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WO2025161569A1 - Semelle de chaussure en tpur à haute résistance à l'usure et à haute résistance au glissement moulée par injection - Google Patents

Semelle de chaussure en tpur à haute résistance à l'usure et à haute résistance au glissement moulée par injection

Info

Publication number
WO2025161569A1
WO2025161569A1 PCT/CN2024/129570 CN2024129570W WO2025161569A1 WO 2025161569 A1 WO2025161569 A1 WO 2025161569A1 CN 2024129570 W CN2024129570 W CN 2024129570W WO 2025161569 A1 WO2025161569 A1 WO 2025161569A1
Authority
WO
WIPO (PCT)
Prior art keywords
tpu
molecular sieve
wear
slip
resistant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/129570
Other languages
English (en)
Chinese (zh)
Inventor
杨蓉
李锋
刘永忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gungdong Zhongding Technology Development Co Ltd
Original Assignee
Gungdong Zhongding Technology Development Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gungdong Zhongding Technology Development Co Ltd filed Critical Gungdong Zhongding Technology Development Co Ltd
Publication of WO2025161569A1 publication Critical patent/WO2025161569A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to the technical field of TPU soles, in particular to a high-wear-resistant and high-slip TPU sole that can be used for injection molding.
  • the TPU sole material is composed of the following components by weight: polyol: 65-75 parts; diphenylmethane diisocyanate: 15-25 parts; 1,4-butanediol: 3-7 parts; antioxidant: 0.2-0.5 parts; and lubricant: 0.2-0.5 parts;
  • the manufacturing process includes the following steps: the first step, the polyol 65g- 75g of propylene glycol, 15g-25g of diphenylmethane diisocyanate, 3g-7g of 1,4-butanediol, 0.2g-0.5g of an antioxidant, and 0.2g-0.5g of a lubricant are added to an internal mixer to prepare a mixture.
  • the mixture prepared in the first step is transferred to a mold for foaming, and then naturally cooled after foaming to obtain a semi-finished product.
  • the semi-finished product obtained in the second step is sprayed with a desired color paint on the heel, and then allowed to dry naturally to form the TPU sole material.
  • the TPU sole materials prepared in the above-mentioned prior art have poor heat resistance. Therefore, the present invention provides a highly wear-resistant and anti-slip TPU sole that can be injection molded to address the above-mentioned problems.
  • the present invention provides a high-wear-resistant and high-slip TPU sole that can be injection molded, which solves the problems mentioned in the above background technology.
  • a high-wear-resistant and high-anti-slip TPU sole that can be used for injection molding, specifically comprising the following raw materials in parts by weight: 10 to 20 parts of modified molecular sieve, 5 to 10 parts of white carbon black, 60 to 90 parts of TPU-NBR composite material, and 0.6 to 1 part of auxiliary additives.
  • the auxiliary additives are an anti-yellowing agent and an antioxidant, wherein the mass ratio of the anti-yellowing agent to the antioxidant is 1:(0.7-1); the anti-yellowing agent is selected from a mixture of one or more of UV-P, UV-327, UV-328 and UV-765, and the antioxidant is selected from a mixture of one or more of 168 antioxidants, 1010 antioxidants, 1076 antioxidants and 1098 antioxidants.
  • the specific modification steps of the modified molecular sieve are:
  • the grinding time is 15 to 20 minutes and the rotation speed is 1100 to 1300 rpm.
  • step 2) washing with distilled water is performed 2 to 3 times.
  • the mixing mass ratio of the molecular sieve, 1-ethyl acetate-3-methylimidazolium hexafluorophosphate and the pure DMF solution is 5:1.
  • the water bath temperature in step 3 is 65-75° C.
  • the water bath time is 10-14 hours
  • the stirring speed is 90-110 rpm.
  • the temperature in the drying oven is 110-130°C.
  • the preparation method of the TPU-NBR composite material is: pouring TPU into a torque rheometer under constant temperature conditions, and after melting, first increasing and then decreasing the torque, and when the torque is stable, adding NBR rubber compound to obtain the TPU-NBR composite material.
  • the TPU is a polyether polyurethane with a Shore hardness of 60A to 45D.
  • the mass ratio of TPU to NBR rubber mixture is 1:0.4.
  • the constant temperature in the moment rheometer is 170-175° C. and the rotation speed is 75-85 r/min.
  • the present invention provides a highly wear-resistant and highly anti-slip TPU sole that can be injection molded.
