TW201800479A - TPU foam material and foams thereof - Google Patents
TPU foam material and foams thereof Download PDFInfo
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- TW201800479A TW201800479A TW105120653A TW105120653A TW201800479A TW 201800479 A TW201800479 A TW 201800479A TW 105120653 A TW105120653 A TW 105120653A TW 105120653 A TW105120653 A TW 105120653A TW 201800479 A TW201800479 A TW 201800479A
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- thermoplastic polyurethane
- tpu
- foaming
- foaming agent
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- 239000006260 foam Substances 0.000 title claims abstract description 12
- 239000006261 foam material Substances 0.000 title abstract 2
- 239000004088 foaming agent Substances 0.000 claims abstract description 33
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 35
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 2
- 239000002666 chemical blowing agent Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 15
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 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 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010097 foam moulding Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical group [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
一種熱塑性聚氨酯彈性體組成，特別是一種熱塑性聚氨酯可發泡原料組成及其發泡體。A thermoplastic polyurethane elastomer composition, in particular a thermoplastic polyurethane foamable raw material composition and a foam thereof.
熱塑性聚氨酯(Thermoplastic polyurethane elastomer, TPU)因其優異的特性，例如耐磨性、硬度高、強度高、彈性佳、良好的耐油、耐化學藥品或耐候性，廣泛應用於工業、軍事、交通、醫學或民生產業製品。特別是製鞋產業，熱塑性聚氨酯(TPU)因其高彈性強度及良好的加工特性，製成的鞋中底或鞋大底品質好又耐用，使其成為製鞋產業的熱門選用材料之一。Thermoplastic polyurethane elastomer (TPU) is widely used in industry, military, transportation, medicine for its excellent properties such as abrasion resistance, high hardness, high strength, good elasticity, good oil resistance, chemical resistance or weather resistance. Or the production of products for the people. Especially in the footwear industry, thermoplastic polyurethane (TPU) is one of the popular materials for the footwear industry due to its high elastic strength and good processing characteristics, resulting in a shoe sole or a shoe sole with good quality and durability.
一般而言，鞋中底或鞋大底除需具備高彈性外，常利用發泡方法進一步將材料達到質輕又高彈的效果，然而，熱塑性聚氨酯(TPU)因結構架橋不易，發泡時熔融強度會大幅下降，無法維持泡孔型態，非常容易破泡，難以製成發泡產品；雖有先前技術將熱塑性聚氨酯(TPU)利用物理性發泡方法，例如超臨界二氧化碳發泡，利用高壓設備將二氧化碳形成液態並打入塑料，釋壓後二氧化碳膨脹使塑料發泡，但此種方法成本及製造設備特殊且昂貴，大大增加生產熱塑性聚氨酯(TPU)發泡產品的成本。In general, in addition to the high elasticity of the midsole or the outsole of the shoe, the foaming method is often used to further achieve the material light and high elastic effect. However, the thermoplastic polyurethane (TPU) is difficult to bridge due to the structure, and when foaming The melt strength will drop drastically, the cell type will not be maintained, and it is very easy to break the foam, making it difficult to make a foamed product. Although the prior art uses thermoplastic foam (TPU) by a physical foaming method, such as supercritical carbon dioxide foaming, High-pressure equipment forms carbon dioxide into a liquid state and breaks into plastic. After decompression, carbon dioxide expands to foam the plastic. However, the cost and manufacturing equipment of this method are special and expensive, which greatly increases the cost of producing thermoplastic polyurethane (TPU) foamed products.
為了解決目前熱塑性聚氨酯(TPU)發泡不易，又物理性發泡製程設備特殊又成本高昂的問題，本發明提供一種熱塑性聚氨酯可發泡原料組成，其包含：In order to solve the problem that the current thermoplastic polyurethane (TPU) foaming is not easy, and the physical foaming process equipment is special and costly, the present invention provides a thermoplastic polyurethane foamable raw material composition, which comprises:
熱塑性聚氨酯 (Thermoplastic polyurethane elastomer, TPU) 50～90 phr；Thermoplastic polyurethane elastomer (TPU) 50 ~ 90 phr;
聚氨酯混煉膠(Millable polyurethane, MPU) 10~50 phr；Millable polyurethane (MPU) 10~50 phr;
架橋劑 1～5 phr；以及Bridging agent 1 to 5 phr;
化學性發泡劑 1~3 phr。Chemical foaming agent 1~3 phr.
其中，該架橋劑為過氧化物型架橋劑或硫磺型架橋劑。Wherein, the bridging agent is a peroxide type bridging agent or a sulfur type bridging agent.
