TWI846317B - 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 - Google Patents
熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 Download PDFInfo
- Publication number
- TWI846317B TWI846317B TW112104670A TW112104670A TWI846317B TW I846317 B TWI846317 B TW I846317B TW 112104670 A TW112104670 A TW 112104670A TW 112104670 A TW112104670 A TW 112104670A TW I846317 B TWI846317 B TW I846317B
- Authority
- TW
- Taiwan
- Prior art keywords
- thermoplastic polyurethane
- foam material
- polyurethane foam
- foaming
- viscosity reducer
- Prior art date
Links
- 239000006261 foam material Substances 0.000 title claims abstract description 62
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 58
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 33
- 238000005187 foaming Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 9
- 229920005903 polyol mixture Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- 239000012749 thinning agent Substances 0.000 abstract 3
- 230000007423 decrease Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 101001042415 Cratylia mollis Mannose/glucose-specific lectin Cramoll Proteins 0.000 description 2
- 229920005983 Infinergy® Polymers 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000037078 sports performance Effects 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
Images
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
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B5/00—Footwear for sporting purposes
-
- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/28—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
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- 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
-
- 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
- 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
- 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
- C08J2201/026—Crosslinking before of after foaming
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Nanotechnology (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本發明提供一種熱塑性聚氨酯發泡材料,其包含二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇、1,4-丁二醇、一成核劑及一降黏劑,且降黏劑具有如式(I)所示的一結構,式(I)中各符號係如說明書中所定義者。藉此,透過使用特定的降黏劑,有助於增加超臨界氮氣在熱塑性聚氨酯發泡材料中的溶解度,進而減少發泡產品的外觀缺陷並有效降低密度,以達到輕量化的需求。
