably over 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or even up to 100% of a thermoplastic polymer.
  • a workpiece is an assembly of materials that is used in manufacturing an end product.
  • a smooth surface is a surface not having a regular or irregular pattern of protrusions that are tactually perceived as "rough" by man, i.e. not having a pattern of protrusions with an average height above 100 ⁇ m, preferably not above 90 ⁇ m, 80 ⁇ m, 70 ⁇ m, 60 ⁇ m, 50 ⁇ m, 40 ⁇ m, 30 ⁇ m, 20 ⁇ m, 10 ⁇ m, 9 ⁇ m, 8 ⁇ m, 7 ⁇ m, 6 ⁇ m, 5 ⁇ m, 4 ⁇ m, 3 ⁇ m, 2 ⁇ m or even 1 ⁇ m, and a surface not having a regular or irregular pattern of indentations or cavities that are visually perceived as the inverse of such protrusions, i.e.
  • thermoplastic material specifically suitable for the sole of the shoe according to the present invention is thermoplastic elastomers.
  • Thermoplastic elastomers (TPE), sometimes referred to as thermoplastic rubbers, are a class of copolymers or a physical mix of polymers which consist of materials with both thermoplastic and elastomeric properties.
  • TPE Thermoplastic elastomers
  • Six generic classes of commercial TPEs can be distinguished: styrenic block copolymers, thermoplastic olefins, elastomeric alloys, thermoplastic polyurethanes, thermoplastic copolyester and thermoplastic polyamides.
  • the shoe according to the invention has a sole that comprises a foamed composition comprising a thermoplastic copolyester elastomer in an amount of 70 to 99wt% based on the total amount of the foamed composition.
  • the foamed composition comprises a thermoplastic copolyester elastomer in an amount of 70 to 99wt% and a plasticizer in an amount of 1 to 30wt% based on the total amount of the foamed composition.
  • Such compositions are disclosed in WO2018134166 .
  • a foamed composition is herein understood to be known to a person skilled in the art.
  • a foamed composition has a density of between 0.1 and 0.7 g/cm 3 , typically between 0.2 and 0.3 g/cm 3 , especially for use in athletic shoes.
  • a thermoplastic copolyester elastomer is herein understood to be a copolymer comprising hard segments built up from polyester repeating units, and soft segments chosen from another type of polymer.
  • thermoplastic copolyester elastomer comprises hard segments built up from polyester repeating units derived from at least one aliphatic diol and at least one aromatic dicarboxylic acid or an ester thereof, and soft segments chosen from the group consisting of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, dimer fatty acids and dimer fatty diols and combinations thereof.
  • Aliphatic diols contain generally 2-10 C-atoms, preferably 2-6 C-atoms. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, 1,2-hexane diol, 1,6-hexamethylene diol, 1,4-butanediol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, and mixtures thereof. Preferably, 1,4-butanediol is used.
  • Suitable aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-diphenyldicarboxylic acid, and mixtures thereof. Also very suitable is a mixture of 4,4'-diphenyldicarboxylic acid and 2,6-naphthalenedicarboxylic acid or a mixture of 4,4'-diphenyldicarboxylic acid and terephthalic acid.
  • the mixing ratio between 4,4'-diphenyldicarboxylic acid and 2,6-naphthalenedicarboxylic acid or 4,4'-diphenyldicarboxylic acid and terephthalic acid is preferably chosen between 40:60 - 60:40 on weight basis in order to optimize the melting temperature of the thermoplastic copolyester.
  • the hard segment preferably has as repeating unit chosen from the group consisting of ethylene terephthalate (PET), propylene terephthalate (PPT), butylene terephthalate (PBT), polyethylene bibenzoate, polyethylene naphthalate, polybutylene bibenzoate, polybutylene naphthalate, polypropylene bibenzoate and polypropylene naphthalate and combinations thereof.
  • the hard segment is butylene terephthalate (PBT), as thermoplastic copolyester elastomers comprising hard segments of PBT exhibit favourable crystallisation behaviour and a high melting point, resulting in thermoplastic copolyester elastomer with good processing properties and excellent thermal and chemical resistance.