其中，該過氧化物型架橋劑包含過氧化二異丙苯。Wherein, the peroxide type bridging agent comprises dicumyl peroxide.
其中，該化學性發泡劑包含吸熱型發泡劑及放熱型發泡劑。Wherein, the chemical foaming agent comprises an endothermic foaming agent and an exothermic foaming agent.
其中，該放熱型發泡劑包含AC發泡劑及該吸熱型發泡劑包含小蘇打。Wherein, the exothermic foaming agent comprises an AC foaming agent and the endothermic foaming agent comprises baking soda.
進一步地，本發明提供一種由上述材料所製成的熱塑性聚氨酯發泡體，其比重介於0.1～1.3 g/cm3 ，發泡率介於1.1～15倍之間。Further, the present invention provides a thermoplastic polyurethane foam produced from the above material, which has a specific gravity of 0.1 to 1.3 g/cm 3 and a foaming ratio of 1.1 to 15 times.
本發明透過導入與熱塑性型聚氨酯具有相容性的聚氨酯混煉膠(Millable polyurethane, MPU)，使熱塑性聚氨酯(TPU)的架橋特性及熔融強度提升，熱塑性聚氨酯(TPU)僅需使用如AC發泡劑及小蘇打等相對價廉的發泡劑即可輕易發泡，並維持泡孔型態不破泡，不需額外增添發泡設備或使用特殊的發泡製程，達到降低生產製造成本的優點。The invention improves the bridging characteristics and the melting strength of the thermoplastic polyurethane (TPU) by introducing a polyurethane adhesive (MPU) compatible with the thermoplastic polyurethane, and the thermoplastic polyurethane (TPU) only needs to use, for example, AC foaming. A relatively inexpensive foaming agent such as a baking agent and baking soda can be easily foamed, and the cell type can be maintained without foaming, and no additional foaming equipment or a special foaming process can be used, thereby achieving the advantage of reducing the manufacturing cost.
一種熱塑性聚氨酯可發泡原料組成，其包含(添加量的單位為phr, parts per hundreds of rubber or resin)：A thermoplastic polyurethane foamable raw material composition comprising (in units of phr, parts per hundred of rubber or resin):
熱塑性聚氨酯(Thermoplastic polyurethane, TPU) 50～90 phr；Thermoplastic polyurethane (TPU) 50 ~ 90 phr;
聚氨酯混煉膠(Millable polyurethane, MPU) 10~50 phr；Millable polyurethane (MPU) 10~50 phr;
架橋劑 1～5 phr；以及Bridging agent 1 to 5 phr;
化學性發泡劑 1~3 phr。Chemical foaming agent 1~3 phr.
本發明上述配方中所述的聚氨酯混煉膠，又稱為混煉型聚氨酯，可採用既有以聚酯、聚醚多元醇及二異氰酸酯為主原料，以不同種類的鏈延長劑混煉反應而成的聚氨酯混煉膠，主要的供應商有TSE Industries, Inc.公司等，其產品型號名稱為Millathane®。The polyurethane rubber compound described in the above formula of the present invention, which is also called a kneading type polyurethane, can be mixed with a different type of chain extender by using polyester, polyether polyol and diisocyanate as main raw materials. The main supplier of polyurethane rubber is TSE Industries, Inc., and its model name is Millathane®.
本發明所使用的架橋劑依據選用的聚氨酯混煉膠(MPU)，可對應選擇包括過氧化二異丙苯(DCP)等過氧化物型架橋劑或硫磺(Sulfer)等硫化型架橋劑，不同的架橋系統可使聚氨酯混煉膠(MPU)達到不同的物理性能及加工性能，例如使用二苯基甲烷二異氰酸酯(MDI)所製備的聚氨酯混煉膠(MPU)多採用過氧化物型的硫化架橋系統；而使用二苯基甲烷二異氰酸酯(MDI)、並在聚合物大分子中含有不飽和鍵的聚氨酯混煉膠(MPU)則可選用硫磺硫化架橋系統或是過氧化物型兩種不同的硫化架橋系統。一般而言使用硫磺硫化系統架橋的聚氨酯混煉膠(MPU)相對於過氧化物型硫化系統，可以提高較高的硬度，但其而高溫永久壓縮變形量性能較差；而過氧化物型的硫化架橋系統其高溫永久壓縮變形量性能較優異，適合應用在反覆壓縮的鞋底材料上。The bridging agent used in the present invention may be selected according to the selected polyurethane rubber compound (MPU), and may be selected to include a peroxide type bridging agent such as dicumyl peroxide (DCP) or a vulcanizing type bridging agent such as sulfur (Sulfer). The bridging system can achieve different physical properties and processing properties of polyurethane rubber (MPU). For example, polyurethane compound (MPU) prepared by using diphenylmethane diisocyanate (MDI) is more resistant to peroxide. Bridging system; polyurethane rubber (MPU) using diphenylmethane diisocyanate (MDI) and containing unsaturated bonds in polymer macromolecules can be sulphur-sulfur bridging system or peroxide type Vulcanized bridge system. In general, the polyurethane compound (MPU) bridged by the sulfur vulcanization system can improve the higher hardness than the peroxide type vulcanization system, but the high temperature permanent compression deformation performance is poor; and the peroxide type vulcanization The bridging system has excellent high-temperature permanent compression deformation and is suitable for use on the sole material of the reverse compression.