Description
本發明是有關一種熱塑性聚氨酯發泡材料,特別是有關一種具有特定降黏劑的熱塑性聚氨酯發泡材料與其所製備的運動鞋中底及其製備方法。
發泡材料因為具有重量輕、彈性佳及阻隔效果好等優點,經常被使用於建築、醫療、航空及運動等領域。在運動產業中,發泡材料可用於製造鞋底,使鞋底滿足輕量、止滑、高支撐度與高彈性等需求,進而提升穿著時的舒適度與安全性,更有助於提升運動表現。
目前市場上用於製造鞋底的發泡材料中,較為成熟的是以超臨界泡珠發泡所製成的發泡熱塑性聚氨酯(expanded thermoplastic polyurethane;ETPU),其製備方式是先將熱塑性聚氨酯以壓降法(pressure drop method)製成泡珠(bead foam),再將泡珠填充至蒸氣室的模具中,透過加溫、降壓、降溫及脫模等步驟,使泡珠彼此熔融黏合並發泡,進而形成鞋底結構。
然而,前述製備方式的工序較為繁瑣,不利於自動化與快速生產,操作上的安全性也有一定疑慮,加上其對於材料的要求度高,容易出現產品尺寸不一的情況。再者,前述製備方式更有耗能、需大量勞力以及設備體積龐大等缺點。
有鑑於此,如何改善製備發泡鞋底結構的製程並獲得良好的品質,遂成為相關業者努力的目標。
為了達成上述目標,本發明提供一種熱塑性聚氨酯發泡材料,其使用特定降黏劑來改變材料性質,進而改善其製備流程。
本發明的一態樣提供一種熱塑性聚氨酯發泡材料,其包含二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇、1,4-丁二醇、一成核劑及一降黏劑,且降黏劑具有如式(I)所示的一結構:
式(I);
其中,R為氫原子、碳數1至5的烷基、
或
,且R
1為碳數1至5的伸烷基。
據此,本發明的熱塑性聚氨酯發泡材料透過使用特定的降黏劑,有助於增加超臨界氮氣在熱塑性聚氨酯發泡材料中的溶解度,並降低熱塑性聚氨酯發泡材料的動態黏度,使熱塑性聚氨酯發泡材料在模具中的流動更快,進而減少發泡產品的外觀缺陷並有效降低密度,以達到輕量化的需求。
依據前述的熱塑性聚氨酯發泡材料,其中二苯基甲烷二異氰酸酯佔熱塑性聚氨酯發泡材料的重量比例可為20 wt%至40 wt%。
依據前述的熱塑性聚氨酯發泡材料,其中聚四亞甲基醚二醇的分子量可為1800至3000,且聚四亞甲基醚二醇佔熱塑性聚氨酯發泡材料的重量比例可為50 wt%至70 wt%。
依據前述的熱塑性聚氨酯發泡材料,其中1,4-丁二醇佔熱塑性聚氨酯發泡材料的重量比例可為5 wt%至10 wt%。
依據前述的熱塑性聚氨酯發泡材料,其中成核劑可為奈米級矽灰或微米級滑石粉,且成核劑佔熱塑性聚氨酯發泡材料的重量比例可為0.1 wt%至1 wt%。
依據前述的熱塑性聚氨酯發泡材料,其中降黏劑的分子量可為500至1500,且降黏劑佔熱塑性聚氨酯發泡材料的重量比例可為0.5 wt%至5 wt%。
本發明的另一態樣提供一種運動鞋中底,其是由如前述的熱塑性聚氨酯發泡材料所製成。
依據前述的運動鞋中底,其中運動鞋中底的密度可為0.18±0.02 g/cm³,運動鞋中底的硬度可為45±3,且運動鞋中底的落球反彈率可大於60%。
本發明的又一態樣提供一種發泡材料製備方法,其是用於製備如前述的熱塑性聚氨酯發泡材料。發泡材料製備方法包含以下步驟:進行一混合步驟、進行一聚合步驟、進行一造粒步驟以及進行一發泡步驟。在混合步驟中,是將聚四亞甲基醚二醇、1,4-丁二醇、成核劑及降黏劑混合,以獲得一多元醇混合物。在聚合步驟中,是將二苯基甲烷二異氰酸酯與多元醇混合物混合並加熱,並待二苯基甲烷二異氰酸酯與多元醇混合物聚合形成一預聚物。在造粒步驟中,是對預聚物進行塑型與切割,使預聚物形成複數個待發泡粒。在發泡步驟中,是對待發泡粒進行發泡,以形成熱塑性聚氨酯發泡材料。
依據前述的發泡材料製備方法,其中待發泡粒可透過一超臨界氮氣射出發泡成型法進行發泡。
下述將更詳細討論本發明各實施方式。然而,此實施方式可為各種發明概念的應用,可被具體實行在各種不同的特定範圍內。特定的實施方式是僅以說明為目的,且不受限於揭露的範圍。
本發明中,有時以鍵線式(skeleton formula)表示化合物結構,此種表示法可以省略碳原子、氫原子以及碳氫鍵。倘若,結構式中有明確繪出官能基的,則以繪示者為準。
本發明中,「降黏劑具有如式(I)所示的一結構」,為了簡潔與通順,有時會表達為式(I)所示的降黏劑或降黏劑(I)。
本發明的一態樣提供一種熱塑性聚氨酯發泡材料,其包含二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇、1,4-丁二醇、一成核劑及一降黏劑。