  • Soft segments chosen from aliphatic polyesters have repeating units derived from an aliphatic diol, and an aliphatic dicarboxylic acid or repeating units derived from a lactone.
  • Suitable aliphatic diols contain generally 2-20 C-atoms, preferably 3-15 C-atoms in the chain and an aliphatic dicarboxylic acid containing 2 - 20 C atoms, preferably 4 - 15 C atoms. Examples thereof include ethylene glycol, propylene glycol, butylene glycol, 1,2-hexane diol, 1,6-hexamethylene diol, 1,4-butanediol, cyclohexane diol, cyclohexane dimethanol, and mixtures thereof.
  • 1,4-butanediol is used.
  • Suitable aliphatic dicarboxylic acids include sebacic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, 2-ethylsuberic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naphtylene dicarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid, decahydro-2,6-naphthylene dicarboxylic acid, 4,4'-methylenebis (cyclohexyl)carboxylic acid and 2,5-furan dicarboxylic acid.
  • Preferred acids are sebacic acid, adipic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid. Most preferred is adipic acid.
  • the soft segment is polybutylene adipate (PBA) which may be obtained from 1,4 butanediol and adipic acid.
  • the soft segment may be aliphatic polyethers, which may comprise units of polyalkylene oxides, such as polyethylene oxide and polypropylene oxide and polytetramethylene oxide and combinations thereof, either as individual segment or combined in one segment.
  • a combination is for example ethylene oxide-capped polypropylene oxide.
  • a preferred soft segment is polytetramethylene oxide (PTMO).
  • soft segments comprising a block copolymer in which two types of glycols are reacted to form a soft segment such as based on polyethylene oxide (PEO) and polypropylene oxide (PPO) can be used.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEO-PPO-PEO PEO-PPO-PEO
  • the soft segment may be an aliphatic polycarbonate and is made up of repeating units from at least one alkylene carbonate.
  • the soft segment may be dimer fatty acids or dimer fatty diols and combinations thereof.
  • the dimerised fatty acids may contain from 32 up to 44 carbon atoms. Preferably the dimerised fatty acids contain 36 carbon atoms.
  • dimer fatty diols which may be derived from the dimer fatty acids as disclosed above.
  • a dimerised fatty diol may be obtained as a derivative of the dimerised fatty acid by hydrogenation of the carboxylic acid groups of the dimerised fatty acid, or of an ester group made thereof. Further derivatives may be obtained by converting the carboxylic acid groups, or the ester groups made thereof, into an amide group, a nitril group, an amine group or an isocyanate group.
  • the foamed composition comprises a thermoplastic copolyester elastomer having hard and soft segments, wherein the hard segment is chosen from PBT or PET, preferably PBT, and the soft segment is chosen from the group consisting of polybutylene adipate (PBA) polyethylene oxide (PEO), polypropylene oxide (PPO), polytetramethylene oxide (PTMO), PEO-PPO-PEO and combinations thereof, preferably PTMO, as this provided an article exhibiting low densities.
  • PBA polybutylene adipate
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PTMO polytetramethylene oxide
  • PEO-PPO-PEO polytetramethylene oxide
  • the foamed composition comprises a thermoplastic copolyether-ester elastomer composed of PBT and PTMO.
  • Plasticizers are known substances to a person skilled in the art per se, and for example lower the hardness and/or increases the strain at break of the composition as compared to the elastomer itself. Plasticizers are present in an amount of between 1 to 30 wt% based on the total amount of the foamed composition, preferably between 5 to 25 wt% and even more preferred between 8 to 20 wt%. Plasticizers include for example phthalate esters, dibasic acid esters, mellitates and esters thereof, cyclohexanoate esters, citrate esters, phosphate esters, modified vegetable oil esters, benzoate esters, and petroleum oils, and combinations thereof.
