TW202142383A - Method for manufacturing a recyclable flexible foam molded product - Google Patents
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[相關申請案之交互參照][Cross-reference of related applications]
本申請案主張標題名稱為「RECYCLABLE AND CHEMICAL-FREE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME」且在2019年5月29日申請之美國臨時專利申請案第62/853,805號之優先權及權益,且為2019年5月21日申請之標題名稱為「BIODEGRADABLE AND INDUSTRIALLY COMPOSTABLE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME」之專利申請案第16/418,968之部分連續案,該專利申請案主張標題名稱為「BIODEGRADABLE AND INDUSTRIALLY COMPOSTABLE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME」且在2018年5月21申請之美國臨時專利申請案第62/674,544號之優先權及權益,該等專利申請案之揭示內容全部以引用方式整體整體併入本文中以用於所有目的。This application claims priority to the U.S. Provisional Patent Application No. 62/853,805 entitled "RECYCLABLE AND CHEMICAL-FREE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME" and filed on May 29, 2019 And rights, and is part of the continuation of the 16/418,968 patent application titled "BIODEGRADABLE AND INDUSTRIALLY COMPOSTABLE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME" filed on May 21, 2019. The patent The application claims the priority and rights of U.S. Provisional Patent Application No. 62/674,544 whose title is "BIODEGRADABLE AND INDUSTRIALLY COMPOSTABLE INJECTION MOLDED MICROCELLULAR FLEXIBLE FOAMS, AND A METHOD OF MANUFACTURING THE SAME" and filed on May 21, 2018, The disclosures of these patent applications are all incorporated herein by reference in their entirety for all purposes.
本揭示案係關於用於由用於使用在例如鞋類組件、座位組件、保護裝置組件及水上運動附件中的可回收或生物可降解、工業上可合成之生物衍生熱塑性聚合物射出模製成形的微氣孔發泡各種可撓性發泡體組成的製程。The present disclosure relates to injection molding of bio-derived thermoplastic polymers that are recyclable or biodegradable and industrially synthesizable for use in, for example, footwear components, seat components, protective device components, and water sports accessories. The micro-pore foaming process is composed of various flexible foams.
藉由堆肥之降解係用於再生使用在生產製成品中的資源之重要製程。然而,當彼等製成品涉及發泡體時,分解可能成為問題。具體而言,存在可撓性發泡體製造之依照慣例已知方法之若干缺點。例如,此類缺點包括不可再生聚合物、化學發泡劑,及化學添加劑之選擇及使用,該等不可再生聚合物、化學發泡劑、及化學添加劑如在發泡體製造工業及固有的處理程序中所利用的,通常不能生物降解,且該等不可再生聚合物、化學發泡劑、及化學添加劑通常被視為有害於環境。此生物降解之缺乏意味許多習知可撓性發泡體材料及與該等習知可撓性發泡體材料一起含有的產品數十年至數百年地終止於任何地方之掩埋場中。Degradation by composting is an important process used to regenerate resources used in the production of finished products. However, when their finished products involve foams, decomposition can become a problem. Specifically, there are several shortcomings of the conventionally known methods for manufacturing flexible foams. For example, such shortcomings include the selection and use of non-renewable polymers, chemical blowing agents, and chemical additives. Such non-renewable polymers, chemical blowing agents, and chemical additives are used in the foam manufacturing industry and inherent processing The ones used in the procedure are usually not biodegradable, and such non-renewable polymers, chemical foaming agents, and chemical additives are usually regarded as harmful to the environment. This lack of biodegradation means that many conventional flexible foam materials and products contained with such conventional flexible foam materials end up in landfills anywhere for decades to hundreds of years.
此亦成為問題的,因為當今世界上掩埋場之過度使用具有對環境及經濟兩者之直接負面衝擊。例如,掩埋場為美國甲烷排放之第三大來源。此外,慣例可撓性發泡體中所使用的前面提到的生物不可降解聚合物及化學品尤其衍生自非再生資源。This has also become a problem because the overuse of landfills in the world today has a direct negative impact on both the environment and the economy. For example, landfills are the third largest source of methane emissions in the United States. In addition, the aforementioned non-biodegradable polymers and chemicals used in conventional flexible foams are especially derived from non-renewable resources.
此等材料並非天然可再生的,如生物衍生原料之狀況,且因此,該等材料之真實產生為環境的淨損失,因為其材料通常經取得、使用,且然後不可持續地丟棄。此外,即使可再生聚合物經選擇來用於使用在可撓性發泡體製造之按照慣例已知方法中,但化學發泡劑及彼等方法之交聯將可能以並不生物降解或堆肥的添加劑污染可再生聚合物。因而,使其為零和增益。仍然進一步地,生物聚合物之交聯將亦可能防礙用於生物降解或堆肥之任何合適的壽命終止解決方案,因為前驅物組分不能分離,藉此導致更多廢棄物產生及去往掩埋場的更多材料。These materials are not naturally renewable, as in the state of bio-derived raw materials, and therefore, the actual production of these materials is a net loss to the environment, because the materials are usually obtained, used, and then unsustainably discarded. In addition, even if renewable polymers are selected for use in conventionally known methods of flexible foam manufacturing, chemical blowing agents and cross-linking by these methods may not be biodegradable or compostable. Of additives contaminate renewable polymers. Therefore, make it zero and gain. Still further, the cross-linking of biopolymers will also likely hinder any suitable end-of-life solutions for biodegradation or composting, because the precursor components cannot be separated, thereby leading to more waste generation and burial. More material for the field.
因此,儘管堆肥及回收為提供可再生且可持續未來中的重要製程,但其在製造工業中之整合為非常有限的。然而,若可使製成材料為可合成的,則該製程將為例如對於環境非常有用的。例如,可撓性發泡體材料之堆肥及生物降解產生表示對於環境及經濟之淨效益的廢棄物處置之機會。例如,藉由將此等材料堆肥,將可能減少傳送至掩埋場及大量燃燒焚化爐的廢棄物之總量。Therefore, although composting and recycling are important processes that provide a renewable and sustainable future, their integration in the manufacturing industry is very limited. However, if the fabricated material can be made synthesizable, the process will be very useful for the environment, for example. For example, the composting and biodegradation of flexible foam materials produces opportunities for waste disposal that represent a net benefit to the environment and economy. For example, by composting these materials, it is possible to reduce the total amount of waste sent to landfills and mass burning incinerators.
除減少廢棄物之外,堆肥製程將亦產生可用產品,該可用產品為富有營養的且可用來改良貧瘠土壤以生長糧食或對花園施肥。因此,將可撓性發泡體堆肥及生物降解之真實概念無論如何新穎,可使整個價值鏈發生巨大變化,同時堅持所謂的循環經濟之原則。存在兩個典型的堆肥形式:工業堆肥及家庭堆肥。此等堆肥方法論中兩者具有效益及缺點。In addition to reducing waste, the composting process will also produce usable products that are nutritious and can be used to improve poor soils to grow food or fertilize gardens. Therefore, no matter how novel the real concept of flexible foam composting and biodegradation is, it can make huge changes in the entire value chain while adhering to the principles of the so-called circular economy. There are two typical forms of composting: industrial composting and household composting. Both of these composting methodologies have benefits and drawbacks.
工業堆肥為經設計以處置非常大體積的有機廢棄物的大規模堆肥形式。工業堆肥係以介於50℃至60℃之間的溫度在大規模設施中實施。家庭堆肥係處置來自一個家庭之有機廢棄物的堆肥形式。特定而言,家庭堆肥係指以相對較低溫度的堆肥,如可見於家庭後院堆肥堆中的彼等堆肥,因此標題「家庭」。與工業堆肥相反,家庭堆肥涉及諸如庭院剪屑、廚房廢料、木刨花、卡紙板、及紙的有機材料或廢棄物之冷卻器需氧分解。在家庭堆肥中處置的體積顯著地小於在工業堆肥中且堆肥通常使用在私人花園中。此製程通常在小規模堆肥器及堆中實施。在此方法中,溫度通常在低溫(0℃至20℃)至中溫(20℃至45℃)範圍內(如以下解釋)。因此,不同的技術存在,但是一般處理為相同的:後面是固化的活性堆肥之受控制製程。Industrial composting is a large-scale composting form designed to dispose of very large volumes of organic waste. Industrial composting is carried out in large-scale facilities at temperatures between 50°C and 60°C. Household composting is a form of composting that disposes of organic waste from a family. Specifically, home composting refers to composting at a relatively low temperature, such as those composts that can be found in a compost pile in a home's backyard, hence the title "family". In contrast to industrial composting, household composting involves aerobic decomposition of organic materials such as garden cuttings, kitchen waste, wood shavings, cardboard, and paper or waste coolers. The volume to be disposed of in home compost is significantly smaller than in industrial compost and compost is usually used in private gardens. This process is usually implemented in small-scale compostors and piles. In this method, the temperature is usually in the range of low temperature (0°C to 20°C) to medium temperature (20°C to 45°C) (as explained below). Therefore, different technologies exist, but the general treatment is the same: the next is the controlled process of solidified reactive compost.
活性堆肥期間通常持續至少21天。在此等條件下,微生物在有機廢棄物上生長,從而將有機廢棄物分解成CO2 及水,使用該有機廢棄物作為營養素。在堆肥期間,有機廢棄物聚積在反應堆內,且因此堆肥之能量之部分作為熱釋放。當堆肥反應堆之溫度增加時,微生物族群移位:適應周圍溫度的微生物例如嗜中溫生物停止其活動、相繼死去,且由適應生活在高溫處的微生物例如嗜熱生物替代。出於衛生化目的,對於家庭堆肥,溫度應維持在60℃以上持續至少一週,以便消除病原微生物。相比之下,工業堆肥之固化期間使分解速率減緩至一致步調,且堆肥在低於40℃之較低中溫範圍內的溫度處成熟。The active composting period usually lasts at least 21 days. Under these conditions, microorganisms grow on the organic waste, thereby decomposing the organic waste into CO 2 and water, and using the organic waste as nutrients. During composting, organic waste accumulates in the reactor, and therefore part of the composting energy is released as heat. When the temperature of the composting reactor increases, the microbial population shifts: microorganisms that adapt to the surrounding temperature, such as mesophilic organisms, cease their activities, die one after another, and are replaced by microorganisms that are adapted to live at high temperatures, such as thermophiles. For the purpose of sanitation, for household composting, the temperature should be maintained above 60°C for at least one week in order to eliminate pathogenic microorganisms. In contrast, the solidification period of industrial compost slows the decomposition rate to a consistent pace, and the compost matures at a temperature in the lower medium temperature range below 40°C.
工業堆肥之主要問題在於輸入原料應適當地安置以便經有效地處理。亦即,後勤挑戰為障礙,因為需要適當的收集、分類、及至工業堆肥設施之運輸。美國的組合堆肥及回收轉換率為約35%,此狀況指示在大多數基礎設施在廢棄物轉換上「關閉環路」之前,社會有很遠的路要走。克服此損失之一個方法將較好地教育終端使用者且建立進料至較大收回方案的收回方案之局部網路。目標將發展足夠的便利性及可及性,使得工業堆肥變得正規化且始終存在於日常生活中。The main problem of industrial composting is that the input raw materials should be properly placed so that they can be effectively processed. That is, logistical challenges are obstacles because of the need for proper collection, sorting, and transportation to industrial composting facilities. The combined composting and recycling conversion rate in the United States is about 35%. This situation indicates that society has a long way to go before most infrastructure "closes the loop" on waste conversion. One way to overcome this loss is to better educate end users and build a local network of recovery options that feed into larger recovery options. The goal is to develop sufficient convenience and accessibility so that industrial composting becomes regular and always present in daily life.
同樣地,家庭堆肥中之盛行缺點為所涉及的努力量。所需要的堆肥原料材料中之全部需要經運載及/或傳遞至堆肥反應堆。一旦堆肥堆大到足以開始產生能量,且藉此產生熱,需要轉向使分解更快速且更徹底,此可為費力的工作。當有機物質經充分分解時,家庭堆肥必須經運走以用於使用在土壤改良中。家庭堆肥之另一缺點為普通人可在家庭環境中產生的有限數量的可用堆肥。有限量的所產生堆肥可能給出有限使用方式,且因而,普通人投入家庭堆肥之努力的動機可為低的。Likewise, the prevalent disadvantage in home composting is the amount of effort involved. All of the required composting raw materials need to be carried and/or delivered to the composting reactor. Once the compost pile is large enough to start generating energy and thereby generating heat, it is necessary to turn to make the decomposition faster and more thorough, which can be laborious work. When the organic matter is fully decomposed, the household compost must be transported away for use in soil improvement. Another disadvantage of home composting is the limited amount of usable compost that ordinary people can produce in the home environment. A limited amount of compost produced may give limited use, and therefore, the motivation of ordinary people to invest in household composting efforts may be low.
由於此等缺點,傳統上,製造工業已避免具有生物降解或堆肥之可能性的原始材料及前驅物成分之使用。另外,此在傳統上已經避免,因為此等材料之所需要的技術效能性質通常劣於習知生物不可降解且不可合成變種之彼性質。例如,一些但並非所有可合成前驅物成分之限制因素可為此等成分在產品之可用壽命之終止之前分解及/或降解之趨勢。此之一實例將為紫外線敏感性產品,藉此生物可降解及可合成前驅物可藉由重複日光暴露攻擊且變弱,在終端使用者即將丟棄產品之前,此最終亦可導致產品故障。Because of these shortcomings, traditionally, the manufacturing industry has avoided the use of raw materials and precursor components that have the possibility of biodegradation or composting. In addition, this has traditionally been avoided, because the required technical performance properties of these materials are generally inferior to the conventional non-biodegradable and non-synthetic variants. For example, some but not all of the limiting factors for synthesizable precursor ingredients may have the tendency of these ingredients to decompose and/or degrade before the end of the product's useful life. An example of this would be UV-sensitive products, whereby the biodegradable and synthesizable precursors can be attacked and weakened by repeated sunlight exposure, which can eventually lead to product failure before the end user is about to discard the product.
在使用化石燃料產生的塑膠、熱塑性塑膠及其他產品之上下文中,回收按照慣例涉及機械地切碎製成品、使切碎的內容物熔化、及然後造粒所得材料以用於稍後使用在製造中。儘管回收降低對化石燃料之需要且將產品自掩埋場轉移,但回收可由於污染或添加至原料的雜質而導致回收聚合物之品質損失,且大多數塑膠及熱塑性產品僅可回收有限的次數。此外,使用在習知可撓性發泡體之製造中的化學發泡劑、交聯聚合物、及化學添加劑導致終端產品,該等終端產品可能並不分解成其構成聚合物以用於稍後使用在製造回收產品中。因此,當產品已到達其可用壽命之終止時,按照慣例製成的可撓性發泡體產品為不可回收的。In the context of plastics, thermoplastics, and other products produced using fossil fuels, recycling conventionally involves mechanically shredding the finished product, melting the shredded content, and then pelletizing the resulting material for later use in manufacturing middle. Although recycling reduces the need for fossil fuels and transfers products from landfills, recycling can result in quality loss of recycled polymers due to pollution or impurities added to the raw materials, and most plastic and thermoplastic products can only be recycled a limited number of times. In addition, the chemical blowing agents, cross-linked polymers, and chemical additives used in the manufacture of conventional flexible foams lead to end products, which may not be decomposed into their constituent polymers for use in minor applications. Later used in the manufacture of recycled products. Therefore, when the product has reached the end of its usable life, the conventionally manufactured flexible foam product is not recyclable.
另外,用於現代製造的當前關注為關於排放量及廢棄物的淨中性的、關於使用在製造製程中的材料的可持續的,且關於產品及其材料之壽命終止的可再生的。如此,除最終產品之可合成性之外,諸如關於CO2 排放量的淨中性已在選擇用於使用在消費品產品之製造中之適當材料中變得重要。In addition, the current concerns for modern manufacturing are about the net neutrality of emissions and waste, about the sustainability of the materials used in the manufacturing process, and about the end-of-life of products and their materials that are renewable. As such, in addition to the synthesizable nature of the final product, such as the net neutrality with respect to CO 2 emissions has become important in selecting appropriate materials for use in the manufacture of consumer products.
因此,與目前呈現的更傳統製造製程相比,其為用於本文所揭示之目前製造製程之關鍵驅動器,因為製造商生產考慮環境的終端產品,且如此,謹慎地考慮使用在該等終端產品之製造中使用的材料,且平衡彼材料與產品之預定可用壽命為有用的。在生產其間此等考慮應該但未解決的挑戰產品之實例為利用發泡體的諸如緩衝器(諸如用於家具)之生產中的標準製成品,及/或諸如用於跑步鞋之製造的發泡體產品。Therefore, compared with the more traditional manufacturing process currently presented, it is a key driver for the current manufacturing process disclosed in this article, because manufacturers produce end products that consider the environment, and thus, carefully consider using them in these end products It is useful to balance the material used in the manufacturing of the material and the expected useful life of the product. Examples of products that should be considered but unresolved challenges during production are standard finished products in the production of foams such as bumpers (such as for furniture), and/or hair products such as those used in the manufacture of running shoes. Foam products.
例如,跑步鞋為在相當大量的時間內暴露於諸如衝擊、磨損及所有環境暴露方式的重複濫用的高技術產品;取決於使用頻率而可能為1年至3年。當考慮用於使用在製造用於家具或用於鞋底、中底之緩衝器,及/或用於跑步鞋之鞋內底之緩衝器中的可持續材料時,考慮以上要求為重要的。在故障之前不能處置重複濫用的材料將不會生一對滿意的跑步鞋。另外,在預定壽命終止之前,在正常產品使用期間具有分解或減弱至故障點之可能性的任何材料將為不可接受的。For example, running shoes are high-tech products that are exposed to repeated abuse such as impact, abrasion and all environmental exposures for a considerable amount of time; depending on the frequency of use, it may be 1 to 3 years. It is important to consider the above requirements when considering sustainable materials used in the manufacture of buffers for furniture or shoe soles, midsoles, and/or shoe insoles for running shoes. Failure to dispose of repetitively abused materials before failure will not produce a satisfactory pair of running shoes. In addition, any material that has the potential to decompose or weaken to the point of failure during normal product use will be unacceptable before the end of the predetermined life.
為解決此問題,技術者必須找出具有技術效能性質及諸如具有管理的壽命終止解決方案之可堆肥性的可持續性態樣之正確平衡的特殊化材料,該管理的壽命終止解決方案為關於有害排放量淨中性的(或負面的)。具體而言,因為家具緩衝墊為龐大的且跑步鞋為苛求的產品,所以家庭堆肥材料並非使用在其製作中的合適的解決方案,因為較低的分解溫度將轉移至家具或跑步鞋,該跑步鞋將傾向於在其預定壽命終止很久以前破碎。在此實例中,工業堆肥的材料為好得多的選擇權,因為該等材料可處置較高的溫度挑戰且提供接近等於或等於其非工業上可合成且不可生物降解之對應物的較大技術效能性質。實質上,以工業上可合成之材料製造的家具或一雙跑步鞋將對於產品之可用壽命很好地起作用,且僅在產品可用壽命終止處,材料具有經導向至用於「封閉迴路」廢棄物轉換之工業堆肥設置中的選擇權。To solve this problem, technicians must find specialized materials that have the correct balance of technical performance properties and sustainable aspects such as compostability with managed end-of-life solutions. The managed end-of-life solutions are about The harmful emissions are net neutral (or negative). Specifically, because furniture cushions are bulky and running shoes are demanding products, household composting materials are not a suitable solution for their production, because the lower decomposition temperature will be transferred to furniture or running shoes. Running shoes will tend to break long before their intended lifespan ends. In this example, industrially composted materials are a much better option because they can handle higher temperature challenges and provide a larger size close to or equal to their non-industrially synthesizable and non-biodegradable counterparts. The nature of technical effectiveness. In essence, furniture or a pair of running shoes made of industrially synthesizable materials will have a good effect on the usable life of the product, and only at the end of the usable life of the product, the material has to be directed to be used in a "closed loop" The right to choose in the industrial composting setting of waste conversion.
因此,在可能的情況下,為減少經常伴隨於製造製程的破壞性覆蓋區,材料及製造製程應以使得在產品之壽命之終止之後允許準備堆肥的方式加以配製。然而,如以上所指示,此係困難的,因為存在商業可利用的非常有限的生物可降解且可合成的前驅物。不存在的彼等未必經設計且能夠解決效能及長期可用性之組合挑戰中之全部,而在其可用壽命終止時容易在受控制的設置中堆肥且生物降解。解決前面提到的挑戰中之一些的彼等前驅物未能解決其他挑戰且此導致消費者中的驚恐可能及含有該等前驅物的產品之可能不良審查。儘管此等顯著缺點,可在工業設施處或在家庭中堆肥的材料理論上將用於在可再生、可持續,及綠色製造中開始產品。Therefore, where possible, in order to reduce the destructive footprint that often accompanies the manufacturing process, the materials and manufacturing process should be formulated in a way that allows the preparation of compost after the end of the product's life. However, as indicated above, this is difficult because there are very limited commercially available biodegradable and synthesizable precursors. Those that do not exist are not necessarily designed and able to solve all of the combined challenges of performance and long-term availability, and are easily composted and biodegradable in a controlled setting at the end of their useful life. Their precursors that solve some of the aforementioned challenges fail to solve other challenges and this leads to panic among consumers and possible bad reviews of products containing these precursors. Despite these significant shortcomings, materials that can be composted at industrial facilities or in the home will theoretically be used to start products in renewable, sustainable, and green manufacturing.
本製造製程之另一態樣係關於可撓性發泡體之生產。可撓性發泡體為藉由將氣包捕獲在液體或固體中形成的一類型物件,藉此所得發泡體部分由於其展性而據稱為可撓性的。可撓性發泡體通常使用在諸如鞋類、家具、墊料及其他運動商品之緩衝應用中。可撓性發泡體通常分成兩個種類:封閉氣孔可撓性熱塑性聚合物發泡體及開放氣孔可撓性聚氨酯發泡體。此等發泡體類型中每一個具有非常不同的製造方法。Another aspect of this manufacturing process concerns the production of flexible foams. Flexible foam is a type of object formed by trapping air pockets in liquid or solid, whereby the resulting foam part is said to be flexible due to its malleability. Flexible foams are commonly used in cushioning applications such as footwear, furniture, padding and other sports goods. Flexible foams are generally divided into two types: closed-cell flexible thermoplastic polymer foams and open-cell flexible polyurethane foams. Each of these foam types has very different manufacturing methods.
封閉氣孔可撓性熱塑性聚合物發泡體通常在乾式製程中生產,其中合適的人工聚合物經選擇且與各種化學添加劑、交聯劑及化學發泡劑摻和以用於生產「麵糰」,該麵糰然後揉合且擠製成平坦薄板。薄板然後堆疊在彼此之頂部上且在受控制的壓力下置放於熱壓機中。材料及化學發泡劑之此混合物在熱壓機空腔內側反應且膨脹。結果為然後經切片至厚度的封閉氣孔可撓性發泡體「圓髻」或「方塊」。相反,開放氣孔可撓性聚氨酯發泡體通常生產於液體澆注製程或液體模製成形製程中,其中人工聚醇、異氰酸鹽化學品及其他化學添加劑在經澆鑄或注射成模製成形形狀諸如「圓髻」或「方塊」時一起反應。結果為然後切片至厚度的開放氣孔可撓性發泡體。Closed-pore flexible thermoplastic polymer foams are usually produced in a dry process, in which suitable artificial polymers are selected and blended with various chemical additives, crosslinking agents and chemical foaming agents for the production of "dough", The dough is then kneaded and extruded into a flat sheet. The sheets are then stacked on top of each other and placed in a heat press under controlled pressure. This mixture of material and chemical blowing agent reacts and expands inside the cavity of the heat press. The result is a "round bun" or "square" of a closed pore flexible foam that is then sliced to a thickness. In contrast, open-cell flexible polyurethane foams are usually produced in a liquid casting process or a liquid molding process, in which artificial polyols, isocyanate chemicals and other chemical additives are cast or injected into a molded shape. Such as "round bun" or "square" when reacting together. The result is an open-cell flexible foam that is then sliced to thickness.
與以上內容一致,現今市場上目前可利用的可撓性發泡體之問題中之一個在於該等可撓性發泡體在其製造中幾乎僅使用不可再生材料及有害化學物品。此外,部分由於發生在製造習知可撓性發泡體之以上所描述的方法中的化學交聯,彼等可撓性發泡體之物理結構不能堆肥、生物降解,或回收。此在很大程度上由於其設計之化學組成及其不能分離回成其根前驅物構成。亦即,在習知可撓性發泡體壽命終止時,該習知可撓性發泡體沒有進一步使用且不能以任何已知的商業上可利的方法成功地重新處理成新材料。Consistent with the above content, one of the problems with the flexible foams currently available on the market is that these flexible foams almost only use non-renewable materials and hazardous chemicals in their manufacture. In addition, due in part to the chemical cross-linking that occurs in the above-described methods of manufacturing conventional flexible foams, the physical structure of these flexible foams cannot be composted, biodegraded, or recycled. This is largely due to its designed chemical composition and its inability to separate back into its root precursor composition. That is, at the end of the life of the conventional flexible foam, the conventional flexible foam is not used further and cannot be successfully reprocessed into a new material by any known commercially advantageous method.
因此,鑒於以上內容,本文所呈現的是可撓性發泡體及製造製程,該等可撓性發泡體及製造製程可經利用來生產終端產品,該等終端產品為可再生的、可持續的及/或環境上可解釋的,該等材料及終端產品能夠持續使用,無斷裂,但在壽命終止之後快速降解且堆肥。可撓性發泡體及半可撓性發泡體兩者可包括在相同種類的可撓性發泡體下,因為其兩者源自於具有低於其服務溫度之玻璃轉變(Tg)之聚合物,該服務溫度通常在室溫處。以下在伴隨描述中且關於所呈現圖式及其特徵闡述一或多個實施例之細節。其他特徵及優點將自說明書、圖式兩者及且自申請專利範圍顯而易見。Therefore, in view of the above content, this article presents flexible foams and manufacturing processes. These flexible foams and manufacturing processes can be used to produce end products. These end products are renewable and renewable. Continuous and/or environmentally explainable, these materials and end products can be used continuously without breakage, but quickly degrade and compost after the end of their life. Both the flexible foam and the semi-flexible foam can be included in the same kind of flexible foam because they are derived from having a glass transition (Tg) lower than their service temperature. For polymers, the service temperature is usually at room temperature. The details of one or more embodiments are set forth below in the accompanying description and regarding the presented drawings and their features. Other features and advantages will be apparent from both the description and the drawings and the scope of the self-applied patent.
本文件呈現用於由生物可降解且工業上可合成之熱塑性樹脂修改射出模製成形微氣孔發泡各種可撓性發泡體組成之製程。目前,世界上幾乎所有已知的可撓性發泡體源自於不可再生原料,且若非全部,大多數可撓性發泡體並不生物降解或工業堆肥。本發明之目的將生產可撓性發泡體,該等可撓性發泡體引起最少量的環境危害,但亦擁有等於或大於習知生物不可降解石化可撓性發泡體之彼技術效能性質的顯著技術效能性質。藉由選擇生產生物聚合物的工廠衍生原料,本發明有助於自大氣螫合溫室氣體,大大地降低對不可再生石油之依賴性,且顯著地減少每年終止於掩埋場中的生物不可降解廢棄物。This document presents a process for the modification of injection molding of biodegradable and industrially synthesizable thermoplastic resins to form various flexible foams with micro-pores. At present, almost all known flexible foams in the world are derived from non-renewable raw materials, and if not all, most flexible foams are not biodegradable or industrially composted. The purpose of the present invention is to produce flexible foams that cause the least amount of environmental hazards, but also have technical performance equal to or greater than that of conventional non-degradable petrochemical flexible foams Significant technical effectiveness of nature. By selecting plant-derived raw materials for the production of biopolymers, the present invention helps to sequester greenhouse gases from the atmosphere, greatly reduces the dependence on non-renewable petroleum, and significantly reduces the bio-non-degradable waste that ends in landfills every year Things.
在各種實施例中,由此生產的可撓性發泡體可經組配來工業上堆肥,而非家庭堆肥,但設想家庭堆肥在一些實例中可具有用途,取決於市場。在各種實例中,工業堆肥係有用的,因為其確保可撓性發泡體將持續該可撓性發泡體功能化成且在成品內在使用中不斷裂或破碎的所得產品之可用壽命。例如,一個人購買僅由本發明之可撓性發泡體製成以使發泡體在鞋之可用壽命終止之前的正常使用期間降解的一雙鞋將為有害的。In various embodiments, the flexible foams thus produced can be formulated to be industrially composted instead of home composting, but it is envisaged that home composting may have uses in some instances, depending on the market. In various instances, industrial composting is useful because it ensures that the flexible foam will continue the useful life of the resultant product that is functionalized into the flexible foam and does not break or break during use in the finished product. For example, it would be harmful for a person to purchase a pair of shoes made only of the flexible foam of the present invention so that the foam degrades during normal use before the end of the useful life of the shoe.
因此,在一個態樣中,製造生物可降解且工業上可合成之可撓性發泡體(無論開放氣孔或封閉氣孔)之製程可在本文中經提供且可包括以下步驟中一或多個:生產用於發泡的熱塑性生物聚合物摻和母料;將熱塑性生物聚合物摻合物射出模製成形成具有惰性氮氣之合適的模具形狀;使用動態模具溫度控制來確保最佳氣孔結構;控制生物聚合物熔體、壓力及時間,使得合意的可撓性發泡體經形成;以及利用射出模製成形製程中之氣體反壓力來確保具有發泡零件外側上的最少量外表缺陷及少量直至無塑膠表皮的最佳發泡體結構。Therefore, in one aspect, the process for manufacturing a biodegradable and industrially synthesizable flexible foam (regardless of open or closed pores) can be provided herein and can include one or more of the following steps : Production of thermoplastic biopolymer blend masterbatch for foaming; injection molding of thermoplastic biopolymer blend into a suitable mold shape with inert nitrogen; dynamic mold temperature control to ensure the best pore structure; Control the biopolymer melt, pressure and time so that the desired flexible foam is formed; and use the gas back pressure in the injection molding process to ensure that there are the smallest number of surface defects and a few on the outside of the foamed part The best foam structure until there is no plastic skin.
與謹慎選擇的生物衍生、可再生的且可回收原料一致,本揭示案之製造進程導致環境友好的閉環製程。此閉環製程始於材料選擇。例如,第三方證明可合成的惰性且快速可再生聚合物原料之選擇確保堅持循環經濟之原理。出於此等目的,選定的快速可再生聚合物原料作為可再生植物或礦物質之形式開始其壽命。一旦轉換成合適的聚合物,此等環境上可解釋的前驅物可與其他環境上可解釋的前驅物及成分組合,用於功能化成定製生物聚合物化合物,該定製生物聚合物化合物可經利用於所揭示的製造製程中。Consistent with carefully selected bio-derived, renewable and recyclable raw materials, the manufacturing process of this disclosure leads to an environmentally friendly closed-loop process. This closed-loop process begins with material selection. For example, the selection of inert and rapidly renewable polymer materials that can be synthesized by third parties ensures that the principles of circular economy are adhered to. For these purposes, the selected fast renewable polymer raw material begins its life as a form of renewable plants or minerals. Once converted into suitable polymers, these environmentally interpretable precursors can be combined with other environmentally interpretable precursors and ingredients for functionalization into custom biopolymer compounds that can be Used in the disclosed manufacturing process.
具體而言,一旦合適的生物聚合物化合物經產生,其在本揭示案之無化學品製造方法中經處理。所得可撓性發泡體係無交聯的,且在許多實例中,為生物可降解且可合成的。因此,在其可用壽命終止時,此等生產的發泡體可經謹慎地磨碎成小塊且在限定的設施中工業堆肥以用於將其組成物分解(例如,100%)回成可用生物質。此可用生物質然後可用來生長更惰性且快速可再生的聚合物原料材料,且製程循環迴路地繼續。因此,此文件描述生物可降解且工業上可合成之微氣孔可撓性發泡體及製造該生物可降解且工業上可合成之微氣孔可撓性發泡體之方法。發泡體可為封閉氣孔發泡體,但亦可能形成為開放氣孔發泡體。Specifically, once a suitable biopolymer compound is produced, it is processed in the chemical-free manufacturing method of this disclosure. The resulting flexible foaming system is non-crosslinked, and in many instances, is biodegradable and synthesizable. Therefore, at the end of its usable life, the foams produced can be carefully pulverized into small pieces and industrially composted in a limited facility to decompose their constituents (for example, 100%) back into usable Biomass. This usable biomass can then be used to grow more inert and rapidly renewable polymer feedstock materials, and the process continues in a loop. Therefore, this document describes a biodegradable and industrially synthesizable microporous flexible foam and a method for manufacturing the biodegradable and industrially synthesizable microporous flexible foam. The foam may be a closed-cell foam, but it may also be formed as an open-cell foam.
在各種實行方案中,生物可降解且工業上可合成之可撓性發泡體可經使得具有習知石化乙烯乙酸乙烯酯(ethylene vinyl acetate; EVA)發泡體等等之相同性質及特性,且仍含有高百分比的生物質碳含量。例如,可撓性EVA發泡體係現今使用在工業中的普存材料。使得EVA發泡體如此盛行的事物係其相對低的成本及處理之容易性,同時維持用於給定產品之通常可接受的技術效能性質。EVA發泡體使用之下側為許多。材料通常源自於不可再生原料,且其與化學發泡劑化學交聯以用於生產並非容易地生物可降解、可合成或可回收的可撓性發泡體。In various implementation schemes, biodegradable and industrially synthesizable flexible foams can be made to have the same properties and characteristics as conventional petrochemical ethylene vinyl acetate (EVA) foams, etc., And still contains a high percentage of biomass carbon content. For example, flexible EVA foaming systems are now commonly used materials in the industry. What makes EVA foam so popular is its relatively low cost and ease of handling, while maintaining the generally acceptable technical performance properties for a given product. EVA foam is used for many undersides. The materials are usually derived from non-renewable raw materials and are chemically cross-linked with chemical blowing agents for the production of flexible foams that are not easily biodegradable, synthesizable, or recyclable.
存在可取決於所要的物理性質及產品之預定最終使用面利用的許多組態及實施例,該等組態及實施例不應受本揭示案限制。There are many configurations and embodiments that can be utilized depending on the desired physical properties and the intended end-use surface of the product, and these configurations and embodiments should not be limited by this disclosure.
使本文呈現的進步如此有用的一個因素在於生物可降解發泡體以類似於EVA的方式執行,且如此,其技術效能性質類似於EVA之彼技術效能性質而無化學添加劑及交聯。結果為商業上可接受的可撓性發泡體,該可撓性發泡體可為用於普存EVA之偶入替換,但彼可撓性發泡體提供大大降低的環境衝擊及環境上可解釋的受管理的壽命終止解決方案。One factor that makes the progress presented herein so useful is that the biodegradable foam performs in a manner similar to EVA, and as such, its technical performance properties are similar to those of EVA without chemical additives and cross-linking. The result is a commercially acceptable flexible foam. The flexible foam can be used as an occasional replacement for universal EVA, but the flexible foam provides greatly reduced environmental impact and environmental impact. Explainable managed end-of-life solutions.
因此,在一個態樣中,提供用於製造生物可降解且工業上可合成之可撓性發泡體模製成形產品之方法。在各種實例中,方法可包括以下步驟中一或多個。例如,方法可包括引入熱塑性生物聚合物摻和母料以用於發泡至模製成形設備之桶中。方法可另外包括在溫度及壓力條件下將流體引入桶中以生產超臨界流體,該超臨界流體在與熱塑性生物聚合物摻和母料接觸時生產熱塑性發泡熔體。此外,方法可包括將熱塑性發泡熔體注射至合適的模具形狀之空腔中,及將氣體反壓力施加至空腔。最後,空腔可經冷卻以生產模製成形的產品。Therefore, in one aspect, a method for manufacturing a biodegradable and industrially synthesizable flexible foam molded product is provided. In various examples, the method may include one or more of the following steps. For example, the method may include the introduction of a thermoplastic biopolymer blend masterbatch for foaming into the barrel of a molding device. The method may additionally include introducing the fluid into the barrel under temperature and pressure conditions to produce a supercritical fluid that produces a thermoplastic foamed melt when in contact with the thermoplastic biopolymer blend masterbatch. In addition, the method may include injecting a thermoplastic foamed melt into a cavity of a suitable mold shape, and applying a gas back pressure to the cavity. Finally, the cavity can be cooled to produce a molded product.
在各種實例中,熱塑性生物聚合物母料中一或多個之引入係藉由澆口襯套,諸如其中熱塑性生物聚合物摻和母料藉由雙螺桿擠出機生產。在一個實施例中,熱塑性生物聚合物摻和母料包括聚乳酸(polylactide acid;PLA)、聚羥基脂肪酸酯(polyhydroxyalkanoate;PHA)、乙酸纖維素(cellulose acetate;CA)、澱粉,及石油衍生熱塑性塑膠中一或多個。在各種實例中,流體係藉由計量單元引入桶中。在具體實例中,超臨界流體包括氮及二氧化碳中一或多個。超臨界流體可在壓力下且在溫度處引入,諸如其中壓力範圍自約150巴至約300巴,且溫度範圍自約150℃至約350℃。同樣地,氣體反壓力範圍自約5巴至約50巴,施加介於1秒至25秒之間的時間長度。在某些實例中,溫度可藉由動態模具溫度控制加以控制。In various examples, the introduction of one or more of the thermoplastic biopolymer masterbatch is through a sprue bushing, such as where the thermoplastic biopolymer blending masterbatch is produced by a twin screw extruder. In one embodiment, the thermoplastic biopolymer blending masterbatch includes polylactide acid (PLA), polyhydroxyalkanoate (PHA), cellulose acetate (CA), starch, and petroleum derivatives. One or more of thermoplastics. In various instances, the flow system is introduced into the barrel by a metering unit. In a specific example, the supercritical fluid includes one or more of nitrogen and carbon dioxide. The supercritical fluid may be introduced under pressure and at temperature, such as where the pressure ranges from about 150 bar to about 300 bar, and the temperature ranges from about 150°C to about 350°C. Likewise, the gas back pressure ranges from about 5 bar to about 50 bar, and is applied for a length of time between 1 second and 25 seconds. In some instances, the temperature can be controlled by dynamic mold temperature control.