  • the invention has the following beneficial effects: the injection moldable highly wear-resistant and highly anti-slip TPU sole improves the wear resistance and thermal stability of the TPU material by adding white carbon black; the addition of an antioxidant delays the oxidation process of the TPU material, thereby extending its service life; the addition of a modified molecular sieve reduces the thermoplasticity and viscosity of the TPU material, making it easier to process; in addition, the modified molecular sieve can control the size and distribution of pores in the TPU material, improving the interfacial adhesion, wettability, and surface smoothness of the TPU material, while enhancing the mechanical properties of the TPU material, increasing its hardness, strength, toughness, and durability.
  • the wear resistance and heat resistance of the sole are improved, thereby extending its service life.
  • FIG1 is a water contact angle test diagram of a high wear-resistant and high anti-slip TPU sole for injection molding according to the present invention.
  • TPU is a polyether polyurethane with a Shore hardness of 60A to 45D;
  • the preparation method of the TPU-NBR composite material is as follows: under a constant temperature condition of 170°C, pouring TPU into a torque rheometer at a rotation speed of 80r/min, and after melting, first increasing and then decreasing the torque. When the torque is stable, adding NBR rubber compound to obtain the TPU-NBR composite material, wherein the mass ratio of TPU to NBR rubber compound is 1:0.4.
  • the mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a herringbone pattern. After cooling and shaping, a TPU tennis shoe sole with a VVVV repeated pattern is obtained.
  • the mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a wavy pattern. After cooling and shaping, a TPU sports shoe sole with a wavy pattern is obtained.
  • the mixed material is then poured into an injection molding machine, and the mixed material is injection-molded into a sole cavity having a continuous block-like shading. After cooling and shaping, a TPU running shoe sole with a continuous block-like shading is obtained.
  • the glass transition temperature of Comparative Example 2 is lower than 0°C, so the damping factor tan ⁇ value corresponding to it at 0°C is very low, which reflects that its anti-slip performance is poor; the damping factor tan ⁇ corresponding to Comparative Example 1 at 0°C is also low; while Examples 1, 2, and 3 increase the glass transition temperature (above 0°C) by adding NBR compound to pure TPU, so that the damping factor tan ⁇ peak is obtained at 0°C, and therefore their anti-slip performance is better.
  • the water contact angle on the sample surface is measured by vertically dripping water droplets.
  • the water contact angle ⁇ in Example 1 is 104.1°, which is greater than 90°; the water contact angle ⁇ of the TPU in Comparative Example 1 is 86.5°, which has a certain hydrophilicity. Therefore, the TPU sole prepared by this technical solution has better hydrolysis resistance and can maintain good mechanical properties even in a high temperature and high humidity environment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte au domaine technique des semelles de chaussures en TPUR. La présente invention divulgue une semelle de chaussure en TPUR à haute résistance à l'usure et à haute résistance au glissement moulée par injection, comprenant spécifiquement les matières premières suivantes en parties en poids : de 10 à 20 parties d'un tamis moléculaire modifié, de 5 à 10 parties de noir de carbone blanc, de 60 à 90 parties d'un matériau composite TPUR-NBR, et de 0,6 à 1 partie d'un additif auxiliaire. Dans semelle de chaussure TPUR à haute résistance à l'usure et à haute résistance au glissement moulée par injection, l'ajout de noir de carbone blanc améliore la résistance à l'usure et la stabilité thermique d'un matériau TPUR ; l'ajout d'un antioxydant retarde le processus d'oxydation du matériau TPUR, ce qui permet de prolonger la durée de vie du matériau TPUR ; et l'ajout du tamis moléculaire modifié peut réduire la teneur en thermoplastique et la viscosité du matériau TPUR, rendant le traitement du matériau TPUR plus facile. De plus, le tamis moléculaire modifié peut également réguler la taille et la distribution de pores dans le matériau TPUR, améliorer l'adhérence interfaciale, la mouillabilité et la planéité de surface du matériau TPUR, et améliorer les propriétés mécaniques du matériau TPUR, ce qui permet d'améliorer la dureté, la résistance, la ténacité et la durabilité du matériau TPUR.
PCT/CN2024/129570 2024-02-03 2024-11-04 Semelle de chaussure en tpur à haute résistance à l'usure et à haute résistance au glissement moulée par injection Pending WO2025161569A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202410152702.5 2024-02-03
CN202410152702.5A CN118027655B (zh) 2024-02-03 2024-02-03 一种可注塑用的高耐磨高止滑tpu鞋底