  • the plasticizer is chosen from the group consisting of Triphenyl phosphate (TPP), tert-Butylphenyl diphenyl phosphate (Mono-t-but-TPP), di-tert-butylphenyl phenyl phosphate (bis-t-but-TPP), Tris(p-tert-butylphenyl) phosphate (tri-t-but-TPP), Resorcinol bis (Diphenyl Phosphate) (RDP), dichloropropyl phosphate, Bisphenol A bis-(Diphenyl Phosphate) (BDP), tricresyl phosphate (TCP), triethyl phosphate, tributyl phosphate (TBP), tri-2-ethylhexyl phosphate, trimethyl phosphate, epoxidized soybean oil (ESO), epoxidized palm oil (EPO), epoxidized linseed oil (ELO), ar
  • the shoe according to the invention comprises a sole of a thermoplastic material adhered to an upper shoe with a hot melt adhesive that is applied between the sole and the upper shoe, wherein the hot melt adhesive is fused with the thermoplastic material and wherein the sole comprises thermoplastic polyurethane (TPU).
  • TPU thermoplastic polyurethane
  • the sole comprises TPU in an amount of 70 to 100 wt% based on the total amount of the sole composition.
  • the sole may comprise expanded, i.e. foamed TPU, such as disclosed in WO94/20568 or US2010/0222442 .
  • Thermoplastic polyurethanes and processes for their production are well known.
  • TPU is a block copolymer consisting of alternating sequences of hard and soft segments or domains formed by the reaction of (1) diisocyanates with short-chain diols (so-called chain extenders) and (2) diisocyanates with long-chain diols.
  • chain extenders diisocyanates with short-chain diols
  • diisocyanates with long-chain diols chain extenders
  • polyester-based TPUs are used for soles, for example those derived from adipic acid esters.
  • the upper shoe comprises a layer of textile material that is contiguous with the sole.
  • a textile material appears to be ideally suitable to be connected to the sole via a hot melt adhesive without any special measures being needed, probably due to the irregular surface that is provided by the constituting yarns.
  • the textile material may comprise polymeric yarns, such as yarns made from polyester polymer. This is particularly advantageous when the sole is also made from a polyester material, allowing easy recycling of the assembly of the upper shoe and sole. Insoles, midsoles and outsoles are all considered a sole in the context of this invention.
  • the hot melt adhesive comprises as a main constituent (i.e. in an amount of at least 50% by weight of the adhesive composition) a polymer selected from the group consisting of (co)polyurethane(s), (co)polycarbonate(s), (co)polyester(s), (co)polyamide(s), (co)poly(ester-amide(s), mixtures thereof and/or copolymers thereof.
  • a polymer selected from the group consisting of (co)polyurethane(s), (co)polycarbonate(s), (co)polyester(s), (co)polyamide(s), (co)poly(ester-amide(s), mixtures thereof and/or copolymers thereof.
  • the hot melt adhesive comprises a (co)polyester as a main constituent.
  • the (co) polyester may be built up from an acid selected from terephthalic acid, isophthalic acid, succinic acid, suberic acid, pimelic acid, adipic acid, fumaric acid, maleic acid, itaconic acid, dimer fatty acid, sebacic acid, azelaic acid, sulfoisophthallic acid or its metal salt, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, furane dicarboxylic acid, trimellitic anhydride and/or dialkyl esters thereof, mixtures thereof together with an alcohol selected from: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, poly
  • the (co)polyester is obtained and/or obtainable from reacting at least one acid selected from terephthalic acid, 2,5-furanedicarboxylic acid, adipic acid, fumaric acid, dimer fatty acid, sebacic acid, azelaic acid, succinic acid, and/or combinations thereof with at least one alcohol selected from ethylene glycol, 1,6-hexandediol, 1,4-butanediol, dimer fatty acid diol and/or combinations thereof.
  • esterification polymerisation processes for making the polyester for use in the invention composition are well known in the art and need not be described here in detail. Suffice to say that they are normally carried out in the melt optionally using catalysts such as titanium- or tin-based catalysts and with the provision for removing any water (or alcohol) formed from the condensation reaction.
  • the polyester resin comprises carboxylic acid functionalities, they are derived from a polyacid and or anhydride.
  • the upper shoe, the hot melt adhesive and the sole are made from a polyester material.
  • the hot melt adhesive is semi-crystalline (i.e. it at least partly transforms into crystals when solidifying under equilibrium conditions), preferably having a melting enthalpy between 1 and 80 J/g, more preferably between 5 and 60 J/g and even more preferably between 10 and 40 J/g.