另外,在另一態樣中,提供用於生產生物可降解且工業上可合成之可撓性發泡體模製成形的產品之射出模製成形設備。在各種實例中,射出模製成形設備可包括以下中一或多個。可包括漏斗,諸如其中漏斗經組配來用於將複數個熱塑性生物聚合物接收且引入模製成形設備中,諸如其中熱塑性生物聚合物形成將要摻和的母料。In addition, in another aspect, an injection molding device is provided for producing biodegradable and industrially synthesizable flexible foam molded products. In various examples, the injection molding equipment may include one or more of the following. A funnel may be included, such as where the funnel is configured to receive and introduce a plurality of thermoplastic biopolymers into a molding device, such as where the thermoplastic biopolymer forms a masterbatch to be blended.
可包括計量單元,諸如其中計量單元經組配來用於接收流體,且在條件下將所接收流體引入模製設備中以便在該引入後生產超臨界流體。模製成形設備可包括桶,該桶具有第一空腔,該第一空腔經組配來用於接收摻和熱塑性生物聚合物母料及流體,使得當它們經引入桶時,當超臨界流體接觸桶之空腔內的摻和熱塑性生物聚合物母料時,熱塑性發泡熔體經生產。氣體反壓力輸送單元亦可經包括,其中GCP經組配來用於將氣體反壓力輸送至第一空腔以便控制發泡熔體之膨脹。另外,亦可包括具有與桶之空腔流體連通的空腔之模具,其中模具之空腔經組配來用於接收發泡熔體且當熔體經冷卻時生產可撓性發泡體模製成形的產品。A metering unit may be included, such as where the metering unit is configured to receive the fluid and, under conditions, introduce the received fluid into the molding equipment so as to produce the supercritical fluid after the introduction. The molding apparatus may include a barrel with a first cavity configured to receive the blended thermoplastic biopolymer masterbatch and fluid so that when they are introduced into the barrel, the supercritical fluid When contacting the blended thermoplastic biopolymer masterbatch in the cavity of the barrel, the thermoplastic foamed melt is produced. The gas back pressure delivery unit may also be included, wherein the GCP is configured to deliver the gas back pressure to the first cavity so as to control the expansion of the foamed melt. In addition, it may also include a mold having a cavity in fluid communication with the cavity of the barrel, wherein the cavity of the mold is configured to receive the foamed melt and produce a flexible foaming mold when the melt is cooled. Shaped products.
在各種實施例中,射出模製成形設備可包括往復螺桿,該往復螺桿經組配來壓縮桶之空腔內之發泡熔體,且將壓縮發泡熔體運送至模具之空腔中。因此,可存在桶之空腔與模具之空腔之間的導管,其中導管包括噴嘴,該噴嘴具有澆口襯套以便在桶與模具之間形成密封件。In various embodiments, the injection molding equipment may include a reciprocating screw that is configured to compress the foamed melt in the cavity of the barrel and transport the compressed foamed melt to the cavity of the mold. Therefore, there may be a duct between the cavity of the barrel and the cavity of the mold, where the duct includes a nozzle with a sprue bushing to form a seal between the barrel and the mold.
因此,射出模製成形設備可包括以下中一或多個:漏斗,熱塑性材料以小丸之形式供應至鑄模機。射出模製成形機上的漏斗保持此等小丸。小丸可經由漏斗喉道自漏斗重力進料至桶及螺桿總成中。亦可包括桶,其中射出模製成形機之桶支撐往復增塑螺桿,且可藉由電加熱器帶材加熱。Therefore, the injection molding equipment may include one or more of the following: a hopper, where the thermoplastic material is supplied to the molding machine in the form of pellets. The funnel on the injection molding machine holds these pellets. The pellets can be gravity fed from the funnel to the barrel and screw assembly through the funnel throat. It can also include a barrel, where the barrel of the injection molding machine supports a reciprocating plasticizing screw and can be heated by an electric heater strip.
往復螺桿亦可存在,其中往復螺桿用來壓縮、熔化,且運送材料。往復螺桿可包括三個區帶:進料區帶、壓縮(或轉變)區帶、及計量區帶。亦可存在噴嘴,其中噴嘴將桶連接至模具之澆口襯套且在桶與模具之間形成密封件。噴嘴之溫度可經設定至材料之熔融溫度或僅低於該熔融溫度。當桶處於其完全向前處理位置中時,噴嘴之半徑可嵌套且密封在具有定位環之澆口襯套中之凹形半徑中。在桶之清洗期間,桶可自澆口收回,如此沖洗化合物可自噴嘴自由降落。Reciprocating screws can also exist, where the reciprocating screws are used to compress, melt, and transport materials. The reciprocating screw can include three zones: a feed zone, a compression (or conversion) zone, and a metering zone. There may also be nozzles where the nozzle connects the barrel to the sprue bushing of the mold and forms a seal between the barrel and the mold. The temperature of the nozzle can be set to the melting temperature of the material or just below the melting temperature. When the barrel is in its fully forward processing position, the radius of the nozzle can be nested and sealed in the concave radius in the sprue bushing with the positioning ring. During the cleaning of the barrel, the barrel can be retracted from the sprue so that the flushing compound can fall freely from the nozzle.
另外,亦可提供模具及液壓系統。模具系統可包括綁帶條、固定及移動平台,以及容置空腔的模製成形板(基底)、澆口及澆道系統、射出器插腳、加熱及冷卻通道、及溫度感測器及壓力感測器。模具實質上為熱交換器,其中熔融熱塑性塑膠固化至所要的形狀及藉由空腔限定的尺寸細節。液壓系統亦可存在於射出模製成形機上,以便提供功率以打開且關閉模具,構建且保持夾持噸數,轉動往復螺桿,驅動往復螺桿,且激發射出器插腳及移動模具核心。需要許多液壓組件以提供此功率,該等液壓組件包括泵、閥、液壓馬達、液壓配件、液壓管道及液壓儲器。In addition, molds and hydraulic systems can also be provided. The mold system can include straps, fixed and mobile platforms, and a molded plate (substrate) containing a cavity, gate and runner system, ejector pins, heating and cooling channels, and temperature sensors and pressure Sensor. The mold is essentially a heat exchanger in which the molten thermoplastic solidifies to the desired shape and dimensional details defined by the cavity. The hydraulic system can also exist on the injection molding machine to provide power to open and close the mold, build and maintain the clamping tonnage, rotate the reciprocating screw, drive the reciprocating screw, and excite the ejector pins and move the mold core. Many hydraulic components are needed to provide this power, including pumps, valves, hydraulic motors, hydraulic fittings, hydraulic pipes, and hydraulic reservoirs.
亦可提供控制系統。控制系統可經組配來在機器操作中提供一致性及可重複性。控制系統監視且控制處理參數,包括溫度、壓力、超臨界流體(supercritical fluid;SCF)配料、射出速度、螺桿速度及位置、及液壓位置。製程控制可具有對最終零件品質及製程之經濟性之直接影響。製程控制系統範圍可自簡單轉播接通/斷開控制至極其複雜的基於微處理器之閉環控制。A control system can also be provided. The control system can be configured to provide consistency and repeatability in machine operation. The control system monitors and controls processing parameters, including temperature, pressure, supercritical fluid (SCF) batching, injection speed, screw speed and position, and hydraulic position. Process control can have a direct impact on the quality of the final part and the economics of the process. The process control system can range from simple relay on/off control to extremely complex microprocessor-based closed-loop control.
亦可提供夾持系統。夾持系統可經組配來打開且關閉模具,支撐且運載模具之構成零件,且產生充分的力以防止模具打開。夾持力可藉由機械(雙態觸變)鎖、液壓鎖,或兩個基本類型之組合產生。亦可提供輸送系統。提供用於熔融塑膠自機器噴嘴至零件空腔之通路的輸送系統通常包括:澆口、冷料井、主澆道、分支澆道、閘等等。A clamping system can also be provided. The clamping system can be assembled to open and close the mold, support and carry the component parts of the mold, and generate sufficient force to prevent the mold from opening. The clamping force can be generated by a mechanical (two-state thixotropic) lock, a hydraulic lock, or a combination of the two basic types. Conveying system can also be provided. The conveying system that provides a path for molten plastic from the machine nozzle to the part cavity usually includes: gates, cold slug wells, main runners, branch runners, gates, and so on.
因此,在又一態樣中,提供用於生產生物可降解且工業上可合成之可撓性發泡體模製成形的產品之系統。系統可包括用於生產如以上所描述之生物可降解且工業上可合成之可撓性發泡體模製成形的產品之射出模製成形設備。系統另外可包括超臨界氣體配料系統,該超臨界氣體配料系統經組配來用於接收流體且在條件下將所接收流體引入桶之第一空腔中,以便在該引入後生產超臨界流體,當超臨界流體接觸第一空腔內之摻和熱塑性生物聚合物母料時,超臨界流體生產發泡熔體。系統可進一步包括動態溫度控制系統,該動態溫度控制系統經組配來用於控制第一空腔及第二空腔中一或多個內之溫度。經組配來用於將氣體反壓力輸送至第一空腔以便控制發泡熔體之膨脹的氣體反壓力輸送單元亦可經包括。另外,可包括具有一或多個微處理器之控制單元,其中控制單元經組配來用於根據一或多個系統參數控制射出模製成形設備、超臨界氣體配料系統、動態溫度控制系統、及氣體反壓力輸送單元。Therefore, in yet another aspect, a system for producing biodegradable and industrially synthesizable flexible foam molded products is provided. The system may include injection molding equipment for producing biodegradable and industrially synthesizable flexible foam molded products as described above. The system may additionally include a supercritical gas batching system that is configured to receive fluid and introduce the received fluid into the first cavity of the barrel under conditions so as to produce supercritical fluid after the introduction When the supercritical fluid contacts the blended thermoplastic biopolymer masterbatch in the first cavity, the supercritical fluid produces a foamed melt. The system may further include a dynamic temperature control system configured to control the temperature in one or more of the first cavity and the second cavity. A gas back pressure delivery unit configured to deliver the gas back pressure to the first cavity so as to control the expansion of the foamed melt may also be included. In addition, it may include a control unit with one or more microprocessors, wherein the control unit is configured to control injection molding equipment, supercritical gas batching system, dynamic temperature control system, And gas back pressure delivery unit.
具體而言,系統組件可包括射出模製成形機系統,該射出模製成形機系統包括漏斗、桶、往復螺桿、噴嘴、模具系統、液壓系統、控制系統、夾持系統、及輸送系統。SCF氣體配料系統可經包括且包括諸如氮的惰性氣體之罐、空氣壓縮機、SCF計量及控制裝置、SCF噴射器、及特別設計的往復螺桿,及前單向閥及後單向閥兩者。動態溫度控制系統亦可經提供且包括加熱單元、冷卻單元、順序閥、及電腦控制。另外,存在位於模具之主體內的加熱元件及冷卻通道,該等加熱元件及冷卻通道藉由動態溫度控制系統進料,加熱介質或冷卻介質藉由該動態溫度控制系統循環。其功能為模具表面上之溫度調節。且可提供氣體反壓力系統,其中該氣體反壓力系統包括例如惰性氣體諸如氮的氣體之罐、空氣壓縮機、氣體泵、氣體釋放閥、氣體壓力感測器、及電腦控制。Specifically, the system components may include an injection molding machine system including a hopper, a barrel, a reciprocating screw, a nozzle, a mold system, a hydraulic system, a control system, a clamping system, and a conveying system. The SCF gas batching system can include and include inert gas tanks such as nitrogen, air compressors, SCF metering and control devices, SCF injectors, and specially designed reciprocating screws, and both front and rear check valves . Dynamic temperature control system can also be provided and includes heating unit, cooling unit, sequence valve, and computer control. In addition, there are heating elements and cooling channels located in the main body of the mold. The heating elements and cooling channels are fed by a dynamic temperature control system, and the heating or cooling medium is circulated by the dynamic temperature control system. Its function is temperature regulation on the mold surface. And a gas back pressure system can be provided, where the gas back pressure system includes, for example, a tank of inert gas such as nitrogen, an air compressor, a gas pump, a gas release valve, a gas pressure sensor, and computer control.
系統及/或其任何子系統可包括一或多個感測器,諸如包括溫度、壓力、加速度計、迴轉儀及定向感測器,諸如其中一或多個感測器經組配來用於與諸如射出模製成形設備之一或多個空腔內的射出模製成形裝置之其他組件中一或多個通訊地定位。在各種實施例中,感測器可為智慧感測器且包括通訊模組,諸如具有網路連接,以便執行無線通訊。因此,系統及/或其各種零件中之任何零件可包括通訊模組,該通訊模組可耦接至控制模組、超臨界氣體配料系統、動態控制溫度系統、及氣體反壓力控制單元中一或多個,諸如其中通訊模組經組配來用於執行一或多個無線通訊協定包括WIFI、藍牙、低能藍牙,及3G、4G,及5G蜂巢式通訊。The system and/or any of its subsystems may include one or more sensors, such as temperature, pressure, accelerometer, gyroscope, and orientation sensors, such as one or more sensors configured for Positioned in communication with one or more of the other components such as the injection molding device in one or more cavities of the injection molding device. In various embodiments, the sensor may be a smart sensor and include a communication module, such as having a network connection, so as to perform wireless communication. Therefore, any part of the system and/or its various parts may include a communication module, which may be coupled to one of the control module, the supercritical gas batching system, the dynamic temperature control system, and the gas back pressure control unit. Or more, such as where the communication module is configured to perform one or more wireless communication protocols including WIFI, Bluetooth, Bluetooth Low Energy, and 3G, 4G, and 5G cellular communication.
在另一態樣中,本揭示案描述可回收微氣孔可撓性發泡體及產生該可回收微氣孔可撓性發泡體之方法。發泡體較佳地為封閉氣孔發泡體,但亦可能形成為開放氣孔發泡體。產生可回收微氣孔可撓性發泡體結構始於合適的高效能聚合物,諸如聚醯胺起源之彼等,等等。合適的聚合物之非限制實例為由Ascend Performance Materials, LLC, Houston, TX以Vydyne之商標名行銷的聚醯胺66共聚物。合適的聚合物之其他非限制實例包括許多聚醯胺嵌段共聚物,諸如聚醚-嵌段-醯胺(polyether-block-amide;PEBA)、PAE、TPA、TPE-A、COPA等等。前面提到的熱塑性聚合物已表明在形成本發明之最佳微氣孔可撓性發泡體結構中的有利技術性質。增強的技術性質中之一些包括異常老化性質、優良伸長、拉伸強度、及壓縮變形,以及其他效益。此外,回收原料可經利用於本發明之合適的可回收聚合物或聚合物摻合物之製造中。例如,在一個態樣中,可回收可撓性發泡體熱塑性聚合物包含源自於消費後或工業後回收的原料的至少一個單體或聚合物,該消費後或工業後回收的原料諸如己內醯胺、回收聚醚嵌段醯胺聚合物等等。藉由說明之方式,己內醯胺可藉由解聚合含有聚醯胺的工業後或消費後材料源自於此類回收的原料,該工業後或消費後材料諸如捕魚網、地毯纖維,或工業廢棄物。解聚合的消費後或工業後回收的己內醯胺之一些非限制實例包括由Aquafil USA Inc., Cartersville, Georgia提供的ECONYL®己內醯胺,無論呈片狀、液體或或熔融。熱塑性聚合物可另外或替代地包含源自於經收集、分類、熔化且再處理的工業後或消費後聚醯胺地毯纖維的聚醯胺聚合物。此之實例將使用經收集、分類、熔化,且再處理成升級再造(upcycled)的可用聚醯胺材料的工業後聚醯胺地毯纖維等等。源自於工業後地毯纖維的示範性聚醯胺聚合物為由the Aquafil USA Inc., Cartersville, Georgia製造的Econyl。另外,聚醯胺廢棄物以捕魚網或類似者之形式在世界海洋中或在世界海洋周圍收集,然後可經分類、熔化,且再處理成升級再造的可用聚醯胺材料。源自於所收集工業後捕魚網的示範性聚醯胺聚合物為由Koninklijke DSM N.V., Heerlen, the Netherlands製造的Akulon Repurposed。本發明之目的將在任何可能的情況下使用回收的聚合物原料。In another aspect, the present disclosure describes a recyclable microporous flexible foam and a method for producing the recyclable microporous flexible foam. The foam is preferably a closed-cell foam, but it may also be formed as an open-cell foam. The production of recyclable micro-pore flexible foam structure starts with suitable high-performance polymers, such as those of polyamide origin, and so on. A non-limiting example of a suitable polymer is polyamide 66 copolymer marketed by Ascend Performance Materials, LLC, Houston, TX under the trade name Vydyne. Other non-limiting examples of suitable polymers include many polyamide block copolymers, such as polyether-block-amide (PEBA), PAE, TPA, TPE-A, COPA, and the like. The aforementioned thermoplastic polymers have shown advantageous technical properties in forming the optimal microcellular flexible foam structure of the present invention. Some of the enhanced technical properties include abnormal aging properties, excellent elongation, tensile strength, and compression set, among other benefits. In addition, recycled raw materials can be utilized in the manufacture of suitable recyclable polymers or polymer blends of the present invention. For example, in one aspect, the recyclable flexible foam thermoplastic polymer contains at least one monomer or polymer derived from a post-consumer or post-industrial recycled raw material such as Caprolactam, recycled polyether block amide polymer, etc. By way of explanation, caprolactam can be derived from such recycled raw materials by depolymerizing post-industrial or post-consumer materials containing polyamide, such as fishing nets, carpet fibers, Or industrial waste. Some non-limiting examples of depolymerized post-consumer or post-industrial recovered caprolactam include ECONYL® caprolactam supplied by Aquafil USA Inc., Cartersville, Georgia, whether in flakes, liquid, or molten. Thermoplastic polymers may additionally or alternatively comprise polyamide polymers derived from post-industrial or post-consumer polyamide carpet fibers that have been collected, sorted, melted, and reprocessed. This example will use post-industrial polyamide carpet fibers that have been collected, sorted, melted, and reprocessed into upcycled usable polyamide materials. An exemplary polyamide polymer derived from post-industrial carpet fibers is Econyl manufactured by the Aquafil USA Inc., Cartersville, Georgia. In addition, polyamide waste is collected in or around the world's oceans in the form of fishing nets or the like, and then can be sorted, melted, and reprocessed into usable polyamide materials for upgrading. An exemplary polyamide polymer derived from collected post-industrial fishing nets is Akulon Repurposed manufactured by Koninklijke DSM N.V., Heerlen, the Netherlands. The purpose of the present invention is to use recycled polymer raw materials whenever possible.
最佳聚醯胺單獨不能在無合適的發泡劑及發泡製程的情況下生產可回收可撓性發泡體。現今使用的最廣泛已知的發泡劑為稱為偶氮二甲醯胺(azodicarbonamide;ADA)之化學品。ADA通常經預先浸漬至用於使用在習知射出模製成形發泡體製程中的習知熱塑性母料樹脂中。不幸地,ADA不是環境友好的,且其為可疑致癌物。此外,使用ADA的習知發泡製程在製造製程期間交聯且因此產生不可回收的可撓性發泡體之類型。為達成可回收可撓性發泡體,將惰性氮氣或二氧化碳用作修改後射出模製成形製程中之物理發泡劑。修改後物理發泡製程與合適的熱塑性聚合物或摻合聚合物母料一致地利用,使得聚合物或摻合聚合物及發泡劑針對可回收且可撓性發泡體協調地工作。本發明之較佳射出模製成形製程利用當聚合物及超臨界流體(SCF)之單相溶液經由射出閘傳送至修改後射出模製成形機之模具空腔中時發生的均質氣孔成核。在溶液進入模具時,壓力下降,使SCF自溶液出來,從而產生氣孔核。氣孔然後生長直至材料填充模具,且SCF之膨脹能力耗盡。此製造製程在射出模製成形機上運行,該等射出模製成形機已經修改以允許將SCF計量、輸送且混合至聚合物中以產生單相溶液。動態模具溫度控制(Dynamic mold temperature control; DMTC)經利用來確保膨脹聚合物熔體內之一致氣孔結構。DMTC可最佳地描述為位於模具之主體內的加熱元件及冷卻通道,該等加熱元件及冷卻通道藉由動態溫度控制系統進料,加熱介質或冷卻介質藉由該動態溫度控制系統循環。其功能為模具表面上之溫度調節。氣體反壓力(Gas counter pressure;GCP)亦在製程中利用來確保具有所得可撓性發泡體上之少量直至無表皮之最佳發泡體結構。GCP可最佳地描述為包括以氮氣注射以抵抗熔體內之氣體之膨脹的加壓模具空腔的製程。在反壓力經釋放時,將按照慣例突破表面的氣體氣泡經捕獲在內側,從而產生光滑表皮。GCP藉由表面品質、發泡體結構及表皮厚度控制發泡。The best polyamide alone cannot produce recyclable flexible foam without a suitable foaming agent and foaming process. The most widely known blowing agent used today is a chemical called azodicarbonamide (ADA). ADA is usually pre-impregnated into the conventional thermoplastic masterbatch resin used in the conventional injection molding foaming process. Unfortunately, ADA is not environmentally friendly, and it is a suspected carcinogen. In addition, the conventional foaming process using ADA is cross-linked during the manufacturing process and thus produces a type of non-recyclable flexible foam. In order to achieve recyclable flexible foam, inert nitrogen or carbon dioxide is used as the physical blowing agent in the modified injection molding process. The modified physical foaming process is used consistently with suitable thermoplastic polymers or polymer blending masterbatches, so that the polymer or blending polymer and foaming agent work in harmony with recyclable and flexible foams. The preferred injection molding process of the present invention utilizes homogeneous pore nucleation that occurs when a single-phase solution of polymer and supercritical fluid (SCF) is delivered to the mold cavity of the modified injection molding machine through the injection gate. When the solution enters the mold, the pressure drops, causing the SCF to come out of the solution, resulting in pore nuclei. The pores then grow until the material fills the mold and the expansion capacity of the SCF is exhausted. This manufacturing process runs on injection molding machines that have been modified to allow SCF to be metered, delivered, and mixed into the polymer to produce a single-phase solution. Dynamic mold temperature control (DMTC) is used to ensure a consistent pore structure in the expanded polymer melt. DMTC can be best described as heating elements and cooling channels located in the main body of the mold. The heating elements and cooling channels are fed by a dynamic temperature control system, and the heating or cooling medium is circulated through the dynamic temperature control system. Its function is temperature regulation on the mold surface. Gas counter pressure (GCP) is also used in the manufacturing process to ensure that the resulting flexible foam has a small amount to the best foam structure without skin. GCP can best be described as a process that includes a pressurized mold cavity that is injected with nitrogen to resist the expansion of the gas in the melt. When the back pressure is released, the gas bubbles that break through the surface as usual are trapped inside to produce a smooth skin. GCP controls foaming by surface quality, foam structure and skin thickness.
其中SCF完全溶解且均勻地分散在熔融聚合物中的單相溶液之產生在謹慎控制的製程條件下發生在射出桶之內側:SCF必須經精確地質量流量計量至聚合物中持續固定量的時間。且在配料週期之期間,必須在桶內建立正確的溫度、壓力及剪力條件。背壓、螺桿速度及桶溫度控制、以及氣體反壓力及SCF輸送系統全部在建立產生單相溶液的製程條件中起作用。The production of a single-phase solution in which SCF is completely dissolved and uniformly dispersed in the molten polymer occurs inside the injection barrel under carefully controlled process conditions: SCF must be accurately measured by mass flow to the polymer for a constant amount of time . And during the batching cycle, the correct temperature, pressure and shear conditions must be established in the barrel. Back pressure, screw speed and barrel temperature control, as well as gas back pressure and SCF delivery system all play a role in establishing the process conditions to produce a single-phase solution.
用來製造可回收且無化學品的可撓性發泡體的熱塑性聚合物可任擇地由許多聚醯胺或聚醯胺共聚物等等產生。合適的聚合物之非限制實例包括聚醯胺6、聚醯胺6/6-6、及聚醯胺12。替代地,熱塑性聚合物可包含許多聚醯胺嵌段共聚物,諸如聚醚-嵌段-醯胺(PEBA)、PAE、TPA、TPE-A、COPA等等。任何合適的聚合物類型可利用於本發明中,只要其滿足所需要的硬度、適度熔體流動、高伸長,及可再利用性。The thermoplastic polymer used to make the flexible foam that is recyclable and chemical-free can be optionally produced from many polyamides or polyamide copolymers and the like. Non-limiting examples of suitable polymers include polyamide 6, polyamide 6/6-6, and polyamide 12. Alternatively, the thermoplastic polymer may include many polyamide block copolymers, such as polyether-block-amide (PEBA), PAE, TPA, TPE-A, COPA, and the like. Any suitable polymer type can be used in the present invention as long as it meets the required hardness, moderate melt flow, high elongation, and reusability.
另外,二或更多個熱塑性聚合物之摻和物提供在單個熱塑性聚合物中未發現的性質及價格之組合。存在用以成功地將聚合物摻和在一起的許多方式。一個方法可使用雙螺桿擠製以使二或更多個聚合物樹脂熔融在一起且然後將熔融聚合物樹脂摻合物擠製成股,該股經冷卻且進料至造粒機中用於生產稱為母料的一系列造粒件。聚合物樹脂摻和之另一方法將使用增容劑來在聚合物摻合物中將不同化學成分接合在一起。此可使用雙螺桿擠製等等來在以上描述的非限制熱塑性聚合物類型中將增容劑及二或更多個聚合物熔融在一起。In addition, blends of two or more thermoplastic polymers provide a combination of properties and prices not found in a single thermoplastic polymer. There are many ways to successfully blend polymers together. One method can use twin screw extrusion to melt two or more polymer resins together and then extrude the molten polymer resin blend into strands that are cooled and fed into a pelletizer for Produce a series of pellets called master batches. Another method of polymer resin blending is to use compatibilizers to join the different chemical components together in the polymer blend. This can use twin screw extrusion or the like to melt the compatibilizer and two or more polymers together in the non-limiting thermoplastic polymer types described above.
在一個實施例中,方法包括藉由將發泡體解聚合成一或多個單體來回收前述可撓性發泡體之步驟。解聚合製程包括以下步驟:將可回收發泡體之熱塑性聚合物與廢棄物機械地分離,將解聚合催化劑引入至分離的熱塑性聚合物,加熱熱塑性聚合物及催化劑以產生餾出物,將水及所得單體與其他副產品分離,氧化含水單體,濃縮氧化含水單體,純化濃縮單體,及再聚合單體以產生用於使用在製作可回收可撓性發泡體之方法中的熱塑性聚合物。所得單體可包括己內醯胺或可再聚合成熱塑性聚合物的其他單體。In one embodiment, the method includes the step of recovering the aforementioned flexible foam by depolymerizing the foam into one or more monomers. The depolymerization process includes the following steps: mechanically separate the thermoplastic polymer of the recyclable foam from the waste, introduce the depolymerization catalyst into the separated thermoplastic polymer, heat the thermoplastic polymer and the catalyst to produce distillate, and remove the water And the obtained monomers are separated from other by-products, oxidized water-containing monomers, concentrated and oxidized water-containing monomers, purified and concentrated monomers, and repolymerized monomers to produce thermoplasticity used in the method of making recyclable flexible foams polymer. The resulting monomers can include caprolactam or other monomers that can be repolymerized into thermoplastic polymers.
取決於應用,添加劑亦可經利用於聚合物配方中。例如,填料諸如沉澱碳酸鈣、鮞狀霰石、澱粉、生物質等等可經利用來降低零件成本,同時維持完成可撓性發泡體之可回收完整性。Depending on the application, additives can also be utilized in polymer formulations. For example, fillers such as precipitated calcium carbonate, oolitic aragonite, starch, biomass, etc. can be used to reduce the cost of parts while maintaining the recyclable integrity of the finished flexible foam.
再者,用於使用在聚合物配方中之額外添加劑可包含以下中一或多個。可包括成核劑,諸如微葉片狀滑石或高深寬比鮞狀霰石。此類成核劑可藉由防止氣孔聚結、降低塊體密度,且改良回彈性以及其他有益地增強之屬性大大地改良所得可撓性發泡體之關鍵性質。用於使用在生產可回收且無化學品的射出模製成形的微氣孔可撓性發泡體之成核劑之若干非限制實例為由Imerys Talc America Inc., Houston, Texas作為Mistrocell®行銷的微葉片狀滑石及由Calcean Minerals & Materials LLC, Gadsden, Alabama作為OceanCal®行銷的高深寬比鮞狀霰石。Furthermore, the additional additives used in the polymer formulation may include one or more of the following. Nucleating agents may be included, such as microlobed talc or high aspect ratio oolitic aragonite. Such nucleating agents can greatly improve the key properties of the resultant flexible foam by preventing pore coalescence, reducing block density, and improving resilience and other beneficially enhanced properties. Several non-limiting examples of nucleating agents used in the production of recyclable and chemical-free injection molded microporous flexible foams are those marketed by Imerys Talc America Inc., Houston, Texas as Mistrocell® Microlobed talc and high aspect ratio oolitic aragonite marketed by Calcean Minerals & Materials LLC, Gadsden, Alabama as OceanCal®.
亦可包括著色劑、染料及顏料。例如,各種著色劑諸如染料或顏料可使用在本發明之聚合物配方中。若干非限制實例為已經定製來用於特定類型的熱塑性聚合物使用的顏料,諸如由Treffert GmBH & Co. KG, Bingen am Rhein, Germany提供的寬範圍或由Holland Colours Americas Inc., Richmond, Indiana提供的彼等。It may also include colorants, dyes and pigments. For example, various coloring agents such as dyes or pigments can be used in the polymer formulation of the present invention. Several non-limiting examples are pigments that have been customized for use with specific types of thermoplastic polymers, such as the wide range provided by Treffert GmBH & Co. KG, Bingen am Rhein, Germany or by Holland Colours Americas Inc., Richmond, Indiana Provided by them.
一或多個實施例之細節在以下伴隨描述中闡述。其他特徵及優點將自描述且自申請專利範圍顯而易見。The details of one or more embodiments are set forth in the accompanying description below. Other features and advantages will be self-descriptive and self-applying patent scope is obvious.
此文件描述生物可降解且工業上可合成之微氣孔可撓性發泡體、可回收微氣孔可撓性發泡體及製造該生物可降解且工業上可合成之微氣孔可撓性發泡體、該可回收微氣孔可撓性發泡體之方法。發泡體較佳地為封閉氣孔發泡體,但亦可能形成為開放氣孔發泡體。在各種實行方案中,生物可降解且工業上可合成且可回收可撓性發泡體可經使得具有習知石化乙烯乙酸乙烯酯(EVA)發泡體等之相同性質及特性,且仍含有高百分的生物量碳含量。 [生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體及用於製造所述生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之方法]This document describes the biodegradable and industrially synthesizable micro-pore flexible foam, the recyclable micro-pore flexible foam, and the production of the biodegradable and industrially-synthesizable micro-pore flexible foam Body, the method for recovering micro-pore flexible foam. The foam is preferably a closed-cell foam, but it may also be formed as an open-cell foam. In various implementation schemes, biodegradable, industrially synthesizable and recyclable flexible foams can be made to have the same properties and characteristics as conventional petrochemical ethylene vinyl acetate (EVA) foams, etc., and still contain High percentage of biomass carbon content. [Biodegradable and industrially synthesizable injection-molded flexible foam and micro-porous flexible foam used to manufacture the biodegradable and industrially synthesizable injection-molded flexible foam Body method]
本揭示案係關於用於生產生物可降解且工業上可合成之微氣孔可撓性發泡體之製程及製造所述生物可降解且工業上可合成之微氣孔可撓性發泡體之方法。如以上所論述,發泡描述涉及液體或固體中之氣包之捕獲的製程。通常,工業使用發泡來生產輕質聚合物材料。此為用於許多類型的產品之有利解決方案,因為發泡材料給予大量附加價值,諸如軟式緩衝、舒適度,及衝擊保護等。The present disclosure relates to a process for producing biodegradable and industrially synthesizable microporous flexible foam and a method for manufacturing the biodegradable and industrially synthesizable microporous flexible foam . As discussed above, the foaming description involves the process of capturing air pockets in liquids or solids. Generally, the industry uses foaming to produce lightweight polymer materials. This is an advantageous solution for many types of products, because foamed materials give a lot of added value, such as soft cushioning, comfort, and impact protection.
在各種實例中,發泡材料呈微氣孔發泡體形式為有用的。微氣孔發泡體係特定地製造以含有許多(例如,數十億)微小氣泡的製成塑膠之形式,該等微小氣泡在大小方面小於約50微米。此類型的發泡體係藉由使氣體在高壓下溶解至各種類型的聚合物中以產生氣體氣泡之均勻佈置形成,該溶解通常被稱為成核。用於控制及調整微氣孔發泡體之密度的主要驅動器為用來產生該等微氣孔發泡體的氣體。取決於使用的氣體,發泡體之密度可在預處理生物塑膠之約5%至約99%之間的任何地方。In various examples, it is useful that the foamed material is in the form of a microcellular foam. Microcellular foaming systems are specifically manufactured in the form of plastics containing many (for example, billions) of tiny bubbles, which are smaller than about 50 microns in size. This type of foaming system is formed by dissolving gas into various types of polymers under high pressure to produce a uniform arrangement of gas bubbles, and this dissolution is commonly referred to as nucleation. The main driver for controlling and adjusting the density of the microporous foam is the gas used to generate the microporous foam. Depending on the gas used, the density of the foam can be anywhere between about 5% to about 99% of the pretreated bioplastic.
因此,在各種實例中,發泡體係封閉氣孔發泡體為有用的。封閉氣孔發泡體通常已知為總體上由其壁包圍且因此不與其他氣孔互連的氣孔。此類型的材料係有用的,因為其有效地減少來自流過氣孔的液體及氣體流。諸如根據本文揭示之方法生產的封閉氣孔發泡體為對於其中液體阻力係關鍵的工業有用的,諸如緩衝器、鞋類、船舶、HVAC、及汽車使用。Therefore, in various examples, the closed-cell foam of the foaming system is useful. Closed-cell foams are generally known as pores that are generally surrounded by their walls and are therefore not interconnected with other pores. This type of material is useful because it effectively reduces the flow of liquid and gas from the pores. Closed-cell foams such as those produced according to the methods disclosed herein are useful for industries where liquid resistance is critical, such as buffers, footwear, marine, HVAC, and automotive applications.
然而,在各種實例中,發泡體是開放氣孔發泡體可為有用的。當其氣孔之超過一半為開放的且與其他氣孔互連時,開放氣孔發泡體通常分類為「開放氣孔」。可在本文揭示之方法中生產且利用的此類型的發泡體可為有用的,因為該類型的發泡體操作起來比封閉胞發泡體更像彈簧,從而在壓縮之後容易地返回至其原始狀態。「彈性」藉由無約束空氣移動及化學補給引起。However, in various examples, it may be useful that the foam is an open-cell foam. When more than half of its pores are open and interconnected with other pores, an open pore foam is usually classified as "open pores". This type of foam that can be produced and utilized in the method disclosed herein can be useful because it operates more like a spring than a closed cell foam, and thus easily returns to it after compression. Original state. "Resilience" is caused by unconstrained air movement and chemical replenishment.
在特定實例中,根據所描述方法,產生的發泡體及由發泡體生產的產品以與可撓性乙烯乙酸乙烯酯(EVA)發泡體類似的方式起作用。特定而言,可撓性EVA發泡體是如今使用在製造工業中的普存材料。使得EVA發泡體如此盛行的事物是其相對低的成本及處理之容易性,同時維持用於給定產品之通常可接受的技術效能性質。因此,以本文揭示之方式生產的發泡體可以相對低的成本加以生產,具有製造之容易性,同時不僅維持可接受,而且通常維持優越的技術效能產品,而同時為環境友好的。In a specific example, according to the described method, the resulting foam and the products produced from the foam function in a similar manner to flexible ethylene vinyl acetate (EVA) foam. In particular, flexible EVA foam is a universal material used in the manufacturing industry today. What makes EVA foam so popular is its relatively low cost and ease of handling, while maintaining the generally acceptable technical performance properties for a given product. Therefore, the foam produced in the manner disclosed herein can be produced at a relatively low cost, has the ease of manufacture, and at the same time maintains acceptable and generally superior technical performance products, while at the same time being environmentally friendly.
更特定而言,如以上所指示,EVA發泡體使用之缺點有許多。材料源自於不可再生原料且與化學發泡劑化學交聯,該等化學發泡劑為不容易生物可降解的、可合成的,或可回收的。然而,不同於可撓性EVA發泡體,本揭示案之生物可降解且工業上可合成之可撓性發泡體不含有化學品或交聯劑,且當將適當生物衍生聚合物使用在其製造中時,該等生物可降解且工業上可合成之可撓性發泡體為容易地生物可降解的且工業上可合成的。More specifically, as indicated above, the use of EVA foam has many disadvantages. The material is derived from non-renewable raw materials and is chemically cross-linked with chemical blowing agents, which are not easily biodegradable, synthesizable, or recyclable. However, unlike flexible EVA foam, the biodegradable and industrially synthesizable flexible foam of this disclosure does not contain chemicals or crosslinking agents, and when appropriate bio-derived polymers are used in During its manufacture, the biodegradable and industrially synthesizable flexible foams are easily biodegradable and industrially synthesizable.
例如,在各種實行方案中,本文呈現的係可使得具有習知石化乙烯乙酸乙烯酯(EVA)發泡體等之類似性質及特性,但含有高百分比的生物量碳含量的生物可降解且工業上可合成之可撓性發泡體。特定而言,在各種實施例中,將生物可降解、淨中性,且工業上可合成之發泡體前驅物使用在諸如以環境友好方式製作生物可降解且工業上可合成之可撓性發泡體中。為達成此等目標,任何數目的合適生物衍生熱塑性原料可經選擇來供使用,且可來源自通常不與動物飼料或人類糧食競爭的迅速可再生原料。有利地,如所指示,精心選擇的生物衍生熱塑性泡沫塑料前驅物具有與按照慣例使用的EVA之技術效能性質近似等效或等效的技術效能性質。For example, in various implementation schemes, the system presented in this paper can make it have the similar properties and characteristics of conventional petrochemical ethylene vinyl acetate (EVA) foams, etc., but contain a high percentage of biomass carbon content, which is biodegradable and industrial The above can be synthesized flexible foam. Specifically, in various embodiments, biodegradable, net neutral, and industrially synthesizable foam precursors are used, such as making biodegradable and industrially synthesizable flexibility in an environmentally friendly manner. In the foam. To achieve these goals, any number of suitable bio-derived thermoplastic raw materials can be selected for use, and can be derived from rapidly renewable raw materials that do not normally compete with animal feed or human food. Advantageously, as indicated, the carefully selected bio-derived thermoplastic foam precursors have technical performance properties approximately equivalent or equivalent to those of conventionally used EVA.
