Classifications

• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
  • A43B23/02—Uppers; Boot legs
  • A43B23/0205—Uppers; Boot legs characterised by the material
  • A43B23/0225—Composite materials, e.g. material with a matrix
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
  • A43B23/02—Uppers; Boot legs
  • A43B23/0205—Uppers; Boot legs characterised by the material
  • A43B23/0215—Plastics or artificial leather
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D35/00—Producing footwear
  • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
  • B29D35/126—Uppers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
  • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

• the present invention relates to an upper for a footwear article, said upper comprising at least one panel having at least one layer made from a composition comprising a fluorinated thermoplastic polyurethane polymer.
• Uppers for footwear articles are generally formed by stitching together a plurality of exterior panel sections.
• These exterior panel sections can be made of several materials, such as natural and leather, plastic, mesh and non-woven fabrics.
• Non-woven fabrics are defined as fabric-like materials made from long fibers, bonded together by chemical, mechanical, heat or solvent treatment. The term is used in the textile manufacturing industry to denote fabrics, such as felt, which are neither woven nor knitted.
• the long fibers consists of hydrogenated thermoplastic polymers, notably based on hydrogenated urethane (H-TPU).
• H-TPU polymers have been disclosed in the art for the manufacturing of the upper part of shoes, for example in US 20100186874 PUMA AKTIENGESELLSCHAFT RUDOLF DASSLER SPORT , US 2013/0169219 PUMA SE and US 2014/0082961 REEBOK INTERNATIONAL LIMITED .
• Heat processable elastomeric polyurethanes comprising (per)fluoropoly- ether blocks were disclosed for example in US 5332798 AUSIMONT S.P.A. .
• the Applicant perceived the need of providing a new polymeric material that can be useful for the manufacture of the upper of footwear articles, notably shoes and boots, characterized by having improved properties when compared to hydrogenated thermoplastic polyurethane polymers (TPU). More in particular, the Applicant focused on providing a polymeric material having improved resistance to stain, improved chemical and wear resistance, low temperature flexibility, silky feel while maintaining good mechanical properties.
• TPU hydrogenated thermoplastic polyurethane polymers
• the present invention relates to an upper, for a footwear article, comprising at least one panel having at least one layer [layer E] made from a composition [composition (C)] comprising at least one fluorinated polyurethane [F-TPU polymer], said F-TPU polymer comprising recurring units derived from: [monomer (a)] at least one diol selected from the group comprising poly-ether type diol, poly-ester type diol, polybutadien-diol and polycarbonate-diol; [monomer (b)] at least one hydroxy-terminated (per)fluoropolyether polymer [PFPE polymer] ; [monomer (c)] at least one aromatic, aliphatic or cycloaliphatic diisocyanate; and [monomer (d)] at least one aliphatic, cycloaliphatic or aromatic diol having from 1 to 14 carbon atoms.
• composition (C)] comprising at least one fluorin
• said panel comprises layer E as single layer
• the Applicant has surprisingly found that when layer E is the outermost layer, it provides a soft silky feeling to the touch, without the addition of plasticizer agents to said composition (C).
• the upper can be manufactured using only one panel or joining together more than one panels.
• the panels can be selected from for example the toe box, the toe cap, the quarter, the vamp, the tongue, the counter and the back strap of a footwear.
• said F-TPU polymer has an average number molecular weight of from 30,000 to about 70,000 Da.
• said F-TPU polymer has a melting point (T m ) of from about 120°C to about 240°C.
• said at least one monomer (b) is a hydroxy-terminated (per)fluoropolyether polymer [PFPE polymer], i.e. a polymer comprising a (per)fluoropolyoxyalkylene chain [chain (R pf )] having two chain ends, wherein one or both chain ends terminates with at least one -OH group.
• PFPE polymer hydroxy-terminated (per)fluoropolyether polymer
• said chain (R pf ) is a chain of formula -O-D-(CFX # ) z1 -O(R f )(CFX * ) z2 -D*-O- wherein z1 and z2, equal or different from each other, are equal to or higher than 1;
• D and D*, equal or different from each other are an alkylene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms;
• (R f ) comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of: (i) -CFXO-, wherein X
• said PFPE polymer complies with the following formula (PFPE-I): HO-(CH 2 CH 2 O) t -CH 2 -(R pf )-CH 2 (OCH 2 CH 2 ) u -OH (PFPE-I) wherein t and u are, each independently, 0 or from 1 to 5; and R pf is as defined above.
• said PFPE polymer has an average number molecular weight of from 400 to 10,000 Da, more preferably from 1,000 to 5,000.
• the molar ratio between monomers (a) and monomers (b) is from 2 to 20, more preferably from 2 to 10.
• the amount of monomers (b) is such that the F-TPU polymer comprises from 4 to 30 wt.% of fluorine.
• said at least one monomer (c) has a number molecular weight of 500 Da or lower, preferably from 10 to 500 Da.