Publications (1)

Publication Number Publication Date
WO2025161569A1 true WO2025161569A1 (fr) 2025-08-07

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ID=90985062

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/129570 Pending WO2025161569A1 (fr) 2024-02-03 2024-11-04 Semelle de chaussure en tpur à haute résistance à l'usure et à haute résistance au glissement moulée par injection

Country Status (2)

Country Link
CN (1) CN118027655B (fr)
WO (1) WO2025161569A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118027655B (zh) * 2024-02-03 2024-10-29 广东中鼎科技发展有限公司 一种可注塑用的高耐磨高止滑tpu鞋底

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US3678129A (en) * 1970-06-22 1972-07-18 Uniroyal Inc Thermoplastic polymer blends containing polyvinyl chloride, polyether urethane and butadiene-acrylonitrile copolymers
KR20150118715A (ko) * 2014-04-15 2015-10-23 한국신발피혁연구원 초임계 발포 사출용 저비중 동적 가교형 열가소성 탄성체 조성물, 이의 제조방법 및 이를 이용하여 제조된 신발 겉창
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CN112795062A (zh) * 2021-01-15 2021-05-14 商丘京威体育用品有限公司 一种耐磨橡胶发泡运动鞋材及其制备方法
CN112831175A (zh) * 2021-01-08 2021-05-25 青岛科技大学 一种耐磨、止滑热塑性弹性体及其制备方法
CN118027655A (zh) * 2024-02-03 2024-05-14 广东中鼎科技发展有限公司 一种可注塑用的高耐磨高止滑tpu鞋底

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JP3343078B2 (ja) * 1998-07-29 2002-11-11 三井化学株式会社 弾性舗装材及び弾性舗装方法
CA2668397A1 (fr) * 2006-11-01 2008-05-15 Dow Global Technologies Inc. Articles comprenant du polyurethane et une polyolefine non polaire et procedes de preparation et d'utilisation de ces derniers
CN110105745A (zh) * 2019-05-23 2019-08-09 厦门扬丰塑胶科技有限公司 一种塑料制品橡胶材料及其制备方法

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US3678129A (en) * 1970-06-22 1972-07-18 Uniroyal Inc Thermoplastic polymer blends containing polyvinyl chloride, polyether urethane and butadiene-acrylonitrile copolymers
KR20150118715A (ko) * 2014-04-15 2015-10-23 한국신발피혁연구원 초임계 발포 사출용 저비중 동적 가교형 열가소성 탄성체 조성물, 이의 제조방법 및 이를 이용하여 제조된 신발 겉창
CN107915986A (zh) * 2017-12-13 2018-04-17 马鞍山市荣亿密封材料有限责任公司 一种高阻隔性混炼聚氨酯‑丁腈橡胶材料的制备方法
CN110591179A (zh) * 2019-10-17 2019-12-20 温州市添荣鞋材有限公司 一种防滑橡胶鞋底及其制备方法
CN112831175A (zh) * 2021-01-08 2021-05-25 青岛科技大学 一种耐磨、止滑热塑性弹性体及其制备方法
CN112795062A (zh) * 2021-01-15 2021-05-14 商丘京威体育用品有限公司 一种耐磨橡胶发泡运动鞋材及其制备方法
CN118027655A (zh) * 2024-02-03 2024-05-14 广东中鼎科技发展有限公司 一种可注塑用的高耐磨高止滑tpu鞋底

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CN118027655A (zh) 2024-05-14
CN118027655B (zh) 2024-10-29

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