具有與習知不可再生EVA之技術效能性質近似等效或等效技術效能性質的用於使用在製作本揭示案之生物可降解且工業上可合成之可撓性發泡體中的此合適熱塑性原料之非限制實例為生物衍生PBAT共聚酯,如本文以下所描述。因此,在各種實例中,本裝置、系統、及其使用方法可經利用,以便生產可由生物可降解且工業上可合成之生物衍生熱塑性樹脂的生物可降解且工業上可合成之微氣孔可撓性發泡體。This suitable thermoplastic material having technical performance properties approximately equivalent to or equivalent technical performance properties of conventional non-renewable EVA for use in the production of the biodegradable and industrially synthesizable flexible foam of the present disclosure A non-limiting example of a raw material is a bio-derived PBAT copolyester, as described herein below. Therefore, in various examples, the device, system, and method of use thereof can be utilized to produce biodegradable and industrially synthesizable micropore flexible biodegradable and industrially synthesizable bio-derived thermoplastic resins.性foam.
更特定而言,根據所揭示方法為有用的發泡體前驅物可為任何合適的類型的熱塑性樹脂,諸如由快速可再生原料生產的生物衍生熱塑性樹脂或生物衍生熱塑性化合物。此類熱塑性樹脂為當加執時熔化且變成液體,且當冷卻時硬化且變成固體的原始、未成形聚合物。More specifically, the foam precursor that is useful according to the disclosed method can be any suitable type of thermoplastic resin, such as a bio-derived thermoplastic resin or a bio-derived thermoplastic compound produced from a rapidly renewable raw material. Such thermoplastic resins are raw, unshaped polymers that melt and become liquid when applied, and harden and become solid when cooled.
熱塑性塑膠之產生不是簡單的任務。需要複雜的化學及機械製程以便製作最終產品。以其最簡單形式,熱塑性塑膠由聚合物組成且彼等聚合物由化合物組成。為了生產製作聚合物且然後製作熱塑性塑膠所需要的化合物,不同類型的分子必須分解且分離。通常,藉由將發泡體前驅物以粒狀形式進料至合適的射出模製成形機中來使用該等發泡體前驅物。顆粒藉由射出模製成形機處理,其中該等顆粒經液化且射注至預成形模具空腔中。在射注完成後,模製成形零件經冷卻且以固態自模具噴出,以下在本文中更詳細地論述如本實施例中實行的此製程。The production of thermoplastics is not a simple task. Complex chemical and mechanical processes are required to make the final product. In its simplest form, thermoplastics are composed of polymers and their polymers are composed of compounds. In order to produce the compounds needed to make polymers and then make thermoplastics, different types of molecules must be broken down and separated. Generally, the foam precursors are used by feeding them into a suitable injection molding machine in the form of pellets. The particles are processed by an injection molding machine, where the particles are liquefied and injected into the cavity of the pre-forming mold. After the injection is completed, the molded part is cooled and ejected from the mold in a solid state. The process implemented in this embodiment will be discussed in more detail below in this article.
生物衍生熱塑性塑膠可藉由類描述。生物基熱塑性塑膠前驅物及生物質之盛行類。存在兩個類型的生物聚酯:聚乳酸(PLA)及聚羥基脂肪酸酯(PHA)。PLA為藉由細菌發酵製作的一個類型的熱塑性塑膠。PLA實際上係許多乳酸分子之長鏈。僅舉幾個例子,存在用於生產PLA之許多不同生物衍生原料,諸如甘蔗、玉米、甜菜、及木質廢材。PHA通常藉由天然發生的細菌及食物廢棄物生產。存在稱為聚羥基丁酸酯(polyhydroxybutyrate;PHB)的PHA之子類,其為亦可廣泛利用的一類PHA。Bio-derived thermoplastics can be described by classes. The prevalence of bio-based thermoplastics precursors and biomass. There are two types of biopolyesters: polylactic acid (PLA) and polyhydroxyalkanoate (PHA). PLA is a type of thermoplastic made by bacterial fermentation. PLA is actually the long chain of many lactic acid molecules. To name just a few examples, there are many different biologically derived raw materials used to produce PLA, such as sugar cane, corn, sugar beet, and wood waste. PHA is usually produced by naturally occurring bacteria and food waste. There is a subclass of PHA called polyhydroxybutyrate (PHB), which is a type of PHA that can also be widely used.
在一些實例中,澱粉或纖維素填料等可任擇地包括在生物聚酯摻合物之形成中,因為其包括使得摻和物更經濟,且在一些實例中,其使用增強分解速率。額外類型的生物衍生熱塑性塑膠已知為乙酸纖維素(CA)。CA係衍生自可見於工廠之每個部分中的纖維素的合成產品。僅舉幾個例子,用於製作CA之目前使用原料係棉花、木材、及作物廢棄物。更進一步,澱粉係又一類型的熱塑性塑膠材料。通常,澱粉以熱、水及增塑劑處置以生產熱塑性塑膠。為給予強度,澱粉通常與由其他材料製成的填料組合。用於生產澱粉之目前可利用原料為玉蜀黍、小麥、馬鈴薯、及木薯。亦已知可為生物可降解的若干石油衍生熱塑性塑膠。常見類型為聚丁烯琥珀酸酯(polybutylene succinate;PBS)、聚己內酯(polycaprolactone;PCL)、及聚己二酸對苯二甲酸丁二酯(polybutyrate adipate terephthalate;PBAT)、及聚乙烯醇(PVOH/PVA)。前面提到的石油衍生熱塑性塑膠可以生物衍生多樣性加以生產。用於生產PBS、PCL、PBAT、及PVOH/PVA之新生物衍生原料正經生產,且由於技術進步及突破正變得越來越可商購獲得。此等前驅物中之一或多個可根據本文揭示之方法加以產生且利用。In some examples, starch or cellulose fillers, etc. can be optionally included in the formation of the biopolyester blend because its inclusion makes the blend more economical, and in some examples, its use enhances the decomposition rate. An additional type of bio-derived thermoplastic is known as cellulose acetate (CA). CA is a synthetic product derived from cellulose found in every part of the factory. To cite a few examples, the currently used raw materials for the production of CA are cotton, wood, and crop waste. Furthermore, starch is another type of thermoplastic plastic material. Usually, starch is treated with heat, water, and plasticizer to produce thermoplastics. To give strength, starch is usually combined with fillers made of other materials. The currently available raw materials for starch production are maize, wheat, potatoes, and cassava. Several petroleum-derived thermoplastics that are biodegradable are also known. Common types are polybutylene succinate (PBS), polycaprolactone (PCL), polybutyrate adipate terephthalate (PBAT), and polyvinyl alcohol (PVOH/PVA). The aforementioned petroleum-derived thermoplastics can be produced from bio-derived diversity. New bio-derived raw materials for the production of PBS, PCL, PBAT, and PVOH/PVA are being produced, and due to technological progress and breakthroughs, they are becoming more and more commercially available. One or more of these precursors can be produced and utilized according to the methods disclosed herein.
一旦前驅物已經產生,該等前驅物可經發泡且用來製作一或多個終端產品,諸如藉由射出模製成形製程,如本文所揭示。例如,在各種實例中,生物衍生熱塑性塑膠前驅物可諸如藉由射出模製成形發泡且利用於終端產品生產製程中。在亦稱為直接射出膨脹發泡體模製成形的習知發泡體射出模製成形中,首先熔化熱塑性聚合物。當熱塑性聚合物均勻地熔化時,化學發泡劑分散至聚合物熔體中以使射出化合物為可發泡的。Once the precursors have been produced, the precursors can be foamed and used to make one or more end products, such as by an injection molding process, as disclosed herein. For example, in various examples, the bio-derived thermoplastic precursor can be foamed, such as by injection molding, and used in the end product production process. In conventional foam injection molding, also called direct injection expanded foam molding, the thermoplastic polymer is first melted. When the thermoplastic polymer is uniformly melted, the chemical blowing agent is dispersed into the polymer melt to make the injection compound foamable.
均質聚合物化合物然後經注射至模具中以製作發泡體產品。通常,射出聚合物化合物未經分類為發泡體,直至加熱模具空腔中之吸熱反應使化學發泡劑活化,從而產生膨脹發泡體零件。因此,模具空腔大小必須小於最終零件大小。實際零件膨脹是在熱塑性聚合物配方內產生,使得當零件自模具噴出時,該零件生長至所需要的零件大小。The homogeneous polymer compound is then injected into a mold to make a foam product. Generally, the injected polymer compound is not classified as a foam until the endothermic reaction in the cavity of the heating mold activates the chemical blowing agent, thereby producing an expanded foam part. Therefore, the size of the mold cavity must be smaller than the size of the final part. The actual part expansion is produced in the thermoplastic polymer formulation so that when the part is ejected from the mold, the part grows to the required part size.
一旦實現所需要的零件大小,在其冷卻下來時,其亦收縮或縮減,此通常需要二次模製成形操作以獲得精確的冷卻零件大小。因此,管理習知射出模製成形發泡體之膨脹-收縮之製程可被視為冗長、耗費時間且複雜的。此射出模製成形技術可經利用來生產前驅物及發泡體,以及藉此生產的產品,如本文所論述。然而,在特定實例中,習知射出模製成形機可經修改,如本文所揭示,以便更好地實現生物可降解、淨中性發泡體前驅物之使用,該等生物可降解、淨中性發泡體前驅物可經利用於修改後製程中,以便產生環境友好的發泡體,該等環境友好的發泡體可經利用於生產發泡體產品中,該等發泡體產品諸如家具緩衝器、鞋組件、運動設備等等。Once the required part size is achieved, when it cools down, it also shrinks or shrinks. This usually requires a secondary molding operation to obtain an accurate cooling part size. Therefore, the process of managing the expansion and contraction of conventional injection molded foams can be regarded as tedious, time-consuming, and complicated. This injection molding technology can be used to produce precursors and foams, as well as products produced therefrom, as discussed herein. However, in a specific example, the conventional injection molding machine can be modified, as disclosed herein, in order to better realize the use of biodegradable, net neutral foam precursors, which are biodegradable and net The neutral foam precursor can be used in the modified process to produce environmentally friendly foams. These environmentally friendly foams can be used in the production of foam products. Such as furniture buffers, shoe components, sports equipment, etc.
因此,儘管習知製程可為在生產發泡產品中有用的,但在某些實例中,該習知製程可遭受一些缺點,尤其關於可合成微氣孔可撓性發泡體之生產。例如,在各種實例中,典型的射出模製成形製程當使用可合成生物衍生熱塑性樹脂來生產可合成可撓性發泡體時可以各種不同方式存在不足。例如,以上提到的習知無修改發泡體注射模製成形製程可為對於生產生物可降解且可合成可撓性發泡體不足的且及不合適的。用於此之主要原因起源於其中聚合物化合物在其製造期間交聯的習知無修改發泡體注射模製成形之真實本性。Therefore, although the conventional process may be useful in the production of foamed products, in some instances, the conventional process may suffer from some disadvantages, especially regarding the production of synthesizable microporous flexible foams. For example, in various examples, the typical injection molding process may have various deficiencies in various ways when synthesizable bio-derived thermoplastic resins are used to produce synthesizable flexible foams. For example, the above-mentioned conventional unmodified foam injection molding process may be insufficient and inappropriate for the production of biodegradable and synthesizable flexible foam. The main reason for this originates from the true nature of conventional unmodified foam injection molding in which the polymer compound is cross-linked during its manufacture.
如以上所指示,交聯可經描述為隨機發生的將若干聚合物鏈之部分保持在一起的共價鍵之形成。結果為發泡體基質內的互連鏈之隨機三維網路。此交聯發泡體不能容易地不交聯,且因而,各種前驅物成分不能容易地被分離回至其單獨類型且經生物降解或堆肥。因此,目前揭示的優點並非在不改變發泡設備及其在製造中之使用方法的情況下可容易達成的。因此,本文呈現製造機器及使用該製造機器來以適合於將無交聯前驅物利用於射出模製成形製程中的方式產生發泡體的製程。As indicated above, cross-linking can be described as the formation of randomly occurring covalent bonds that hold parts of several polymer chains together. The result is a random three-dimensional network of interconnected chains within the foam matrix. This cross-linked foam cannot be easily uncross-linked, and thus, various precursor components cannot be easily separated back to their individual types and biodegraded or composted. Therefore, the advantages currently disclosed are not easily achieved without changing the foaming equipment and its method of use in manufacturing. Therefore, this article presents a manufacturing machine and a process of using the manufacturing machine to produce a foam in a manner suitable for using the non-crosslinked precursor in the injection molding process.
因此,在一個態樣中,本文所呈現的是新射出模製成形機。模製成形機可經配置以便利用各種可撓性發泡體組成,包括生物衍生熱塑性塑膠前驅物,該等可撓性發泡體組成可藉由將前驅物施加至新射出模製成形機中來以生產可合成微氣孔可撓性發泡體結構的方式發泡,該新射出模製成形機然後可用來生產一或多個可撓性發泡體產品。因此,在一個態樣中,本文所提供的是新射出模製成形機。Therefore, in one aspect, this article presents a new injection molding machine. The molding machine can be configured to utilize various flexible foam compositions, including bio-derived thermoplastic plastic precursors, which can be formed by applying the precursors to the new injection molding machine To foam in a way to produce a microporous flexible foam structure that can be synthesized, the new injection molding machine can then be used to produce one or more flexible foam products. Therefore, in one aspect, what this article provides is a new injection molding machine.
設定本揭示案之製造機器分離的因素中之一些為特殊化輔助設備之使用,該特殊化輔助設備與可附著的微氣孔氣體配料系統耦接並藉此修改且改良標準射出模製成形機。實質上,如本文所呈現,標準射出模製成形機已經全面改革且重組以用於根據本揭示案使用之合適方式起作用。用於修改之一般方法始於變換射出模製成形機上之射出模製成形螺桿以能夠處置超臨界惰性氣體,諸如氮、CO2 、及/或無抗及/或惰性氣體。Some of the factors that set the manufacturing machine separation of the present disclosure are the use of specialized auxiliary equipment, which is coupled with an attachable micro-pore gas batching system to modify and improve the standard injection molding machine. In essence, as presented herein, the standard injection molding machine has been completely reformed and reorganized to function in a suitable manner for use in accordance with this disclosure. The general method for modification starts with changing the injection molding screw on the injection molding machine to be able to handle supercritical inert gases, such as nitrogen, CO 2 , and/or non-resistant and/or inert gases.
氣體配料系統然後可經裝配至射出模製成形機,用於諸如在射出至溫度控制的模具空腔中之前將適當氣體以適當量配料至螺釘內之聚合物熔體中。另外,可利用特殊化模具空腔,其中模具之熱溫度循環可更好地控制所得發泡體外皮織理及表皮厚度,並且減少用於零件生產之循環時間。此外,輔助氣體反壓力系統可經裝配至射出模製機以用於將惰性氣體推回至模具中以抵抗正射注至模具中的液體聚合物熔體。The gas dosing system can then be assembled to an injection molding machine for, for example, dosing the proper amount of gas into the polymer melt in the screw before injection into a temperature-controlled mold cavity. In addition, a special mold cavity can be used, in which the thermal temperature cycle of the mold can better control the texture and thickness of the resulting foamed outer skin, and reduce the cycle time for the production of parts. In addition, the auxiliary gas back pressure system can be fitted to the injection molding machine for pushing the inert gas back into the mold to resist the liquid polymer melt ortho-injected into the mold.
此反壓力為對於確保熔化射出射注實質上(若未完全)填充模具空腔且防止零件翹曲及收縮,以及控制氣孔分佈及氣孔密度有用的。此外,適當的反壓力具有對零件之表皮織理及表皮厚度之有益影響。因此,當零件自模具空腔噴出時,不存在可辨別的皺縮且不存在立即使用模製成形的發泡體零件所需要的二次步驟。有益地,零件未交聯,且因此,該零件可生物降解或堆肥,只要將合適的生物衍生聚合物化合物使用在發泡體產生中。This back pressure is useful for ensuring that the melted injection injection substantially (if not completely) fills the cavity of the mold, prevents warping and shrinkage of parts, and controls the distribution of pores and the density of pores. In addition, proper back pressure has a beneficial effect on the surface texture and thickness of the parts. Therefore, when the part is ejected from the mold cavity, there is no discernible shrinkage and there is no secondary step required to immediately use the molded foam part. Advantageously, the part is not cross-linked, and therefore, the part is biodegradable or compostable, as long as a suitable bio-derived polymer compound is used in the foam production.
鑒於以上內容,在一個態樣中,本揭示案針對產生生物可降解且可合成(例如,工業上)的微氣孔可撓性發泡體結構。特定而言,在一個實施例中,製程始於合適的生物聚合物或生物聚合物摻和物。例如,在各種實例中,生物聚合物可為諸如由自然資源生產的一或多個聚合物,由生物材料化學合成或藉由活機體完全生物合成。In view of the foregoing, in one aspect, the present disclosure is directed to the production of a microporous flexible foam structure that is biodegradable and can be synthesized (for example, industrially). In particular, in one embodiment, the process starts with a suitable biopolymer or biopolymer blend. For example, in various examples, the biopolymer may be one or more polymers such as those produced from natural resources, chemically synthesized from biological materials or completely biosynthesized by living organisms.
主要存在兩種類型的生物聚合物,一種生物聚合物是自活生物體獲得且另一種生物聚合物是由可再生資源生產但需要聚合作用。藉由活生物體產生的彼等生物聚合物包括蛋白質及碳水化合物。不同於合成聚合物,生物聚合物具有明顯標誌的結構。此類型的聚合物是基於其化學結構加以區分。使本揭示案之生物聚合物尤其有用的事物在於該生物聚合物就技術效能性質而言緊密地模擬不可再生EVA。There are mainly two types of biopolymers, one biopolymer is obtained from living organisms and the other biopolymer is produced from renewable resources but requires polymerization. These biopolymers produced by living organisms include proteins and carbohydrates. Unlike synthetic polymers, biopolymers have clearly marked structures. This type of polymer is differentiated based on its chemical structure. What makes the biopolymer of this disclosure particularly useful is that the biopolymer closely mimics non-renewable EVA in terms of technical performance properties.
同樣地,在特定實例中,生物聚合物摻和物可經利用於生產發泡體結構中,諸如其中生物聚合物摻和物可為二或更多個生物聚合物之定製化合物。若干無限類型的生物聚合物為糖基生物聚合物、澱粉基生物聚合物、基於合成材料的生物聚合物、及纖維素基生物聚合物。生物聚合物摻和物組合之典型比率將取決於正製造的產品之類型及所得零件之所需要的技術性質。Likewise, in certain examples, biopolymer blends can be utilized in the production of foam structures, such as custom compounds where the biopolymer blend can be two or more biopolymers. Several unlimited types of biopolymers are sugar-based biopolymers, starch-based biopolymers, biopolymers based on synthetic materials, and cellulose-based biopolymers. The typical ratio of the biopolymer blend combination will depend on the type of product being manufactured and the required technical properties of the resulting part.
更特定而言,在一特定實施例中,可用作發泡體前驅物的生物聚合物摻和物包括複數個樹脂,諸如可諸如在固化之後添加至聚合物之熔體的一或多個固體或黏性材料。因此,在聚合作用或固化之後,樹脂形成聚合物。例如,合適的樹脂可為以下中一或多個:脂肪族及脂肪族-芳香族共聚酯起源。一般而言,脂肪族或脂族化合物係指或指示其中碳原子形成開放鏈而非芳環的有機化合物。同樣地,合適的脂肪族-芳香族化合物通常為碳原子(脂肪族部分)及原子之穩定環或多個環(芳香族部分)之開放鏈之隨機組合。More specifically, in a particular embodiment, the biopolymer blend that can be used as a foam precursor includes a plurality of resins, such as one or more that can be added to the melt of the polymer after curing. Solid or viscous materials. Therefore, after polymerization or curing, the resin forms a polymer. For example, suitable resins can be one or more of the following: aliphatic and aliphatic-aromatic copolyester origin. Generally speaking, aliphatic or aliphatic compound refers to or indicates an organic compound in which carbon atoms form an open chain rather than an aromatic ring. Likewise, suitable aliphatic-aromatic compounds are usually random combinations of carbon atoms (aliphatic parts) and stable rings of atoms or open chains of multiple rings (aromatic parts).
通常,鏈中之芳香族酸之量低於49%,但最近的技術進步已表明用於增加此且進一步幫助生物降解的大承諾。脂肪族-芳香族之實例為可由任何數目的不可再生及可再生原料生產的脂肪族-芳香族共聚酯(aliphatic-aromatic copolyester;AAPE),但可再生來源的AAPE尤其是有用的。因此,在各種實施例中,此等脂肪族及/或脂肪族中一或多個可具有共聚酯起源。當聚酯經修改時,產生此類共聚酯。例如,當將多於一個二酸或二醇使用在聚合作用過程中時,共聚酯經生產。在脂肪族-芳香族共聚酯之狀況下,使得前驅物變化之組合實質上雜交或「橋接」脂肪族-芳香族鏈且在聚合作用過程中組合多於一個額外前驅物。Generally, the amount of aromatic acids in the chain is less than 49%, but recent technological advances have shown a great promise to increase this and further aid biodegradation. Examples of aliphatic-aromatics are aliphatic-aromatic copolyesters (AAPE) that can be produced from any number of non-renewable and renewable raw materials, but AAPE from renewable sources is particularly useful. Therefore, in various embodiments, one or more of these aliphatic and/or aliphatic groups may have a copolyester origin. When the polyester is modified, this type of copolyester is produced. For example, when more than one diacid or diol is used in the polymerization process, a copolyester is produced. In the case of aliphatic-aromatic copolyesters, the combination of changes in the precursors essentially hybridizes or "bridges" the aliphatic-aromatic chain and combines more than one additional precursor during the polymerization process.
合適的生物聚合物摻和物之非限制實例為聚乳酸(PLA)及聚(己二酸丁二酯-共-對苯二甲酸酯)(poly(butylene adipate-co-terephthalate);PBAT)。聚乳酸(PLA)為衍生自可再生生物質的生物可降解熱塑性脂肪族聚酯。使用在PLA之產生中的典型原料包括發酵工廠澱粉諸如玉米、木薯、甘蔗、甜菜渣,及在較小程度上木質素廢材。同樣地,聚己二酸對苯二甲酸丁二酯(PBAT)為生物可降解隨機共聚物,特定而言,通常衍生自己二酸、1,4-丁二醇及對苯二甲酸的共聚酯。使用可再生來源的PBAT而非來源於不可再生石油來源之PBAT為有利的。在各種實例中,此等組分中一或多個可經摻和。Non-limiting examples of suitable biopolymer blends are polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (poly(butylene adipate-co-terephthalate); PBAT) . Polylactic acid (PLA) is a biodegradable thermoplastic aliphatic polyester derived from renewable biomass. Typical raw materials used in the production of PLA include fermentation plant starches such as corn, cassava, sugar cane, sugar beet residue, and to a lesser extent lignin waste materials. Similarly, polybutylene adipate terephthalate (PBAT) is a biodegradable random copolymer. In particular, it is usually derived from a copolymer of adipic acid, 1,4-butanediol and terephthalic acid ester. It is advantageous to use PBAT from renewable sources instead of PBAT from non-renewable petroleum sources. In various examples, one or more of these components may be blended.
二或更多個熱塑性生物聚合物之摻和物提供在單個聚合物或共聚物中未發現的性質及價格之組合。存在用以成功地將生物聚合物摻和在一起的許多方式。常見方法將使用雙螺桿擠製來將二或更多個生物聚合物樹脂熔化在一起且然後將熔化生物聚合物樹脂摻合物擠製成股,該股經冷卻且進料至造粒機中以用於生產稱為母料的一系列造粒件。生物聚合物樹脂摻和之另一方法將使用增容劑(compatibilizing agent)在生物聚合物摻和物中將不同化學面分接合在一起。通常,此亦使用雙螺桿擠製或類似者來在以上所描述之製程中將增容劑及二或更多個生物聚合物熔融在一起。A blend of two or more thermoplastic biopolymers provides a combination of properties and prices not found in a single polymer or copolymer. There are many ways to successfully blend biopolymers together. A common method is to use twin screw extrusion to melt two or more biopolymer resins together and then extrude the melted biopolymer resin blend into strands, which are cooled and fed into a pelletizer Used to produce a series of pellets called master batches. Another method of biopolymer resin blending is to use a compatibilizing agent in the biopolymer blend to bond different chemical components together. Usually, twin screw extrusion or the like is also used to melt the compatibilizer and two or more biopolymers together in the process described above.
因此,本文中已決定前面提到的摻和熱塑性生物聚合物樹脂表明在形成本揭示案之最佳微氣孔可撓性發泡體結構中的有利技術性質。增強的技術性質中之一些包括:可接受的老化性質、優良伸長、及異常壓縮變形,以及其他效益。例如,如本文所揭示,使用生物聚合物摻和物之優點為由給定生物聚合物摻和物之形成及使用產生的增強技術效能性質。特定而言,當生物聚合物及/或生物聚合物-增容劑摻和物之正確組合經實現時,增強性質諸如改良的伸長、拉伸強度、衝擊強度及熔流等可全部經實現。Therefore, it has been determined in this article that the aforementioned blended thermoplastic biopolymer resins show advantageous technical properties in forming the optimal microporous flexible foam structure of the present disclosure. Some of the enhanced technical properties include: acceptable aging properties, excellent elongation, and abnormal compression set, among other benefits. For example, as disclosed herein, the advantage of using biopolymer blends is the enhanced technical performance properties resulting from the formation and use of a given biopolymer blend. In particular, when the correct combination of biopolymer and/or biopolymer-compatibilizer blend is achieved, enhanced properties such as improved elongation, tensile strength, impact strength, and melt flow can all be achieved.
因此,可根據本文揭示之方法及機器利用此等樹脂,以便生產發泡劑。因此,在一個態樣中,本揭示案針對發泡製程。如以上所描述,本文揭示之機器及製程可經配置來用於執行發泡操作,藉此將氣包捕獲在液體或固體中,該發泡可用來生產輕質聚合物材料。此為用於許多類型的產品之有利解決方案,因為發泡材料給予大量的附加價值諸如軟式緩衝、舒適度、技術運動裝置,包括鞋組件、及衝擊保護等。然而,在各種實例中,前面提到的最佳脂肪族及脂肪族-芳香族共聚酯生物聚合物或生物聚合物摻和物單獨為對於生產可撓性發泡體有用的,在各種實例中,其在可撓性發泡體之生產中之使用可藉由將合適的發泡劑包括在發泡製程內增強。Therefore, these resins can be used according to the methods and machines disclosed herein to produce foaming agents. Therefore, in one aspect, the present disclosure is directed to the foaming process. As described above, the machines and processes disclosed herein can be configured to perform foaming operations, thereby trapping air pockets in liquids or solids, and the foaming can be used to produce lightweight polymer materials. This is an advantageous solution for many types of products, because foamed materials give a lot of added value such as soft cushioning, comfort, technical sports equipment, including shoe components, and impact protection. However, in various examples, the aforementioned optimal aliphatic and aliphatic-aromatic copolyester biopolymers or biopolymer blends alone are useful for producing flexible foams. In various examples Among them, its use in the production of flexible foams can be enhanced by including a suitable foaming agent in the foaming process.
例如,現今使用的廣泛已知的發泡劑為稱為偶氮二甲醯胺(ADA)的化學品。偶氮二甲醯胺通常經預先浸漬至用於使用在習知射出模製成形發泡體製程中的石化熱塑性母料樹脂中。特定而言,化學發泡劑諸如ADA之預先浸漬通常在發泡之前包括在生物塑膠摻和物中。用於此之原因在於需要諸如ADA之化學發泡劑之預先浸漬,因為習知射出模製發泡不允許發泡體模製成形可變性之定製。亦即,化學發泡劑諸如ADA在其在製造點期間修改或影響發泡製程之實體態樣之能力方面受限制。For example, a widely known blowing agent used today is a chemical called azodimethamide (ADA). Azodimethamide is usually pre-impregnated into the petrochemical thermoplastic masterbatch resin used in the conventional injection molding foaming process. In particular, pre-impregnation of chemical foaming agents such as ADA is usually included in the bioplastic blend before foaming. The reason for this is that it requires pre-impregnation of chemical foaming agents such as ADA, because conventional injection molded foaming does not allow customization of foam molding variability. That is, chemical blowing agents such as ADA are limited in their ability to modify or influence the physical aspect of the foaming process during the point of manufacture.
相反地,本揭示案之特殊化發泡製程受益於鈍氣或惰性氣體諸如氮提供的物理發泡。在此製程中,氣體(例如,氮)配料可在生物聚合物熔體內在濃度方面加以調整,且此具有對發泡結果之直接影響,此可視為定製所得發泡體之特定態樣的主要優點。儘管存在已知為生物可降解且工業上可合成的若干石化衍生熱塑性塑膠,諸如PBAT共聚酯,但使用可再生來源的原料諸如純PBAT共聚酯之線路為有利的。In contrast, the specialized foaming process of the present disclosure benefits from physical foaming provided by inert gas or inert gas such as nitrogen. In this process, the gas (for example, nitrogen) ingredients can be adjusted in terms of concentration in the biopolymer melt, and this has a direct impact on the foaming result, which can be regarded as the specific aspect of the customized foam main advantage. Although there are several petrochemical-derived thermoplastics that are known to be biodegradable and industrially synthesizable, such as PBAT copolyesters, it is advantageous to use renewable sources of raw materials such as pure PBAT copolyesters.
例如,在生產發泡劑中,首先生產諸如生物塑膠摻和物的定製母料可為有用的,該生物塑膠摻和物適合於生產用於給定產品類型之給定類型的生物可降解且工業上可合成之可撓性發泡體。例如,不同類型的定製母料化合物可經生產來用於不同類型的產品應用。此可藉由指示何物為製作例如一雙鞋中之特定類型的發泡體可不同於需要何物來用於製作諸如用於使用在製作一件家具中的特定類型的發泡體加以解釋。此外,定製母料可各自含有用於給定產品使用之不同著色劑。另外在此,不同的產品類型需要不同的定製態樣,且唯一地生產單獨母料之能力為對於此等特定使用高度有利的。For example, in the production of foaming agents, it may be useful to first produce a customized masterbatch such as a bioplastic blend that is suitable for producing a given type of biodegradable for a given product type And it is a flexible foam that can be synthesized industrially. For example, different types of customized masterbatch compounds can be produced for different types of product applications. This can be explained by indicating what is used to make a specific type of foam in a pair of shoes, for example, can be different from what is needed to make a specific type of foam, such as used in making a piece of furniture . In addition, customized masterbatches can each contain different colorants for use in a given product. In addition, here, different product types require different customization aspects, and the unique ability to produce a single masterbatch is highly advantageous for these specific uses.
不幸地,ADA不是環境友好的,且其為人類健康之可疑致癌物。因此,其在本方法及藉此生產的產品中之使用在其優點方面為有限的。此外,習知石化熱塑性母料樹脂不是生物可降解的,亦不是工業上可合成的,且因而,其優點亦受限制。鑒於ADA及習知石化品對於生產母料之使用中的此等不足,本文所呈現的是可用來生產用於產生生物可降解且工業上可合成之微氣孔可撓性發泡體之母料的生物可降解、工業上可合成、熱塑性生物聚合物樹脂。Unfortunately, ADA is not environmentally friendly, and it is a suspected carcinogen for human health. Therefore, its use in the present method and the products produced therefrom is limited in terms of its advantages. In addition, conventional petrochemical thermoplastic masterbatch resins are not biodegradable, nor are they industrially synthesizable, and therefore, their advantages are also limited. In view of these deficiencies in the use of ADA and conventional petrochemicals for the production of masterbatches, this article presents the masterbatches that can be used to produce biodegradable and industrially synthesizable microporous flexible foams. The biodegradable, industrially synthesizable, thermoplastic biopolymer resin.
在各種實例中,如以上所論述,為達成用於使用在例如以環境排放中立方式製造模製成形的終端產品中的更佳生物可降解且工業上可合成之可撓性發泡體,超臨界流體可藉由系統注射至模製成形製程中。特定而言,超臨界流體為處於其臨界溫度(Tc)及臨界壓力(Pc)以上的狀態中的物質(液體或氣體)。在此臨界點處,氣體及液體共存,且超臨界流體表明例如在標準條件下不同於液體或氣體之彼等性質的獨特性質。使用諸如處於超臨界流體狀態中的惰性超臨界流體諸如氮、CO2 、He、Ne、Ar、Xe及其他此類惰性氣體為有利的,可根據本文揭示之方法利用該等氣體作為發泡製程中之發泡劑。In various instances, as discussed above, in order to achieve better biodegradable and industrially synthesizable flexible foams for use in, for example, environmentally neutral manufacturing molded end products, ultra The critical fluid can be injected into the molding process by the system. Specifically, a supercritical fluid is a substance (liquid or gas) in a state above its critical temperature (Tc) and critical pressure (Pc). At this critical point, gas and liquid coexist, and the supercritical fluid exhibits unique properties that are different from those of liquid or gas, for example, under standard conditions. It is advantageous to use inert supercritical fluids such as nitrogen, CO 2 , He, Ne, Ar, Xe and other such inert gases in a supercritical fluid state, and these gases can be used as the foaming process according to the method disclosed herein In the foaming agent.
前面提到的超臨界流體藉由溶解在射出模製成形機桶內的聚合物基質中工作。在特殊化射出模製成形製程在受控制的壓力及溫度下將液體生物塑膠化合物注射至射出模具空腔中時,氣體推動聚合物熔體以完全展開至模具空腔之最大限制。在此製程中,氣體為對於在發泡製程內最大化聚合物基質之胞狀結構有用的。特殊化發泡製程之此最大化確保最小化最終發泡零件內的不合需要的縮痕或翹曲。此非常不同於習知化學發泡劑生產的可撓性發泡體,因為習知發泡劑不受相同類型的超臨界狀態或壓力,且因此按照慣例生產的發泡體在最終發泡零件中缺乏一致性,且其可含有不合需要的縮痕及翹曲。The aforementioned supercritical fluid works by dissolving in the polymer matrix in the barrel of the injection molding machine. When the liquid bioplastic compound is injected into the injection mold cavity under controlled pressure and temperature during the special injection molding process, the gas pushes the polymer melt to fully expand to the maximum limit of the mold cavity. In this process, the gas is useful for maximizing the cell structure of the polymer matrix during the foaming process. This maximization of the specialized foaming process ensures that undesirable sink marks or warpage in the final foamed part are minimized. This is very different from the flexible foam produced by the conventional chemical foaming agent, because the conventional foaming agent is not subject to the same type of supercritical state or pressure, and therefore the conventionally produced foam lacks in the final foamed part. Consistency, and it can contain undesirable sink marks and warpage.
更特定而言,在各種實例中,可在超臨界流體狀態中配製惰性氣體諸如氮或二氧化碳,該惰性氣體然後可用作物理發泡劑,諸如在本文所論述之新穎射出模製成形機及製程中。在此實例中,所揭示的修改後物理發泡製程可與以下各者一起使用:合適的熱塑性生物聚合物或可為摻和生物聚合物母料,使得生物聚合物或生物聚合物摻和物及發泡劑協調地工作,以用於生產最佳生物可降解且工業上可合成之可撓性發泡體。More specifically, in various examples, an inert gas such as nitrogen or carbon dioxide can be formulated in a supercritical fluid state, which can then be used as a physical blowing agent, such as the novel injection molding machine and In process. In this example, the disclosed modified physical foaming process can be used with each of the following: a suitable thermoplastic biopolymer or can be a blended biopolymer masterbatch such that a biopolymer or biopolymer blend And the foaming agent work in coordination to produce the best biodegradable and industrially synthesizable flexible foam.
本揭示案之合適的生物聚合物、生物塑膠、及生物塑膠摻和物可源自於可再生資源,該等可再生資源諸如不與動物飼料及人類糧食競爭的彼等資源、及源自於可再生資源之廢棄物流的彼等資源。在生產生物聚合物或生物聚合物摻和物中找到使用的合適的生物聚合物之非限制實例由以下各者組成:聚乳酸(PLA)、聚L乳酸(poly(L-lactic acid);PLLA)、聚(己二酸丁二酯-共-對苯二甲酸酯)(PBAT)、聚己內酯(PCL)、聚羥基烷酸酯(PHA)、聚丁烯琥珀酸酯(PBS)、聚己內酯(PCL)、聚丁烯琥珀酸酯已二酸( polybutylene succinate adipate;PBSA)、聚丁烯已二酸(polybutylene adipate;PBA)、及熱塑性澱粉(thermoplastic starch;TPS)。本揭示案之合適的生物聚合物摻和物為以上所列生物聚合物及生物塑膠類型之任何組合,以及由含生物質聚(己二酸丁二酯-共-對苯二甲酸酯)(PBAT)組成的任何混合生物聚合物摻和物。此狀況之非限制實例將為含木質素PBAT摻和物,其中木質素來源於廢木材且PBAT來源於可再生資源。Suitable biopolymers, bioplastics, and bioplastic blends of this disclosure can be derived from renewable resources, such as those that do not compete with animal feed and human food, and are derived from Renewable resources are their resources in the waste stream. Non-limiting examples of suitable biopolymers found for use in the production of biopolymers or biopolymer blends consist of the following: polylactic acid (PLA), poly(L-lactic acid); PLLA ), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polybutene succinate (PBS) , Polycaprolactone (PCL), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), and thermoplastic starch (TPS). Suitable biopolymer blends of the present disclosure are any combination of the above-listed biopolymers and bioplastic types, and are made of biomass-containing poly(butylene adipate-co-terephthalate) (PBAT) any hybrid biopolymer blend composed of. A non-limiting example of this situation would be a lignin-containing PBAT blend, where lignin is derived from waste wood and PBAT is derived from renewable resources.