• said at least one monomer (c) is selected in the group comprising, preferably consisting of, 4,4’-methylene-diphenylene-di- isocyanate (MDI), 1,6-hexan-diisocyanate (HDI), 2,4-toluene-diisocyanate, 2,6-toluene-diisocyanate, xylilen-diisocyanate, naphthalene-diisocyanate, paraphenylen-diisocyana- te, hexamaethylen-diisocyanate, isophorone-diisocyanate, 4,4’-dicyclohexyl-methane-diisocyanate and cyclohexyl-1,4-diisocyanate. MDI and HDI being particularly preferred.
• the sum of blocks deriving from monomers (c) and (d) is from 10 to 60 wt.% based on the total weight of the F-TPU polymer.
• blocks comprising recurring units derived from monomers (a) and (b) are rubber-like blocks, while blocks comprising recurring units derived from monomers (c) and (d) are hard blocks.
• At least 80% of the blocks comprising recurring units derived from said monomers (b) [blocks B] are linked, at least one of their ends, to a block comprising recurring units derived from monomers (a) [blocks A] through a block comprising recurring units derived from monomers (c) [blocks C].
• at least 80% of blocks B are contained in a sequence of the following type: -[A-C-B-C]-.
• the F-TPU polymer can be prepared following the procedures disclosed in US 5332798 AUSIMONT S.P.A. , in particular in Example 15.
• composition (C) can optionally comprise further additives, such as for example antioxidants, thermal stabilizers, dyestuffs and fillers.
• composition (C) is essentially made of said F-TPU polymer in combination with an amount of up to 1 wt.% of any of the additives listed above are also encompassed by the present invention.
• said upper comprises a plurality of panels stitched together, each panel comprising a layer E as defined above.
• said upper comprises one single panel, which extends for the entire surface of the upper and comprises a layer E as defined above.
• Uppers comprising one single panel are also known as “unitary upper design”.
• Layer E can be manufactured following methods known in the art, for example by melt-blown process as disclosed in US 2010/0186874 cited above
• step (iv) comprises two steps, wherein the first step comprises heating at a first temperature for a time from 10 seconds to 10 minutes and the second step comprises heating at a second temperature, said second temperature being lower than said first temperature, for a time of from 30 seconds to 24 hours.
• said first temperature is from 120°C to 300°C.
• said second temperature is from 50°C to 200°C.
• said at least one panel comprises layer E as the only layer.
• said at least one panel comprises layer E as defined above and at least one texture layer [layer T] consisting of texture yarns.
• the upper according to the present invention comprises at least one panel comprising layer E as defined above, said layer E having an external surface and an internal surface, wherein at least a part of said internal surface is connected with a texture layer [layer T] consisting of texture yarns.
• the upper according to the present invention comprises at least one panel comprising layer E as defined above and two layers T consisting of texture yarns, wherein layer E is interposed between two layers T.
• the upper comprises layer E and layer(s) T
• the upper is obtained by welding together layer E and layer(s) T.
• the welding can be performed for example using a high-frequency welding process or an ultrasonic sound welding process.
• the present invention relates to a footwear article comprising an upper as defined above.
• F-TPU polymer specimens Preparation of F-TPU polymer specimens – method A F-TPU polymer specimens 1 to 4 in the form of sheet were prepared starting from the abovementioned monomers following the same procedure detailed in Example 15 of US 5,332,798 (to Ausimont S.p.A.) cited above. F-TPU polymers thus obtained contained 20 wt.% of recurring units derived from monomers (b).
• H-TPU 9* a commercially available hydrogenated TPU
• the monomers ratio for H-TPU 9* is not publicly available.
• Table 1 Monomers (ratio by mol) a1 a2 a3 a4 b1 b2 c1 c2 d1 d2 F-TPU 1 0.8 - - - 0.2 - 2.0 - 1.0 - F-TPU 2 - 0.7 - - 0.3 - 3.0 - 2.0 - F-TPU 3 - 0.6 - - - 0.4 2.5 - 1.5 - F-TPU 4 - - - 0.75 0.25 - - 2.0 - 1.0 F-TPU 5 0.75 - - - - 0.25 - 3.0 2.0 - F-TPU 6 - - 0.75 - - 0.25 - 2.0 1.0 - F-TPU 7 4.0 - - - - 0.3 - 0.7 3.0 - H-TPU 8(
• Tests were performed once with dry denim and once with wet denim on F-TPU 1, F-TPU 2, F-TPU 3, F-TPU 5 and F-TPU 7.
• the tests were performed as follows: a denim sample measuring approximately 30 mm x 30 mm was fixed to a fixture in order to prevent shifting of the sample during the test. A sample of each F-TPU and of H-TPU was then placed on the denim sample and fixed to the fixture as well.
• a drop of each staining agent listed above was put into contact with the surface of a specimen made from F-TPU 1 and let for 24 hours at ambient conditions. The specimen was then cleaned with water.

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• 2017
  • 2017-07-04 US US16/315,944 patent/US20200221825A1/en not_active Abandoned
  • 2017-07-04 KR KR1020197000011A patent/KR20190024951A/ko unknown
  • 2017-07-04 CN CN201780042427.XA patent/CN109476810A/zh active Pending
  • 2017-07-04 WO PCT/EP2017/066581 patent/WO2018007359A1/en unknown
  • 2017-07-04 EP EP17742658.2A patent/EP3481882A1/en not_active Withdrawn
  • 2017-07-04 JP JP2019500318A patent/JP2019523043A/ja active Pending

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