  • the determination of the melting enthalpy is based on ASTM standard D3418 ("Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry") using a Mettler STARe differential scanning calorimeter. For the actual measurement an adhesive sample of approximately 10 mg is placed in a sample cup. This sample is kept in an oven for 15 minutes at 150°C.
  • the sample is cooled to 50°C and then heated to 250°C at a speed of 5°C/min.
  • the sample is kept at 250°C for 1 minute and thereafter directly cooled to 25°C at a speed of 5°C/min. From the obtained DSC data the melting enthalpy of the sample polymer is obtained.
  • the present invention is also embodied in a method of assembling a workpiece that can be used to manufacture a shoe according to the invention, which workpiece comprises a first body (i.c. the upper shoe) mechanically connected to a second body (i.c. the sole) by adhering the first body to a surface of the second body, the second body being composed of a thermoplastic material that has a melting temperature T M , the method comprising:
  • the second body is heated in its entirety.
  • Such heating can for example be established by warming the whole second body in an oven or microwave or in a heated mold.
  • Such heating thus differs from partial heating of the upper region, which can be achieved by external radiation or convection, i.e. heating only the outer side of the second body.
  • the temperatures are chosen such that (T HM + T SUB )/2 differs from T M by a number of degrees chosen from the group consisting of -10, -9, -8, -7, -6, - 5, -4, -3, -2, -1, 0, +1, +2, +3, +4, +5, +6, +7, +8, +9, +10, +11, +12, +13, +14, +15, +16, +17, +18, +19 or +20°C.
  • a higher number leads to a larger part of the upper region of the thermoplastic body to be melted. However, advantageously, this part should not become too thick, since it will not increase the bonding strength, but may negatively influence the shape and mechanical properties of the thermoplastic body. Hence the preferred upper limit of 20°C.
  • the second body is heated such that the thermoplastic material obtains a temperature T SUB that is at most X °C less than T M , X being chosen from the group that consists of 100, 90, 80, 70, 60, 55, 50, 45, 40, 35 and 30. It was found that the thermoplastic body preferably is not heated to temperature too close to its melting temperature.
  • Example 1 describes the connection of two thermoplastic bodies using a hot melt adhesive.
  • Figure 1 schematically shows the interaction between hot melt adhesive 4 and various substrates (200, 200' and 200").
  • FIG 1A the interaction between a layer 4 of hot melt adhesive in its hardened form (thus after application in liquid form and subsequent cooling down to below its solidification temperature) and a non-smooth surface of a body 200 is depicted.
  • the surface of the body has various protrusions (201) and indentations (202) which serve as anchoring point for the hardened hot melt adhesive. This brings about a good mechanical connection between the hot melt adhesive 4 and the body 200.
  • FIG 1B a situation is depicted wherein the body 200' has a smooth surface, leading to the absence of anchoring points for the hot melt adhesive 4. This means that the mechanical connection, if any, between the layer of hot melt adhesive 4 and the body 200' is very weak. The layers can be easily separated by using a slight pulling force to either of the layers.
  • FIG 1C the situation is depicted where body 200" is made of a thermoplastic material and the hot melt adhesive is heated sufficiently just before application thereof, to make sure that the upper region of the body 200" is heated to above its melting temperature.
  • the molecules of the molten hot melt adhesive and the molten body 200" may be able to mix and unite (to fuse) to form one new intermediate material 204, which material may ultimately (after solidification of all molten material) serve as a mechanical bridge between the layer of hot melt adhesive 4 and the body 200".
  • the layers 4 and 200" gradually change from one pure material to another with the mixed material of a gradually changing composition in between.
  • Figure 2 schematically shows in a cross section the constituting parts of a workpiece 1 for use in the manufacture of a shoe (which need not be more than the workpiece itself).
  • part 2 is the (mid-)sole of the shoe, in this case consisting of a foamed composition comprising a copolyether-ester elastomer (55wt% PTMO and 45wt% PBT with respect to the amount of copolyether-ester elastomer) in an amount of 85wt%, and 15wt% epoxidised soybean oil as a plasticizer with respect to the total amount of foamed composition, leading to a foam having a density of 0.24 g/cm 3 and having T M of 160°C.