因此,在各種實施例中,本文揭示之射出模製成形裝置及其使用方法為對於生產具有均勻氣孔成核的發泡體有用的。如所論述,本文揭示之設備及其使用方法可用來生產均質氣孔成核以便生產發泡體,藉此發泡體核經隨機地且自發地產生,且因而不可逆地生長於具有極少直至無雜質的單相溶液系統中。例如,如以下本文中所闡述,在一個態樣中,提供製造可撓性及/或剛性發泡體之製程。方法可經實行,以便衍生開放氣孔或封閉氣孔發泡體,諸如其中發泡體具有固有可合成、抗微生物及/或耐燃性質。Therefore, in various embodiments, the injection molding device and method of use disclosed herein are useful for producing foams with uniform pore nucleation. As discussed, the equipment and method of use disclosed herein can be used to produce homogeneous pore nucleation in order to produce foam, whereby the foam core is randomly and spontaneously generated, and thus grows irreversibly with little to no impurities The single-phase solution system. For example, as described in this article below, in one aspect, a process for manufacturing a flexible and/or rigid foam is provided. The method can be implemented to derive open-cell or closed-cell foam, such as where the foam has inherently synthesizable, antimicrobial, and/or flame-resistant properties.
在某些實例中,方法可包括形成母料之步驟中之一或多個,諸如包括摻和一或多個樹脂,例如,共聚物載體樹脂,及各種發泡成分。在後續步驟中,方法可包括添加抗微生物化合物,使得發泡體材料可使用在抗微生物、抗菌及/或抗病毒的鞋類組件、家具組件、瑜珈墊、服裝、運動商品組件、醫療裝置,及/或耐燃製品,及其他合適的使用之生產中。特定而言,根據本文揭示之方法,所生產產品可經使用在一大系列應用中,且通常其生產方法可分解成三個相異階段。第一,製作塊體聚合物產品。接下來,使聚合物暴露於各種處理步驟。最後,將聚合物變換成其最終產品,諸如服裝、抗微生物地毯、家具、汽車組件、瑜珈墊、鞋組件,包括鞋底、中底、鞋內底等等。In some instances, the method may include one or more of the steps of forming a masterbatch, such as including blending one or more resins, for example, copolymer carrier resins, and various foaming ingredients. In the subsequent steps, the method may include adding antimicrobial compounds so that the foam material can be used in antimicrobial, antibacterial and/or antiviral footwear components, furniture components, yoga mats, clothing, sports goods components, medical devices, And/or flame-resistant products, and other suitable use in the production. In particular, according to the method disclosed in this article, the produced product can be used in a large range of applications, and the production method can usually be decomposed into three distinct stages. First, make bulk polymer products. Next, the polymer is exposed to various processing steps. Finally, the polymer is transformed into its final products, such as clothing, antimicrobial carpets, furniture, automotive components, yoga mats, shoe components, including soles, midsoles, insoles, and so on.
具體而言,此單相溶液可經利用,以便生產成核位點,其中氣孔生長且藉由氣體擴散至氣泡中膨脹。本文揭示之機器及製程為對於引發發泡製程尤其有用的,該發泡製程以使得小氣泡均勻地分散在發泡體基質內的方式導致均質氣孔成核之產生。特定而言,不同於習知發泡,本揭示案之超臨界流體形成的可撓性發泡體受益於可直接歸因於小氣泡大小的大大地改良之機械性質。更特定而言,本文揭示之裝置及方法經組配來生產大約100微米或更大至約1微米或更少,諸如約50微米至約10微米,或更少,諸如自約20微米至約40微米,包括約30微米的氣泡直徑,且該等氣泡直徑係藉由使用熱力學不穩定性,且全部在發泡體之產生中不使用習知化學發泡劑的情況下生產。Specifically, this single-phase solution can be utilized to produce nucleation sites in which pores grow and expand by gas diffusion into bubbles. The machines and processes disclosed herein are particularly useful for initiating the foaming process, which results in the generation of homogeneous pore nucleation in such a way that small bubbles are uniformly dispersed in the foam matrix. In particular, unlike conventional foaming, the flexible foam formed by the supercritical fluid of the present disclosure benefits from greatly improved mechanical properties that can be directly attributed to the size of the small bubbles. More specifically, the devices and methods disclosed herein are configured to produce from about 100 microns or more to about 1 micron or less, such as from about 50 microns to about 10 microns, or less, such as from about 20 microns to about 40 microns, including a bubble diameter of about 30 microns, and these bubble diameters are produced by using thermodynamic instability, and all of them are produced without using conventional chemical blowing agents in the production of the foam.
例如,在特定實施例中,系統可經組配來用於將本文揭示之本新穎射出模製成形機使用於生產生物可降解且工業上可合成之微氣孔可撓性發泡體,該生物可降解且工業上可合成之微氣孔可撓性發泡體具有當生物聚合物或生物聚合物摻和物及超臨界流體(SCF)之單相溶液穿過射出閘傳送至射出模製成形機之模具空腔中時可發生的均質氣孔成核。特定而言,如本文以下更詳細地解釋,本射出模製成形機經組配來用於生產熔融材料,諸如藉由將模具前驅物注射至用於生產製成零件或組件零件的模具中。射出模製成形機可包括材料漏斗、射出撞鎚或螺桿式柱塞,及加熱單元。此類射出模製成形機就噸位而言經定額,此表達機器可施加的夾緊力之量。For example, in certain embodiments, the system can be configured to use the novel injection molding machine disclosed herein for the production of biodegradable and industrially synthesizable microporous flexible foams. The degradable and industrially synthesizable microporous flexible foam can be used as a single-phase solution of biopolymer or biopolymer blend and supercritical fluid (SCF) to pass through the injection gate to the injection molding machine Homogeneous pore nucleation can occur in the cavity of the mold. In particular, as explained in more detail below, the injection molding machine is configured to produce molten material, such as by injecting mold precursors into a mold used to produce finished parts or component parts. The injection molding machine may include a material hopper, an injection ram or screw plunger, and a heating unit. This type of injection molding machine is rated in terms of tonnage, which expresses the amount of clamping force the machine can apply.
因此,製程可始於藉由強制撞鎚將粒狀生物塑膠化合物自漏斗進料至加熱桶中。在顆粒藉由特殊化往復螺桿式柱塞緩慢向前移動時,藉由單獨超臨界計量輔助機器經由噴射器引入超臨界流體,該單獨超臨界計量輔助機器可直接連接至進料至螺桿中的射出模製成形設備。因此,超臨界流體在螺桿旋轉期間在生物聚合物熔體內飽和且此產生單相溶液。Therefore, the manufacturing process can start with feeding the granular bioplastic compound from the hopper into the heating barrel by forced hammers. When the particles are slowly moved forward by the special reciprocating screw plunger, the supercritical fluid is introduced through the ejector by a separate supercritical metering auxiliary machine, which can be directly connected to the feed to the screw Injection molding equipment. Therefore, the supercritical fluid is saturated in the biopolymer melt during the rotation of the screw and this produces a single-phase solution.
熔融混合物然後以高背壓推動至加熱腔室中,其中該熔融混合物在藉由電腦介面控制的溫度處熔化。在柱塞前進時,推動熔融生物塑膠化合物穿過噴嘴,該噴嘴抵靠模具,從而允許該熔化生物塑膠化合物穿過閘進入模具空腔。因此,本發泡製程可經組配來用於使聚合物材料經受熱及壓力藉以在有發泡劑的情況下施加至聚合物材料的機械或物理製程。發泡劑可具有化學起源,如習知封閉氣孔EVA發泡之狀況,或該發泡劑可具有惰性起源,如本揭示案之生物可降解且工業上可合成之可撓性發泡體之狀況。因此,鑒於前述內容,在溶液進入模具時,壓力下降,此舉使SCF從產生氣孔核的溶液出來。The molten mixture is then pushed into the heating chamber with high back pressure, where the molten mixture melts at a temperature controlled by a computer interface. As the plunger advances, the molten bioplastic compound is pushed through the nozzle, which abuts the mold, allowing the molten bioplastic compound to pass through the gate and into the cavity of the mold. Therefore, the foaming process can be configured to be used in a mechanical or physical process of subjecting the polymer material to heat and pressure to be applied to the polymer material in the presence of a foaming agent. The foaming agent may have a chemical origin, such as the conventional closed-cell EVA foaming condition, or the foaming agent may have an inert origin, such as the biodegradable and industrially-synthesizable flexible foam of the present disclosure situation. Therefore, in view of the foregoing, when the solution enters the mold, the pressure drops, which causes the SCF to come out of the solution that produces pore nuclei.
具體而言,超臨界流體在螺桿旋轉期間在生物聚合物熔體內飽和,且此在一定溫度及壓力下產生單相溶液。熔融混合物以高背壓推動至加熱模具腔室中,且單相溶液之壓力自微氣孔製程壓力下降至大氣壓力,因此快速壓力減負載發生。成核現象由於自混合物分離出來的氣體而發生。此時,核生長至穩定氣泡中。氣泡大小藉由全部可藉由本系統及方法控制的飽和、微氣孔製程壓力,及混合物溫度決定。因此,當數百萬的核經產生且核為穩定的時,氣泡生長開始。Specifically, the supercritical fluid is saturated in the biopolymer melt during the rotation of the screw, and this produces a single-phase solution at a certain temperature and pressure. The molten mixture is pushed into the heated mold cavity with high back pressure, and the pressure of the single-phase solution drops from the microporous process pressure to atmospheric pressure, so rapid pressure reduction occurs. The nucleation phenomenon occurs due to the gas separated from the mixture. At this time, the nucleus grows into a stable bubble. The bubble size is determined by the saturation, microporous process pressure, and mixture temperature that can all be controlled by the system and method. Therefore, when millions of nuclei are produced and the nuclei are stable, bubble growth begins.
氣泡形態學藉由SCF濃度以及射出模製成形製程參數決定。因此,此等參數可經選擇來用於由系統控制,以便生產有用及/或決定的氣泡形態學。在零件之模製成形結束時,模具經冷卻且熔體溫度降低,此迫使熔體凍結且固化。另外,此等參數可藉由系統緊密地控制,諸如取決於將要生產的終端產品。特定而言,此時,氣泡停止生長且所得零件之形狀經固定。氣孔然後生長直至材料填充模具,且SCF之膨脹能力耗盡。The bubble morphology is determined by the SCF concentration and injection molding process parameters. Therefore, these parameters can be selected for control by the system in order to produce useful and/or determined bubble morphology. At the end of the molding of the part, the mold is cooled and the melt temperature is reduced, which forces the melt to freeze and solidify. In addition, these parameters can be tightly controlled by the system, such as depending on the end product to be produced. Specifically, at this time, the growth of bubbles stops and the shape of the resulting part is fixed. The pores then grow until the material fills the mold and the expansion capacity of the SCF is exhausted.
因此,在此製程中,熔融生物聚合物及SCF摻和物經可控制地射注至加熱模具空腔中,且經歷突然壓降。數百萬的微小氣泡由核生長生產,且此等氣泡物理地迫使熔融混合物膨脹至模具空腔之最大約束。在熔融混合物膨脹至最大物理可能時,材料在模具內快速冷卻且氣泡停止形成,熔融混合物停止膨脹,且最終固化零件經形成。所有此舉在射出模製成形系統內發生在幾秒內。Therefore, in this process, the molten biopolymer and SCF blend is controllably injected into the cavity of the heated mold and undergoes a sudden pressure drop. Millions of tiny bubbles are produced by nuclear growth, and these bubbles physically force the molten mixture to expand to the maximum confinement of the mold cavity. When the molten mixture expands to the maximum physical possibility, the material cools rapidly in the mold and the formation of bubbles stops, the molten mixture stops expanding, and finally a solidified part is formed. All this happens within a few seconds in the injection molding system.
如所指示,此製造製程在以上描述的射出模製成形機上運行,該等射出模製成形機已經修改以精細地控制:計量、輸送、混合、溫度、壓力、射出、速度等等。例如,輔助計量單元可用來控制用於將精確的SCF氣體配料輸送至聚合物熔體中的計量。特定而言,合適的氣體配料輔助機器可經組配來將惰性氣體轉換成超臨界流體狀態,且計量輸送至射出模製成形機中的SCF輸送之配料,諸如藉由電腦控制機構。As indicated, this manufacturing process runs on the injection molding machines described above, which have been modified to finely control: metering, conveying, mixing, temperature, pressure, injection, speed, etc. For example, the auxiliary metering unit can be used to control the metering used to deliver precise SCF gas ingredients into the polymer melt. In particular, a suitable gas batching auxiliary machine can be configured to convert the inert gas into a supercritical fluid state, and to meter the batches delivered by the SCF in the injection molding machine, such as by a computer control mechanism.
例如,操作者或適當組配的微控制器可將氣體配料輔助機器程式設計至預先決定的SCF氣體配料量。實質上,氣體配料輔助機器為SCF輸送系統,該SCF輸送系統可電子地及/或實體地耦接至射出模製成形機。特定而言,用於使用在本揭示案中之合適的SCF氣體配料輔助機器可經組配來生產氣體配料系統之線路,該等氣體配料系統經設計以將工業級氮或其他惰性氣體轉換成超臨界流體。氣體配料設備可經組配來以高達且甚至超過275巴之壓力將SCF準確地配料且注射至射出模製成形機中。For example, the operator or a properly configured microcontroller can program the gas batching auxiliary machine to a predetermined SCF gas batching volume. In essence, the auxiliary gas batching machine is an SCF delivery system, which can be electronically and/or physically coupled to the injection molding machine. In particular, the appropriate SCF gas batching auxiliary machine used in this disclosure can be assembled to produce the circuit of the gas batching system, which is designed to convert industrial-grade nitrogen or other inert gases into Supercritical fluid. The gas batching equipment can be assembled to accurately batch and inject SCF into the injection molding machine at a pressure of up to and even more than 275 bar.
為操作氣體配料設備,操作者可利用相關聯的計算裝置,諸如桌上型或膝上型計算裝置,該相關聯的計算裝置經組配來用於生產用於控制系統設備及各別控制參數諸如配料設備之圖形化使用者介面(graphical user interface;GUI)。例如,操作者可將選定的參數,例如,所要的SCF氣體配料射注參數,輸入至GUI中。系統之處理元件然後即時地計算所有子參數且最佳化輸送至射出模製成形機中的SCF輸送。因此,系統之控制單元確保氣體配料系統及射出模製成形機一起協作地工作,諸如藉由電腦控制之網路。因此,此氣體配料系統係本揭示案之獨特屬性,因為超臨界惰性氣體可代替使用在習知可撓性發泡體中的化學反應性發泡劑而不費力地用作用於生產本揭示案之生物可降解且工業上可合成之可撓性發泡體之物理發泡劑。對將SCF混合至生物聚合物中之此控制為對於產生單相溶液有用的。In order to operate the gas batching equipment, the operator can use the associated computing device, such as a desktop or laptop computing device, the associated computing device is configured for the production of control system equipment and individual control parameters Such as the graphical user interface (GUI) of the batching equipment. For example, the operator can input selected parameters, such as the desired SCF gas injection parameters, into the GUI. The processing components of the system then calculate all sub-parameters in real time and optimally deliver them to the SCF delivery in the injection molding machine. Therefore, the control unit of the system ensures that the gas batching system and the injection molding machine work cooperatively, such as a network controlled by a computer. Therefore, this gas dosing system is a unique attribute of this disclosure, because supercritical inert gas can replace the chemically reactive blowing agent used in conventional flexible foams and effortlessly be used to produce this disclosure. The biodegradable and industrially synthesizable flexible foam physical foaming agent. This control of mixing SCF into biopolymers is useful for producing single-phase solutions.
此外,在本揭示案之射出模製成形製程期間,SCF經注射至聚合物熔體中。聚合物-SCF混合溶液之單相係在射出模製成形機螺桿及桶內之明確溫度及壓力下獲得。溫度及壓力可為可變可控制的,且直接涉及正生產的可撓性發泡體之類型及終端產品將使被使用的應用之類型。在此級段中,SCF之濃度藉由飽和、微氣孔製程壓力,及混合溫度決定。實例可經提供來用於製作用於使用在製作發泡家具、汽車、運動、及/或鞋零件,特定而言鞋中底中的本揭示案之生物可降解且工業上可合成之可撓性發泡體。用於使用在此非限制實例中的合適的生物聚合物摻和物之非限制實例為形成至生物聚合物化合物中的可快速再生的PBAT生物聚酯。In addition, during the injection molding process of the present disclosure, SCF is injected into the polymer melt. The single phase of the polymer-SCF mixed solution is obtained under a clear temperature and pressure in the screw and barrel of the injection molding machine. Temperature and pressure can be variable and controllable, and are directly related to the type of flexible foam being produced and the type of application in which the end product will be used. In this stage, the concentration of SCF is determined by saturation, microporous process pressure, and mixing temperature. Examples can be provided for use in making foamed furniture, automobiles, sports, and/or shoe parts, specifically the biodegradable and industrially synthesizable flexible of the present disclosure in the midsole of the shoe性foam. A non-limiting example of a suitable biopolymer blend for use in this non-limiting example is a rapidly renewable PBAT biopolyester formed into a biopolymer compound.
因此,顆粒狀生物聚合物化合物首先經由漏斗進料至射出模製成形機中。接下來,當特定SCF氣體配料經引入且均質地混合至現在熔融的生物聚合物化合物中,從而使該熔融生物聚合物化合物完全飽和時,生物聚合物緩慢地穿過射出模製成形機螺桿及桶移動。熔融生物聚合物化合物及SCF現在為單相溶液。初始SCF氣體濃度之非限制實例可為Co = 0.25%,具有介於176℃與250℃之間的熔融溫度範圍,且更佳地在180℃之範圍內。Therefore, the particulate biopolymer compound is first fed into the injection molding machine via the hopper. Next, when a specific SCF gas ingredient is introduced and homogeneously mixed into the currently molten biopolymer compound, so that the molten biopolymer compound is completely saturated, the biopolymer slowly passes through the injection molding machine screw and The barrel moves. The molten biopolymer compound and SCF are now single-phase solutions. A non-limiting example of the initial SCF gas concentration may be Co = 0.25%, with a melting temperature range between 176°C and 250°C, and more preferably in the range of 180°C.
另外,在各種實施例中,可與壓力一起精細地控制模具內的溫度,諸如在動態模具溫度控制(DMTC)協定中。例如,DMTC製程可經利用來確保膨脹生物聚合物熔體內的一致氣孔結構。具體而言,DMTC可經組配以便包括射出填充級段期間的模具溫度及/或壓力之快速變化及控制。此藉此在有或無壓力的情況下就熱及冷熱循環兩者而言動態地控制模具溫度及/或壓力。Additionally, in various embodiments, the temperature within the mold can be finely controlled along with the pressure, such as in a dynamic mold temperature control (DMTC) protocol. For example, the DMTC process can be used to ensure a consistent pore structure in the expanded biopolymer melt. Specifically, the DMTC can be configured to include rapid changes and control of mold temperature and/or pressure during the injection and filling stage. This thereby dynamically controls the mold temperature and/or pressure in terms of both heat and cold heat cycles with or without pressure.
例如,系統之控制模組可經組配,以便在射出填充級段期間控制模具溫度,例如,在此類實例中,可利用動態模具溫度控制。更具體而言,與按照慣例已知的射出模製成形製程相比,本文所利用的動態模具溫度控制之重要特性在於模具溫度自身可經動態地控制。在單相溶液之熔體射出之前,模具可首先經加熱至預設上限。在熔體填充級段期間,模具空腔表面之溫度可保持高於上限以防止熔體過早地固化。當熔體填充製程已結束時,模具快速冷卻至下限(噴出溫度),且然後模製成形的發泡體零件經噴出模具空腔。For example, the control module of the system can be configured to control the mold temperature during the injection and filling stage, for example, in such instances, dynamic mold temperature control can be utilized. More specifically, compared with the conventionally known injection molding process, the important feature of the dynamic mold temperature control used herein is that the mold temperature itself can be dynamically controlled. Before the melt of the single-phase solution is injected, the mold can be heated to a preset upper limit first. During the melt filling stage, the temperature of the mold cavity surface can be kept above the upper limit to prevent the melt from solidifying prematurely. When the melt filling process has ended, the mold is rapidly cooled to the lower limit (spray temperature), and then the molded foam parts are sprayed out of the mold cavity.
如本文實行的動態模具溫度控制(DMTC)依賴基於快速電氣桿加熱及快速水冷卻的控制方法。具體而言,由本揭示案利用的DMTC由五個主要組件組成:空氣壓縮機、閥交換裝置、電腦控制的模具溫度控制單元、電氣加熱模具、及冷卻塔。冷卻塔可用來將充分的水冷卻供應至模具。空氣壓縮機用來生產壓縮空氣作為氣動閥之驅動氣體且用來在冷卻之後排除殘餘冷卻水以免進入模具。閥交換裝置用來切換閥以將不同介質自管線傳遞至模具,諸如熱及冷熱循環。The dynamic mold temperature control (DMTC) implemented in this paper relies on a control method based on rapid electric pole heating and rapid water cooling. Specifically, the DMTC used in the present disclosure is composed of five main components: an air compressor, a valve exchange device, a computer-controlled mold temperature control unit, an electric heating mold, and a cooling tower. The cooling tower can be used to supply sufficient water cooling to the mold. The air compressor is used to produce compressed air as the driving gas of the pneumatic valve and to remove the residual cooling water after cooling to avoid entering the mold. The valve exchange device is used to switch the valve to transfer different media from the pipeline to the mold, such as heat and cold heat cycles.
因此,在各種實例中,本文機器及製程可包括用於反應材料之傳送的管道及其他導管,該等導管與一或多個熱交換單元相關聯,以便在反應物經泵送至導管及管道中且/或穿過導管及管道時加熱且/或冷卻了反應物。在此實例中,交換器可經控制以將溫度調整至反應水平。在管道之一個末端上可包括分配頭,該分配頭可與一或多個閥相關聯。此外,分配頭可向上鉤掛至處理線路。電氣加熱模具用於模製成形發泡零件之最終形狀。模具溫度控制之功能將控制模具之加熱及冷卻;所有此舉藉由電腦控制與射出模製成形機協調。Therefore, in various examples, the machines and processes herein may include pipes and other conduits for the transfer of reactive materials, and these pipes are associated with one or more heat exchange units so that the reactants are pumped to the conduits and pipes. The reactants are heated and/or cooled while passing through conduits and pipes. In this example, the exchanger can be controlled to adjust the temperature to the reaction level. A dispensing head may be included on one end of the pipe, which may be associated with one or more valves. In addition, the dispensing head can be hooked up to the processing line. Electric heating molds are used to mold the final shape of foamed parts. The function of mold temperature control will control the heating and cooling of the mold; all this is coordinated with the injection molding machine by computer control.
同樣地,如所指示,壓力亦可諸如藉由氣體反壓力(GCP)協定精細地控制。例如,GCP協定可經利用於製造製程中,以便更好地確保終端產品之最佳發泡體結構,且以在所得可撓性發泡體上存在極小直至無表皮的方式進行此舉。例如,使用此GCP製程,可以SCF注射加壓模具空腔,該SCF單獨且一起可起作用以抵抗熔體內之氣體之膨脹。具體而言,在反壓力經釋放時,將按照慣例突破表面的氣體氣泡經捕獲在內側,從而產生光滑表皮。Likewise, as indicated, the pressure can also be finely controlled, such as by the gas back pressure (GCP) protocol. For example, the GCP protocol can be used in the manufacturing process to better ensure the best foam structure of the end product, and this is done in a way that there is very little to no skin on the resulting flexible foam. For example, using this GCP process, SCF can be injected to pressurize the mold cavity, and the SCF alone and together can act to resist the expansion of the gas in the melt. Specifically, when the back pressure is released, the gas bubbles that have conventionally broken through the surface are trapped inside to produce a smooth skin.
在發泡零件經形成時,此氣體反壓製製程防止氣體氣泡接觸且穿透發泡材料之表面。此係藉由抵抗壓力達成,該抵抗壓力係藉由GCP系統在熔融單相溶液射出射注及保持時間的相同時間或圍繞該相同時間施加至模具空腔中。惰性氣體氣泡經受巨大的力,且因此熔融單相溶液在正形成時未被給予將所捕獲氣泡釋放至發泡結構外側的機會。結果為模製成形發泡體零件於零件外側上形成具有美觀外表光滑之表皮。When the foamed part is formed, the gas back pressure process prevents gas bubbles from contacting and penetrating the surface of the foamed material. This is achieved by resisting pressure, which is applied to the mold cavity by the GCP system at the same time or around the same time when the molten single-phase solution is injected and held. The inert gas bubbles experience great force, and therefore the molten single-phase solution is not given an opportunity to release the trapped bubbles to the outside of the foamed structure when the molten single-phase solution is being formed. The result is that the molded foam part forms an aesthetically smooth skin on the outside of the part.
因此,如本文實行的,系統之控制器可實行氣體反壓力(GCP)程序,該氣體反壓力程序經組配來藉由在發泡體注射模製成形之熔體射出級段施加不同的氣體壓力來改良發泡製程之控制。例如,藉由控制系統之各種組件,控制系統可經組配來施加變化的螺桿含有的SCF單相溶液壓力及GCP壓力,諸如與適當射注大小、射注保持時間、熔體溫度、及模具溫度一致。Therefore, as implemented in this article, the controller of the system can implement a gas back pressure (GCP) program that is configured to apply different gases to the melt injection stage of foam injection molding. Pressure to improve the control of the foaming process. For example, by controlling the various components of the system, the control system can be configured to apply changes in the SCF single-phase solution pressure and GCP pressure contained in the screw, such as the appropriate injection size, injection holding time, melt temperature, and mold The temperature is the same.
以此方式,產生可藉以生產高品質且商業上可接受的生物可降解且工業上可合成之可撓性發泡體零件的整個系統。特定而言,GCP壓力之微小變化影響發泡體之表面品質。例如,在不使用GCP的情況下,位於模具空腔內的聚合物熔體中之所形成氣泡可釋放且所得發泡零件之外表外觀可並非可接受的。另外,在不使用GCP的情況下,表皮厚度可為不合需要地厚的,因為在熔融單相溶液膨脹至模具中時,不存在反壓力來抵抗熔融單相溶液之快速冷卻。具體而言,單相溶液將在射出射注期間碰撞鋼模邊界,且立即固化,具有對於大多數商業應用為不可接受的不合需要的厚表皮。總之,製程參數具有對最終零件品質之可論證衝擊。因此,以此等方式,可以控制發泡的方式實行GCP製程,諸如藉由表面品質、發泡體結構、表皮厚度等等中之一或多個。In this way, an entire system can be produced by which high-quality and commercially acceptable biodegradable and industrially synthesizable flexible foam parts can be produced. In particular, small changes in GCP pressure affect the surface quality of the foam. For example, without using GCP, the bubbles formed in the polymer melt located in the cavity of the mold can be released and the appearance of the resulting foamed part may not be acceptable. In addition, without using GCP, the skin thickness can be undesirably thick because when the molten single-phase solution expands into the mold, there is no back pressure to resist the rapid cooling of the molten single-phase solution. Specifically, a single-phase solution will hit the steel mold boundary during injection and solidify immediately, with an undesirable thick skin that is unacceptable for most commercial applications. In short, the process parameters have a demonstrable impact on the quality of the final part. Therefore, in this way, the GCP process can be controlled in the manner of foaming, such as by one or more of the surface quality, foam structure, skin thickness, and so on.
因此,在各種實施例中,系統可經組配以便以一方式生產SCF以便形成單相溶液。具體而言,在各種實施例中,產生單相溶液,其中SCF可經:完全溶解且均勻分散在熔融生物聚合物中,此在謹慎控制的製程條件下發生在射出桶內側。例如,如所論述,單相溶液之形成係對於生產本揭示案之一致可大量生產的模製成形發泡體零件關鍵的。Therefore, in various embodiments, the system can be configured to produce SCF in a manner so as to form a single phase solution. Specifically, in various embodiments, a single-phase solution is produced in which SCF can be completely dissolved and uniformly dispersed in the molten biopolymer, which occurs inside the injection barrel under carefully controlled process conditions. For example, as discussed, the formation of a single-phase solution is critical for producing molded foam parts that can be mass-produced consistent with this disclosure.
因此,射出模製成形系統製程應經組配為以非常一致的方式可控制且可重複的。為達成此舉,第一防線將確保生物聚合物化合物及SCF經同質地混合至單相溶液中,諸如其中單相溶液完全飽和且分散在射出模製成形機桶內的生物聚合物熔體內。一旦達成單相溶液,系統可以可靠地輸入所要的射注重量、射注保持時間、及GCP氣體配料,以用於以時間最佳化且可大量生產的方式定製不斷可再生的模製成形發泡體零件。Therefore, the injection molding system process should be configured to be controllable and repeatable in a very consistent manner. To achieve this, the first line of defense will ensure that the biopolymer compound and SCF are homogeneously mixed into a single-phase solution, such as the biopolymer melt in which the single-phase solution is fully saturated and dispersed in the barrel of the injection molding machine. Once a single-phase solution is reached, the system can reliably input the required injection weight, injection holding time, and GCP gas ingredients for customizing continuous and renewable molding in a time-optimized and mass-produced manner Foam parts.
如此,SCF應經精確地質量流量計量至生物聚合物中持續固定量的時間。例如,系統控制模組可經組配,使得在配料週期期間,在桶內建立以下正確條件:溫度、壓力及剪力。同樣地,背壓、螺桿速度及桶溫度可藉由系統之一或多個控制元件精細地控制。另外,SCF輸送系統可經調變,以便建立產生最佳單相溶液的製程條件。In this way, the SCF should be accurately measured by mass flow rate into the biopolymer for a constant amount of time. For example, the system control module can be configured so that during the batching cycle, the following correct conditions are established in the barrel: temperature, pressure, and shear. Similarly, back pressure, screw speed and barrel temperature can be finely controlled by one or more control elements of the system. In addition, the SCF delivery system can be adjusted to establish process conditions that produce the best single-phase solution.
例如,如以上所論述,控制模組可經可通訊地耦接至系統相關聯的質量流量計量裝置,該系統相關聯的質量流量計量裝置經組配來量測穿過系統之一或多個容器(例如,管材)行進的流體之質量流率。質量流率為每單位時間行進經過固定點的流體之質量。在其涉及本揭示案時,質量流計量之原理經實行來確保發泡體模製成形製程中之一致可重複性。特定而言,如以上所描述,特別設計的噴射器耦接至射出模製成形桶,該射出模製成形桶能夠藉由系統之處理器之電腦控制的程式設計控制。因此,系統可經組配來實行輸送至生物聚合物熔體中的特定SCF氣體配料輸送,且電腦控制的程式可基於來自質量流率之即時資料之收集來最佳化輸送,諸如藉由來自一或多個系統感測器之回饋。質量流量計量之此使用確保用於本發明之單相溶液之最多最佳製程控制。For example, as discussed above, the control module may be communicably coupled to a mass flow measurement device associated with the system, and the mass flow measurement device associated with the system is configured to measure through one or more of the systems The mass flow rate of the fluid traveling through the container (for example, a pipe). The mass flow rate is the mass of the fluid that travels through a fixed point per unit time. When it relates to the present disclosure, the principle of mass flow measurement is implemented to ensure consistent repeatability in the foam molding process. In particular, as described above, a specially designed ejector is coupled to the injection molded barrel, which can be controlled by a computer-controlled programming control of the processor of the system. Therefore, the system can be configured to deliver specific SCF gas ingredients to the biopolymer melt, and the computer-controlled program can optimize the delivery based on the collection of real-time data from the mass flow rate, such as by Feedback from one or more system sensors. This use of mass flow metering ensures the most optimal process control of the single-phase solution used in the present invention.
因此,在配料週期期間,遍及系統(諸如桶內)的溫度可經控制以便介於100℃與600℃之間,諸如介於200℃與500℃之間,例如,介於300℃與400℃之間,且更具體而言,介於320℃與380℃之範圍之間,包括桶內介於360℃與380℃之間。同樣地,SCF輸送壓力可經精細地控制,以便在介於1,000 PSI與8,000 PSI之間的範圍內,諸如在1,500 PSI與6,000 PSI之間,例如,在2,000 PSI與5,500 PSI之間,具體而言,在3,000 PSI與4,000 PSI之間,且更具體而言在2,600 PSI與2,800 PSI之範圍之間。Therefore, during the batching cycle, the temperature throughout the system (such as the barrel) can be controlled so as to be between 100°C and 600°C, such as between 200°C and 500°C, for example, between 300°C and 400°C Between, and more specifically, between 320°C and 380°C, including between 360°C and 380°C in the barrel. Similarly, the SCF delivery pressure can be finely controlled so as to be within a range between 1,000 PSI and 8,000 PSI, such as between 1,500 PSI and 6,000 PSI, for example, between 2,000 PSI and 5,500 PSI, and In other words, between 3,000 PSI and 4,000 PSI, and more specifically between 2,600 PSI and 2,800 PSI.
以此方式,控制模組可經組配,使得溫度及壓力一致地工作以產生最佳核及生物聚合物熔體內之所得氣泡及所得發泡基質。另外,關於剪力,當熔融生物聚合物之層相對於彼此流動時,在桶內建立剪力。因此,在射出期間,可使熔融生物聚合物化合物流過桶噴嘴之熔體輸送通道,諸如在如噴泉進入模具之前。In this way, the control module can be configured so that the temperature and pressure work consistently to produce the optimal core and the resulting bubbles in the biopolymer melt and the resulting foamed matrix. In addition, with regard to the shear force, when the layers of molten biopolymer flow relative to each other, a shear force is established in the barrel. Therefore, during injection, the molten biopolymer compound can be allowed to flow through the melt delivery channel of the barrel nozzle, such as before entering the mold such as a fountain.
剪切為旋轉螺桿與固定桶之間的生物聚合物之伸展,從而使熱在材料內顯現。因此,應在射出模製成形製程中控制剪力。因此,系統之一或多個控制單元可經組配,諸如用於控制射出速度、填充時間、及其中的公差,以便在給定射出模製成形機大小的情況下,且在給定射出模製成形機螺桿及桶大小的情況下,達成用於生產給定生物聚合物化合物之正確條件。Shearing is the stretching of the biopolymer between the rotating screw and the fixed barrel, so that the heat appears in the material. Therefore, the shear force should be controlled during the injection molding process. Therefore, one or more control units of the system can be configured, such as used to control the injection speed, filling time, and tolerances therein, so that in the case of a given injection molding machine size, and in a given injection mold In the case of the size of the screw and barrel of the forming machine, the correct conditions for the production of a given biopolymer compound are achieved.
背壓亦可經控制。例如,背壓為射出模製成形機內的當生物聚合物注射至模具中時由該生物聚合物施加的壓力。特定而言,背壓為在射出螺桿收回以裝載射注至模具中的下一生物聚合物時施加至射出螺桿的阻力。如以上所指示,系統之各種參數可經組配以便控制且/或調變背壓。Back pressure can also be controlled. For example, the back pressure is the pressure applied by the biopolymer when the biopolymer is injected into the mold in the injection molding machine. Specifically, the back pressure is the resistance applied to the injection screw when the injection screw is retracted to load the next biopolymer injected into the mold. As indicated above, various parameters of the system can be configured to control and/or adjust the back pressure.
此外,系統之控制器可經組配來控制且調變螺桿速度。螺桿速度可藉由電腦控制加以控制。如所指示,在射出模製成形操作之初始階段期間,螺桿在桶內旋轉以與SCF氣體一致地使熔融生物聚合物化合物混合物均質。本揭示案之螺桿速度之非限制實例可為自1 rpm或5 rpm或10 rpm至75 rpm或100 rpm或200 rpm,例如,自20 rpm、25 rpm,或30 rpm至40 rpm、50 rpm或60 rpm。In addition, the controller of the system can be configured to control and adjust the screw speed. The screw speed can be controlled by computer control. As indicated, during the initial stage of the injection molding operation, the screw rotates within the barrel to homogenize the molten biopolymer compound mixture in accordance with the SCF gas. Non-limiting examples of the screw speed of the present disclosure can be from 1 rpm or 5 rpm or 10 rpm to 75 rpm or 100 rpm or 200 rpm, for example, from 20 rpm, 25 rpm, or 30 rpm to 40 rpm, 50 rpm or 60 rpm.
系統可包括加熱及/或冷卻控制單元,該加熱及/或冷卻控制單元可與桶相關聯,以便控制其中的溫度。因此,控制模組可經組配來控制桶溫度。因此,桶溫度可經控制以便根據發泡製程之需要使其中的溫度更熱或更冷。The system may include a heating and/or cooling control unit, which may be associated with the barrel in order to control the temperature therein. Therefore, the control module can be configured to control the barrel temperature. Therefore, the barrel temperature can be controlled to make the temperature hotter or colder according to the needs of the foaming process.
因此,鑒於以上內容,SCF輸送系統可包括控制單元,該控制單元經組配來控制SCF輸送壓力及SCF劑量重量之組合,該SCF劑量重量通常以克為單位量測。SCF壓力及劑量可以一方式控制以便影響單相溶液。亦即,SCF劑量越小,生物聚合物熔體內的SCF飽和需求越小,而SCF劑量越大,熔體內的SCF飽和需求越大。同樣地,SCF輸送壓力越小,飽和之攝取越低,且因此可生長以在熔融生物聚合物熔體內形成氣泡的核之生長越低。同樣地,SCF輸送壓力越大,飽和之攝取越大,且因此可生長以在熔融熔體內形成氣泡的核之生長越大。Therefore, in view of the above, the SCF delivery system may include a control unit that is configured to control the combination of the SCF delivery pressure and the SCF dose weight. The SCF dose weight is usually measured in grams. SCF pressure and dosage can be controlled in a way to affect single-phase solutions. That is, the smaller the SCF dose, the smaller the SCF saturation requirement in the biopolymer melt, and the larger the SCF dose, the greater the SCF saturation requirement in the melt. Likewise, the lower the SCF delivery pressure, the lower the uptake of saturation, and therefore the lower the growth of the nucleus that can grow to form bubbles in the molten biopolymer melt. Likewise, the greater the SCF delivery pressure, the greater the uptake of saturation, and therefore the greater the growth of nuclei that can grow to form bubbles in the molten melt.
