JP2021522368A - 熱可塑性エラストマーに基づく発泡体 - Google Patents
熱可塑性エラストマーに基づく発泡体 Download PDFInfo
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- JP2021522368A JP2021522368A JP2020558494A JP2020558494A JP2021522368A JP 2021522368 A JP2021522368 A JP 2021522368A JP 2020558494 A JP2020558494 A JP 2020558494A JP 2020558494 A JP2020558494 A JP 2020558494A JP 2021522368 A JP2021522368 A JP 2021522368A
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/50—Footwear, e.g. shoes or parts thereof
- B29L2031/504—Soles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/50—Footwear, e.g. shoes or parts thereof
- B29L2031/507—Insoles
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- 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
- C08G2350/00—Acoustic or vibration damping material
-
- 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
- C08G2410/00—Soles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2207/00—Foams characterised by their intended use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2300/22—Thermoplastic resins
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- C08J2300/26—Elastomers
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
Abstract
本発明は、成形体を製造する熱可塑性ポリウレタン及びポリスチレンから製造されたビーズ発泡体、当該ビーズ発泡体及び成形体を製造するための方法に関し、及びまた、靴用中間インソール、靴用インソール、靴用コンビソール、靴用クッション材のための成形体の使用方法にも関する。
【選択図】なし
Description
a)成分Iとして、70〜95質量%の熱可塑性ポリウレタン
b)成分IIとして、5〜30質量%のスチレンポリマー
を含有する組成物(Z)から作られ、
前記組成物I及び成分IIの全量が100質量%であり;
前記成形体は、靴の中敷き、靴の挿入物又は靴のクッション材である、
前記成形体により達成された。
4,4′−MDI及び2,4′−MDI、又は、
4,4′−MDI及び3,3′−ジメチル−4,4′−ジイソシアナトビフェニル(TODI)又は
4,4′−MDI及びH12MDI(4,4′−メチレンジシクロヘキシルジイソシアネート)又は
4,4′−MDI及びTDI;又は
4,4′−MDI及び1,5−ナフチレンジイソシアネート(NDI)
を含有するポリイソシアネート組成物である。
成分Iとして、70〜95質量%の熱可塑性ポリウレタン
成分IIとして、5〜30質量%のスチレンポリマー
を含有し、前記成分I及び成分IIが全量で100質量%である。
成分Iとして、80〜90質量%の熱可塑性ポリウレタン
成分IIとして、10〜20質量%のスチレンポリマー
を含有し、前記成分I及び成分IIが全量で100質量%である。
i.本発明の組成物(Z)の提供;
ii.加圧下での発泡剤を用いた組成物の含侵;
iii.減圧による組成物の膨張、
を介して、従来広範に使用されている既知のプロセスによって製造され得る。
i.ペレットの形態の本発明の組成物(Z)の提供;
ii.加圧下での発泡剤を用いたペレットの含侵;
iii.減圧によるペレットの膨張、
を包含する。
i.ペレットの形態の本発明の組成物(Z)の提供;
ii.加圧下での発泡剤を用いたペレットの含侵;
iii.任意に事前の温度低下を経由した、ペレットの発泡なしの大気圧までの圧力の低下
iv.温度上昇を介したペレットの発泡
を包含する。
ii.適した密閉反応容器(例えば、オートクレーブ)中での昇温における加圧下での発泡剤の存在下におけるペレットの含侵
iii.冷却無しの急速除圧
におけるペレットの膨張を包含する。
ii.押出機内における昇温加圧下での発泡剤の存在下のペレットの含侵
iii.制御されない発泡を防止する条件下での、押出機から押出される溶融物のペレット化
におけるペレットの膨張が続くプロセスを含む。
あるいは、国際公開第2014/150122号公報又は国際公開第2014/150124号公報に記載された方法において、任意に実際に既に着色された対応するビーズ発泡体は、対応するペレットが超臨界液体により飽和されそして超臨界液体から除去されるように直接製造され得、そしてこれより下記
(i)加熱流体中での生成物の含浸、及び
(ii)高エネルギー照射(例えば、赤外線照射又はマイクロ波照射)を用いた生成物の照射
が次いで行われる。
(i)発泡ビーズを適切な金型への導入、
(ii)段階(i)からの発泡ビーズの融合
を包含する。
さらに、国際公開第2014/150122号公報に記載されたプロセスにおいて、超臨界液体又は加熱された液体が着色剤を含有することも可能である。
a)成分Iとして、70〜95質量%の熱可塑性ポリウレタン
b)成分IIとして、5〜30質量%のスチレンポリマー
含有する組成物(Z)から作られ、
前記成分I及び成分IIが全量で100質量%であり;
前記成形体は、靴用中敷き、靴用挿入物又は靴用クッション材である、