詳言之,二苯基甲烷二異氰酸酯佔熱塑性聚氨酯發泡材料的重量比例可為20 wt%至40 wt%,聚四亞甲基醚二醇的分子量可為1800至3000,聚四亞甲基醚二醇佔熱塑性聚氨酯發泡材料的重量比例可為50 wt%至70 wt%,且1,4-丁二醇佔熱塑性聚氨酯發泡材料的重量比例可為5 wt%至10 wt%。透過控制二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇及1,4-丁二醇的分子量或比例,可以調整最終熱塑性聚氨酯發泡材料的特性,使其具有所需的彈性、硬度或其他加工性質。
成核劑可為奈米級矽灰(silica fume)或微米級滑石粉,且成核劑佔熱塑性聚氨酯發泡材料的重量比例可為0.1 wt%至1 wt%。透過選用特定的成核劑,可以改善熱塑性聚氨酯發泡材料的聚合反應,使聚合後的產物具有更佳的材料性質並減少外觀上的缺陷。
降黏劑具有如式(I)所示的一結構:
式(I);
其中,R為氫原子、碳數1至5的烷基、
或
,且R
1為碳數1至5的伸烷基。降黏劑的分子量可為500至1500,且降黏劑佔熱塑性聚氨酯發泡材料的重量比例可為0.5 wt%至5 wt%。本發明的降黏劑具有特定的化學結構,可以增加超臨界氮氣在熱塑性聚氨酯發泡材料中的溶解度,在射出成型的過程中,超臨界氮氣可同時扮演發泡劑和塑化劑的角色,有助於改善熱塑性聚氨酯發泡材料的發泡效果。再者,當熱塑性聚氨酯發泡材料中的超臨界氮氣濃度增加,可降低熱塑性聚氨酯發泡材料的動態黏度,使熱塑性聚氨酯發泡材料在模具中的流動更快,進而減少發泡產品的外觀缺陷並有效降低密度,以達到輕量化的需求,使發泡產品具有更優秀的物理性質。
在式(I)所示的降黏劑中,R較佳為氫原子、甲基、
或
,且R
1為碳數1至3的伸烷基。再者,R更佳為
,因為此化學結構有兩個可與二苯基甲烷二異氰酸酯反應的羥基(-OH),與二苯基甲烷二異氰酸酯反應後,降黏劑會位於側支鏈的位置,更容易與超臨界氮氣接觸,使整體的發泡效果更好。
本發明的另一態樣提供一種運動鞋中底,其是由如前述的熱塑性聚氨酯發泡材料所製成,其中運動鞋中底的密度可為0.18±0.02 g/cm³,運動鞋中底的硬度可為45±3,且運動鞋中底的落球反彈率可大於60%。由此可知,本發明的熱塑性聚氨酯發泡材料所製成的運動鞋中底具有輕量化的特性,能提供良好彈性並提升穿著時的舒適度及運動表現。
請參照第1圖,第1圖為本發明一實施方式的發泡材料製備方法100的步驟流程圖。本發明的又一態樣提供一種發泡材料製備方法100,其包含步驟110、步驟120、步驟130及步驟140。
步驟110為進行一混合步驟,是將聚四亞甲基醚二醇、1,4-丁二醇、成核劑及降黏劑混合,以獲得一多元醇混合物。
步驟120為進行一聚合步驟,是將二苯基甲烷二異氰酸酯與多元醇混合物混合並加熱,並待二苯基甲烷二異氰酸酯與多元醇混合物聚合形成一預聚物。
步驟130為進行一造粒步驟,是對預聚物進行塑型與切割,使預聚物形成複數個待發泡粒。
步驟140為進行一發泡步驟,是對待發泡粒進行發泡,以形成熱塑性聚氨酯發泡材料,其中待發泡粒可透過一超臨界氮氣射出發泡成型法進行發泡。
茲以下列具體實施例進一步示範說明本發明,用以有利於本發明所屬技術領域通常知識者,可在不需過度解讀的情形下完整利用並實踐本發明,而不應將這些實施例視為對本發明範圍的限制,但用於說明如何實施本發明的材料及方法。
<實施例與比較例>
實施例1至實施例4與比較例1至比較例4的熱塑性聚氨酯發泡材料均包含二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇、1,4-丁二醇、成核劑及降黏劑,惟個別實施例/比較例所使用的原料種類或比例有所差異,以下將逐一說明各原料的材料性質。
Iso1:二苯基甲烷二異氰酸酯,其異氰酸酯基含量(NCO content)為33.5%且分子量為250。
Poly1:聚四亞甲基醚二醇(大連化學工業產品代號PTG1000),其羥基值(OH value;OHv)為112.2 mg KOH/g且分子量為1000。
Poly2:聚四亞甲基醚二醇(大連化學工業產品代號PTG1400),其羥基值為80.1 mg KOH/g且分子量為1400。
Poly3:聚四亞甲基醚二醇(大連化學工業產品代號PTG1800),其羥基值為62.3 mg KOH/g且分子量為1800。
Poly4:聚四亞甲基醚二醇(大連化學工業產品代號PTG2000),其羥基值為56.1 mg KOH/g且分子量為2000。
Poly5:聚四亞甲基醚二醇(大連化學工業產品代號PTG3000),其羥基值為37.4 mg KOH/g且分子量為3000。
CE1:1,4-丁二醇,其分子量為90。
VR1:降黏劑,其羥基值為90 mg KOH/g且分子量為1246。
VR2:降黏劑,其羥基值為110 mg KOH/g且分子量為1020。
VR3:降黏劑,其羥基值為180 mg KOH/g且分子量為623。