關於飽和,系統及設備經組配來用於在一溫度及一壓力下將氣體輸送至熔體腔室,使得超臨界流體在生物聚合物熔體內形成且飽和,諸如在螺桿旋轉期間。因此,在受控制的溫度及壓力下產生單相溶液。特定而言,聚合物-SCF混合溶液之單相在本文中可在射出模製成形機螺桿及桶內之明確溫度及壓力下獲得。更特定而言,系統控制器可以取決於正生產的可撓性發泡體之類型及正生產的終端產品用於何類型的方式可變地控制溫度及壓力。Regarding saturation, the system and equipment are configured to deliver gas to the melt chamber at a temperature and a pressure such that supercritical fluid is formed and saturated in the biopolymer melt, such as during screw rotation. Therefore, a single-phase solution is produced at a controlled temperature and pressure. In particular, the single phase of the polymer-SCF mixed solution can be obtained in this article at a specific temperature and pressure in the screw and barrel of the injection molding machine. More specifically, the system controller can variably control the temperature and pressure in a manner that depends on the type of flexible foam being produced and the type of end product being produced.
在此級段中,SCF之濃度可諸如藉由回饋迴路決定且控制,藉此諸如藉由感測器決定飽和量,該感測器評估飽和製程進展且然後基於達成用於飽和水平之決定設定點來調變微氣孔製程壓力及混合溫度。在此實例中,超臨界流體(SCF)在螺桿旋轉期間在生物聚合物熔體內可控制地飽和,且此在明確的溫度及壓力下產生單相溶液。SCF為兩部分熔融生物聚合物化合物混合物之一個部分,且其在存在本射出模具中之明確的壓力及溫度的情況下用作物理發泡劑。In this stage, the concentration of SCF can be determined and controlled, such as by a feedback loop, thereby determining the amount of saturation, such as by a sensor, which evaluates the progress of the saturation process and then sets it based on reaching a determination for the saturation level Click to adjust the micro-pore process pressure and mixing temperature. In this example, the supercritical fluid (SCF) is controllably saturated in the biopolymer melt during the rotation of the screw, and this produces a single-phase solution at a defined temperature and pressure. SCF is one part of a two-part molten biopolymer compound mixture, and it is used as a physical blowing agent in the presence of a clear pressure and temperature in the injection mold.
因此,鑒於以上內容,在一個態樣中,本文提供的是機器及將該機器使用於生物可降解且工業上可合成之微氣孔可撓性發泡體之生產的方法。具體而言,在一個實例中,發泡體經生產及/或使用在發泡產品之生產中,諸如藉由微氣孔射出模製成形(microcellular injection molding;MuCell)製程,例如,MuCell製造。MuCell製造利用超臨界流體,如以上所描述,該超臨界流體經受極高壓力且溶解至製造工具之螺桿桶內之聚合物熔體中,諸如以下所描述,該製造工具經組配來用於最佳化SCF配料以用於產生熔融生物聚合物之目的,該熔融生物聚合物經加熱至液態。Therefore, in view of the above content, in one aspect, what is provided herein is a machine and a method for using the machine in the production of a biodegradable and industrially synthesizable microporous flexible foam. Specifically, in one example, the foam is produced and/or used in the production of foamed products, such as by a microcellular injection molding (MuCell) process, for example, MuCell manufacturing. MuCell manufacturing utilizes supercritical fluid, as described above, the supercritical fluid is subjected to extremely high pressure and dissolves into the polymer melt in the screw barrel of the manufacturing tool, such as described below, the manufacturing tool is assembled for The SCF formulation is optimized for the purpose of producing molten biopolymer, which is heated to a liquid state.
因此,在射出模製成形機之中心部處為含於其中的射出模製成形機桶及螺桿,該射出模製成形機桶及螺桿兩者通常由工具鋼製成。桶為用於本單相溶液在經計量且然後按壓或「射注」至動態溫度控制的模組件中之前的主要輸送入口。因此,生物聚合物熔體藉由射出模製成形機漏斗輸送至桶中。且系統控制器將給定量的粒狀生物塑膠小丸進料至漏斗中,作為射出模具機器操作中之第一步驟中之一個。Therefore, at the center of the injection molding machine are the injection molding machine barrel and screw contained therein, and both the injection molding machine barrel and the screw are usually made of tool steel. The barrel is the main delivery inlet for this single-phase solution before it is metered and then pressed or "injected" into the dynamic temperature control mold assembly. Therefore, the biopolymer melt is transported into the barrel through the hopper of the injection molding machine. And the system controller feeds a given amount of granular bioplastic pellets into the hopper as one of the first steps in the operation of the injection mold machine.
特定而言,在射出期間,SCF蒸發且變成氣體氣泡,例如,呈完成模製成形零件之形式的發泡體。因為氣泡達到微米大小,所以製程生產微氣孔發泡。本文所描述之製程為相對於習知射出技術有利的,因為該製程導致生成產品,該生成產品證實以下各者中之一或多個:較少皺縮、輕重量產品,具有少數縮痕,且可藉由低成本前驅物產生。更具體而言,關於較少皺縮,皺縮可藉由理解體積皺縮係由熱收縮引起加以控制,該熱收縮影響所有聚合物,且因而,可藉由經由系統感測器追蹤皺縮進展,且精細地控制桶條件以便調變皺縮製程來避免皺縮。Specifically, during injection, the SCF evaporates and becomes gas bubbles, for example, a foam in the form of a finished molded part. Because the bubbles reach the micron size, the process produces micro-pore foaming. The process described in this article is advantageous over the conventional injection technology because the process results in a product that confirms one or more of the following: less shrinkage, light weight product, with a few sink marks, And can be produced by low-cost precursors. More specifically, with regard to less shrinkage, shrinkage can be controlled by understanding that volume shrinkage is caused by thermal shrinkage, which affects all polymers, and thus, shrinkage can be tracked by the system sensor Advance and finely control barrel conditions in order to adjust the shrinking process to avoid shrinking.
實質上,皺縮描述在材料自液體改變至固體時材料體積變化的程度。在習知射出模製成形中,模具在壓力下未經溫度控制,因此由習知方法使用的熔融聚合物在與射出模具之冷工具鋼接觸時收縮,且此引起皺縮。在本機器及系統中,皺縮可經控制,且通常由於確保熔融生物聚合物在沒有過早冷卻的情況下填充模具內側之最大表面區域的溫度受控制的加壓模具,以及在此方面進一步輔助的加壓模具空腔自身之所施加均勻應力而沒有問題。In essence, shrinkage describes the degree to which the volume of a material changes when it changes from a liquid to a solid. In the conventional injection molding, the mold is not temperature controlled under pressure, so the molten polymer used by the conventional method shrinks when it comes into contact with the cold tool steel of the injection mold, and this causes shrinkage. In this machine and system, shrinkage can be controlled, and is usually due to a pressure-controlled mold that ensures that the molten biopolymer fills the largest surface area inside the mold without premature cooling, and further The auxiliary pressurized mold cavity itself applies uniform stress without problems.
關於作為一般規則的輕重量產品之生產,聚合物膨脹得越多,重量之減少越大。然而,本系統經組配來用於藉由經由適當壓力、溫度及時間之施加調變條件來最佳化單相溶液,使得可達成輕型發泡體之最優品質。此對於需要輕型發泡體的產品應用適用,諸如例如在緩衝墊、鞋類發泡體,及用來生產運動設備的發泡體中。同樣地,關於在習知可撓性發泡體製造中控制縮痕,縮痕及孔隙係在當零件正冷卻時無充分補償的情況下厚區段處的材料之局部化皺縮引起。Regarding the production of lightweight products as a general rule, the more the polymer swells, the greater the weight loss. However, this system is configured to optimize the single-phase solution by applying adjustment conditions of appropriate pressure, temperature, and time, so that the optimal quality of light-weight foam can be achieved. This is suitable for product applications that require lightweight foams, such as, for example, cushions, foams for footwear, and foams used to produce sports equipment. Similarly, with regard to the control of sink marks in the manufacture of conventional flexible foams, sink marks and voids are caused by localized shrinkage of the material at the thick section without sufficient compensation when the part is cooling.
具體而言,縮痕通常發生在與支腳或肋狀物相反及/或鄰接支腳或肋狀物的表面上。此由於不平衡的熱移除及/或類似因素而發生。在發泡零件之外側上的材料已冷卻且固化之後,核心材料開始冷卻。其皺縮向內拉動主壁之表面,從而引起縮痕。若表皮為足夠剛性的,則表皮之變形可藉由核心中之孔隙之形成替換。Specifically, sink marks usually occur on the surface opposite and/or adjacent to the feet or ribs. This occurs due to unbalanced heat removal and/or similar factors. After the material on the outer side of the foamed part has cooled and solidified, the core material begins to cool. The shrinkage pulls the surface of the main wall inward, causing sink marks. If the skin is sufficiently rigid, the deformation of the skin can be replaced by the formation of pores in the core.
不同於習知可撓性發泡體模製成形面臨的縮痕及孔隙挑戰,機器組態及本系統參數是可控制的,以便生產本揭示案之生物可降解且工業上可合成之可撓性發泡體,該生物可降解且工業上可合成之可撓性發泡體最小化此等問題之遭遇。具體而言,在本製程中,以一方式控制SCF氣體,以便調變,例如,最大化,發泡製程內之聚合物基質之氣孔結構。特殊化發泡製程之此最大化更好地確保在最終發泡零件內不存在不合需要的縮痕或孔隙。Different from the challenges of sink marks and pores in conventional flexible foam molding, the machine configuration and the system parameters are controllable in order to produce the biodegradable and industrially synthesizable flexible of the present disclosure. The flexible foam, which is biodegradable and industrially synthesizable, minimizes these problems. Specifically, in this process, the SCF gas is controlled in a way to adjust, for example, maximize the pore structure of the polymer matrix in the foaming process. This maximization of the specialized foaming process better ensures that there are no undesirable sink marks or voids in the final foamed part.
另外,如所指示,本系統之有用效益在於其利用低成本材料,且所生產終端產品具有較少翹曲。具體而言,出於以上所論述之許多原因,本揭示案受益於其中SCF氣體負責最大化發泡製程內之聚合物基質之氣孔結構的製程。特殊化發泡製程之此最大化確保在最終發泡零件內存在最少翹曲。In addition, as indicated, the useful benefits of this system are that it utilizes low-cost materials and the end products produced have less warpage. Specifically, for many of the reasons discussed above, the present disclosure benefits from a process in which SCF gas is responsible for maximizing the pore structure of the polymer matrix in the foaming process. This maximization of the specialized foaming process ensures that there is minimal warpage in the final foamed part.
本系統之另一效益在於其可經組配以便控制公差。例如,系統可經組配來用於執行緊密公差可撓性發泡射出模製成形。具體而言,如本文呈現的緊密公差可撓性發泡射出模製成形可經利用以便生產零件,該等零件一起平滑地工作且有助於產品之總體較低的故障率。Another benefit of this system is that it can be configured to control tolerances. For example, the system can be configured to perform tight tolerance flexible foam injection molding. Specifically, the tight tolerance flexible foam injection molding as presented herein can be used to produce parts that work smoothly together and contribute to the overall lower failure rate of the product.
為使產品可靠地且如預期工作,其零件中之全部必須平滑地配合在一起。因此,本設備及其組件零件已經設計以緊密地控制公差。通常,此等零件係以可能的最佳公差生產。存在可接受公差之不同範圍;例如,非常緊密公差為+/- 0.001”。有時,甚至幾千分之一吋可意味配合的零件與未配合的零件之間的差異。In order for the product to work reliably and as expected, all of its parts must fit together smoothly. Therefore, the equipment and its component parts have been designed to tightly control tolerances. Usually, these parts are produced with the best possible tolerances. There are different ranges of acceptable tolerances; for example, very tight tolerances of +/- 0.001". Sometimes even a few thousandths of an inch can mean the difference between a mated part and an unfitted part.
因此,早期在設計階段中識別緊密公差為有用的。此是因為設計工程師必須將用於發泡零件幾何形狀、總發泡零件大小,及發泡零件壁厚度之要求納入考慮,該發泡零件幾何形狀、該總發泡零件大小,及該發泡零件壁厚度中之全部具有對公差控制之影響,且該發泡零件幾何形狀、該總發泡零件大小,及該發泡零件壁厚度中之全部若未謹慎地管理,則可加重縮痕、翹曲,及不一致零件公差。本系統及設備克服大多數此等設計挑戰,而仍然使用最佳設計實踐,因為SCF氣體在發泡製程內負責最大化聚合物基質之氣孔結構。同樣地,系統可經組配以便在模具內更快速地冷卻。Therefore, it is useful to identify tight tolerances early in the design phase. This is because the design engineer must take into account the requirements for the geometry of the foamed part, the size of the total foamed part, and the wall thickness of the foamed part, the geometry of the foamed part, the size of the total foamed part, and the foamed part All of the part wall thickness has an impact on tolerance control, and if all of the foamed part geometry, the total foamed part size, and the foamed part wall thickness are not managed carefully, sink marks can be aggravated, Warpage, and inconsistent part tolerances. This system and equipment overcome most of these design challenges and still use best design practices because SCF gas is responsible for maximizing the pore structure of the polymer matrix during the foaming process. Likewise, the system can be configured for faster cooling in the mold.
作為前文之結果,大大地減少縮痕、翹曲及公差之不一致性。此在很大程度上係由於發泡體基質內的均勻大小且均勻分佈的顯微氣孔。因此,為達成此等利益,應精細地控制微氣孔發泡製程。例如,如所指示,當發泡沿著熔體前面發生時,前進可在模製成形表面上引入條痕及流痕,藉此引起瑕疵。As a result of the foregoing, sink marks, warpage and tolerance inconsistencies are greatly reduced. This is largely due to the uniform size and uniform distribution of microscopic pores in the foam matrix. Therefore, in order to achieve these benefits, the microcellular foaming process should be carefully controlled. For example, as indicated, when foaming occurs along the front of the melt, advancement can introduce streaks and flow marks on the molded surface, thereby causing flaws.
除上文所述之外,此等瑕疵可在本文中藉由利用共射出及模內裝飾技術中之一或多個進一步最小化。然而,在許多實例中,此可為成本過高的。然而,本系統藉由選擇高級產品機會克服此類成本過高的實例,其中本揭示案之附加價值可經接受且瞭解。In addition to the above, these defects can be further minimized herein by using one or more of co-injection and in-mold decoration techniques. However, in many instances, this can be cost prohibitive. However, this system overcomes such cases of excessive costs by choosing advanced product opportunities, in which the added value of the present disclosure can be accepted and understood.
應注意,在各種實例中,可存在SCF發泡之缺點,如在一些實例中,其可引起熔體黏度及其他實質性質之變化。具體而言,當將SCF均勻地擴散至聚合物熔體中時,單相溶液藉由藉由增加自由體積降低聚合物之黏度而充當可逆增塑劑。此效應亦降低聚合物之玻璃轉變溫度以及聚合物之拉伸強度。此可導致不均勻的氣泡大小。It should be noted that in various examples, there may be disadvantages of SCF foaming. For example, in some examples, it may cause changes in melt viscosity and other substantial properties. Specifically, when the SCF is uniformly diffused into the polymer melt, the single-phase solution acts as a reversible plasticizer by reducing the viscosity of the polymer by increasing the free volume. This effect also reduces the glass transition temperature of the polymer and the tensile strength of the polymer. This can lead to uneven bubble size.
不均勻的氣泡大小可能導致具有遍及零件的不一致技術效能性質以及可能不合意的外表問題的模製成形發泡體零件之生產。當試圖生產在大量生產期間自零件至零件含有相同技術效能性質的一致可再生之生物可降解且工業上可合成之可撓性發泡體時,此兩者為問題。本系統經組配來克服此等困難。Uneven bubble sizes can lead to the production of molded foam parts with inconsistent technical performance properties throughout the part and possibly undesirable appearance problems. When trying to produce consistent, renewable, biodegradable and industrially synthesizable flexible foams that contain the same technical performance properties from part to part during mass production, these two are problems. The system is configured to overcome these difficulties.
因此,如以上所論述,為克服此等缺點,且為更精細地控制微氣孔發泡製程,利用以上論述的氣體反壓力(GCP)。如以上所論述,氣體反壓力經精細地控制,使得在發泡零件經形成時,氣體氣泡經調節以免接觸且穿透發泡材料之表面。此藉由抵抗壓力達成,該抵抗壓力是藉由GCP系統施加至模具空腔中,此舉可在熔融單相溶液經注射的相同時間或大約相同時間,同時控制模具內之保持時間。模具溫度及壓力亦可經精細地控制以用於此等目的。Therefore, as discussed above, in order to overcome these shortcomings and to more finely control the micro-cell foaming process, the gas back pressure (GCP) discussed above is used. As discussed above, the gas back pressure is finely controlled so that when the foamed part is formed, the gas bubbles are adjusted so as not to contact and penetrate the surface of the foamed material. This is achieved by resisting pressure, which is applied to the cavity of the mold by the GCP system, which can control the holding time in the mold at the same time or about the same time that the molten single-phase solution is injected. Mold temperature and pressure can also be finely controlled for these purposes.
一旦注射,惰性氣體氣泡經受巨大的力,且因此熔融單相溶液未被給予在經形成時將所捕獲氣泡釋放至發泡結構外側的機會。同樣地,施加於單相溶液上的巨大的力幫助將數百萬的微小氣泡分佈在模具內側的發泡結構內,並且幫助氣泡大小一致性。結果為模製成形發泡體零件,該模製成形發泡體零件具有形成於零件外側上的外表光滑之表皮,及在大量生產期間自零件至零件的可重複技術效能性質的一致氣泡大小。Once injected, the inert gas bubbles experience great force, and therefore the molten single-phase solution is not given an opportunity to release the trapped bubbles to the outside of the foamed structure when formed. Likewise, the huge force exerted on a single-phase solution helps distribute millions of tiny bubbles within the foaming structure inside the mold, and helps the bubble size uniformity. The result is a molded foam part that has a smooth-surfaced skin formed on the outside of the part and a consistent bubble size with repeatable technical performance properties from part to part during mass production.
例如,系統可經組配以便允許GCP之引入以控制發泡製程,諸如藉由在不同熔體射出級段處施加不同的氣體壓力及/或溫度。因此,GCP經引入模具空腔內之發泡製程中,該模具空腔安放在射出模製成形機內。首先,惰性氣體係藉由氣體壓縮機及氣體泵經由氣體控制閥泵送至模具空腔中。氣體壓力感測器將來自氣體控制值之即時資料饋送回至電腦控制器。For example, the system can be configured to allow the introduction of GCP to control the foaming process, such as by applying different gas pressures and/or temperatures at different melt injection stages. Therefore, the GCP is introduced into the foaming process in the cavity of the mold, and the cavity of the mold is placed in the injection molding machine. First, the inert gas system is pumped into the mold cavity by a gas compressor and a gas pump through a gas control valve. The gas pressure sensor feeds real-time data from the gas control value back to the computer controller.
系統藉由在電腦系統內設定配料參數及保持時間來引發至模具空腔中的GCP配料。電腦系統然後引發至模具空腔中之惰性GCP射注之適當配料。在不使用GCP的情況下,生物聚合物熔體將進入模具空腔且立即開始發泡,從而產生不均勻的氣體氣泡,該等不均勻的氣體氣泡突破表面且在發泡體之外部上產生不合需要的渦流標記,此狀況為成問題的。The system triggers the GCP batching into the mold cavity by setting the batching parameters and holding time in the computer system. The computer system then initiates the proper ingredients for the inert GCP injection into the mold cavity. In the case of not using GCP, the biopolymer melt will enter the cavity of the mold and start to foam immediately, resulting in uneven gas bubbles, which break through the surface and are generated on the outside of the foam Undesirable eddy current markers, this situation is problematic.
同樣地,射出速度亦可經精細地控制,諸如其中射出速度可藉由螺桿壓力(Pscrew)與氣體壓力(Pgas)之間的差異決定。特定而言,當Pscrew稍微高於Pgas,且兩者參數為足夠高的時,SCF溶解熔體流動至模具空腔中而未發泡。設定高於Pgas的Pscrew及低於臨界壓力的Pgas導致局部發泡。最後,Pscrew、Pgas,及與動態模具溫度組合的壓力差之適當選擇致能氣泡大小之更精確控制。因此,藉由微調此等參數,流動誘發的條痕若未完全消除則可經最小化。Similarly, the injection speed can also be finely controlled. For example, the injection speed can be determined by the difference between the screw pressure (Pscrew) and the gas pressure (Pgas). Specifically, when Pscrew is slightly higher than Pgas, and both parameters are sufficiently high, the SCF dissolved melt flows into the mold cavity without foaming. Setting Pscrew higher than Pgas and Pgas lower than the critical pressure causes local foaming. Finally, the proper selection of Pscrew, Pgas, and the pressure difference combined with the dynamic mold temperature enables more precise control of the bubble size. Therefore, by fine-tuning these parameters, flow-induced streaks can be minimized if they are not completely eliminated.
特定而言,此等參數可部分地藉由流動行為之考慮決定。例如,在一個實施例中,流變(流動)係以聚合物熔體之行為生產,在不同模具溫度(185℃、195℃、205℃)、射出速度(5 mm/s、10 mm/s、15 mm/s螺桿速度),及GCP (50巴、100巴、200巴及300巴)下,該聚合物熔體已以N2 之0.4wt% SCF溶解。在此實例中,量測剪切速率在3000-11000s-1範圍內,且當GCP為300巴時,玻璃轉變溫度Tg自96℃降低至50℃。同樣地,在此實例中,與習知射出模製成形相比,當GCP自50巴增加至200巴時,熔體黏度下降約30%。In particular, these parameters can be determined in part by considerations of flow behavior. For example, in one embodiment, the rheology (flow) is produced by the behavior of polymer melt, and the mold temperature (185℃, 195℃, 205℃), injection speed (5 mm/s, 10 mm/s) , 15 mm/s screw speed), and GCP (50 bar, 100 bar, 200 bar and 300 bar), the polymer melt has been dissolved in 0.4wt% SCF of N 2. In this example, the measured shear rate is in the range of 3000-11000 s-1, and when the GCP is 300 bar, the glass transition temperature Tg decreases from 96°C to 50°C. Similarly, in this example, compared with the conventional injection molding, when the GCP is increased from 50 bar to 200 bar, the melt viscosity decreases by about 30%.
特定而言,當GCP為300巴時,無任何發泡的單相射出熔體之黏度可降低多至50%,取決於射出條件。此係有用的,因為其降低壓力要求及溫度要求,此舉藉此降低製造成本,特定而言能量成本,且在生產期間亦降低發泡零件循環時間。因此,此等系統參數由於較低的壓力及溫度要求,及較少循環時間而全部用於較大的能量節省,此狀況轉化至更快地生產且用於較少金錢之更多零件,諸如藉由選擇正確的生物聚合物化合物且定製製程溫度、壓力,及保持時間以配合材料機械性質。Specifically, when the GCP is 300 bar, the viscosity of the single-phase injection melt without any foaming can be reduced by up to 50%, depending on the injection conditions. This is useful because it reduces pressure requirements and temperature requirements, thereby reducing manufacturing costs, in particular energy costs, and also reducing the cycle time of foamed parts during production. Therefore, these system parameters are all used for greater energy savings due to lower pressure and temperature requirements, and less cycle time. This situation translates to faster production and more parts for less money, such as By selecting the correct biopolymer compound and customizing the process temperature, pressure, and holding time to match the mechanical properties of the material.
另外,如所指示,本機器及系統之重要特徵在於其可經組配來用於控制氣泡大小以便為更均勻的。如以上所論述,此可部分地藉由控制溫度、壓力、SCF配料控制、GCP、DMTC及以上論述之其他參數實現。此等屬性中之全部一致地工作來確保最佳、最均勻氣泡大小及其在發泡基質內之最佳均質分散。此外,可藉由控制流體沿著熔體前面之漂移改良表面品質。In addition, as indicated, the important feature of this machine and system is that it can be configured to control the size of the bubbles so as to be more uniform. As discussed above, this can be achieved in part by controlling temperature, pressure, SCF batching control, GCP, DMTC, and other parameters discussed above. All of these attributes work in unison to ensure the best, most uniform bubble size and its best homogeneous dispersion within the foam matrix. In addition, the surface quality can be improved by controlling the drift of the fluid along the front of the melt.
如其名稱表明,熔體前面為熔融單相溶液進入模具空腔所在之點。熔體前面速度為熔體前面前進速度。對於具有複雜空腔幾何形狀的任何模具,空腔之部分可比其他區域填充得更快。藉由控制熔體前面速度,諸如藉由控制溫度、壓力,及SCF配料控制,以及控制其他參數,可達成更均勻的模具空腔填充速度,且此確保所得發泡體零件之表面品質可為外表可接受的。As its name indicates, the front of the melt is the point where the molten single-phase solution enters the cavity of the mold. The speed in front of the melt is the forward speed in front of the melt. For any mold with complex cavity geometry, part of the cavity can be filled faster than other areas. By controlling the front speed of the melt, such as by controlling temperature, pressure, and SCF batching control, as well as controlling other parameters, a more uniform mold cavity filling speed can be achieved, and this ensures that the surface quality of the resulting foam parts can be Appearance acceptable.
因此,一旦單相溶液已經產生,如以上所描述,修改後射出模製成形機將溶液維持在加壓狀態中,直至射出開始。例如,機器可經組配來藉由關斷噴嘴及螺桿位置控制之組合努力達成此舉,如以上所指示。具體而言,關斷噴嘴可經組配以便充當增塑桶(具有往復螺桿)與模具之間的連接。此類關斷噴嘴可經自我控制或外部控制,且其可用來避免熔融注射之間的熔體之流淌且因而防止洩壓及至模具中之過早發泡。Therefore, once the single-phase solution has been produced, as described above, the modified injection molding machine maintains the solution in a pressurized state until the injection starts. For example, the machine can be configured to achieve this by a combination of turning off the nozzle and controlling the screw position, as indicated above. Specifically, the shut-off nozzle can be configured to act as a connection between the plasticizing barrel (with a reciprocating screw) and the mold. Such shut-off nozzles can be self-controlled or externally controlled, and they can be used to avoid the flow of melt between melt injections and thus prevent pressure relief and premature foaming into the mold.
因此,關斷噴嘴防止洩壓及至模具中之過早發泡。例如,在無關斷噴嘴的情況下,單相溶液將不具有模具空腔內之充分壓力,且所要的模製成形發泡體零件將未生產。同樣地,主動或被動螺桿位置控制可經利用來藉由螺桿之向後移動防止洩壓。Therefore, shut off the nozzle to prevent pressure relief and premature foaming into the mold. For example, in the case of an unbroken nozzle, the single-phase solution will not have sufficient pressure in the mold cavity, and the desired molded foam part will not be produced. Likewise, active or passive screw position control can be used to prevent pressure relief by moving the screw backwards.
具體而言,系統可經組配以便實行主動螺桿位置控制,諸如其中螺桿之位置經連續地監視,且施加至螺桿之背部的壓力經調節以維持決定的位置設定點或保持在螺桿之背部上的恆定壓力。例如,在被動位置控制中,防止用來調節背壓力的油在螺桿復原之終點處排至其槽。此殘油阻止螺桿由於單相溶液之壓力而向後移動。Specifically, the system can be configured to implement active screw position control, such as where the position of the screw is continuously monitored, and the pressure applied to the back of the screw is adjusted to maintain a determined position set point or remain on the back of the screw Constant pressure. For example, in passive position control, the oil used to adjust the back pressure is prevented from draining to its groove at the end of the screw recovery. This residual oil prevents the screw from moving backward due to the pressure of the single-phase solution.
另外,如以上所指示,適當的模具設計幫助維持單相溶液。特定而言,在其中模具包括熱澆道系統的彼等實例中,一或多個閥閘可經包括且控制,以便防止材料自噴嘴滴漏,諸如在模具開放時。更具體而言,熱澆道系統(hot runner system)可在本文中使用於射出模製成形設備中,且可包括零件系統,該等零件經物理加熱,使得該等零件可更有效地用來將熔融塑膠自機器之噴嘴傳遞至模具工具空腔。例如,可使用「冷澆道」或「熱澆道」,諸如其中冷澆道為未加熱的實體通道,該未加熱的實體通道經利用來在熔融塑膠離開噴嘴之後將熔融塑膠導向至模具空腔中,且熱澆道經加熱而冷澆道不加熱。In addition, as indicated above, proper mold design helps maintain a single-phase solution. In particular, in those instances where the mold includes a hot runner system, one or more valve gates may be included and controlled to prevent material from dripping from the nozzle, such as when the mold is open. More specifically, a hot runner system can be used in injection molding equipment herein, and can include a part system that is physically heated so that the parts can be used more effectively Transfer the molten plastic from the nozzle of the machine to the cavity of the mold tool. For example, a "cold runner" or "hot runner" can be used, such as the cold runner is an unheated physical channel that is used to guide the molten plastic to the mold cavity after the molten plastic leaves the nozzle. In the cavity, and the hot runner is heated while the cold runner is not heated.
同樣地,在各種實例中,設備可包括噴嘴斷路器,該噴嘴斷路器經組配來在正常操作期間斷開與澆口襯套之接觸。此組態為在堆疊或串聯模具中有用的,該等堆疊或串聯模具利用澆口襯套上之關斷。具體而言,澆口襯套可經組配來接受機器噴嘴且藉此允許熔融生物聚合物化合物進入模具。在機器噴嘴必須自與澆口襯套進行接觸脫離的情況下,熔融生物聚合物化合物可自澆口襯套向後流淌,且模具之洩壓可發生。任何熔融流淌廢棄物可增加生產成本,不利地影響熔體之下一射注,且甚至可防止模具之適當關閉,此將可能引起甚至更多問題。Likewise, in various examples, the equipment may include a nozzle circuit breaker that is configured to break contact with the gate bushing during normal operation. This configuration is useful in stacked or tandem molds that utilize shut-off on the gate bushing. Specifically, the sprue bushing can be configured to accept the machine nozzle and thereby allow the molten biopolymer compound to enter the mold. In the case where the machine nozzle must be separated from contact with the gate bushing, the molten biopolymer compound can flow backwards from the gate bushing, and pressure relief of the mold can occur. Any melt flow waste can increase production costs, adversely affect a shot below the melt, and can even prevent proper closing of the mold, which may cause even more problems.
為克服此,可利用選擇具有關斷之澆口襯套。否則,來自熱澆道之壓力將藉由澆口襯套解除。具體而言,當澆口襯套需要關斷時,除以上提到的其他效益之外,關斷防止組合模內壓力逸出。模具之任何洩壓將可能防止熔融零件之發泡,且因此所要的模製成形零件將未經形成。To overcome this, a gate bushing with shut-off can be selected. Otherwise, the pressure from the hot runner will be relieved by the gate bushing. Specifically, when the gate bushing needs to be shut off, in addition to the other benefits mentioned above, the shutoff prevents the pressure in the combined mold from escaping. Any pressure relief from the mold may prevent foaming of the molten part, and therefore the desired molded part will not be formed.
如以上所指示,各種發泡劑可經利用於生物可降解且工業上可合成之微氣孔發泡體之射出模製成形。在具體實例中,此等發泡劑可包括惰性氣體及/或鈍性氣體,諸如惰性氮氣或二氧化碳或能夠轉換成超臨界流體(SCF)狀態的其他氣體。根據本文揭示之設備、系統,及其使用方法,SCF可經引入(例如,注射)至機器中,例如,諸如藉由特別設計的電腦控制的噴射器引入(例如,注射)至熔體桶,該特別設計的電腦控制的噴射器可耦接,例如,附著至射出模製成形機桶,諸如用於將發泡劑進料至桶內之熔融生物聚合物熔體中。射出模製成形機控制器可經程式設計來將特定SCF氣體配料量(氮或二氧化碳等等)輸送至生物聚合物熔體中,該輸送可藉由系統控制器最佳化。As indicated above, various foaming agents can be used for injection molding of biodegradable and industrially synthesizable microporous foams. In a specific example, these blowing agents may include inert gases and/or passive gases, such as inert nitrogen or carbon dioxide or other gases that can be converted into a supercritical fluid (SCF) state. According to the equipment, system, and method of use disclosed herein, the SCF can be introduced (e.g., injected) into the machine, for example, such as introduced (e.g., injected) into the melt barrel by a specially designed computer-controlled ejector, The specially designed computer-controlled ejector can be coupled, for example, attached to the barrel of an injection molding machine, such as for feeding blowing agent into the molten biopolymer melt in the barrel. The controller of the injection molding machine can be programmed to deliver a specific amount of SCF gas (nitrogen or carbon dioxide, etc.) to the biopolymer melt. The delivery can be optimized by the system controller.
因此,前面提到的SCF發泡劑中每一者具有其地位,取決於正生產的最終零件之技術要求。具體而言,如所指示,有用的SCF為處於其超臨界狀態中之二氧化碳,二氧化碳在相同壓力處比氮更稠密但具有高得多的熱容。實驗已表明超臨界狀態中之二氧化碳生產可為在某些緩衝應用中有用的稠密發泡體。相反,超臨界氮可用來生產具有較小氣孔之低密度發泡零件,該低密度發泡零件為對於本揭示案之鞋類及運動商品應用有用的。Therefore, each of the aforementioned SCF blowing agents has its status, depending on the technical requirements of the final part being produced. Specifically, as indicated, a useful SCF is carbon dioxide in its supercritical state, which is denser than nitrogen at the same pressure but has a much higher heat capacity. Experiments have shown that carbon dioxide production in the supercritical state can be a dense foam useful in certain buffer applications. In contrast, supercritical nitrogen can be used to produce low-density foamed parts with smaller pores, which are useful for the footwear and sports product applications of the present disclosure.
因此,用於生產運動商品諸如鞋的有用發泡劑為SCF氮氣,因為SCF氮氣以相較於SCF二氧化碳的低得多的重量百分比提供改良之重量減少及精細氣孔結構,但是對於家具及汽車使用,有用的發泡劑為二氧化碳,二氧化碳生產大得多的氣孔結構,即使處於較大的大小及/或重量處。特定而言,在各種實例中,發泡零件之增強的重量減少為用於需要最少量的重量之產品應用之有用特性。作為一非限制實例,持續需要跑鞋含有非常輕型且表明承受重複濫用之能力的可撓性發泡體。Therefore, a useful blowing agent for the production of sports goods such as shoes is SCF nitrogen, because SCF nitrogen provides improved weight reduction and fine pore structure at a much lower weight percentage compared to SCF carbon dioxide, but is used for furniture and automobiles A useful blowing agent is carbon dioxide. Carbon dioxide produces a much larger pore structure, even at larger sizes and/or weights. In particular, in various instances, the enhanced weight reduction of foamed parts is a useful feature for product applications that require the least amount of weight. As a non-limiting example, there is a continuing need for running shoes to contain flexible foams that are very light and demonstrate the ability to withstand repeated abuse.
藉由提供前面提到的實例中之具有精細氣孔結構的增強之重量減少,射出模製成形可撓性發泡體零件將由於其藉由製作可接收輕型鞋提高跑步者之效率的能力而被依賴。此外,前面提到的發泡體之精細氣孔結構將確保具有組件零件之非常耐用的跑步鞋,該等組件零件將能夠處置由跑步者引起的重複衝擊力,當在加速運動中時,該跑步者不斷地將壓力及衝擊施加至鞋之發泡零件上。By providing the enhanced weight reduction with the fine pore structure in the aforementioned example, injection molded flexible foam parts will be improved due to their ability to improve the efficiency of runners by making light-weight shoes that can be received. rely. In addition, the aforementioned fine pore structure of the foam will ensure a very durable running shoe with component parts that will be able to handle the repeated impact force caused by the runner. When accelerating, the running shoe The person continuously applies pressure and impact to the foamed parts of the shoe.
實際上,SCF氮水平將通常比達成可比較零件所需要的SCF二氧化碳水平低至少75%。如此,當大量生產如在製作鞋組件中利用的本揭示案之生物可降解且工業上可合成之可撓性發泡體時,大大降低的SCF氮水平要求當與SCF二氧化碳相比時確保最佳材料節省及時間節省。然而,SCF二氧化碳在各種具體情形下為有用的發泡劑,諸如當黏度降低為主要處理目標時,及/或當應用不能忍受SCF氮之更侵略性的發泡動作時。In fact, the SCF nitrogen level will usually be at least 75% lower than the SCF carbon dioxide level required to achieve comparable parts. Thus, when mass production of the biodegradable and industrially synthesizable flexible foam of the present disclosure as used in the production of shoe components, the greatly reduced SCF nitrogen level requires that the highest level of nitrogen is ensured when compared with SCF carbon dioxide. Good material saving and time saving. However, SCF carbon dioxide is a useful blowing agent in a variety of specific situations, such as when viscosity reduction is the main processing goal, and/or when the application cannot tolerate the more aggressive foaming action of SCF nitrogen.
在某些實例中,SCF二氧化碳係合適的發泡劑,具體而言在半可撓性發泡體中。可撓性發泡體及半可撓性發泡體兩者可包括在相同種類的可撓性發泡體下,因為其兩者源自於具有低於其服務溫度之玻璃轉變(Tg)之聚合物,該服務溫度通常在室溫處。在具有物理發泡劑之物理發泡製程期間,看到玻璃轉變中之凹陷。氮及二氧化碳發泡劑之有效性之此等差異起源於其在生物聚合物熔體中之行為。In some instances, SCF carbon dioxide is a suitable blowing agent, specifically in semi-flexible foams. Both the flexible foam and the semi-flexible foam can be included in the same kind of flexible foam because they are derived from having a glass transition (Tg) lower than their service temperature. For polymers, the service temperature is usually at room temperature. During the physical foaming process with physical foaming agent, depressions in the glass transition are seen. These differences in the effectiveness of nitrogen and carbon dioxide blowing agents originate from their behavior in biopolymer melts.