  • the upper shoe 3 consists of a textile base layer and a top coat of polyurethane (see figure 3 ).
  • Part 30 is a segment of the upper shoe 3 that is used for adhering the upper shoe 3 to the sole 2 using a hot melt adhesive (see Example 1).
  • an outer sole 20 is depicted.
  • Figure 3 schematically shows a cross section of a material used for an upper shoe 3 of an athletic shoe.
  • the upper shoe 3 consists of a textile base layer 31 and a top coat of polyurethane (32).
  • the textile layer 31 is the layer that will be used to make the connection with the sole as indicated in Figure 2 .
  • Figure 4 schematically shows a test set-up for measuring the strength of a mechanical connection brought about by a hot melt adhesive (in line with standardised method ASTM D3936).
  • a hot melt adhesive in line with standardised method ASTM D3936.
  • two bodies 2 and 3 having a width L are mechanically connected with a layer of hot melt adhesive 4. These layers are separated at one of the ends, exerting a separating force F.
  • Example 1 describes the connection of a thermoplastic body using a hot melt adhesive.
  • a hot melt adhesive In order to assess whether a hot melt adhesive could be used to adhere a first body to a thermoplastic body, two thermoplastic bodies were chosen, in this case foamed thermoplastic bodies as described in connection with figure 2 .
  • the melting temperature T M of these bodies is 160°C (determined with ASTM D3418-03 as described in this patent application).
  • a polyester hot melt adhesive having a melting enthalpy of 27t3 J/g was used (the determination of which is based on ASTM standard D3418 using a Mettler STARe differential scanning calorimeter), showing a first order transition temperature (solid to liquid) around 110°C.
  • the hot melt was heated to a temperature of 180°C, thus well above its melting temperature and at a level that is common for using this hot melt to obtain strong connections.
  • the thermoplastic bodies were preheated to various temperatures, ranging from 80°C to 100°C before the hot melt adhesive was applied, meaning that (T HM + T SUB )/2 varied from 130 to 140°C, i.e. 30° to 20° below T M . Directly after application of the adhesive, both bodies were pressed together. In none of the cases a good mechanical connection could be obtained. F/L was less than 5 N/inch value for each workpiece. This confirmed the common knowledge that thermoplastic materials cannot be adequately connected using a hot melt adhesive.
  • the hot melt adhesive was heated to 210°C (i.e. still well below the temperature at which the polyester hot melt adhesive would (start to) degrade, i.e. around 250°C) and the thermoplastic bodies to a temperature ranging from 120 to 130°C, meaning that (T HM + T SUB )/2 varied from 165 to 170°C, i.e. 5° to 10° over T M . Either one or both sides of the bodies were provided with the melted adhesive. In addition to the type of polyester adhesive used in the first experiment (“Type 1”), another type was used ("Type 2"). Keeping all other variables the same as in the first experiment, this way a very good mechanical connection between the two thermoplastic bodies could be obtained. The data are indicated in table 1 below.
  • FIG 5 a Scanning Electronic Microscopy (SEM) picture is shown, which demonstrates that at an enlargement of 650 times no boundary between the thermoplastic bodies can be distinguished for the example with the Type 2 adhesive.
  • the upper shoe 3 is connected to midsole 2 in the same way as is schematically depicted in figure 2 .