VR4:降黏劑,其羥基值為92 mg KOH/g且分子量為1219。
前述VR1至VR4的降黏劑皆具有如式(I)所示的結構:
式(I);
其中,R為
,且n視VR1至VR4各自的分子量大小而定。
F1:成核劑(日本滑石株式會社產品代號MICRO ACE SG-95),其為一種微米級滑石粉。
F2:成核劑(Evonik產品代號AEROSIL R972),其為一種奈米級矽灰。
AO1:抗氧化劑(BASF產品代號Irganox 245)。
AO2:紫外光吸收劑(BASF產品代號Tinuvin 329)。
W1:蠟(Clariant產品代號Licowax E)。
再請參照下表1,其列出了實施例1至實施例4與比較例1至比較例4的熱塑性聚氨酯發泡材料所使用的原料比例,其中空白處代表對應的實施例/比較例未添加該成分。
表1 | ||||||||
實施例1 (kg) | 實施例2 (kg) | 實施例3 (kg) | 實施例4 (kg) | 比較例1 (kg) | 比較例2 (kg) | 比較例3 (kg) | 比較例4 (kg) | |
Iso1 | 8.75 | 9.95 | 8.04 | 8.42 | 9.43 | 8.84 | 8.50 | 8.23 |
Poly1 | 16.95 | |||||||
Poly2 | 17.81 | |||||||
Poly3 | 16.12 | 18.19 | 19.21 | 17.55 | ||||
Poly4 | 17.98 | |||||||
Poly5 | 19.27 | |||||||
CE1 | 2.25 | 2.69 | 2.25 | 2.02 | 1.70 | 1.91 | 2.19 | 1.98 |
VR1 | 1.24 | |||||||
VR2 | 1.02 | 1.92 | 1.44 | 0.10 | 2.24 | |||
VR3 | 0.44 | |||||||
VR4 | 1.37 | |||||||
F1 | 0.019 | 0.0175 | 0.0195 | 0.0195 | 0.019 | 0.0195 | 0.0195 | 0.02 |
F2 | 0.019 | 0.0175 | 0.0195 | 0.0195 | 0.019 | 0.0195 | 0.0195 | 0.02 |
AO1 | 0.08 | 0.07 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
AO2 | 0.10 | 0.09 | 0.10 | 0.10 | 0.09 | 0.10 | 0.10 | 0.10 |
W1 | 0.038 | 0.035 | 0.039 | 0.039 | 0.038 | 0.039 | 0.039 | 0.04 |
總計 | 30.247 | 30.226 | 30.256 | 30.254 | 30.245 | 30.250 | 30.251 | 30.257 |
接著,將實施例1至實施例4與比較例1至比較例4的熱塑性聚氨酯發泡材料製成發泡試片並進行相關測試,測試結果如下表2所示。
表2 | ||||||||
實施例1 | 實施例2 | 實施例3 | 實施例4 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | |
熔體流動指數 (g/10 min, /205 °C /8.7kg) | 55 | 57 | 60 | 53 | 55 | 56 | 59 | 54 |
硬度 | 42 | 46 | 44 | 47 | 43 | 45 | 48 | 43 |
密度 (g/cm 3) | 0.162 | 0.181 | 0.173 | 0.193 | 0.165 | 0.179 | 0.197 | 0.168 |
抗拉強度 (kgf/cm 2) | 11.2 | 12.6 | 12.0 | 13.3 | 13.8 | 12.9 | 13.4 | 9.1 |
斷裂伸長率 (%) | 472.9 | 420.1 | 444.2 | 398.2 | 383.6 | 411.2 | 408.2 | 521.2 |
撕裂強度 (kgf/cm) | 5.461 | 6.143 | 5.812 | 6.485 | 6.533 | 6.283 | 6.521 | 4.421 |
落球反彈率 (%) | 62 | 60 | 65 | 62 | 53 | 55 | 61 | 50 |
壓縮永久變形 (%) | 22.27 | 23.10 | 20.33 | 21.57 | 19.32 | 23.32 | 24.12 | 30.47 |
泡孔尺寸評價 | Pass | Pass | Pass | Pass | Pass | Pass | NG | Pass |
整體評價 | Pass | Pass | Pass | Pass | NG | NG | NG | NG |