例如,在31.1攝氏溫度及72.2巴處變成SCF流體的二氧化碳比在-147攝氏溫度及34巴處變成超臨界流體的氮更可溶於生物聚合物中4倍至5倍。例如,未填充生物聚合物中之飽和點為約1.5重量%至2重量%之氮,取決於溫度及壓力條件,而二氧化碳之飽和水平較接近於8重量%。二氧化碳亦展現生物聚合物中之較大遷移率,從而允許二氧化碳比氮遷移至現有氣泡中更遠。自氣孔成核之觀點,較大溶解度及遷移率意味較少的氣孔將成核,且成核的彼等氣孔將傾向於為較大的。For example, carbon dioxide that becomes an SCF fluid at a temperature of 31.1 degrees Celsius and 72.2 bar is four to five times more soluble in biopolymers than nitrogen that becomes a supercritical fluid at a temperature of -147 degrees Celsius and 34 bar. For example, the saturation point of the unfilled biopolymer is approximately 1.5% to 2% by weight of nitrogen, depending on temperature and pressure conditions, while the saturation level of carbon dioxide is closer to 8% by weight. Carbon dioxide also exhibits a greater mobility in biopolymers, allowing carbon dioxide to migrate farther into existing bubbles than nitrogen. From the viewpoint of pore nucleation, greater solubility and mobility means that fewer pores will nucleate, and those nucleated pores will tend to be larger.
然而,當目標為黏度降低時,溶解度變成優點。溶解在生物聚合物中的SCF充當增塑劑,從而降低生物聚合物之黏度。因為黏度降低部分地隨添加至生物聚合物的SCF之量而變且因為二氧化碳具有相較於氮的較高溶解度極限,所以以二氧化碳降低黏度之能力為較大的。當生產零件所需要的氮量低至使得不可能一致地處理零件時,二氧化碳亦為有用的。However, when the goal is viscosity reduction, solubility becomes an advantage. The SCF dissolved in the biopolymer acts as a plasticizer, thereby reducing the viscosity of the biopolymer. Because the viscosity reduction partly varies with the amount of SCF added to the biopolymer and because carbon dioxide has a higher solubility limit than nitrogen, the ability of carbon dioxide to reduce the viscosity is greater. Carbon dioxide is also useful when the amount of nitrogen required to produce parts is so low that it is impossible to treat the parts consistently.
因為二氧化碳為侵略性小得多的發泡劑,所以存在較容易運行低水平的二氧化碳之時機。例如,0.15%或0.2%的二氧化碳與小於0.05%的極低氮水平相比。如先前實例中所指示的實例主要在軟材料及具有厚橫截面之零件的情況下發生。因此,物理發泡劑(其為SCF氮或SCF二氧化碳或其他SCF)在最終發泡零件及將含有該物理發泡劑的最終產品中起到有用的作用。Because carbon dioxide is a much less aggressive blowing agent, there is an easier time to run low levels of carbon dioxide. For example, carbon dioxide of 0.15% or 0.2% is compared to very low nitrogen levels of less than 0.05%. The examples as indicated in the previous examples mainly occur in the case of soft materials and parts with thick cross-sections. Therefore, the physical blowing agent (which is SCF nitrogen or SCF carbon dioxide or other SCF) plays a useful role in the final foamed part and the final product that will contain the physical blowing agent.
首先,選擇相容生物聚合物或生物聚合物化合物及相關聯SCF氣體之適當組合是有用的。其次,藉由最佳配料重量及壓力適當地利用SCF氣體為關鍵的,以確保單相溶液內之最大飽和,且用於確保用於生產發泡基質內之數百萬均勻氣泡的核之最佳產生。另外,最終結果,同質地形成的射出模製成形可撓性發泡體零件,依賴於SCF及GCP氣體配料製程之所有態樣,該等態樣與射出模製成形機溫度、壓力及保持時間協作地工作,以用於達成商業上可接受的模製成形發泡零件,如以上所解釋。First, it is useful to select a suitable combination of compatible biopolymers or biopolymer compounds and the associated SCF gas. Secondly, proper use of SCF gas with optimal ingredient weight and pressure is critical to ensure the maximum saturation in the single-phase solution and to ensure the minimum of the nuclei used to produce millions of uniform bubbles in the foamed matrix. Good production. In addition, the final result is that the injection molded flexible foam parts formed with the same texture depend on all aspects of the SCF and GCP gas batching process. These aspects are related to the temperature, pressure and holding time of the injection molding machine. Work collaboratively to achieve commercially acceptable molded foam parts, as explained above.
如所指示,在一個態樣中,提供製造生物可降解且工業上可合成之可撓性發泡體(無論開放氣孔或封閉氣孔)之製程。在各種實例中,製造製程包括以下步驟中之一或多個。第一,可將熱塑性生物聚合物摻合至母料中用於發泡。作為一非限制實例,所涉及母料可藉由雙螺桿擠出機生產,其中二或更多個生物聚合物、填料及/或添加劑可經同質地摻合至諸如擠製桶內之單個聚合物熔體中。熔融生物聚合物摻和物然後經成股擠製、冷卻,且造粒成稱為母料的顆粒,該等顆粒然後可如以上所描述地經處理。合適的生物聚合物、生物塑膠、填料、添加劑及著色劑之任何組合可經併入母料生產中。因此,一旦生產,熱塑性生物聚合物摻和物可經射出模製成形成具有SCF諸如惰性氮或二氧化碳氣體之合適的模具形狀。As indicated, in one aspect, a process for manufacturing a flexible foam that is biodegradable and industrially synthesizable (regardless of open pores or closed pores) is provided. In various examples, the manufacturing process includes one or more of the following steps. First, thermoplastic biopolymers can be blended into master batches for foaming. As a non-limiting example, the masterbatch involved can be produced by a twin-screw extruder, in which two or more biopolymers, fillers and/or additives can be homogenously blended into a single polymer such as an extrusion barrel. In the melt. The molten biopolymer blend is then strand-extruded, cooled, and pelletized into particles called master batches, which can then be processed as described above. Any combination of suitable biopolymers, bioplastics, fillers, additives, and colorants can be incorporated into the masterbatch production. Therefore, once produced, the thermoplastic biopolymer blend can be injection molded into a suitable mold shape with SCF such as inert nitrogen or carbon dioxide gas.
如以上所描述,本射出模製成形可利用在用於藉由將熔融物料注射至產品模具中生產零件的製造製程中。在本揭示案中,選擇合適的生物聚合物或生物聚合物摻和化合物,諸如呈顆粒形式。前面提到的顆粒可在輔助小丸乾燥器中預乾燥以確保移除任何潛在濕氣。預乾燥小丸然後可經引入射出模製成形機漏斗中。操作者然後選擇射出模製成形機之最佳桶溫度、噴嘴溫度,及模具溫度,且藉由電腦控制輸入此等值。As described above, the injection molding can be used in a manufacturing process for producing parts by injecting molten material into a product mold. In the present disclosure, a suitable biopolymer or biopolymer blending compound is selected, such as in the form of particles. The aforementioned particles can be pre-dried in an auxiliary pellet dryer to ensure the removal of any potential moisture. The pre-dried pellets can then be introduced into the hopper of the injection molding machine. The operator then selects the best barrel temperature, nozzle temperature, and mold temperature of the injection molding machine, and inputs these values through computer control.
此外,最佳SCF氣體配料百分比及壓力以及最佳GCP氣體配料及壓力可經定標且此等值可經輸入至系統控制單元中或以其他方式藉由系統控制單元決定,例如,動態地。一旦系統經適當地組配,射出模製成形機準備好操作。顆粒可以藉由電腦控制指定的量釋放至射出模製成形機之螺桿及桶中,其中該等顆粒在特定溫度或溫度設定處熔融。In addition, the optimal SCF gas ingredient percentage and pressure and the optimal GCP gas ingredient and pressure can be calibrated and these values can be input to the system control unit or determined by the system control unit in other ways, for example, dynamically. Once the system is properly configured, the injection molding machine is ready for operation. The particles can be released into the screw and barrel of the injection molding machine in a specified amount controlled by a computer, where the particles are melted at a specific temperature or temperature setting.
SCF氣體係在受控制的壓力及劑量大小下藉由電腦控制經由SCF噴射器引入射出模製成形機桶中。SCF使現在熔融的顆粒飽和且單相溶液經產生。然後,在適當背壓力及螺桿定位的情況下,射出模製成形機將單相溶液之量測射注發送至動態溫度控制的模具空腔中。熔體內經歷核生長,且數百萬微氣孔氣泡形成於生物聚合物熔體內。實質上同時地,GCP系統藉由電腦控制將反壓力氣體之預先計量的劑量發送至模具中,該電腦控制最佳化氣孔之均勻性且調節用於最佳外表外觀之表面織理。動態溫度控制的模具溫度然後可經切換至水冷卻,且氣泡之形成及熔體之膨脹停止。此時,可撓性發泡體模製成形零件現在經形成且其自模具噴出。The SCF gas system is introduced into the barrel of the injection molding machine through the SCF ejector under the controlled pressure and dosage by the computer. SCF saturates the now molten particles and produces a single-phase solution. Then, under the condition of proper back pressure and screw positioning, the injection molding machine sends the measurement injection of the single-phase solution to the mold cavity under dynamic temperature control. The melt undergoes nuclear growth, and millions of microporous bubbles are formed in the biopolymer melt. At substantially the same time, the GCP system sends a pre-metered dose of backpressure gas to the mold under computer control, which optimizes the uniformity of pores and adjusts the surface texture for the best appearance. The mold temperature of the dynamic temperature control can then be switched to water cooling, and the formation of bubbles and the expansion of the melt stop. At this point, the flexible foam molded part is now formed and it is ejected from the mold.
具體而言,如以上所指示,系統可經組配以便實行動態模具溫度控制,該動態模具溫度控制可用來生產最佳氣孔結構。例如,如所描述,動態模具溫度控制(DMTC)實行快速電氣桿加熱及快速水冷卻。更具體而言,本文利用之DMTC程序可包括以下五個主要組件中一或多個:空氣壓縮機、閥交換裝置、電腦控制的模具溫度控制單元、電氣加熱模具、及冷卻塔。冷卻塔經組配來將水冷卻提供至模具,用於冷卻操作之執行,而適當地組配的空氣壓縮機產生壓縮空氣以驅動氣體穿過氣動閥以便排除任何殘餘冷卻水以免在冷卻之後進入模具。一或多個閥交換裝置可經組配且利用來使閥切換以將來自不同機器管線之不同介質傳遞至模具,諸如用於熱執循環及冷熱循環。電氣控制的加熱元件可經包括且組配來用於模製成形發泡零件之最終形狀。水塔及加熱元件可一起起作用,以便精細地控制模具溫度,使得模具之加熱及冷卻可在模製成形製程之執行中快速加熱及/或冷卻。Specifically, as indicated above, the system can be configured to implement dynamic mold temperature control, which can be used to produce the best pore structure. For example, as described, dynamic mold temperature control (DMTC) implements rapid electric pole heating and rapid water cooling. More specifically, the DMTC program used herein may include one or more of the following five main components: air compressor, valve exchange device, computer-controlled mold temperature control unit, electrical heating mold, and cooling tower. The cooling tower is configured to provide water cooling to the mold for the execution of the cooling operation, and the properly configured air compressor generates compressed air to drive the gas through the pneumatic valve to remove any residual cooling water to avoid entering after cooling Mold. One or more valve exchange devices can be assembled and used to switch valves to transfer different media from different machine lines to the mold, such as for heat-acting cycles and cold-heat cycles. Electrically controlled heating elements can be included and assembled to mold the final shape of the foamed part. The water tower and the heating element can work together to finely control the mold temperature, so that the heating and cooling of the mold can be quickly heated and/or cooled during the execution of the molding process.
所有此舉藉由適當組配的電腦處理器與射出模製成形機協調。例如,本發明之DMTC系統之冷卻水溫度控制之非限制實例可為15℃至30℃,且DMTC系統之加熱元件溫度範圍之進一步非限制實例可在60℃與150℃之間,且可在90℃與130℃之範圍內,且可為其間之任何溫度。以此等方式,生物聚合物熔體、壓力、及時間可經控制,使得形成合意的可撓性發泡體。All this is coordinated with the injection molding machine through a properly configured computer processor. For example, a non-limiting example of the cooling water temperature control of the DMTC system of the present invention may be 15°C to 30°C, and a further non-limiting example of the heating element temperature range of the DMTC system may be between 60°C and 150°C, and may be Within the range of 90°C and 130°C, and can be any temperature in between. In this way, the biopolymer melt, pressure, and time can be controlled to form a desired flexible foam.
具體而言,在本揭示案之射出模製成形製程期間,SCF經注射至聚合物熔體中。聚合物-SCF混合溶液之單相係在射出模製成形機螺桿及桶內之明確溫度及壓力下獲得。溫度及壓力可藉由電腦控制可變地控制,且直接涉及正生產的可撓性發泡體之類型及終端產品應用用於何類型。藉由施加變化的螺桿含有的SCF單相溶液壓力及GCP壓力,與適當射注大小、射注保持時間、熔體溫度、及模具溫度一致,整個系統經產生,高品質且商業上可接受的生物可降解且工業上可合成之可撓性發泡體零件可藉由該整個系統生產,諸如藉由將氣體反壓力利用於射出模製製程中,以便確保具有最少外觀缺陷及在發泡零件外側上幾乎沒有甚至沒有塑膠表皮的最佳發泡體結構。Specifically, during the injection molding process of the present disclosure, SCF is injected into the polymer melt. The single phase of the polymer-SCF mixed solution is obtained under a clear temperature and pressure in the screw and barrel of the injection molding machine. Temperature and pressure can be variably controlled by computer control, and directly relate to the type of flexible foam being produced and the type of end product application. By applying varying pressure of the SCF single-phase solution contained in the screw and GCP pressure, consistent with the appropriate injection size, injection holding time, melt temperature, and mold temperature, the entire system is produced, high-quality and commercially acceptable Biodegradable and industrially synthesizable flexible foam parts can be produced by the entire system, such as by using gas back pressure in the injection molding process to ensure that there are minimal appearance defects and foam parts There is hardly or even no optimal foam structure on the outside of the plastic skin.
如所指示,根據本文揭示之裝置、系統及其方法生產的產品之有用效益在於該等產品可為生物可降解及/或可合成的,諸如在家庭或工業堆肥協定中。具體而言,生產經組配來用於在工業堆肥體系中分解的商品確保可撓性發泡體將持續所得產品之可用壽命,諸如藉由以使得該所得產品在成品內在使用中不斷裂或破碎的方式使該所得產品功能化。例如,一個人購買僅由本揭示案之可撓性發泡體製成以使發泡體在產品可用壽命終止之前,在正常使用期間降解的家具、一雙鞋或其他運動裝備將為有害的。As indicated, a useful benefit of products produced according to the devices, systems, and methods disclosed herein is that the products can be biodegradable and/or synthesizable, such as in household or industrial composting agreements. Specifically, the production of commodities that are assembled for decomposition in an industrial composting system ensures that the flexible foam will last the useful life of the resultant product, such as by preventing the resultant product from breaking or breaking during use in the finished product. The crushing method functionalizes the resulting product. For example, a person buying furniture, a pair of shoes or other sports equipment that is made only of the flexible foam of the present disclosure so that the foam degrades during normal use before the end of the product's useful life will be harmful.
更具體而言,本揭示案受益於惰性物理發泡劑及生物可降解且工業上可合成之生物聚合物或生物聚合物化合物之使用。此等兩個態樣一起達到形成在特殊化可撓性發泡體射出模製成形系統內功能化的單相溶液。結果為用於使用在許多類型的終端產品之生物可降解且工業上可合成之可撓性發泡體;該等生物可降解且工業上可合成之可撓性發泡體之非限制實例為用於使用在製作鞋的鞋類發泡體。所得可撓性發泡體為無交聯的、無化學品的,且環境有益的。More specifically, the present disclosure benefits from the use of inert physical foaming agents and biodegradable and industrially synthesizable biopolymers or biopolymer compounds. These two aspects together achieve the formation of a functionalized single-phase solution in a specialized flexible foam injection molding system. The result is a biodegradable and industrially synthesizable flexible foam used in many types of end products; non-limiting examples of such biodegradable and industrially synthesizable flexible foam are It is used to make footwear foam for making shoes. The resulting flexible foam is non-crosslinked, chemical-free, and environmentally friendly.
在生物可降解且工業上可合成之可撓性發泡體壽命之終止處,該生物可降解且工業上可合成之可撓性發泡體可藉由廢棄物轉向重新導向至適當的工業堆肥設施,藉此發泡體經磨碎且工業堆肥成可用生物質。最終結果生產藉以堅持所謂的循環經濟之態樣的系統。本揭示案之可撓性發泡體作為「廢屑-至-廢屑」開始且結束,從而意味天然生物製程已經調適來製作具有最少量的環境衝擊之用於人類使用之材料及產品。此等可撓性發泡體即不在其可用壽命期間的技術效能性質上,亦不在其環境意識設計上折衷。At the end of the life of the biodegradable and industrially synthesizable flexible foam, the biodegradable and industrially synthesizable flexible foam can be redirected to appropriate industrial compost by turning waste Facility, whereby the foam is ground and industrially composted into usable biomass. The end result is a system whereby the so-called circular economy is adhered to. The flexible foam of the present disclosure starts and ends as "waste-to-waste", which means that the natural biological process has been adapted to produce materials and products for human use with the least amount of environmental impact. These flexible foams are neither in their technical performance properties during their useful life, nor are they compromised in their environmentally conscious design.
如本文以上所論述,本文裝置、系統、及其使用方法可經利用於生產一或多個模製成形終端產品之目的,諸如用於使用在鞋類、座位、汽車、保護裝置,及/或運動裝置中的組件。因此,在各種實施例中,本文所提供的是在鞋諸如其鞋底、中底及/或鞋內底之構造中有用的一或多個組件,諸如其中鞋底形成鞋之基底,且經組配來用於與地面接觸,中底形成中間結構及緩衝元件,且鞋內底經組配來用於插入鞋內且藉此提供緩衝及/或對鞋之支撐。As discussed above, the devices, systems, and methods of use herein can be used to produce one or more molded end products, such as for use in shoes, seats, automobiles, protective devices, and/or Components in sports equipment. Therefore, in various embodiments, what is provided herein is one or more components useful in the construction of a shoe, such as its sole, midsole, and/or insole, such as where the sole forms the base of the shoe and is assembled For contact with the ground, the midsole forms an intermediate structure and a cushioning element, and the shoe insole is assembled for insertion into the shoe and thereby provides cushioning and/or support for the shoe.
在某些實施例中,鞋組件可包括本文生產之發泡體材料,該發泡體材料可為環境友好的、生物可降解的,且可合成的。在各種實例中,每個單獨組件可構成自複數個層包括基底層及緩衝層,諸如其中緩衝層。例如,在具體實施例中,可包括支撐構件諸如耦接至基底層的支撐構件,且在組件為鞋內底的情況下,可包括弓形接觸部分或足跟接觸部分中一或多個。In certain embodiments, the shoe component may include the foam material produced herein, which may be environmentally friendly, biodegradable, and synthetic. In various examples, each individual component can be constructed from a plurality of layers including a base layer and a buffer layer, such as the buffer layer therein. For example, in a specific embodiment, a support member such as a support member coupled to the base layer may be included, and in the case where the component is an insole, it may include one or more of an arcuate contact portion or a heel contact portion.
具體而言,在各種實施例中,可生產發泡體材料,諸如其中發泡體材料可使用在緩衝墊、緩衝家具、鞋組件諸如其鞋內底、墊、纖維、織物等之生產中。其他有用產品可包括填隙諸如聚矽氧填隙、聚矽氧醫用手套、用於藥物輸送系統之聚矽氧管路、聚矽氧黏合劑、聚矽氧潤滑劑、聚矽氧塗料、及其他合適的聚矽氧產品,例如保險套。在各種實施例中,發泡體產品可以發泡體材料可具有一或多個抗微生物、抗細菌、抗真菌、抗病毒、及/或抗易燃性質的方式加以生產。Specifically, in various embodiments, foam materials can be produced, such as where the foam materials can be used in the production of cushions, cushioning furniture, shoe components such as insoles, cushions, fibers, fabrics, and the like. Other useful products can include gap fillers such as silicone gap fillers, silicone medical gloves, silicone tubing for drug delivery systems, silicone adhesives, silicone lubricants, silicone coatings, And other suitable silicone products, such as condoms. In various embodiments, the foam product can be produced in such a way that the foam material can have one or more anti-microbial, anti-bacterial, anti-fungal, anti-viral, and/or anti-flammability properties.
更具體而言,在一個態樣中,本揭示案可一般地針對用於家具製造之製程,該家具諸如裝軟墊家具及/或其緩衝墊,諸如包括發泡體或以其他方式由發泡體組成的家具,例如,該發泡體係生物可降解及/或可合成的。因此,本揭示案之發泡體為對於使用在包括如此生產的發泡體插入物的家具之製造中有利的。樹脂及所生產且利用的發泡體已證明為對於用作緩衝材料有利的,諸如用於枕頭、長椅、床、座墊,或用於其他裝軟墊家具等等。More specifically, in one aspect, the present disclosure may generally be directed to the manufacturing process for furniture, such as upholstered furniture and/or cushions thereof, such as foams or hair-made in other ways. Furniture made of foam, for example, the foaming system is biodegradable and/or synthesizable. Therefore, the foam of the present disclosure is advantageous for use in the manufacture of furniture including the foam insert produced in this way. Resins and the foams produced and utilized have proven to be beneficial for use as cushioning materials, such as pillows, benches, beds, seat cushions, or other upholstered furniture.
例如,根據以上本文所揭示之方法,可生產發泡體之小至大塊體之模具,以便形成發泡體插入物,諸如用於使用在家具或汽車附件組件中。方塊發泡體然後可基於正生產的家具之類型及形式而經切割成所要的尺寸及形狀之較小方塊。特定而言,經設定尺寸且切割的方塊然後可經施加至或以其他方式配合在家具或車架或其他界限材料內,該等各者一起可經覆蓋以生產最終家具產品,該最終家具產品為枕頭、沙發、緩衝墊,例如,沙發或汽車緩衝墊等等。另外,在需要的情況下,外罩殼或界限材料可經附接至框架材料,諸如藉由釘住及/或縫接,或以其他方式緊固至將要裝軟墊的製品之框架且以織品或其他材料覆蓋。For example, according to the methods disclosed herein, small to large foam molds can be produced to form foam inserts, such as for use in furniture or automobile accessory components. The cube foam can then be cut into smaller cubes of the desired size and shape based on the type and form of the furniture being produced. In particular, the sized and cut squares can then be applied to or otherwise fit within the furniture or frame or other boundary materials, and each of these together can be covered to produce the final furniture product, the final furniture product For pillows, sofas, cushions, such as sofas or car cushions, etc. In addition, if necessary, the outer cover or boundary material can be attached to the frame material, such as by nailing and/or sewing, or otherwise fastened to the frame of the article to be upholstered and made of fabric Or covered with other materials.
因此,在各種實施例中,當製造裝軟墊家具諸如長椅或汽車座椅時,框架可經生產。家具之各種內部(例如結構)組件可安裝在框架內,諸如彈簧等等,且然後根據以上本文揭示之方法生產的發泡薄板可經定位在彈簧中、在彈簧上,且在彈簧周圍,諸如用於緩衝及/或隔離。當然,可包括其他材料,諸如棉花層、羊毛層、毛氈層、橡膠基產品層等等,且然後可添加覆蓋材料以便覆蓋框架且完成產品製造。Therefore, in various embodiments, when manufacturing upholstered furniture such as benches or car seats, the frame may be produced. Various internal (such as structural) components of the furniture can be installed in the frame, such as a spring, etc., and then the foamed sheet produced according to the method disclosed above can be positioned in the spring, on the spring, and around the spring, such as Used for buffering and/or isolation. Of course, other materials may be included, such as a cotton layer, a wool layer, a felt layer, a rubber-based product layer, etc., and then a covering material may be added to cover the frame and complete the product manufacturing.
特定而言,本發泡體與本文揭示之其他材料可一起充當襯墊料或填充料,在覆蓋材料在框架上伸展時,該襯墊料或填充料可在覆蓋物下方成形、調整且褶起。另外,如所指示,在各種實例中,由於多種原因,本文生產之發泡體產品可用於本領域已知的發泡體產品中及之外,其中最重要的是典型的PU及/或EVA發泡體並非以任何方式生物可降解的,而本文生產之發泡體之組件為生物可降解的。因此,在各種實施例中,提供在開放框架上構造家具之方法。例如,在一個實例中,方法可包括以下步驟中一或多個。In particular, the foam and other materials disclosed herein can serve as a cushion or filler together. When the cover material is stretched on the frame, the cushion or filler can be shaped, adjusted and pleated under the cover. rise. In addition, as indicated, in various examples, for a variety of reasons, the foam products produced herein can be used in and outside of foam products known in the art, the most important of which is typical PU and/or EVA The foam is not biodegradable in any way, and the components of the foam produced herein are biodegradable. Therefore, in various embodiments, a method of constructing furniture on an open frame is provided. For example, in one example, the method may include one or more of the following steps.
具體而言,方法可包括提供框架,框架限定背部、複數個側壁、及底座部分,諸如其中後框架部分大致上垂直地延伸,且底座部分以使得底座部分橫切垂直部分的方式相對於彼此大致上水平地延伸。方法可進一步包括將平坦發泡體薄板切割至適當大小及形狀以提供用於背部及底座及/或側壁部分之襯墊料,將平坦覆蓋材料切割至適當大小及形狀以完成背部、底座及/或側壁部分,在間隔位置處將發泡體薄板及覆蓋材料附接在一起,及壓縮發泡體以在其外表面中形成波狀預定設計,且形成大致上平坦的次總成,其中發泡體薄板及覆蓋材料在附接位置中間自由地相對移動,及將次總成成形且附接至框架。用於發泡體緩衝墊或緩衝墊製品的覆蓋可為通常使用在裝軟墊家具中且覆蓋裝飾枕頭等的任何合適的覆蓋材料,諸如編織紡毛織物、編織耐綸織物,或由各種合成纖維以及諸如皮革等之材料編織的織物。Specifically, the method may include providing a frame that defines a back, a plurality of side walls, and a base portion, such as where the rear frame portion extends substantially vertically, and the base portion is substantially relative to each other in such a manner that the base portion crosses the vertical portion. Extend horizontally. The method may further include cutting the flat foam sheet to an appropriate size and shape to provide spacers for the back and base and/or side wall portions, and cutting the flat covering material to an appropriate size and shape to complete the back, base and/or Or the side wall part, attach the foam sheet and the covering material together at the spaced position, and compress the foam to form a wavy predetermined design in its outer surface, and form a substantially flat sub-assembly, wherein The foam sheet and the covering material are free to move relative to each other in the middle of the attachment position, and the sub-assembly is formed and attached to the frame. The covering used for foam cushions or cushion products can be any suitable covering materials commonly used in upholstered furniture and covering decorative pillows, such as woven spun woolen fabric, woven nylon fabric, or made of various synthetic fibers And fabrics woven from materials such as leather.
此外,在另一態樣中,本揭示案一般針對用於諸如鞋之鞋底、中底及/或鞋內底的鞋組件之製造的製程,該等鞋組件諸如包括發泡體或以其他方式由發泡體組成的鞋組件,該發泡體例如可合成發泡體。特定而言,在具體實施例中,提供用於製作鞋底、中底、鞋內底、及/或其他鞋插入物的方法。例如,本發明之鞋插入物可為緩衝裝置之形式,該緩衝裝置適於插入或以其他方式配合在例如跑步鞋或運動鞋的鞋內,該鞋可經組配以便降低在跑步或步行時碰撞表面(例如,地面)的腳之衝擊,藉此吸收對腳之震動及/或使對腳之震動減弱。In addition, in another aspect, the present disclosure is generally directed to the manufacturing process of shoe components such as shoe soles, midsoles, and/or shoe insoles, such as shoe components including foams or in other ways A shoe component composed of a foamed body, which can be synthesized into a foamed body, for example. In particular, in specific embodiments, methods for making shoe soles, midsoles, insoles, and/or other shoe inserts are provided. For example, the shoe insert of the present invention may be in the form of a cushioning device adapted to be inserted into or otherwise fitted into shoes such as running shoes or sports shoes. The impact of the foot that hits the surface (for example, the ground), thereby absorbing the vibration to the foot and/or reducing the vibration to the foot.
具體而言,鞋底組件包括中底及插入物可包括一個層或許多層。例如,在一些實例中,可提供基底層、發泡體層及/或織物層。特定而言,可包括相對彈性材料之基底層,及/或例如安置在基底層上的發泡體層,及/或安置在發泡體層上的織物層。因此,方法可包括將基底層、發泡體層及織物整體地形成為三層板薄板。在各種實例中,支撐層可安置至少一足跟區域,該支撐層可由諸如相較於積層之彼密度的較高密度之剛性材料構造。黏合劑、膠或其他附接機構可經提供且利用於附接且形成具有支撐層之三層板。Specifically, the sole component including the midsole and the insert may include one layer or multiple layers. For example, in some examples, a base layer, a foam layer, and/or a fabric layer may be provided. In particular, it may include a base layer of relatively elastic material, and/or, for example, a foam layer disposed on the base layer, and/or a fabric layer disposed on the foam layer. Therefore, the method may include integrally forming the base layer, the foam layer, and the fabric into a three-layer sheet. In various examples, the support layer may be provided with at least one heel area, and the support layer may be constructed of a rigid material with a higher density than the density of the build-up layer. Adhesives, glues or other attachment mechanisms can be provided and utilized for attachment and forming a three-layer board with a supporting layer.
更具體而言,在其他實例中,用於製作鞋組件諸如插入物之方法可包括以下步驟:提供發泡體層及/或提供織物層;加熱發泡體層;接合發泡體及織物層;提供基底層,例如,具有關於發泡體層之相同、較大,或較小密度之密度的基底層;以及加熱基底層及發泡體層中之至少一個以便耦接基底層與發泡體層以便形成雙層板或三層板。More specifically, in other examples, the method for making shoe components such as inserts may include the following steps: providing a foam layer and/or providing a fabric layer; heating the foam layer; joining the foam and the fabric layer; providing The base layer, for example, the base layer having the same, greater, or lower density with respect to the foam layer; and heating at least one of the base layer and the foam layer to couple the base layer and the foam layer to form a double Layer board or three-layer board.
方法可進一步包括提供預形成支撐構件,諸如,弓形支撐件及/或足跟構件,該等構件可具有相較於發泡體層之密度實質上相同,或較小,或較大的密度。在具體實例中,支撐構件可由壓縮發泡體材料形成,以便獲得較大密度,及因而與發泡體層之彼剛性相比的較大剛性。另外,熱及/或壓力可反應黏合劑可經施加在支撐及/或足跟構件與積層之間。模製成形壓力然後可經施加至組成物,以便引起將三層板形成及/或成形為支撐及/或足跟構件,以便形成整體一件式鞋插入物,其中預形成的足跟構件形成後部分及/或支撐構件形成成品鞋插入物之底部表面之中間部分,例如,在其中間及/或足跟區域處,且基底層形成其前方區域處的成品鞋插入物之底部表面。The method may further include providing pre-formed support members, such as arcuate supports and/or heel members, which members may have substantially the same density as compared to the foam layer, or a smaller, or larger density. In a specific example, the support member may be formed of a compressed foam material in order to obtain a greater density and thus greater rigidity compared to the other rigidity of the foam layer. In addition, a heat and/or pressure reactive adhesive may be applied between the support and/or heel member and the build-up layer. Molding pressure can then be applied to the composition to cause the three-layer panel to be formed and/or shaped into a support and/or heel member to form a one-piece shoe insert, wherein the pre-formed heel member is formed The back part and/or support member form the middle part of the bottom surface of the finished shoe insert, for example, at its middle and/or heel area, and the base layer forms the bottom surface of the finished shoe insert at its front area.
然而,應注意,支撐及/或足跟構件不必包括在內,且在一些實例中,可經添加積層組件中一或多個可經排除或其他積層層。進一步應注意,在某些實施例中,發泡體層可為更可撓性及/或緩衝的,例如,具有相較於基底層的較大硬度計,該基底層轉而可為更可撓性的及/或緩衝的,例如,具有相較於支撐構件的較大硬度計。因此,更可撓性發泡體及基底層可為相對彈性的且在形狀上符合所要的鞋大小及組態,而支撐層(多個)可為相對更剛性的。However, it should be noted that the support and/or heel member need not be included, and in some examples, one or more of the build-up components may be added and may be excluded or other build-up layers. It should be further noted that in certain embodiments, the foam layer may be more flexible and/or cushioned, for example, having a greater durometer than the base layer, which in turn may be more flexible Sexual and/or cushioned, for example, with a larger durometer than the supporting member. Therefore, the more flexible foam and the base layer can be relatively elastic and conform to the desired shoe size and configuration in shape, while the support layer(s) can be relatively more rigid.
具體而言,如所指示,發泡體層及/或支撐層中一或多個可由本文揭示的生物可降解及/或環境友好發泡體材料構造。特定而言,支撐層可具有稠密發泡體,因而使得支撐層為更剛性的。因此,在各種實施例中,發泡體層可具有約2磅/立方英尺或約3磅/立方英尺或約5磅/立方英尺至約10磅/立方英尺或更大之密度,諸如在介於約4磅/立方英尺至6磅/立方英尺之間的範圍內之密度。另外,發泡體層可具有1/8” +或-5%之厚度,諸如在約3/32”-5/32”之厚度範圍內。Specifically, as indicated, one or more of the foam layer and/or support layer may be constructed from the biodegradable and/or environmentally friendly foam materials disclosed herein. In particular, the support layer may have dense foam, thus making the support layer more rigid. Therefore, in various embodiments, the foam layer may have a density of about 2 pounds/cubic feet or about 3 pounds/cubic feet or about 5 pounds/cubic feet to about 10 pounds/cubic feet or more, such as between The density is within the range of about 4 pounds/cubic foot to 6 pounds/cubic foot. In addition, the foam layer may have a thickness of 1/8"+ or -5%, such as in the thickness range of about 3/32"-5/32".
同樣地,基底層亦可具有約2磅/立方英尺或約3磅/立方英尺或約5磅/立方英尺至約10磅/立方英尺或更大之密度,諸如在介於約4磅/立方英尺至6磅/立方英尺之間的範圍內之密度。基底層之厚度可為大約5/16”+或-10%。然而,在各種實例中,基底層之厚度在厚度方面範圍可自約1/4”或更少至約7/16”。關於支撐層,該支撐層可主要形成在插入物之弓形及/或足跟區域處,該支撐層亦可由本文揭示之生物可降解且/或可合成發泡體製成。Similarly, the base layer may also have a density of about 2 pounds/cubic foot or about 3 pounds/cubic foot or about 5 pounds/cubic foot to about 10 pounds/cubic foot or greater, such as between about 4 pounds/cubic foot Density within the range of feet to 6 pounds per cubic foot. The thickness of the base layer can be about 5/16"+ or -10%. However, in various examples, the thickness of the base layer can range from about 1/4" or less to about 7/16" in terms of thickness. The support layer, which can be mainly formed at the arch and/or heel area of the insert, can also be made of the biodegradable and/or synthetic foam disclosed herein.
然而,支撐層可藉由經壓縮使得最終密度為大約22磅/立方英尺至23磅/立方英尺製成。織物層可由任何合適的材料例如棉花、聚酯或聚丙烯針織物構造。在各種實例中,材料及發泡體層可藉由火焰膠合技術積層在一起,該火焰膠合技術利用導向至發泡體層的裸火。裸火產生表面上之充分的熱以引起平坦薄板發泡體層之熔化。一旦熔化,織物層可與其接合且兩個夾層在一起的層可在淬冷輥輪之間延伸,同時充分的壓力施加在輥輪之間,使得兩個層接合在一起。However, the support layer can be made by being compressed so that the final density is about 22 pounds/cubic foot to 23 pounds/cubic foot. The fabric layer can be constructed of any suitable material such as cotton, polyester or polypropylene knitted fabric. In various examples, the material and foam layers can be laminated together by a flame gluing technique, which utilizes bare fire directed to the foam layer. The bare fire generates sufficient heat on the surface to cause the melting of the flat sheet foam layer. Once melted, the fabric layer can be joined to it and the two sandwiched layers can extend between the quenched rollers, while sufficient pressure is applied between the rollers so that the two layers are joined together.
在製程中之此時,此等層仍然維持呈平坦薄板形式。此等整合層然後接下來亦藉由火焰膠合接合至基底層。先前整合的材料及發泡體層可經接合至支撐層,且此等多層壓層然後可在淬冷輥輪之間延伸。在階段之此級段處,此等層仍然維持呈平坦薄板形式。至此層壓的層因而然後準備好模製成形。此可藉由將層壓層加熱至近似250 F之模製成形溫度,諸如持續約1分鐘至約5分鐘或更多,例如,約225秒之週期來執行。此充分地加熱先前層壓的層,以允許該等層壓層插入模具中。At this point in the manufacturing process, these layers still remain in the form of a flat sheet. These integrated layers are then joined to the base layer by flame gluing. The previously integrated material and foam layers can be joined to the support layer, and these multilayer layers can then extend between the quenched rollers. At this stage of the stage, these layers still remain in the form of flat sheets. The layers laminated so far are then ready for moulding. This can be performed by heating the laminated layer to a molding temperature of approximately 250 F, such as for a period of about 1 minute to about 5 minutes or more, for example, about 225 seconds. This heats the previously laminated layers sufficiently to allow them to be inserted into the mold.
以下為參考所附圖式的本揭示案之各種實行方案之描述。因此,在一個態樣中,提供鞋類組件。具體而言,如圖1中所例示,本揭示案之實施例為鞋類組件,亦即由生物可降解且工業上可合成之熱塑性生物聚合物摻和物(可撓性發泡體102)製成的微氣孔可撓性發泡體鞋中底100。The following is a description of various implementation schemes of the present disclosure with reference to the accompanying drawings. Therefore, in one aspect, footwear components are provided. Specifically, as illustrated in FIG. 1, an embodiment of the present disclosure is a shoe component, that is, a blend of biodegradable and industrially synthesizable thermoplastic biopolymers (flexible foam 102) The manufactured micro-pore flexible
特定而言,生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體鞋中底係由生物聚合物及生物聚合物摻和物諸如包括熱塑性生物聚合物中一或多個製成。具體而言,用來製造生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體的熱塑性生物聚合物或生物聚合物摻和物可任擇地自任何數目的脂肪族及脂肪族-芳香族共聚酯等等產生。Specifically, the biodegradable and industrially synthesizable injection-molded flexible foam shoe midsole is made of biopolymers and biopolymer blends, such as one or more of thermoplastic biopolymers. Multiple made. Specifically, the thermoplastic biopolymers or biopolymer blends used to produce biodegradable and industrially synthesizable injection-molded flexible foams can be optionally made from any number of fats. And aliphatic-aromatic copolyesters and so on.