  • thermoplastic bodies consisting of a foamed composition comprising TPU. Similar results were obtained and connections with high mechanical strengths were provided accordingly.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Claims (17)

  1. Schuh, umfassend eine Sohle bestehend aus einem thermoplastischen Material, die durch einen Heißschmelzklebstoff an einem Oberschuh befestigt ist, der zwischen der Sohle und dem Oberschuh aufgebracht ist, dadurch gekennzeichnet, dass der Oberschuh durch Anhaften des Oberschuhs an eine Oberfläche der Sohle mechanisch mit der Sohle verbunden ist, wobei die Sohle aus einem thermoplastischen Material besteht, das eine Schmelztemperatur TM aufweist, wobei das Verfahren umfasst:
    - Erhitzen des Heißschmelzklebstoffs auf eine Temperatur THM, so dass er weich wird;
    - Erhitzen der Sohle, so dass das thermoplastische Material eine Oberflächentemperatur TSUB von unter TM erhält;
    - Aufbringen des erhitzten Heißschmelzklebstoffs auf die Oberfläche der erhitzten Sohle;
    - Aufbringen des Oberschuhs auf die Sohle, um ein Werkstück zu bilden;
    - Abkühlen des Werkstücks, so dass der Heißschmelzklebstoff härtet;
    - wobei die Temperaturen so ausgewählt werden, dass (THM + TSUB) /2 gleich oder größer als (TM - 10 °C) ist;
    - wobei das Werkstück zum Herstellen des Schuhs verwendet wird,
    wobei das Verfahren zum Fehlen einer Grenzlinie und/oder klaren Grenze zwischen Materialien in rasterelektronenmikroskopischen (REM) Aufnahmen bei einer 500- bis 1000-fachen Vergrößerung führt.
  2. Schuh gemäß Anspruch 1, dadurch gekennzeichnet, dass die Sohle eine geschäumte Zusammensetzung umfasst, die ein thermoplastisches Copolyesterelastomer in einer Menge von 70 bis 99 Gew.-%, bezogen auf die Gesamtmenge der geschäumten Zusammensetzung, umfasst.
  3. Schuh gemäß Anspruch 2, dadurch gekennzeichnet, dass die geschäumte Zusammensetzung ein thermoplastisches Copolyesterelastomer in einer Menge von 70 bis 99 Gew.-% und einen Weichmacher in einer Menge von 1 bis 30 Gew.-%, bezogen auf die Gesamtmenge der geschäumten Zusammensetzung, umfasst.
  4. Schuh gemäß Anspruch 2 oder 3, dadurch gekennzeichnet, dass das thermoplastische Copolyesterelastomer harte Segmente, die aus Polyester-Wiederholungseinheiten aufgebaut sind, die von wenigstens einem aliphatischen Diol und wenigstens einer aromatischen Dicarbonsäure oder einem Ester davon abgeleitet sind, und weiche Segmente ausgewählt aus der Gruppe bestehend aus aliphatischem Polyether, aliphatischem Polyester, aliphatischem Polycarbonat, dimeren Fettsäuren und dimeren Fettdiolen und Kombinationen davon umfasst.
  5. Schuh gemäß Anspruch 4, dadurch gekennzeichnet, dass die harten Segmente ausgewählt sind aus der Gruppe bestehend aus Ethylenterephthalat (PET), Propylenterephthalat (PPT), Butylenterephthalat (PBT), Polyethylenbibenzoat, Polyethylennaphthalat (PEN), Polybutylenbibenzoat, Polybutylennaphthalat, Polypropylenbibenzoat und Polypropylennaphthalat und Kombinationen davon, und die weichen Segmente ausgewählt sind aus der Gruppe bestehend aus aliphatischem Polyether, aliphatischem Polyester, aliphatischem Polycarbonat, dimeren Fettsäuren und dimeren Fettdiolen und Kombinationen davon.
  6. Schuh gemäß Anspruch 5, dadurch gekennzeichnet, dass das harte Segment ausgewählt ist aus PBT und PET und das weiche Segment ausgewählt ist aus der Gruppe bestehend aus Polybutylenadipat (PBA), Polyethylenoxid (PEO), Polypropylenoxid (PPO), Polytetramethylenoxid (PTMO), PEO-PPO-PEO und Kombinationen davon.
  7. Schuh gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Oberschuh eine Schicht von Textilmaterial umfasst, das an der Sohle anliegt.
  8. Schuh gemäß Anspruch 7, dadurch gekennzeichnet, dass das Textilmaterial Polymergarne umfasst.
  9. Schuh gemäß Anspruch 8, dadurch gekennzeichnet, dass die Polymergarne Polyesterpolymer umfassen.
  10. Schuh gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Heißschmelzklebstoff ein Polymer umfasst, das ausgewählt ist aus der Gruppe bestehend aus (Co)polyurethan(en), (Co)polycarbonat(en), (Co)polyester(n), (Co)polyamid(en), (Co)poly(ester-amid(en)), Gemischen davon und/oder Copolymeren davon.