上述測試所採用的標準如下:熔體流動指數採用DIN 53735測試標準、硬度採用Type C測試標準、密度採用ASTM D297測試標準、抗拉強度採用ASTM D412測試標準、斷裂伸長率採用ASTM D412測試標準、撕裂強度採用ASTM D624測試標準、落球反彈率採用ASTM D2632測試標準且壓縮永久變形採用CNS 3560測試標準。
泡孔尺寸評價則是以目視方式進行,其是以目視方式檢查面積為400 cm
2的發泡試片剖面,剖面上不得有直徑大於5 mm的泡孔,且直徑2 mm至5 mm的泡孔不得超過20顆。若通過則判定Pass,不通過則判定NG。
整體評價則是判斷發泡試片是否符合運動鞋中底的物理性質規格(即密度為0.18±0.02 g/cm³、硬度為45±3且落球反彈率大於60%)並同時通過前述的泡孔尺寸評價。若通過則判定Pass,不通過則判定NG。
由表1及表2可以看出,當聚四亞甲基醚二醇的分子量較小或降黏劑的比例過高時,其所製備的發泡試片的落球反彈率均明顯不足,而當降黏劑的比例過低時,則會形成明顯泡孔,導致發泡試片的結構缺陷。是以本發明的熱塑性聚氨酯發泡材料透過選用適當的原料及比例,可以獲得良好的材料性質。
綜上所述,本發明的熱塑性聚氨酯發泡材料透過使用特定的降黏劑,有助於增加超臨界氮氣在熱塑性聚氨酯發泡材料中的溶解度,並降低熱塑性聚氨酯發泡材料的動態黏度,使熱塑性聚氨酯發泡材料在模具中的流動更快,進而減少發泡產品的外觀缺陷並有效降低密度,以達到輕量化的需求。
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明的精神和範圍內,當可作各種的更動與潤飾,因此本發明的保護範圍當視後附的申請專利範圍所界定者為準。
100:發泡材料製備方法
110,120,130,140:步驟
為讓本發明的上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式的說明如下:
第1圖為本發明一實施方式的發泡材料製備方法的步驟流程圖。
100:發泡材料製備方法
110,120,130,140:步驟
Claims (5)
- 一種熱塑性聚氨酯發泡材料,其包含二苯基甲烷二異氰酸酯、聚四亞甲基醚二醇、1,4-丁二醇、一成核劑及一降黏劑,且該降黏劑具有如式(I)所示的一結構:
- 一種運動鞋中底,其是由如請求項1所述的熱塑性聚氨酯發泡材料所製成。
- 如請求項2所述的運動鞋中底,其中該運動鞋中底的密度為0.18±0.02g/cm3,該運動鞋中底的硬度為45±3,且該運動鞋中底的落球反彈率大於60%。
- 一種發泡材料製備方法,其是用於製備如請求項1所述的熱塑性聚氨酯發泡材料,該發泡材料製備方法包含:進行一混合步驟,是將該聚四亞甲基醚二醇、該1,4-丁二醇、該成核劑及該降黏劑混合,以獲得一多元醇混合物;進行一聚合步驟,是將該二苯基甲烷二異氰酸酯與該多元醇混合物混合並加熱,並待該二苯基甲烷二異氰酸酯與該多元醇混合物聚合形成一預聚物;進行一造粒步驟,是對該預聚物進行塑型與切割,使該預聚物形成複數個待發泡粒;以及進行一發泡步驟,是對該些待發泡粒進行發泡,以形成該熱塑性聚氨酯發泡材料。
- 如請求項4所述的發泡材料製備方法,其中該些待發泡粒是透過一超臨界氮氣射出發泡成型法進行發泡。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW112104670A TWI846317B (zh) | 2023-02-09 | 2023-02-09 | 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 |
CN202311755685.6A CN118459707A (zh) | 2023-02-09 | 2023-12-18 | 热塑性聚氨酯发泡材料、运动鞋中底及发泡材料制备方法 |
US18/428,196 US20240279418A1 (en) | 2023-02-09 | 2024-01-31 | Thermoplastic polyurethane foam material, midsole of athletic shoe and manufacturing method of foam material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW112104670A TWI846317B (zh) | 2023-02-09 | 2023-02-09 | 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
TWI846317B true TWI846317B (zh) | 2024-06-21 |
TW202432653A TW202432653A (zh) | 2024-08-16 |
Family
ID=92167254