而本發明之化學性發泡劑係混合吸熱型及放熱型發泡劑的吸放熱混合型發泡劑，包含放熱型的偶氮苯二甲醯胺發泡劑(Azodicarbonamide, AC發泡劑)及吸熱型的小蘇打(碳酸氫鈉)，此二種發泡劑具有成本低廉的優勢，且不需要額外使用特殊的發泡設備或發泡製程，大幅降低熱塑性聚氨酯(TPU)發泡的生產製造成本。The chemical foaming agent of the present invention is a heat-absorption and heat-dissipating type foaming agent for mixing an endothermic type and an exothermic type foaming agent, and comprises an exothermic azomethine foaming agent (Azodicarbonamide). And endothermic baking soda (sodium bicarbonate), these two blowing agents have the advantage of low cost, and do not require the use of special foaming equipment or foaming process, which greatly reduces the production of thermoplastic polyurethane (TPU) foaming. manufacturing cost.
偶氮苯二甲醯胺(AC發泡劑)此種放熱型發泡劑的特色是發泡速率快且發泡倍率高，塑料需要具備足夠的架橋度以及融熔結構強度，才可支撐快速膨脹的氣體而成功發泡；小蘇打則係相對於AC發泡劑，對於塑料的架橋度及融熔強度要求沒這麼高的吸熱型發泡劑，屬於發泡倍率及速率較低的發泡劑；本發明透過混合此兩種發泡劑，並搭配使用聚氨酯混煉膠(MPU)，不僅可使熱塑性聚氨酯(TPU)成功發泡外，更可達到調控發泡速率及發泡倍率的功效。Azophthalic acid (AC foaming agent) This exothermic foaming agent is characterized by high foaming rate and high expansion ratio. Plastics need to have sufficient bridging degree and melting structure strength to support fast. Successfully foamed with expanded gas; baking soda is relative to AC foaming agent. It does not require such high endothermic foaming agent for bridging degree and melting strength of plastic, and it is foaming with low expansion rate and speed. The invention can not only achieve the foaming of the thermoplastic polyurethane (TPU), but also achieve the effect of regulating the foaming rate and the foaming ratio by mixing the two foaming agents and using the polyurethane rubber compound (MPU). .
熱塑性聚氨酯(TPU)因無法良好架橋，若以一般化學性發泡劑發泡時，材料結構無法支撐快速形成的發泡氣體而容易破泡產生破孔，發泡效率不佳，故熱塑性聚氨酯(TPU)無法以化學性發泡等成本較低的化學性發泡劑發泡；而本發明為了可使用成本較低廉的化學性發泡劑，透過添加聚氨酯混煉膠(MPU)此種與熱塑性聚氨酯(TPU)具有相容性的第二相材料，且聚氨酯混煉膠(MPU)本身具有良好的架橋性，可進一步增加熱塑性聚氨酯(TPU)的架橋性，整體材料的架橋性及熔融強度得以提升，使熱塑性聚氨酯(TPU)不需使用例如超臨界二氧化碳發泡等特殊且昂貴的發泡製程，以一般的化學性發泡劑即可成功發泡，並且結構足以支撐其發泡泡體不破泡。Since thermoplastic polyurethane (TPU) cannot be bridged well, if it is foamed with a general chemical foaming agent, the material structure cannot support the rapidly formed foaming gas, and it is easy to break and cause breakage, and the foaming efficiency is not good, so the thermoplastic polyurethane ( TPU) cannot be foamed with a chemical foaming agent such as chemical foaming; however, in order to use a lower cost chemical foaming agent, it is possible to add a polyurethane compound (MPU) and thermoplastic Polyurethane (TPU) has a compatible second phase material, and the polyurethane compound (MPU) itself has good bridging property, which can further increase the bridging property of thermoplastic polyurethane (TPU), and the bridging property and melt strength of the whole material can be obtained. The lifting, so that the thermoplastic polyurethane (TPU) does not need to use a special and expensive foaming process such as supercritical carbon dioxide foaming, can be foamed successfully with a general chemical foaming agent, and the structure is sufficient to support the bubble body without breaking bubble.