  11. Schuh gemäß Anspruch 10, dadurch gekennzeichnet, dass der Heißschmelzklebstoff einen (Co)polyester umfasst.
  12. Schuh gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Heißschmelzklebstoff halbkristallin ist, vorzugsweise mit einer Schmelzenthalpie zwischen 1 und 80 J/g.
  13. Verfahren zum Zusammensetzen eines Werkstücks, das einen ersten Körper umfasst, der mechanisch mit einem zweiten Körper verbunden ist, durch Anhaften des ersten Körpers an eine Oberfläche des zweiten Körpers, wobei der zweite Körper aus einem thermoplastischen Material besteht, das eine Schmelztemperatur TM aufweist, wobei das Verfahren umfasst:
    - Erhitzen eines Heißschmelzklebstoffs auf eine Temperatur THM, so dass er weich wird;
    - Erhitzen des zweiten Körpers, so dass das thermoplastische Material eine Oberflächentemperatur TSUB von unter TM erhält;
    - Aufbringen des erhitzten Heißschmelzklebstoffs auf die Oberfläche des erhitzten zweiten Körpers;
    - Aufbringen des ersten Körpers auf den zweiten Körper, um das Werkstück zu bilden;
    - Abkühlen des Werkstücks, so dass der Heißschmelzklebstoff härtet;
    - wobei die Temperaturen so ausgewählt werden, dass (THM + TSUB) /2 gleich oder größer als (TM - 10 °C) ist.
  14. Verfahren gemäß Anspruch 13, dadurch gekennzeichnet, dass Temperaturen so ausgewählt werden, dass sich (THM + TSUB) /2 von TM um eine Anzahl von Graden unterscheidet, die ausgewählt ist aus der Gruppe bestehend aus -10, -9, -8, -7, -6, -5, -4, -3, -2, -1, 0, +1, +2, +3, +4, +5, +6, +7, +8, +9, +10, +11, +12, +13, +14, +15, +16, +17, +18, +19 und +20 °C.
  15. Verfahren gemäß einem der Ansprüche 13 oder 14, dadurch gekennzeichnet, dass der zweite Körper erhitzt wird, so dass das thermoplastische Material eine Temperatur TSUB erhält, die höchstens X °C kleiner als TM ist, wobei X ausgewählt ist aus der Gruppe bestehend aus 100, 90, 80, 70, 60, 55, 50, 45, 40, 35 und 30.
  16. Verfahren gemäß einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, dass der zweite Körper in seiner Gesamtheit erhitzt wird.
  17. Werkstück, umfassend einen ersten Körper, der mechanisch mit einem zweiten Körper verbunden ist, durch Anhaften des ersten Körpers an eine Oberfläche des zweiten Körpers, wobei der zweite Körper aus einem thermoplastischen Material besteht, das eine Schmelztemperatur TM aufweist,
    wobei das Werkstück durch ein Verfahren gemäß einem der Ansprüche 13 bis 16 erhältlich ist,
    wobei das Verfahren Fehlen einer Grenzlinie und/oder klaren Grenze zwischen Materialien in rasterelektronenmikroskopischen (REM) Aufnahmen bei einer 500- bis 1000-fachen Vergrößerung ergibt.
EP19759626.5A 2018-09-03 2019-09-03 Schuh mit einer sohle aus einem thermoplastischen material und verfahren zur verwendung bei der herstellung solch eines schuhs Active EP3846655B1 (de)

Applications Claiming Priority (2)

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EP18192327 2018-09-03
PCT/EP2019/073475 WO2020048989A1 (en) 2018-09-03 2019-09-03 A shoe comprising a sole of a thermoplastic material and a method for use in manufacturing such a shoe

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CN112638192A (zh) 2021-04-09
KR102660597B1 (ko) 2024-04-26
KR20210047305A (ko) 2021-04-29
EP3846655C0 (de) 2023-10-04
WO2020048989A1 (en) 2020-03-12

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