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW112104670A TWI846317B (zh) | 2023-02-09 | 2023-02-09 | 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20240279418A1 (zh) |
CN (1) | CN118459707A (zh) |
TW (1) | TWI846317B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW202206496A (zh) * | 2020-07-31 | 2022-02-16 | 日勝化工股份有限公司 | 無溶劑聚氨酯材料及其製備之鞋中底 |
-
2023
- 2023-02-09 TW TW112104670A patent/TWI846317B/zh active
- 2023-12-18 CN CN202311755685.6A patent/CN118459707A/zh active Pending
-
2024
- 2024-01-31 US US18/428,196 patent/US20240279418A1/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW202206496A (zh) * | 2020-07-31 | 2022-02-16 | 日勝化工股份有限公司 | 無溶劑聚氨酯材料及其製備之鞋中底 |
Also Published As
Publication number | Publication date |
---|---|
CN118459707A (zh) | 2024-08-09 |
US20240279418A1 (en) | 2024-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107698860B (zh) | 一种鞋底用高回弹组合物发泡材料及其制备方法 | |
US5965778A (en) | Polyurethane elastomers having improved green strength and demold time, and polyoxyalkylene polyols suitable for their preparation | |
CN101402719B (zh) | 透明高弹性热塑性聚氨酯及其制备方法 | |
CN109111720B (zh) | 一种超轻高回弹etpu复合减震鞋中底材料及其成型方法 | |
CN1961016B (zh) | 低密度聚氨酯泡沫材料及其在鞋底中的用途 | |
CN101768250B (zh) | 一种高阻燃聚氨酯组合物及其制备方法 | |
CN101585901A (zh) | 一种聚氨酯泡沫材料及其制备方法和用途 | |
KR20160012100A (ko) | 저함량 유리 단량체 프리폴리머로 제조된 열가소성 폴리우레탄 | |
CN110698627B (zh) | 高透气型聚氨酯片材鞋垫组合料及其制备方法 | |
KR20010079916A (ko) | 미세다공성 폴리우레탄 엘라스토머의 제조 방법 | |
CN113185666B (zh) | 一种良好弹性鞋垫及制作工艺 | |
CN108440783A (zh) | 一种聚氨酯发泡珠粒及其制备方法 | |
CN111548475B (zh) | 一种慢回弹记忆棉及其制备方法 | |
CN111234492A (zh) | 一种pla/tpu超临界发泡复合材料及其制备方法 | |
JP2022522466A (ja) | 熱可塑性ポリウレタンからなる軟質粒子フォーム | |
TWI846317B (zh) | 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 | |
TW202432653A (zh) | 熱塑性聚氨酯發泡材料、運動鞋中底及發泡材料製備方法 | |
CN113197392A (zh) | 一种石墨烯透气鞋垫 | |
JPH03172315A (ja) | 軟質ポリウレタン発泡体の製造方法 | |
CN106810668B (zh) | 聚氨酯鞋底用树脂及制备方法和应用 | |
CN111019081B (zh) | 一种pu连续发泡运动垫的生产工艺 | |
JP2022532665A (ja) | 引裂きの強い低密度ポリウレタンフォームシステム | |
CN105524251A (zh) | 一种具有高回弹性的海绵及其制备工艺 | |
CN110144111A (zh) | 一种轻质加麻聚氨酯鞋底及其制备方法 | |
CN114921048B (zh) | 一种抗寒中底材料及其制备方法、鞋 |