成形体。
a)成分Iとして、80〜90質量%の熱可塑性ポリウレタン
b)成分IIとして、10〜20質量%のスチレンポリマー
を含有し、
前記成分I及び成分IIが全量で100質量%である、態様1に記載の成形体。
(i)発泡ビーズの適切な金型への導入、
(ii)段階(i)からの発泡ビーズの融合、
を包含する、態様1〜17の何れか1態様に記載の成形体の製造方法。
WO94/20568A1
WO2007/082838A1
WO2017/030835A1
WO2013/153190A1
WO2010/010010A1
PCT/EP2017/079049
Plastics Additives Handbook, 5th Edition, H. Zweifel,edn.,Hanser Publishers,Munich, 2001([1]),pp.98−136
Kunststoff−Handbuch Band 4,“Polystyrol”[Plastics handbook vol.4,“Polystyrene”], by Becker/Braun(1996)
Saechtling(ed.),Kunststoff−Taschenbuch [Plastics handbook],27th edn.,Hanser−Verlag Munich 1998,chapters 3.2.1 and 3.2.4
WO2014/150122A1
WO2014/150124A1
EP1979401B1
US2015/0337102A1
EP2872309B1
EP3053732A
WO2016/146537A1
Claims (15)
- ビーズ発泡体で作られる成形体であって、
a)成分Iとして、70〜95質量%の熱可塑性ポリウレタン
b)成分IIとして、5〜30質量%のスチレンポリマー
を含有する組成物(Z)から作られ、
前記成分I及び成分IIが全量で100質量%であり;
前記成形体は、靴用中敷き、靴用挿入物又は靴用クッション材である、
前記成形体。 - 前記組成物Zが、
a)成分Iとして、80〜90質量%の熱可塑性ポリウレタン
b)成分IIとして、10〜20質量%のスチレンポリマー
を含有し、
前記成分I及び成分IIが全量で100質量%である、請求項1に記載の成形体。 - 前記靴が、アウトドアシューズ、スポーツシューズ、サンダル、ブーツ又は安全靴である、請求項1又は2に記載の成形体。
- 前記成形体の引張強度が、600kPaを超えるものである、請求項1〜3の何れか1項に記載の成形体。
- 破断点伸びが100%を超えるものである、請求項1〜4の何れか1項に記載の成形体。
- 10%圧縮における圧縮応力が、15kPaを超えるものである、請求項1〜5の何れか1項に記載の成形体。
- 前記成形体の密度が、75〜375kg/m3である、請求項1〜6の何れか1項に記載の成形体。
- 前記成形体の反発弾性が、55%を超えるものである、請求項1〜7の何れか1項に記載の成形体。
- 前記成形体の密度の、前記ビーズ発泡体のかさ密度に対する比率が、1.5〜2.5である、請求項1〜8の何れか1項に記載の成形体。
- 下記段階:
(i)発泡ビーズの適切な金型への導入、
(ii)段階(i)からの発泡ビーズの融合、
を包含する、請求項1〜9の何れか1項に記載の成形体の製造方法。 - 前記段階(ii)の融合が、密閉金型中で行われる、請求項10に記載の方法。
- 前記段階(ii)の融合が、蒸気、熱風又は高エネルギー照射により行われる、請求項10又は11に記載の方法。
- 請求項1〜9の何れか1項に記載の成形体を有する靴。
- 靴用中間インソール、靴用インソール、靴用コンビソール(combisole)、靴用クッション材、自転車サドル、自転車タイヤ、減衰要素、クッション材、マットレス、下敷き、グリップ、保護フィルム、自動車内装分野又は自動車外装分野における部品における、ボール及びスポーツ備品における、又は床の敷物としてのための、請求項1〜9の何れか1項に記載の成形体の製造のための、請求項1〜3の何れか1項に記載の組成物を有するビーズ発泡体の使用方法。
- 靴用中間インソール、靴用インソール、靴用コンビソール、又は靴用クッション材のための、請求項14に記載の使用方法であって、前記靴が、アウトドアシューズ、スポーツシューズ、サンダル、ブーツ又は安全靴である、使用方法。
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EP18168425.9 | 2018-04-20 | ||
EP18168425 | 2018-04-20 | ||
PCT/EP2019/060123 WO2019202090A1 (de) | 2018-04-20 | 2019-04-18 | Schaumstoffe auf basis thermoplastischer elastomere |
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US (1) | US11773231B2 (ja) |
EP (1) | EP3781617A1 (ja) |
JP (1) | JP2021522368A (ja) |
KR (1) | KR20210005657A (ja) |
CN (1) | CN111989360A (ja) |
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CN111989360A (zh) | 2020-11-24 |
CA3096988A1 (en) | 2019-10-24 |
KR20210005657A (ko) | 2021-01-14 |
US20210122894A1 (en) | 2021-04-29 |
TW201943795A (zh) | 2019-11-16 |
EP3781617A1 (de) | 2021-02-24 |
BR112020019980A2 (pt) | 2021-01-26 |
WO2019202090A1 (de) | 2019-10-24 |
US11773231B2 (en) | 2023-10-03 |
MX2020011118A (es) | 2020-11-11 |
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