目前台灣製鞋產業多為代工為主，設備多為傳統的化學發泡製程設備，該設備無法直接應用TPU物理性的發泡技術，需要額外增設或修改機台成為物理性發泡設備才可生產TPU發泡產品。而本發明可以直接應用於傳統的發泡設備上，例如批次式的熱壓發泡、連續式的射出發泡，均可以直接使用，不用額外增設或修改機台，降低生產製造成本。At present, the footwear industry in Taiwan is mostly OEM, and the equipment is mostly traditional chemical foaming process equipment. This equipment cannot directly apply TPU physical foaming technology. It is necessary to add or modify the machine to become a physical foaming equipment. Can produce TPU foam products. The invention can be directly applied to the traditional foaming equipment, for example, batch type hot pressing foaming and continuous type injection foaming, all of which can be directly used without additional addition or modification of the machine table, thereby reducing the manufacturing cost.
請參考下表1，本發明之配方及製成發泡體後的物性量測表。添加單位為phr，打*號者僅係製程中之添加助劑，為非必要之添加，即使不添加、添加極少量或置換其他具有相同效能之添加助劑，亦不影響本發明之功效。 【表1】
請參考圖1～圖2，其係由本發明配方A及C所製成的發泡體SEM圖，由圖1及圖2可看出本發明成功利用化學性發泡劑將熱塑性聚氨酯(TPU)發泡為發泡體，且泡孔完整、大小均一無破泡。Please refer to FIG. 1 to FIG. 2 , which are SEM images of the foams prepared by the formulations A and C of the present invention. It can be seen from FIGS. 1 and 2 that the present invention successfully utilizes a chemical foaming agent to thermoplastic polyurethane (TPU). The foam is foamed, and the cells are complete in size and uniform in size without breaking.
本發明之製程方法可以是將所有材料以混煉機共同混煉後，再以目前已知的熱成型發泡方法，例如熱壓發泡成型、模壓發泡成型或射出發泡成型等，形成發泡板片材、發泡鞋底、護具或地墊等質輕且高彈性的塑膠緩衝材。請參考下表2，其為本發明表1各配方加工與成型的較佳製程參數。 【表2】
本發明透過導入與熱塑性型聚氨酯具有相容性的聚氨酯混煉膠(Millable polyurethane, MPU)，使熱塑性聚氨酯(TPU)的架橋特性及熔融強度提升，熱塑性聚氨酯(TPU)僅需使用如AC發泡劑及小蘇打等相對價廉的發泡劑即可輕易發泡，並維持泡孔型態不破泡，不需額外增添發泡設備或使用特殊的發泡製程，達到降低生產製造成本的優點。The invention improves the bridging characteristics and the melting strength of the thermoplastic polyurethane (TPU) by introducing a polyurethane adhesive (MPU) compatible with the thermoplastic polyurethane, and the thermoplastic polyurethane (TPU) only needs to use, for example, AC foaming. A relatively inexpensive foaming agent such as a baking agent and baking soda can be easily foamed, and the cell type can be maintained without foaming, and no additional foaming equipment or a special foaming process can be used, thereby achieving the advantage of reducing the manufacturing cost.
圖1為本發明實施例配方A的熱塑性聚氨酯發泡彈性體之SEM圖。 圖2為本發明實施例配方C的熱塑性聚氨酯發泡彈性體之SEM圖。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an SEM image of a thermoplastic polyurethane foamed elastomer of Formula A of the present invention. 2 is an SEM image of a thermoplastic polyurethane foamed elastomer of Formula C in accordance with an embodiment of the present invention.
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| CN108485240A (en) * | 2018-04-28 | 2018-09-04 | 广州顺力聚氨酯科技有限公司 | Polyurethane elastomer material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108485240A (en) * | 2018-04-28 | 2018-09-04 | 广州顺力聚氨酯科技有限公司 | Polyurethane elastomer material and its preparation method and application |
| CN108485240B (en) * | 2018-04-28 | 2021-02-12 | 广州顺力聚氨酯科技有限公司 | Polyurethane elastomer material and preparation method and application thereof |
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