在生產生物聚合物或生物聚合物摻和物中找到使用的合適的生物聚合物之非限制實例由以下各者組成:聚乳酸(PLA)、聚L乳酸(PLLA)、聚(己二酸丁二酯-共-對苯二甲酸酯)(PBAT)、聚己內酯(PCL)、聚羥基烷酸酯(PHA)、聚丁烯琥珀酸酯(PBS)、聚己內酯(PCL)、聚丁烯琥珀酸酯已二酸(PBSA)、聚丁烯已二酸(PBA)、及熱塑性澱粉(TPS)。另外,混合生物聚合物摻和物可經利用在生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之製造中。混合生物聚合物摻和物之非限制實例由含藻類聚(己二酸丁二酯-共-對苯二甲酸酯)(PBAT)組成。Non-limiting examples of suitable biopolymers found for use in the production of biopolymers or biopolymer blends consist of the following: polylactic acid (PLA), poly-L-lactic acid (PLLA), poly(butylene adipate) Diester-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polycaprolactone (PCL) , Polybutene succinate adipic acid (PBSA), polybutene adipic acid (PBA), and thermoplastic starch (TPS). In addition, the mixed biopolymer blends can be used in the production of biodegradable and industrially synthesizable injection-molded flexible foams with micro-pores. A non-limiting example of a hybrid biopolymer blend consists of algae-containing poly(butylene adipate-co-terephthalate) (PBAT).
在所提供實例中,混合生物聚合物之藻類部分由呈乾燥粉末形式的藻類之任何合適物種組成。合適的藻類物種之若干非限制實例包括藍綠藻、綠藻、紅藻、褐藻,及矽藻、及其組合。前面提到的乾燥藻類粉末可以PBAT生物聚合物在標準設備上雙螺桿擠製,使得藻類粉末變性成PBAT之聚合物鏈。此藉此形成用於使用在本揭示案之生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之製造中的混合生物聚合物。In the example provided, the algae portion of the hybrid biopolymer is composed of any suitable species of algae in dry powder form. Some non-limiting examples of suitable algae species include blue-green algae, green algae, red algae, brown algae, and diatoms, and combinations thereof. The dry algae powder mentioned above can be extruded by twin-screw PBAT biopolymer on standard equipment, so that the algae powder can be denatured into PBAT polymer chains. This thereby forms a hybrid biopolymer for use in the production of the biodegradable and industrially synthesizable injection-molded flexible foam of the present disclosure.
所生產發泡體產品可包括或以其它方式併入許多以下成分:填料粉末及/或一或多個添加劑。具體而言,取決於應用,添加劑亦可經利用於生物聚合物配方中。例如,寡聚聚(天冬氨酸-丙交酯)(poly(aspartic acid-co-lactide);PAL)可任擇地化合成用於加速生物降解之母料。另外,填料諸如來自霰石、澱粉等等的沉澱碳酸鈣可經利用來降低零件成本,同時維持完成可撓性發泡體之可再生且生物可降解的完整性。The foam product produced may include or otherwise incorporate many of the following ingredients: filler powder and/or one or more additives. Specifically, depending on the application, additives may also be utilized in biopolymer formulations. For example, oligomeric (aspartic acid-co-lactide) (poly(aspartic acid-co-lactide); PAL) can optionally be synthesized into a masterbatch for accelerated biodegradation. In addition, fillers such as precipitated calcium carbonate from aragonite, starch, etc. can be used to reduce the cost of parts while maintaining the renewable and biodegradable integrity of the finished flexible foam.
此外,用於使用在生物聚合物配方中的額外添加劑可由以下中一或多個組成。成核劑諸如微葉片狀滑石或高深寬比鮞狀霰石可經包括。此類成核劑可藉由防止氣孔聚結、降低塊體密度,且改良回彈性以及其他有益地增強之屬性大大地改良所得可撓性發泡體之關鍵性質。用於使用在生產生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之成核劑之若干非限制實例為由Imerys Talc America Inc., Houston, Texas作為Mistrocell®行銷的微葉片狀滑石及由Calcean Minerals & Materials LLC, Gadsden, Alabama作為OceanCal®行銷的高深寬比鮞狀霰石。In addition, additional additives for use in biopolymer formulations can consist of one or more of the following. Nucleating agents such as microlobed talc or high aspect ratio oolitic aragonite may be included. Such nucleating agents can greatly improve the key properties of the resultant flexible foam by preventing pore coalescence, reducing block density, and improving resilience and other beneficially enhanced properties. Some non-limiting examples of nucleating agents used in the production of biodegradable and industrially synthesizable injection molded microporous flexible foams are by Imerys Talc America Inc., Houston, Texas as Mistrocell® Marketed microlobed talc and high aspect ratio oolitic aragonite marketed by Calcan Minerals & Materials LLC, Gadsden, Alabama as OceanCal®.
亦可包括著色劑、染料及顏料。例如,各種著色劑諸如染料、顏料或生物顏料可任擇地使用在本發明之生物聚合物配方中。若干非限制實例為已經定製來用於生物聚合物使用的植物來源之天然顏料,諸如由Treffert GmBH & Co. KG, Bingen am Rhein, Germany提供的寬範圍或由Holland Colours Americas Inc., Richmond, Indiana提供的彼等。It may also include colorants, dyes and pigments. For example, various coloring agents such as dyes, pigments or biological pigments can be optionally used in the biopolymer formulation of the present invention. Some non-limiting examples are natural pigments of plant origin that have been customized for use in biopolymers, such as the wide range provided by Treffert GmBH & Co. KG, Bingen am Rhein, Germany or by Holland Colours Americas Inc., Richmond, They are provided by Indiana.
存在可取決於以下各者而利用的許多組態及實施例:所要的物理性質,及鞋中底100之預定終端使用、其用於工作、遊憩、水上使用等,彼不應受此等實例限制。There are many configurations and embodiments that can be utilized depending on the following: the desired physical properties, and the intended end use of the
系統之合適的裝置200可例證於圖2中且可經利用於如以上本文所提示之發泡體材料之生產中。例如,在使用中,生物聚合物母料202經進料至任何合適的射出模製成形機206之漏斗204中。生物聚合物母料在經由射出模製成形機螺桿208運輸時藉由加熱液化。氮或CO2
氣體210經注射至生物聚合物熔體212且混合。此外,生物聚合物氣體混合物處於壓力下且經注射至射出模製成形工具214中與生物聚合物氣體射出一致,氣體反壓力系統216藉由氣體控制閥220將計量氮或CO2
氣體218之劑量發送至加壓模製成形工具中。A
此後不久,動態模具溫度控制系統(DMTC) 222控制且調整模製成形工具214內側之溫度。模製成形工具214然後經充分地冷卻且所得生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體零件自射出模製成形機噴出。Soon thereafter, the dynamic mold temperature control system (DMTC) 222 controls and adjusts the temperature inside the molding tool 214. The molding tool 214 is then sufficiently cooled and the resulting biodegradable and industrially synthesizable injection molded microporous flexible foam parts are ejected from the injection molding machine.
圖3提供用以例示生產生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之方法300。在步驟302處,生物聚合物混合物經選擇,且在步驟304處,混合物藉由材料漏斗抽吸至射出模製成形機中。在步驟306處,生物聚合物混合物在藉由射出模製成形機螺桿運輸時液化且均質化。在步驟308處,氮或CO2
氣體經注射至生物聚合物熔體中。在步驟310處,生物聚合物氣體混合物處於壓力下且經注射至射出模製成形工具中。在步驟312處,射出模製成形工具溫度經動態地控制以確保最佳氣孔結構。在步驟314處,氣體反壓力之最佳劑量經施加至射出模製成形工具持續充分量的時間,以確保具有最小表皮厚度之理想發泡體結構。在步驟316處,射出模製成形工具經充分地冷卻了,且所得模製成形的發泡體零件自射出模製成形機噴出。FIG. 3 provides an example of a
在一些實行方案中,且在不將限制給予本文揭示內容的情況下,生物可降解且工業上可合成之可撓性發泡體製造製程包括以下概括的步驟。製程裝設程序環繞將受控制的SCF配料建立至射出桶中:在導致單相溶液的螺桿速度、溫度及壓力條件下。In some implementations, and without limiting the content disclosed herein, the biodegradable and industrially synthesizable flexible foam manufacturing process includes the steps outlined below. The process setup program surrounds the establishment of controlled SCF ingredients into the injection barrel: at the screw speed, temperature and pressure conditions that result in a single-phase solution.
確保滿足SCF配料之基本條件,主要存在七個製程設定點以調整:SCF輸送壓力:設定生物塑膠壓力,SCF抵抗該生物塑膠壓力而在螺桿旋轉期間配料。此係指螺桿復原期間的特定生物聚合物背壓力且亦係指螺桿閒置期間的螺桿位置控制。作為非限制實例,用於生物聚合物輸送之壓力設定點可在2,000 psi與3,000 psi之範圍內,且更佳地在2,700 psi與2,800 psi之範圍內。此設定點設定SCF配料開始所在的螺桿位置,此舉然後可將SCF噴射器設定至開放或封閉位置。位置應經設定,以便在螺桿復原期間桶中之壓力已在配料開始之前變得穩定。作為非限制實例,開放位置可在0.3吋與0.4吋之範圍內。To ensure that the basic conditions of SCF batching are met, there are mainly seven process setting points to adjust: SCF delivery pressure: set the pressure of the bioplastic, the SCF resists the pressure of the bioplastic and mixes during the rotation of the screw. This refers to the specific biopolymer back pressure during the screw recovery period and also refers to the screw position control during the screw idle period. As a non-limiting example, the pressure set point for biopolymer delivery can be in the range of 2,000 psi and 3,000 psi, and more preferably in the range of 2,700 psi and 2,800 psi. This set point sets the screw position where the SCF dosing starts, which can then set the SCF injector to the open or closed position. The position should be set so that the pressure in the barrel during the screw recovery period has stabilized before the start of the batching. As a non-limiting example, the open position can be in the range of 0.3 inches and 0.4 inches.
射注大小及SCF之百分比亦可經控制。此控制在每個循環期間配料的SCF之實際質量。作為非限制實例,射注大小可在100克至300克之範圍內,且更佳地為200克。SCF百分比之非限制實例可在0.45%與0.75%之範圍內,且更佳地為0.5%。系統亦可經組配來用於最佳化配料。此藉由最大化配料時間且最小化流動速率(預計量壓力與輸送壓力之間的壓力差)實現。配料時間之非限制實例在1秒至2秒之間,且更佳地為1.7秒。The injection size and the percentage of SCF can also be controlled. This controls the actual quality of the SCF batched during each cycle. As a non-limiting example, the shot size can be in the range of 100 grams to 300 grams, and more preferably 200 grams. Non-limiting examples of the SCF percentage may be in the range of 0.45% and 0.75%, and more preferably 0.5%. The system can also be configured to optimize ingredients. This is achieved by maximizing the dosing time and minimizing the flow rate (the pressure difference between the expected volume pressure and the delivery pressure). A non-limiting example of the batching time is between 1 second and 2 seconds, and more preferably 1.7 seconds.
動態模具溫度控制(DMTC)亦可經實行。此為涉及模具溫度在射出填充級段期間之快速變化及控制以便藉此就熱熱循環及冷熱循環而言動態地控制模具溫度的製程。在熔體射出之前,模具首先經加熱至預設上限。在熔體填充級段期間,模具空腔表面之溫度可保持高於上限以防止熔體過早地固化。Dynamic mold temperature control (DMTC) can also be implemented. This is a process involving the rapid change and control of the mold temperature during the injection and filling stage in order to thereby dynamically control the mold temperature in terms of thermal and thermal cycles. Before the melt is injected, the mold is first heated to a preset upper limit. During the melt filling stage, the temperature of the mold cavity surface can be kept above the upper limit to prevent the melt from solidifying prematurely.
當熔體填充製程已結束時,模具快速冷卻至稱為噴出溫度的下限,該噴出溫度為零件噴出模具空腔的溫度。本揭示案之最佳模具溫度範圍之非限制實例在40℃與150℃之間,其中冷卻速度在每秒1℃與每秒15℃之間,且更佳地為每秒11℃。本發明之模型冷卻時間之非限制實例在80秒與100秒之間。When the melt filling process is over, the mold quickly cools to the lower limit called the ejection temperature, which is the temperature at which the part is ejected from the cavity of the mold. A non-limiting example of the optimal mold temperature range of the present disclosure is between 40°C and 150°C, where the cooling rate is between 1°C per second and 15°C per second, and more preferably 11°C per second. A non-limiting example of the cooling time of the model of the present invention is between 80 seconds and 100 seconds.
同樣地,氣體反壓力(GCP)亦可經控制。此為包括以氮氣注射以抵抗熔體內之氣體之膨脹的加壓模具空腔的製程。在反壓力經釋放時,將按照慣例突破表面的氣體氣泡經捕獲在內側,從而產生光滑表皮。GCP藉由表面品質、發泡體結構及表皮厚度控制發泡。本發明之氣體反壓力之非限制實例為0巴/10巴/30巴/50巴,並且保持時間在1秒與25秒之間,且更佳地為5秒。本發明之平均微氣孔氣孔直徑之非限制實例可以微米(µm)量測為介於1微米與100微米之間,且更佳地為40微米。Likewise, the gas back pressure (GCP) can also be controlled. This is a process that involves injecting nitrogen gas to resist the expansion of the gas in the melt to pressurize the mold cavity. When the back pressure is released, the gas bubbles that break through the surface as usual are trapped inside to produce a smooth skin. GCP controls foaming by surface quality, foam structure and skin thickness. A non-limiting example of the gas counter pressure of the present invention is 0 bar/10 bar/30 bar/50 bar, and the holding time is between 1 second and 25 seconds, and more preferably 5 seconds. A non-limiting example of the average micro-pore pore diameter of the present invention can be measured in micrometers (µm) between 1 micron and 100 microns, and more preferably 40 microns.
鑒於以上內容,在一些實行方案中,生產合適的熱塑性生物聚合物摻和物。一旦熱塑性摻和物經生產,熱塑性生物聚合物摻和物可經射出模製成形為合適的模具形狀,諸如在添加惰性氣體諸如氮氣的情況下。另外,壓力亦可經精細地控制。In view of the above, in some implementation schemes, suitable thermoplastic biopolymer blends are produced. Once the thermoplastic blend is produced, the thermoplastic biopolymer blend can be injection molded into a suitable mold shape, such as with the addition of an inert gas such as nitrogen. In addition, the pressure can also be finely controlled.
例如,可實行在射出模製成形製程中利用氣體反壓力。此亦為對於進一步確保具有最少量的外表缺陷,及發泡零件外側上的少量直至無塑膠表皮的最佳發泡體結構有用的,此為在製作發泡產品中重要的,該發泡產品可基於模具形狀而具有多個最終使用。模製成形製程可包括動態模具溫度控制之實行方案。例如,在各種實施例中,動態地控制模製成形製程之溫度為對於達成最佳氣孔結構有用的。可控制的模製成形製程之其他元素:生物聚合物熔體、壓力,及時間,使得形成合意的可撓性發泡體。For example, the use of gas back pressure in the injection molding process can be implemented. This is also useful for further ensuring that there is the smallest number of surface defects and the best foam structure on the outer side of the foamed part until there is no plastic skin. This is important in the production of foamed products. This foamed product There can be multiple end uses based on the mold shape. The molding process may include the implementation of dynamic mold temperature control. For example, in various embodiments, dynamically controlling the temperature of the molding process is useful for achieving an optimal pore structure. Controllable other elements of the molding process: biopolymer melt, pressure, and time, so that the desired flexible foam is formed.
因此,鑒於以上內容,本揭示案係關於用於由用於使用在例如鞋類組件、座位組件、保護裝置組件及水上運動附件的生物可降解且工業上可合成之生物衍生熱塑性樹脂射出模製成形的微氣孔發泡各種可撓性發泡體組成之製程。Therefore, in view of the above, the present disclosure relates to injection molding of biodegradable and industrially synthesizable bio-derived thermoplastic resins for use in, for example, footwear components, seat components, protective device components, and water sports accessories. The formed micro-pore foaming process consists of various flexible foams.
產生生物可降解且工業上可合成之微氣孔可撓性發泡體結構始於合適的生物聚合物或生物聚合物摻和物諸如脂肪族及脂肪族-芳香族共聚酯起源之彼等。合適的生物聚合物摻和物之非限制實例為聚乳酸(PLA)及聚(己二酸丁二酯-共-對苯二甲酸酯)(PBAT)。前面提到的摻和熱塑性生物聚合物樹脂已表明在形成本發明之最佳微氣孔可撓性發泡體結構中的有利技術性質。增強的技術性質中之一些包括:可接受的老化性質、優良伸長,及異常壓縮變形,以及其他效益。The production of biodegradable and industrially synthesizable microporous flexible foam structures begins with suitable biopolymers or biopolymer blends such as aliphatic and aliphatic-aromatic copolyesters. Non-limiting examples of suitable biopolymer blends are polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT). The aforementioned blended thermoplastic biopolymer resins have shown advantageous technical properties in forming the optimal microcellular flexible foam structure of the present invention. Some of the enhanced technical properties include: acceptable aging properties, excellent elongation, and abnormal compression set, among other benefits.
最佳脂肪族及脂肪族-芳香族共聚酯生物聚合物或生物聚合物摻和物在無合適的發泡劑及發泡製程的情況下不能單獨生產可撓性發泡體。現今使用的最廣泛已知的發泡劑為稱為偶氮二甲醯胺(ADA)之化學品。偶氮二甲醯胺通常經預先浸漬至用於使用在習知射出模製成形發泡體製程中的石化熱塑性母料樹脂中。不幸地,ADA不是環境友好的,且其為人類健康之可疑致癌物。此外,習知石化熱塑性母料樹脂既非生物可降解的,亦非工業上可合成的。為達成用於前面提到的發明之大多數最佳生物可降解且工業上可合成之可撓性發泡體,將超臨界流體狀態中之惰性氮氣或二氧化碳用作修改後射出模製成形製程中之物理發泡劑。修改後物理發泡製程與合適的熱塑性生物聚合物或摻和生物聚合物母料一致地利用,使得生物聚合物或生物聚合物摻和物及發泡劑協調地工作,用於生產大多數最佳生物可降解且工業上可合成之可撓性發泡體。The best aliphatic and aliphatic-aromatic copolyester biopolymers or biopolymer blends cannot produce flexible foams alone without suitable foaming agents and foaming processes. The most widely known blowing agent used today is a chemical called azodimethamide (ADA). Azodimethamide is usually pre-impregnated into the petrochemical thermoplastic masterbatch resin used in the conventional injection molding foaming process. Unfortunately, ADA is not environmentally friendly, and it is a suspected carcinogen for human health. In addition, conventional petrochemical thermoplastic masterbatch resins are neither biodegradable nor industrially synthesizable. In order to achieve most of the best biodegradable and industrially synthesizable flexible foams used in the aforementioned inventions, inert nitrogen or carbon dioxide in a supercritical fluid state is used as a modified injection molding process Physical foaming agent in China. The modified physical foaming process is consistent with the use of suitable thermoplastic biopolymers or blended biopolymer masterbatches, so that the biopolymers or biopolymer blends and foaming agents work in harmony and are used to produce most of the most advanced biopolymers. Good biodegradable and industrially synthesizable flexible foam.
本揭示案之射出模製成形製程依賴於當生物聚合物或生物聚合物摻和物及超臨界流體(SCF)之單相溶液經由射出閘傳送至模具空腔中時發生的均質氣孔成核。在溶液進入模具時,壓力下降,使SCF自溶液出來,從而產生氣孔核。氣孔然後生長直至材料填充模具,且SCF之膨脹能力耗盡。此製造製程在射出模製成形機上運行,該等射出模製成形機已經修改以允許將SCF計量、輸送且混合至生物聚合物中以產生單相溶液。動態模具溫度控制(DMTC)經利用來確保膨脹生物聚合物熔體內之一致氣孔結構。DMTC可經最佳地描述為射出填充級段期間的模具溫度之快速變化及控制;此藉此就熱熱循環及冷熱循環兩者而言動態地控制模具溫度。氣體反壓力(GCP)亦在製造製程中利用來確保具有所得可撓性發泡體上之少量直至無表皮之最佳發泡體結構。GCP可最佳地描述為包括以SCF注射以抵抗熔體內之氣體之膨脹的加壓模具空腔的製程。在反壓力經釋放時,將按照慣例突破表面的氣體氣泡經捕獲在內側,從而產生光滑表皮。GCP藉由表面品質、發泡體結構及表皮厚度控制發泡。The injection molding process of the present disclosure relies on homogeneous pore nucleation that occurs when a single-phase solution of biopolymer or biopolymer blend and supercritical fluid (SCF) is delivered to the cavity of the mold through an injection gate. When the solution enters the mold, the pressure drops, causing the SCF to come out of the solution, resulting in pore nuclei. The pores then grow until the material fills the mold and the expansion capacity of the SCF is exhausted. This manufacturing process runs on injection molding machines that have been modified to allow SCF to be metered, delivered, and mixed into biopolymers to produce a single-phase solution. Dynamic mold temperature control (DMTC) is used to ensure a consistent pore structure in the expanded biopolymer melt. DMTC can be best described as the rapid change and control of the mold temperature during the injection and filling stage; this thereby dynamically controls the mold temperature in terms of both thermal and thermal cycles. Gas counter pressure (GCP) is also used in the manufacturing process to ensure the best foam structure with a small amount to no skin on the resulting flexible foam. GCP can best be described as a process involving pressurized mold cavities injected with SCF to resist the expansion of gas in the melt. When the back pressure is released, the gas bubbles that break through the surface as usual are trapped inside to produce a smooth skin. GCP controls foaming by surface quality, foam structure and skin thickness.
其中SCF完全溶解且均勻地分散在熔融生物聚合物中的單相溶液之產生在謹慎控制的製程條件下發生在射出桶內側:SCF必須經精確地質量流量計量至生物聚合物中持續固定量的時間。且在配料週期期間,可在桶內建立正確的溫度、壓力及剪力條件。背壓、螺桿速度及桶溫度控制,以及SCF輸送系統全部在建立產生單相溶液的製程條件中起作用。The production of a single-phase solution in which SCF is completely dissolved and uniformly dispersed in the molten biopolymer occurs on the inside of the injection barrel under carefully controlled process conditions: SCF must be accurately measured by a mass flow rate to a constant constant amount in the biopolymer time. And during the batching cycle, the correct temperature, pressure and shear conditions can be established in the barrel. Back pressure, screw speed and barrel temperature control, as well as the SCF delivery system all play a role in establishing the process conditions to produce a single-phase solution.
一旦單相溶液已經產生,修改後射出模製成形機將溶液維持在加壓狀態中,直至射出開始。機器藉由關斷噴嘴及螺桿位置控制之組合努力達成此舉。關斷噴嘴防止洩壓及過早發泡至模具中。主動或被動螺桿位置控制藉由螺桿之向後移動防止洩壓。在主動螺桿位置控制期間,螺桿之位置經連續地監視,且施加至螺桿之背部的壓力經調節以維持位置設定點或在螺桿之背部上保持恆定壓力。在被動位置控制中,防止用來調節背壓力的油在螺桿復原之終點處排至其槽。此殘油阻止螺桿由於單相溶液之壓力而向後移動。Once the single-phase solution has been produced, the modified injection molding machine maintains the solution in a pressurized state until the injection begins. The machine strives to achieve this by turning off the nozzle and the combination of screw position control. Turn off the nozzle to prevent pressure relief and premature foaming into the mold. Active or passive screw position control prevents pressure relief by moving the screw backwards. During active screw position control, the position of the screw is continuously monitored, and the pressure applied to the back of the screw is adjusted to maintain the position set point or to maintain a constant pressure on the back of the screw. In passive position control, the oil used to adjust the back pressure is prevented from draining to its groove at the end of the screw recovery. This residual oil prevents the screw from moving backward due to the pressure of the single-phase solution.
適當的模具設計亦幫助維持單相溶液。具有熱澆道系統之模具需要閥閘來防止材料在模具開放時自噴嘴滴漏。機器噴嘴斷路器在正常操作期間與澆口襯套接觸的模具,諸如在堆疊或串聯模具的情況下,需要澆口襯套上的關斷。否則,來自熱澆道之壓力將藉由澆口襯套解除。Proper mold design also helps maintain a single-phase solution. A mold with a hot runner system requires a valve gate to prevent material from dripping from the nozzle when the mold is open. Molds that are in contact with the sprue bushing during normal operation of the machine nozzle circuit breaker, such as in the case of stacked or tandem molds, require shut-off on the sprue bushing. Otherwise, the pressure from the hot runner will be relieved by the gate bushing.
利用於射出模製成形生物可降解及工業上可合成之微氣孔發泡體的發泡劑為處於超臨界流體(SCF)狀態中之惰性氮氣或二氧化碳。前面提到的發泡劑中每一者具有其地位,取決於正生產的最終零件之技術要求。The blowing agent used in injection molding to form biodegradable and industrially synthesizable microcellular foams is inert nitrogen or carbon dioxide in a supercritical fluid (SCF) state. Each of the aforementioned blowing agents has its status, depending on the technical requirements of the final part being produced.
用於本發明之有用發泡劑為SCF氮氣,因為該SCF氮氣以相較於SCF二氧化碳的低得多的重量百分比提供改良之重量減少及精細氣孔結構。實際上,SCF氮水平將通常比達成可比較零件所需要的SCF二氧化碳水平低至少75%。然而,SCF二氧化碳為以下兩個情形中之較佳發泡劑:當黏度降低為主要處理目標時或當應用不能忍受SCF氮之更侵略性發泡動作時。A useful blowing agent for use in the present invention is SCF nitrogen because the SCF nitrogen provides improved weight reduction and fine pore structure at a much lower weight percentage compared to SCF carbon dioxide. In fact, the SCF nitrogen level will usually be at least 75% lower than the SCF carbon dioxide level required to achieve comparable parts. However, SCF carbon dioxide is the preferred blowing agent in two situations: when viscosity reduction is the main processing goal or when the application cannot tolerate the more aggressive foaming action of SCF nitrogen.
兩個成泡劑之有效性之差異起源於其在生物聚合物熔體中之行為。例如,在31.1攝氏溫度及72.2巴處變成SCF流體的二氧化碳比在-147攝氏溫度及34巴處變成超臨界流體的氮更可溶於生物聚合物中4倍至5倍。例如,未填充生物聚合物中之飽和點為約1.5至2重量%之氮,取決於溫度及壓力條件,而二氧化碳之飽和水平較接近於8重量%。二氧化碳亦展現生物聚合物中之較大遷移率,從而允許二氧化碳比氮遷移至現有氣泡中更遠。自氣孔成核之觀點,較大溶解度及遷移率意味較少的氣孔將成核,且成核的彼等氣孔將傾向於為較大的。The difference in the effectiveness of the two foaming agents originates from their behavior in the biopolymer melt. For example, carbon dioxide that becomes an SCF fluid at a temperature of 31.1 degrees Celsius and 72.2 bar is four to five times more soluble in biopolymers than nitrogen that becomes a supercritical fluid at a temperature of -147 degrees Celsius and 34 bar. For example, the saturation point of unfilled biopolymers is approximately 1.5 to 2% by weight of nitrogen, depending on temperature and pressure conditions, while the saturation level of carbon dioxide is closer to 8% by weight. Carbon dioxide also exhibits a greater mobility in biopolymers, allowing carbon dioxide to migrate farther into existing bubbles than nitrogen. From the viewpoint of pore nucleation, greater solubility and mobility means that fewer pores will nucleate, and those nucleated pores will tend to be larger.
然而,當目標為黏度降低時,溶解度變成優點。溶解在生物聚合物中的SCF充當增塑劑,從而降低生物聚合物之黏度。因為黏度降低部分地隨添加至生物聚合物的SCF之量而變且因為二氧化碳具有相較於氮的較高溶解度極限,所以以二氧化碳降低黏度之能力為較大的。However, when the goal is viscosity reduction, solubility becomes an advantage. The SCF dissolved in the biopolymer acts as a plasticizer, thereby reducing the viscosity of the biopolymer. Because the viscosity reduction partly varies with the amount of SCF added to the biopolymer and because carbon dioxide has a higher solubility limit than nitrogen, the ability of carbon dioxide to reduce the viscosity is greater.
當生產零件所需要的氮量低至使得不可能一致地處理零件時,二氧化碳亦為較佳的。因為二氧化碳為侵略性小得多的發泡劑,所以存在較容易運行低水平的二氧化碳之時機。例如,0.15%或0.2%的二氧化碳與小於0.05%的極低氮水平相比。如先前實例中所指示的實例主要在軟材料及具有厚橫截面之零件的情況下發生。 [可回收射出模製成形的微氣孔可撓性發泡體及製造該等可回收射出模製成形的微氣孔可撓性發泡體之方法]Carbon dioxide is also preferable when the amount of nitrogen required to produce parts is so low that it is impossible to treat the parts consistently. Because carbon dioxide is a much less aggressive blowing agent, there is an easier time to run low levels of carbon dioxide. For example, carbon dioxide of 0.15% or 0.2% is compared to very low nitrogen levels of less than 0.05%. The examples as indicated in the previous examples mainly occur in the case of soft materials and parts with thick cross-sections. [Recyclable injection-molded micro-porous flexible foam and method for manufacturing such recyclable injection-molded micro-porous flexible foam]
圖4及圖6例示根據本揭示案之可回收射出模製成形的微氣孔可撓性發泡體402及製作該可回收射出模製成形的微氣孔可撓性發泡體之方法。參考圖4,可撓性發泡體402較佳地為封閉氣孔發泡體,但亦可能形成為開放氣孔發泡體。在各種實行方案中,可使得可撓性發泡體402具有至少近似類似於習知不可回收乙烯乙酸乙烯酯(EVA)發泡體等等之彼等的性質及特性。4 and 6 illustrate the micro-porous
如以下更詳細地論述,可回收可撓性發泡體402係藉由使用圖5中所例示之射出模製成形機處於熱塑性聚合物製成。用來製造可回收可撓性發泡體402的熱塑性聚合物可任擇地由許多聚醯胺基熱塑性聚合物、聚醯胺共聚物等等產生。在本發明中找到使用的合適的聚合物之非限制實例由聚醯胺6、聚醯胺6/6-6、聚醯胺12組成。替代地,熱塑性聚合物可包含許多聚醯胺嵌段共聚物,諸如聚醚-嵌段-醯胺(PEBA)、PAE、TPA、TPE-A、COPA等等。合適的聚合物及共聚物之其他非限制實例包括由Ascend Performance Materials, LLC, Houston, TX以Vydyne之商標名行銷的聚醯胺66共聚物。前面提到的熱塑性聚合物樹脂已表明在形成本發明之最佳微氣孔可撓性發泡體結構中的有利技術性質。增強的技術性質中之一些包括異常老化性質、優良伸長、拉伸強度,及壓縮變形,以及其他效益。As discussed in more detail below, the recyclable
另外,二或更多個熱塑性聚合物之摻和物提供在單個熱塑性聚合物中未發現的性質及價格之組合。存在用以成功地將熱塑性聚合物摻和在一起的許多方式。如以下更詳細地論述,雙螺桿擠製用以使二或更多個熱塑性聚合物熔融在一起且然後將熔融聚合物樹脂摻合物擠製成股,該股經冷卻且進料至造粒機中以用於生產稱為母料的一系列造粒件。聚合物樹脂摻和之另一方法將使用增容劑來在聚合物摻合物中將不同化學成分接合在一起。通常,此亦使用雙螺桿擠製等等來在以上描述的非限制熱塑性聚合物類型中使增容劑及二或更多個聚合物熔融在一起。In addition, blends of two or more thermoplastic polymers provide a combination of properties and prices not found in a single thermoplastic polymer. There are many ways to successfully blend together thermoplastic polymers. As discussed in more detail below, twin screw extrusion is used to melt two or more thermoplastic polymers together and then extrude the molten polymer resin blend into strands, which are cooled and fed to pelletization The machine is used to produce a series of pellets called master batches. Another method of polymer resin blending is to use compatibilizers to join the different chemical components together in the polymer blend. Typically, twin screw extrusion or the like is also used here to melt the compatibilizer and two or more polymers together in the non-limiting thermoplastic polymer types described above.
在一個實施例中,熱塑性聚合物包含源自於消費後或工業後回收的原料的至少一個單體或聚合物。例如,熱塑性聚合物可包含己內醯胺、回收的聚醚嵌段醯胺聚合物等等。藉由說明之方式,己內醯胺可藉由解聚合含有聚醯胺的工業後或消費後材料源自於回收的原料,該工業後或消費後材料諸如捕魚網、地毯纖維,或工業廢棄物。解聚合的消費後或工業後回收的己內醯胺之非限制實例包括由Aquafil USA Inc., Cartersville, Georgia提供的ECONYL®己內醯胺,無論呈片狀、液體或或熔融。熱塑性聚合物可另外或替代地包含源自於經收集、分類、熔化且再處理的工業後或消費後聚醯胺地毯纖維的聚醯胺聚合物。源自於工業後地毯纖維的一個此聚醯胺聚合物為由Aquafil USA Inc., Cartersville, Georgia製造的Econyl。另外,聚醯胺廢棄物以捕魚網或類似者之形式在世界海洋中或在世界海洋周圍收集,然後可經分類、熔化,且再處理成升級再造的可用聚醯胺材料。源自於所收集工業後捕魚網的示範性聚醯胺聚合物為由Koninklijke DSM N.V., Heerlen, the Netherlands製造的Akulon Repurposed。In one embodiment, the thermoplastic polymer comprises at least one monomer or polymer derived from raw materials recovered after consumption or after industry. For example, the thermoplastic polymer may include caprolactam, recycled polyether block amide polymer, and the like. By way of illustration, caprolactam can be derived from recycled raw materials by depolymerizing post-industrial or post-consumer materials containing polyamide, such as fishing nets, carpet fibers, or industrial Waste. Non-limiting examples of depolymerized post-consumer or post-industrial recovered caprolactam include ECONYL® caprolactam supplied by Aquafil USA Inc., Cartersville, Georgia, whether in flake, liquid or molten. Thermoplastic polymers may additionally or alternatively comprise polyamide polymers derived from post-industrial or post-consumer polyamide carpet fibers that have been collected, sorted, melted, and reprocessed. One such polyamide polymer derived from post-industrial carpet fibers is Econyl manufactured by Aquafil USA Inc., Cartersville, Georgia. In addition, polyamide waste is collected in or around the world's oceans in the form of fishing nets or the like, and then can be sorted, melted, and reprocessed into usable polyamide materials for upgrading. An exemplary polyamide polymer derived from collected post-industrial fishing nets is Akulon Repurposed manufactured by Koninklijke DSM N.V., Heerlen, the Netherlands.
取決於應用,添加劑亦可經利用於聚合物配方中。例如,填料諸如沉澱碳酸鈣、鮞狀霰石、澱粉、生物質等等可經利用來降低零件成本,同時維持完成可撓性發泡體之可回收完整性。Depending on the application, additives can also be utilized in polymer formulations. For example, fillers such as precipitated calcium carbonate, oolitic aragonite, starch, biomass, etc. can be used to reduce the cost of parts while maintaining the recyclable integrity of the finished flexible foam.
此外,用於使用在聚合物配方中的添加劑可由以下中一或多個組成。成核劑諸如微葉片狀滑石或高深寬比鮞狀霰石可經包括。此類成核劑可藉由防止氣孔聚結、降低塊體密度,且改良回彈性以及其他有益地增強之屬性大大地改良所得可撓性發泡體之關鍵性質。用於使用在生產可回收射出模製成形的微氣孔可撓性發泡體中之成核劑之若干非限制實例為由Imerys Talc America Inc., Houston, Texas作為Mistrocell®行銷的微葉片狀滑石及由Calcean Minerals & Materials LLC, Gadsden, Alabama作為OceanCal®行銷的高深寬比鮞狀霰石。In addition, the additives used in the polymer formulation can be composed of one or more of the following. Nucleating agents such as microlobed talc or high aspect ratio oolitic aragonite may be included. Such nucleating agents can greatly improve the key properties of the resultant flexible foam by preventing pore coalescence, reducing block density, and improving resilience and other beneficially enhanced properties. Some non-limiting examples of nucleating agents for use in the production of microporous flexible foams that are recyclable injection molding are microlobe-shaped marketed by Imerys Talc America Inc., Houston, Texas as Mistrocell® Talc and high aspect ratio oolitic aragonite marketed by Calcean Minerals & Materials LLC, Gadsden, Alabama as OceanCal®.
著色劑、染料及顏料亦可經包括。例如,各種著色劑諸如染料、顏料或顏料可任擇地使用在本發明之聚合物配方中。若干非限制實例為已經定製來用於特定類型的熱塑性聚合物使用的顏料,諸如由Treffert GmBH & Co. KG, Bingen am Rhein, Germany提供的寬範圍或由Holland Colours Americas Inc., Richmond, Indiana提供的彼等。Colorants, dyes and pigments can also be included. For example, various coloring agents such as dyes, pigments or pigments can be optionally used in the polymer formulation of the present invention. Several non-limiting examples are pigments that have been customized for use with specific types of thermoplastic polymers, such as the wide range provided by Treffert GmBH & Co. KG, Bingen am Rhein, Germany or by Holland Colours Americas Inc., Richmond, Indiana Provided by them.
回收原料對於產生微氣孔可撓性發泡體之使用減少環境衝擊,該環境衝擊通常藉由尋找可持續材料的來源與膨脹熱塑性聚合物發泡體之產生相關聯。如以下更詳細地論述,用於產生本揭示案之微氣孔可撓性發泡體之方法增加使用回收原料之環境效益,因為所得產品可進一步回收成熱塑性聚合物,該等熱塑性聚合物隨後可利用來產生來自微氣孔可撓性發泡體的新產品或替代地利用熱塑性聚合物的其他產品。 [製作可撓性發泡體之方法]The use of recycled raw materials to generate micro-pore flexible foams reduces the environmental impact, which is usually associated with the production of expanded thermoplastic polymer foams by looking for sources of sustainable materials. As discussed in more detail below, the method used to produce the microcellular flexible foam of the present disclosure increases the environmental benefits of using recycled raw materials because the resulting product can be further recycled into thermoplastic polymers, which can subsequently be Use to create new products from micro-porous flexible foams or alternatively use other products of thermoplastic polymers. [Method of Making Flexible Foam]
圖5及圖6例示用於製造圖4中所示之回收可撓性發泡體402的射出模製成形機506及方法600。因此,在一個態樣中,本揭示案針對發泡熱塑性聚合物之方法。如以下更詳細地描述,方法可經利用來由可撓性發泡體402產生許多終端產品中之任何終端產品,諸如包括鞋組件的技術運動裝置,及需要諸如緩衝、衝擊保護、舒服及其他之特徵的其他產品。5 and 6 illustrate an
如圖5中所圖示500,射出模製成形機506包括漏斗504,該漏斗經組配來用於將複數個熱塑性聚合物502接收且引入射出模製成形機506中。桶507連接至漏斗504且經組配來用於接收熱塑性聚合物502且包括特殊化往復螺桿型柱塞508。桶507亦包括溫度控制單元(未示出)以加熱且冷卻桶507之內容。如圖5中所示,具有溫度及壓力量測裝置505的電腦控制器503經組配來感測桶507內之溫度及壓力。氣體配料系統509流體地連接至桶507且包括計量單元512,該計量單元經組配來用於將流體510接收且引入桶507中。氣體配料系統509將流體510維持在臨界溫度及壓力(分別為Tc及Pc)以產生超臨界流體(SCF) 510。在本揭示案之方法中,SCF 510用作替代可撓性發泡體生產之習知方法中所利用的諸如偶氮二甲醯胺(ADA)之化學發泡劑的物理發泡劑。藉由實例之方式,SCF 510可包含惰性氣體或鈍氣諸如氮、二氧化碳、氦、氖、氬或氙。本揭示案之方法與習知可撓性發泡體模製成形方法相比不僅藉由自製程消除環境有害且可疑致癌物ADA且以惰性SCF或鈍SCF替代該環境有害且可疑致癌物ADA來改良環境衝擊,而且如以下將進一步詳細地論述,本揭示案之可撓性發泡體402可作為本文所描述之方法之結果而在該等可撓性發泡體之有用壽命之終點處經回收。As shown 500 in FIG. 5, the
參考圖6,用於製造可回收可撓性發泡體 102之方法可始於步驟602:選擇熱塑性聚合物502且將熱塑性聚合物502供應至射出模製成形機506之漏斗504。隨後,在步驟604中,熱塑性聚合物502然後自漏斗504進料至桶507中且經加熱。在步驟606中,在螺桿型柱塞508移動熱塑性聚合物502穿過射出模製成形機506時,加熱桶507使熱塑性聚合物502熔融。此外,控制器503可經組配來控制且調變螺桿速度。Referring to FIG. 6, the method for manufacturing the recyclable
在步驟608中,SCF 510藉由噴射器511經由連接至射出模製成形機506的計量單元512引入桶507中,且SCF 510溶解在熔融熱塑性聚合物502中以產生單相溶液。SCF 510可在熔體內之濃度方面經調整,此影響獲得的發泡程度。參考圖5,計量系統512經組配來用於將SCF以適當量配料至熔融熱塑性聚合物502中。初始SCF氣體濃度之非限制實例可為Co = 0.25%,並且熔體溫度範圍在176℃與250℃之間,且更佳地在180℃之範圍內。此外,控制器503控制SCF 510藉由SCF噴射器引入桶507中的壓力。SCF 510使熔融熱塑性聚合物502飽和,從而產生單相溶液。此外,螺桿型柱塞508以使熱塑性聚合物502及SCF 510均質且產生單相溶液所必需的的速度在桶507內旋轉。螺桿508可在桶507內在1 rpm至200 rpm之間,且較佳地,自近似20 rpm至近似60 rpm旋轉。In
關於飽和,射出模製成形機506經組配來用於在溫度及壓力下將氣體輸送至桶507,以在螺桿旋轉期間使熔融熱塑性聚合物502飽和。特定而言,控制器503經組配來控制SCF輸送壓力及SCF劑量重量之組合。SCF壓力及劑量可以一方式控制以便影響單相溶液。亦即,SCF劑量越小,生物聚合物熔體內的SCF飽和需求越小,而SCF劑量越大,熔體內的SCF飽和需求越大。同樣地,SCF輸送壓力越小,飽和之攝取越低,且因此可生長以在熔融生物聚合物熔體內形成氣泡的核之生長越低。此外,SCF輸送壓力越大,飽和之攝取越大,且因此可生長以在熔融熔體內形成氣泡的核之生長越大。Regarding saturation, the
控制器503以取決於正生產的可撓性發泡體之類型及正生產的終端產品用於何類型的方式可變地控制溫度及壓力。特定而言,遍及系統(諸如桶507內)的溫度可經控制以便介於100℃與600℃之間,諸如介於200℃與500℃之間,例如,介於300℃與400℃之間,且更具體而言,介於320℃與380℃之範圍之間,包括桶內介於360℃與380℃之間。同樣地,SCF輸送壓力可經精細地控制,以便在介於1,000 PSI與8,000 PSI之間的範圍內,諸如在1,500 PSI與6,000 PSI之間,例如,在2,000 PSI與5,500 PSI之間,具體而言,在3,000 PSI與4,000 PSI之間,且更具體而言在2,600 PSI與2,800 PSI之範圍之間。The
在圖5中所例示之實施例中,控制器503使用感測器來決定且控制SCF 510濃度,該感測器決定飽和之量且評估飽和製程進展且調變壓力及溫度。SCF 510在往復螺桿508之旋轉期間可控制地使熔融熱塑性聚合物502飽和,以在明確的溫度及壓力下產生單相溶液。SCF為兩部分熔融熱塑性聚合物化合物混合物之一個部分,且其在存在本射出模具中之明確的壓力及溫度的情況下用作物理發泡劑。In the embodiment illustrated in FIG. 5, the
如以下更詳細地論述,SCF 510發泡劑可基於最終可撓性發泡體402產品之技術要求而選自以上所列舉的鈍流體及惰性流體之列表。例如,處於其超臨界狀態中之二氧化碳在相同壓力處比氮稠密但具有較高熱容。處於超臨界狀態中之二氧化碳生產可使用於某些緩衝應用中的稠密發泡體。相反,超臨界氮可用來生產當產生用於鞋類及運動商品之可撓性發泡體402時可使用的具有較小核之密度低發泡零件。As discussed in more detail below, the
然而,當目標為黏度降低時,溶解度變成優點。溶解在可回收熱塑性聚合物502中的SCF充當增塑劑,從而降低熱塑性聚合物502之黏度。因為黏度降低部分地隨添加至可回收熱塑性聚合物502的SCF之量而變且因為二氧化碳具有相較於氮的較高溶解度極限,所以以二氧化碳降低黏度之能力為較大的。當生產零件所需要的氮量低至使得不可能一致地處理終端產品時,二氧化碳亦為有用的。However, when the goal is viscosity reduction, solubility becomes an advantage. The SCF dissolved in the recyclable
因為二氧化碳為侵略性較小的發泡劑,所以存在較容易運行低水平的二氧化碳之時機。例如,0.15%或0.2%的二氧化碳與小於0.05%的極低氮水平相比。如先前實例中所指示的實例主要在軟材料及具有厚橫截面之零件的情況下發生。因此,無論物理發泡劑為氮、二氧化碳,或以上列舉的其他惰性及惰性氣體中之一者,物理發泡劑在最終發泡零件及將含有該等物理發泡劑的最後產品中起到有用的作用。Because carbon dioxide is a less aggressive blowing agent, there are opportunities to run low levels of carbon dioxide more easily. For example, carbon dioxide of 0.15% or 0.2% is compared to very low nitrogen levels of less than 0.05%. The examples as indicated in the previous examples mainly occur in the case of soft materials and parts with thick cross-sections. Therefore, regardless of whether the physical blowing agent is nitrogen, carbon dioxide, or one of the other inert and inert gases listed above, the physical blowing agent plays a role in the final foamed part and the final product containing the physical blowing agent. Useful role.
選擇相容熱塑性聚合物或熱塑性聚合物化合物及相關聯SCF氣體之適當組合為有用的。其次,藉由最佳配料重量及壓力適當地利用SCF氣體提供單相溶液內之較佳飽和水平,且影響核之產生(發泡體基質內之許多均勻氣泡之生產,如以下將更詳細地描述)。另外,終端結果,同質地形成的射出模製成形可撓性發泡體零件,依賴於SCF氣體氣體配料製程之所有態樣及與射出模製成形機溫度、壓力及保持時間協作地工作,以用於達成商業上可接受的模製成形發泡零件的氣體反壓力之使用。It is useful to choose an appropriate combination of compatible thermoplastic polymers or thermoplastic polymer compounds and associated SCF gases. Secondly, use SCF gas appropriately to provide a better saturation level in the single-phase solution by the optimal ingredient weight and pressure, and affect the generation of nuclei (the production of many uniform bubbles in the foam matrix, as described in more detail below) describe). In addition, as a final result, injection molded flexible foam parts formed with the same texture depend on all aspects of the SCF gas compounding process and work in coordination with the temperature, pressure and holding time of the injection molding machine. The use of gas counterpressure to achieve commercially acceptable molded foam parts.
參考圖5,往復螺桿508進一步經組配來壓縮且移動桶507之空腔內之熔融熱塑性聚合物502。氣體反壓力(GCP)系統516經組配來用於將氣體反壓力輸送至桶507,以便控制熔融熱塑性聚合物502之膨脹。在圖5中所例示之實施例中,GCP系統516包括氣體泵515、氣體儲器518包括惰性氣體諸如氮或二氧化碳、壓縮機517、壓力感測器519,及氣體控制閥520。往復螺桿型柱塞508及桶507亦經組配來提供背壓力且將熱塑性聚合物502輸送至具有空腔的模具514中,該空腔與桶507流體連通地安置,且經組配來接收熔融熱塑性聚合物502 (以下更詳細地描述)。在圖5中所示之實施例中,螺桿型柱塞508及桶507經組配來施加在近似2,000 psi與近似3,000 psi之間,且更佳地在2,700 psi與2,800 psi之範圍內。螺桿型柱塞508及桶507之組態亦設定SCF 510配料開始所在的位置,且此舉然後可將SCF噴射器設定至開放或封閉位置。位置應經設定,以便在螺桿復原期間桶中之壓力在SCF 510配料開始之前變得穩定。作為非限制實例,開放位置可在0.3吋與0.4吋之範圍內。5, the
除GCP系統之外,圖5中所例示之射出模製成形機506包括動態模具溫度控制(DMTC) 522,該動態模具溫度控制經組配來控制模具514內之溫度。DMTC 522可與GCP系統516一致地利用來確保膨脹熱塑性聚合物502內之一致氣孔結構。DMTC 522可經組配以便在射出填充級段期間影響模具溫度及/或壓力之快速變化及控制,且在有或沒有反壓力的情況下藉由熱熱循環及冷熱循環之使用動態地控制模具溫度及/或壓力。In addition to the GCP system, the
繼續參考圖5,控制器503經組配以便在射出級段610期間藉由DMTC 522控制模具514溫度。更具體而言,與按照慣例已知的射出模製成形製程相比,本文所利用的動態模具溫度控制之重要特性在於模具溫度自身可經動態地控制。圖5中所例示之DMTC 522利用快速電氣桿加熱及快速水冷卻。特定而言,DMTC 522包括五個主要組件:空氣壓縮機(未示出)、閥交換裝置526、電腦控制的模具溫度控制單元(安置在控制器503內)、電氣加熱桿(安置在模具514內),及冷卻塔532。冷卻塔532可用來將充分的水冷卻供應至模具。空氣壓縮機用來生產壓縮空氣作為氣動閥之驅動氣體且用來在冷卻之後排除殘餘冷卻水以免進入模具。在圖5中所示之實施例中,水加熱單元534亦經包括,且閥交換裝置526用來切換閥以將來自管線之不同介質傳遞至模具514,從而提供熱熱循環及冷熱循環。例如,DMTC 522可提供介於近似15℃與近似30℃之間的範圍內之水冷卻,且電氣加熱桿可將模具加熱至介於近似60℃與近似150℃之間,且可最佳地將模具加熱至90℃至130℃之範圍內。Continuing to refer to FIG. 5, the
圖5中所描繪之射出模製成形機506包括管道及用於反應材料之傳送的其他導管,該等導管與一或多個熱交換單元相關聯,以便在反應物經泵送至導管及管道中及/或穿過導管及管道時加熱且/或冷卻該等反應物。在此實例中,交換器可經控制以將溫度調整至反應水平。在管道之一個末端上可包括分配頭,該分配頭可與一或多個閥相關聯。此外,分配頭可向上鉤掛至處理線路。電氣加熱模具用於模製成形發泡零件之最終形狀。模具溫度控制之功能將控制模具之加熱及冷卻;所有此舉藉由電腦控制與射出模製成形機協調。The
因此,如本文所實行,控制器503實行氣體反壓力以藉由在射出級段施加不同的氣體壓力來改良發泡製程之控制,如以下所描述。控制器503經組配來操縱GCP系統516及DMTC 522,以調節溫度及壓力且藉此控製成核及熔融熱塑性聚合物502內之所得氣泡及所得發泡基質。Therefore, as implemented herein, the
如圖6中所例示,在步驟610中,熱塑性柱塞508前進,從而推動熔融熱塑性聚合物502穿過噴嘴(未示出),該噴嘴抵靠模具514且該噴嘴將熱塑性聚合物502注射至模具514中。射出模製成形機506將單相熱塑性聚合物502之量測射注發送至動態溫度控制的模具514空腔中。在射出步驟610之前,DMTC 522將模具514加熱至預設上限。在射出步驟610期間,DMTC 522將模具514空腔之溫度維持為高於上限,以防止熔融熱塑性聚合物502過早地固化。GCP系統516輸送模具514內之氣體反壓力以控制核生長,從而在發泡零件經形成時防止氣體氣泡接觸且突破塑性聚合物502之表面。此藉由抵抗壓力達成,該抵抗壓力係藉由GCP系統516在熱塑性聚合物502單相溶液經注射至模具514空腔中的相同時間或大約相同時間施加至模具空腔中。惰性氣體氣泡經受足以在射出步驟610期間將SCF 510保持在熱塑性聚合物502內的力。As illustrated in Figure 6, in
參考圖6,在步驟612及步驟614中,控制器503操縱模具514內之壓力及溫度,以控制熱塑性聚合物502之物理發泡。儘管動態地控制模具612之溫度及將氣體反壓力施加至模具614之步驟在圖6之流程圖中例示為單獨步驟,但步驟612及614可同時或相繼地實施,使得控制器503控制模具內之溫度及壓力。在步驟612及614中,在熔融熱塑性聚合物502內經歷核生長且形成許多微氣孔氣泡。在控制器503 (圖5)在步驟612中使溫度上升且下降時,SCF 510蒸發且變成氣體氣泡,從而使熱塑性聚合物502在模具514內發泡。在步驟614中,GCP系統516藉由電腦控制將反壓力氣體之預計量劑量發送至模具中以產生實質上均勻的氣泡,且氣體反壓力調節用於最佳外表外觀之表面織理。氣體氣泡生長,直至熱塑性聚合物502填充模具514,且SCF 510之膨脹能力耗盡。因為氣泡達到微米大小,所以製程生產微氣孔發泡。SCF 510濃度可影響氣體氣泡之結構。因此,控制器503選擇溫度及氣體反壓力參數,以便生產有用的及/或決定的氣體氣泡結構。在零件之模製成形結束時,模具冷卻且熱塑性聚合物固化。在圖6中所描繪之實施例中,在步驟616中,動態地溫度控制的模具溫度經切換至水冷卻,且氣體氣泡之形成及熱塑性聚合物502之膨脹減緩且停止。DMTC 522將模具514快速冷卻至下限(噴出溫度),可撓性發泡體402模製成形零件現在經形成且其自模具噴出。
[可回收射出模製成形的微氣孔可撓性發泡體產品]Referring to FIG. 6, in
圖4示出本揭示案之鞋類組件。更特定而言,可回收微氣孔可撓性發泡體鞋中底400,其係由可回收可撓性發泡體402製成。Figure 4 shows the footwear component of the present disclosure. More specifically, the recyclable micro-pore flexible
如以上簡要地論述,用於製造以上所論述之可回收物之方法強化利用自回收的原料開發的單體及聚合物之環境上有益的效應,因為所得產品可進一步回收成單體,該等單體可再聚合成熱塑性聚合物以用於使用在製作新的其他塑膠材料中。具體而言,生產經組配來用於回收的商品確保可撓性發泡體將持續所得產品之可用壽命,諸如藉由以使得該所得產品在成品內在使用中不斷裂或破碎的方式使該所得產品功能化。例如,一個人購買僅由本揭示案之可回收可撓性發泡體製成以使發泡體在產品可用壽命終止之前,在正常使用期間降解的家具、一雙鞋或其他運動裝備將為有害的。As briefly discussed above, the methods used to make the recyclables discussed above enhance the environmentally beneficial effects of monomers and polymers developed from recycled raw materials, because the resulting products can be further recycled into monomers. Monomers can be polymerized into thermoplastic polymers for use in making new plastic materials. Specifically, the production of commodities assembled for recycling ensures that the flexible foam will last the useful life of the resultant product, such as by making the resultant product not break or break during use in the finished product. The resulting product is functionalized. For example, if a person purchases furniture, a pair of shoes or other sports equipment that is only made of the recyclable flexible foam of the present disclosure so that the foam will degrade during normal use before the end of the product’s useful life, it will be harmful .
更具體而言,本揭示案受益於以上列舉的惰性物理發泡劑及熱塑性聚合物化合物之使用,該等惰性物理發泡劑及熱塑性聚合物化合物在製造製程期間不交聯。所得可回收可撓性發泡體402為非交聯的,無有害化學發泡劑諸如ADA的,且環境友好的。此外,可回收可撓性發泡體 402可使用在許多類型的終端產品中,該終端產品諸如用於使用在製作鞋中的鞋類發泡體。More specifically, the present disclosure benefits from the use of the above-listed inert physical blowing agents and thermoplastic polymer compounds, which do not crosslink during the manufacturing process. The resulting recyclable
可回收可撓性發泡體402可在產品使用壽命之終點處藉由廢棄物轉向重新導向至適當回收設施。因為可回收可撓性發泡體402不使用諸如ADA之化學發泡劑,且因為本文所描述之方法不利用在其製造期間交聯的熱塑性聚合物,所以可回收可撓性發泡體402可經磨碎、預處理且解聚合成一或多個單體。一個此解聚合單體為藉由Aquafil USA Inc., Cartersville, Georgia提供的己內醯胺諸如ECONYL®己內醯胺,無論呈片狀、液體或熔體,或藉由DSM Engineering Plastics Americas, Troy Michigan提供的解聚合己內醯胺,無論薄片、液體或熔體。The recyclable
參考圖7,本揭示案之方法涵蓋利用熱及化學解聚合製程回收可回收可撓性發泡體402之方法700,根據該方法,使聚合物諸如PEBA之溫度上升至超過最高溫度,且許多化學試劑或催化劑中之任何化學試劑或催化劑經利用來解聚合成其構成單體。在圖7中所例示之實施例中,解聚合製程始於步驟702,該步驟機械地將可回收可撓性發泡體402之熱塑性聚合物與任何廢棄物分離。在步驟704中,將解聚合催化劑引入至分離的熱塑性聚合物。解聚合催化劑之非限制實例包括諸如磷酸及硼酸的酸。在步驟706中,諸如藉由過熱蒸汽施加熱,該過熱蒸汽可作用來蒸餾己內醯胺及任何其他揮發性化合物且生產含有己內醯胺單體的餾出物。施加的溫度範圍可自約100℃至約325℃。在步驟708中,餾出物經分餾以將水及己內醯胺與解聚合方法之其他副產品分離。在步驟710中,將氧化劑引入至分離的含水己內醯胺。氧化劑之一些非限制實例包括過錳酸鉀、氫、氧、重鉻酸鉀、次氯酸鈉或次氯酸鉀、高氯酸鹽或過硼酸。在步驟712中,諸如藉由蒸發濃縮氧化含水己內醯胺。在步驟714中,諸如藉由真空蒸餾純化濃縮己內醯胺單體。Referring to FIG. 7, the method of the present disclosure covers a
在步驟714中之己內醯胺單體之純化之後,解聚合單體可經再聚合成熱塑性聚合物且利用來製作更可回收的可撓性發泡體402。因而,與使用新原始化石燃料或其他不可再生原料相反,本揭示案之方法建立循環製程,藉此工業產品可經分解,製造成新產品,且重新插入商業流中。此外,本揭示案之可回收可撓性發泡體402既不折衷該等可回收發泡體之可用壽命期間的技術效能性質,亦不折衷其環境意識設計。After the purification of the caprolactam monomer in
如本文以上所論述,裝置、系統,及其使用方法可經利用於生產一或多個模製成形終端產品之目的,諸如用於使用在鞋類、座位、汽車、保護裝置,及/或運動裝置中的組件。因此,在各種實施例中,本文所提供的是在鞋諸如其鞋底、中底及/或鞋內底之構造中有用的一或多個組件,諸如其中鞋底形成鞋之基底,且經組配來用於與地面接觸,中底形成中間結構及緩衝元件,且鞋內底經組配來用於插入鞋內且藉此提供緩衝及/或對鞋之支撐。As discussed above, devices, systems, and methods of use can be used to produce one or more molded end products, such as for use in shoes, seats, automobiles, protective devices, and/or sports Components in the device. Therefore, in various embodiments, what is provided herein is one or more components useful in the construction of a shoe, such as its sole, midsole, and/or insole, such as where the sole forms the base of the shoe and is assembled For contact with the ground, the midsole forms an intermediate structure and a cushioning element, and the shoe insole is assembled for insertion into the shoe and thereby provides cushioning and/or support for the shoe.
在某些實施例中,鞋組件可包括根據本文揭示之方法600生產的可回收可撓性發泡體402,該可回收發泡體可為環境友好的且可回收的。在各種實例中,各單獨組件可構成自包括基底層及緩衝層的複數個層。例如,在具體實施例中,支撐構件諸如耦接至基底層的支撐構件可經包括,且在組件為鞋內底的情況下,具有弓形接觸部分或足跟接觸部分中一或多個。In certain embodiments, the shoe component may include a recyclable
具體而言,在各種實施例中,可生產發泡體材料,諸如其中發泡體材料可使用在緩衝墊、緩衝家具、鞋組件諸如其鞋內底、墊、纖維、織物等之生產中。其他有用產品可包括填隙諸如聚矽氧填隙、聚矽氧醫用手套、用於藥物輸送系統之聚矽氧管路、聚矽氧黏合劑、聚矽氧潤滑劑、聚矽氧塗料,及其他合適的聚矽氧產品,例如保險套。在各種實施例中,發泡體產品可以發泡體材料可具有一或多個抗微生物、抗細菌、抗真菌、抗病毒,及/或抗易燃性質的方式加以生產。Specifically, in various embodiments, foam materials can be produced, such as where the foam materials can be used in the production of cushions, cushioning furniture, shoe components such as insoles, cushions, fibers, fabrics, and the like. Other useful products can include gap fillers such as silicone gap fillers, silicone medical gloves, silicone tubing for drug delivery systems, silicone adhesives, silicone lubricants, silicone coatings, And other suitable silicone products, such as condoms. In various embodiments, the foam product may be produced in such a way that the foam material may have one or more anti-microbial, anti-bacterial, anti-fungal, anti-viral, and/or anti-flammability properties.
更具體而言,在一個態樣中,本揭示案可一般地針對用於家具製造之製程,該家具諸如裝套墊家具及/或其緩衝墊,諸如包括發泡體或以其他方式由發泡體組成的家具,例如,該發泡體係生物可降解且/或可合成的。因此,本揭示案之回收發泡體為對於使用在包括如此生產的發泡體插入物的家具之製造中有利的。根據本揭示案之方法生產的可回收發泡體已證明為對於用作緩衝材料有利的,諸如用於枕頭、長椅、床、座墊,或用於其他裝軟墊家具等等。More specifically, in one aspect, the present disclosure may generally be directed to the manufacturing process for furniture, such as upholstered furniture and/or cushions thereof, such as foams or made in other ways. Furniture made of foam, for example, the foaming system is biodegradable and/or synthesizable. Therefore, the recycled foam of the present disclosure is advantageous for use in the manufacture of furniture including the foam insert produced in this way. The recyclable foam produced according to the method of the present disclosure has proven to be advantageous for use as a cushioning material, such as for pillows, benches, beds, seat cushions, or for other upholstered furniture, etc.
例如,方法600可用來生產可回收可撓性發泡體402之小至大方塊,以便形成用於使用在家具或汽車附件組件中的發泡體插入物。方塊發泡體然後可基於正生產的家具之類型及形式而經切割成所要的大小及形狀之較小方塊。特定而言,定大小且切割的方塊然後可經施加至或以其他方式配合在家具或車架或其他界限材料內,該等各者一起可經覆蓋以生產最終家具產品,該最終家具產品為枕頭、沙發、緩衝墊,例如,沙發或汽車緩衝墊等等。另外,在需要的情況下,外罩殼或界限材料可經附接至框架材料,諸如藉由釘住及/或縫接,或以其他方式緊固至將要裝軟墊的製品之框架且以織品或其他材料覆蓋。For example, the
因此,在各種實施例中,當製造裝軟墊家具諸如長椅或汽車座椅時,框架可經生產。家具之各種內部(例如結構)組件可安裝在框架內,諸如彈簧等等,且然後可回收可撓性發泡體402之薄板可經定位在彈簧中,彈簧上及彈簧周圍,諸如用於緩衝及/或隔離。當然,可包括其他材料,諸如棉花層、羊毛層、毛氈層、橡膠基產品層等等,且然後可添加覆蓋材料以便覆蓋框架且完成產品製造。Therefore, in various embodiments, when manufacturing upholstered furniture such as benches or car seats, the frame may be produced. Various internal (such as structural) components of the furniture can be installed in the frame, such as springs, etc., and then the thin plate of the recyclable
特定而言,本揭示案之可回收發泡體與本文揭示之其他材料一起可充當襯墊料或填充料,在覆蓋材料在框架上伸展時,該襯墊料或填充料可在覆蓋物下方成形、調整且褶起。另外,如所指示,在各種實例中,本文生產之可回收發泡體出於許多原因而為在此項技術中已知的彼等中及上有用的,其中最重要的是典型的PU及/或EVA發泡體並非可回收的,而本文生產之發泡體之組件為可回收的。因此,在各種實施例中,提供在開放框架上構造家具之方法。In particular, the recyclable foam of the present disclosure and other materials disclosed herein can serve as a cushioning material or a filling material. When the covering material is stretched on the frame, the cushioning material or the filling material can be under the cover Shaped, adjusted and pleated. In addition, as indicated, in various examples, the recyclable foams produced herein are useful among those known in the art for many reasons, the most important of which are typical PU and / Or EVA foam is not recyclable, and the components of the foam produced in this article are recyclable. Therefore, in various embodiments, a method of constructing furniture on an open frame is provided.
此外,在另一態樣中,本揭示案一般針對用於諸如鞋之鞋底、中底及/或鞋內底的鞋組件之製造的製程,該等鞋組件諸如包括習知發泡體或以其他方式由習知發泡體組成的鞋組件。特定而言,在具體實施例中,提供用於製作可回收鞋底、中底、鞋內底,及/或其他鞋插入物的方法。例如,本鞋插入物可為緩衝裝置之形式,該緩衝裝置適於插入或以其他方式配合在例如跑步鞋或運動鞋的鞋內,該鞋可經組配以便降低在跑步或步行時碰撞表面(例如,地面)的腳之衝擊,藉此吸收對腳之震動且/或使對腳之震動減弱。In addition, in another aspect, the present disclosure is generally directed to the manufacturing process of shoe components such as shoe soles, midsoles, and/or shoe insoles, such as shoe components including conventional foams or in other ways Shoe components composed of conventional foams. In particular, in specific embodiments, methods for making recyclable shoe soles, midsoles, shoe insoles, and/or other shoe inserts are provided. For example, the shoe insert may be in the form of a cushioning device that is adapted to be inserted into or otherwise fit into a shoe such as a running shoe or a sports shoe. The shoe may be configured to reduce the impact on the surface during running or walking. The impact of the foot (for example, the ground), thereby absorbing the vibration to the foot and/or weakening the vibration to the foot.
具體而言,鞋底組件包括中底及插入物可包括一個層或許多層。例如,在一些實例中,基底層、可回收發泡體層及/或織物層可經提供。特定而言,可包括相對彈性材料之基底層,及/或例如安置在基底層上的可回收發泡體層,及/或安置在可回收發泡體層上的織物層。因此,方法可包括將基底層、可回收發泡體層及織物整體地形成為三層板薄板。在各種實例中,支撐層可安置足跟區域處,該支撐層可由諸如相較於積層之其他組件之彼密度的較高密度之剛性材料構造。黏合劑、膠或其他附接機構可經提供且利用於附接且形成具有支撐層之三層板。Specifically, the sole component including the midsole and the insert may include one layer or multiple layers. For example, in some examples, a base layer, a recyclable foam layer, and/or a fabric layer may be provided. In particular, it may include a base layer of relatively elastic material, and/or a recyclable foam layer disposed on the base layer, and/or a fabric layer disposed on the recyclable foam layer. Therefore, the method may include integrally forming the base layer, the recyclable foam layer, and the fabric into a three-layer sheet. In various examples, a support layer may be placed at the heel area, and the support layer may be constructed of a rigid material such as a higher density than the other components of the build-up. Adhesives, glues or other attachment mechanisms can be provided and utilized for attachment and forming a three-layer board with a supporting layer.
更具體而言,在其他實例中,用於製作鞋組件諸如鞋內底之方法可包括以下步驟:提供可回收發泡體層,提供織物層,加熱可回收發泡體層,接合可回收發泡體及織物層,提供基底層,例如,具有與可回收發泡體層之彼密度相比的相同、較大,或較小密度之密度的基底層;以及加熱基底層及發泡體層中之至少一個以便耦接基底層與可回收發泡體層以便形成雙層板或三層板。More specifically, in other examples, the method for making shoe components such as shoe insoles may include the following steps: providing a recyclable foam layer, providing a fabric layer, heating the recyclable foam layer, and joining the recyclable foam And a fabric layer, providing a base layer, for example, a base layer having the same, greater, or lower density than that of the recyclable foam layer; and heating at least one of the base layer and the foam layer In order to couple the base layer and the recyclable foam layer to form a double-layer board or a three-layer board.
方法可進一步包括提供預形成支撐構件,諸如,弓形支撐件及/或足跟構件,該等構件可具有相較於發泡體層之密度實質上相同,或較小,或較大的密度。在具體實例中,支撐構件可由壓縮發泡體材料形成,以便獲得與可回收發泡體層之彼相比的較大密度,及因而較大剛性。另外,熱及/或壓力可反應黏合劑可經施加在支撐及/或足跟構件與積層之間。模製成形壓力然後可經施加至組成物,以便引起將三層板形成及/或成形為支撐及/或足跟構件,以便形成整體一件式鞋插入物,其中預形成的足跟構件形成後部分且/或支撐構件形成成品鞋插入物之底部表面之中間部分,例如,在其中間及/或足跟區域處,且基底層形成其前方區域處的成品鞋插入物之底部表面。The method may further include providing pre-formed support members, such as arcuate supports and/or heel members, which members may have substantially the same density as compared to the foam layer, or a smaller, or larger density. In a specific example, the support member may be formed of a compressed foam material in order to obtain a greater density than the recyclable foam layer, and thus greater rigidity. In addition, a heat and/or pressure reactive adhesive may be applied between the support and/or heel member and the build-up layer. Molding pressure can then be applied to the composition to cause the three-layer panel to be formed and/or shaped into a support and/or heel member to form a one-piece shoe insert, wherein the pre-formed heel member is formed The rear part and/or support member forms the middle part of the bottom surface of the finished shoe insert, for example, at its middle and/or heel area, and the base layer forms the bottom surface of the finished shoe insert at its front area.
然而,應注意,支撐及/或足跟構件無需經包括,且在一些實例中,積層組件中一或多個可經排除或其他積層層可經添加。進一步應注意,在某些實施例中,可回收發泡體層可為更可撓性且/或緩衝的,例如,具有相較於基底層的較大硬度計,該基底層轉而可為更可撓性的及/或緩衝的,例如,具有相較於支撐構件的較大硬度計。因此,更可撓性發泡體及基底層可為相對彈性的且在形狀上符合所要的鞋大小及組態,而支撐層(多個)可為相對更剛性的。However, it should be noted that the support and/or heel member need not be included, and in some examples, one or more of the layered components may be excluded or other layered layers may be added. It should be further noted that in certain embodiments, the recyclable foam layer may be more flexible and/or cushioned, for example, with a larger durometer than the base layer, the base layer may in turn be more flexible. Flexible and/or cushioned, for example, having a larger durometer than the supporting member. Therefore, the more flexible foam and the base layer can be relatively elastic and conform to the desired shoe size and configuration in shape, while the support layer(s) can be relatively more rigid.
特定而言,支撐層可具有較稠密的可回收發泡體,因而使得支撐層為更剛性的。因此,在各種實施例中,可回收發泡體層可具有約2磅/立方英尺或約3磅/立方英尺或約5磅/立方英尺至約10磅/立方英尺或更大之密度,諸如在介於約4磅/立方英尺至6磅/立方英尺之間的範圍內之密度。另外,可回收發泡體層可具有近似1/8”之厚度,諸如在約3/32”至5/32”之厚度範圍內。In particular, the support layer may have a denser recyclable foam, thereby making the support layer more rigid. Therefore, in various embodiments, the recyclable foam layer may have a density of about 2 pounds/cubic foot or about 3 pounds/cubic foot or about 5 pounds/cubic foot to about 10 pounds/cubic foot or greater, such as in Density in the range of about 4 pounds/cubic foot to 6 pounds/cubic foot. In addition, the recyclable foam layer may have a thickness of approximately 1/8", such as in the thickness range of about 3/32" to 5/32".
同樣地,基底層亦可具有約2磅/立方英尺或約3磅/立方英尺或約5磅/立方英尺至約10磅/立方英尺或更大之密度,諸如在介於約4磅/立方英尺至6磅/立方英尺之間的範圍內之密度。基底層之厚度可為大約5/16”+或-10%。然而,在各種實例中,基底層之厚度在厚度方面範圍可自約1/4”或更少至約7/16”。關於支撐層,該支撐層可主要形成在插入物之弓形及/或足跟區域處,該支撐層亦可由本文揭示之可回收發泡體製成。Similarly, the base layer may also have a density of about 2 pounds/cubic foot or about 3 pounds/cubic foot or about 5 pounds/cubic foot to about 10 pounds/cubic foot or greater, such as between about 4 pounds/cubic foot Density within the range of feet to 6 pounds per cubic foot. The thickness of the base layer can be about 5/16"+ or -10%. However, in various examples, the thickness of the base layer can range from about 1/4" or less to about 7/16" in terms of thickness. The support layer, which can be mainly formed at the arch and/or heel area of the insert, can also be made of the recyclable foam disclosed herein.
然而,支撐層可藉由壓縮可回收可撓性發泡體402使得最終密度為大約22磅/立方英尺至23磅/立方英尺製成。織物層可由任何合適的材料例如棉花、聚酯或聚丙烯針織物構造。在各種實例中,材料及可回收發泡體層可可能藉由火焰膠合技術積層在一起,該火焰膠合技術利用裸火,該裸火產生充分的熱以使可回收發泡體層之表面熔融。一旦熔融,織物層經接合至回收的發泡體層及淬冷輥輪,使得兩個層經接合在一起。However, the support layer can be made by compressing the recyclable
在製程中之此時,此等層仍然維持呈平坦薄板形式。此等整合層然後接下來亦藉由火焰膠合接合至基底層。先前整合的材料及發泡體層可經接合至支撐層,且此等多積層層然後可在淬冷輥輪之間延伸。在階段之此級段處,此等層仍然維持呈平坦薄板形式。至此積層的層因而然後準備好模製成形。此可藉由將積層層加熱至近似250 F之模製成形溫度,諸如持續約1分鐘至約5分鐘或更多,例如,約225秒之週期來執行。此充分地加熱先前積層的層,以允許該等積層層插入模具中。At this point in the manufacturing process, these layers still remain in the form of a flat sheet. These integrated layers are then joined to the base layer by flame gluing. The previously integrated material and foam layers can be joined to the support layer, and these multi-layered layers can then extend between the quenched rollers. At this stage of the stage, these layers still remain in the form of flat sheets. The layers laminated so far are then ready for moulding. This can be performed by heating the build-up layer to a molding temperature of approximately 250 F, such as for a period of about 1 minute to about 5 minutes or more, for example, about 225 seconds. This heats the previously laminated layers sufficiently to allow them to be inserted into the mold.
如以上提到的,SCF物理發泡劑可取決於終端產品之所要的特性而選擇。在31.1攝氏溫度及72.2巴處變成SCF流體的二氧化碳比在-147攝氏溫度及34巴處變成超臨界流體的氮更可溶於熱塑性聚合物502中4倍至5倍。例如,未填充的可回收熱塑性聚合物中之飽和點為約1.52重量%至2重量%之氮,取決於溫度及壓力條件,而二氧化碳之飽和水平較接近於8重量%。二氧化碳亦展現生物聚合物中之較大遷移率,從而允許二氧化碳比氮遷移至現有氣泡中更遠。自氣孔成核之觀點,較大溶解度及遷移率意味較少的氣孔將成核,且成核的彼等氣孔將傾向於為較大的。As mentioned above, SCF physical blowing agent can be selected depending on the desired characteristics of the end product. Carbon dioxide that becomes an SCF fluid at a temperature of 31.1 degrees Celsius and 72.2 bar is 4 to 5 times more soluble in the
在以上論述之實施例中,其中方法600用來生產運動商品諸如鞋,SCF 510包含處於臨界狀態中之氮。氮在相較於SCF二氧化碳的低得多的重量百分比處提供改良之重量降低及精細核。SCF 510氮水平比達成可比較的零件所需要的SCF二氧化碳水平低至少75%。如此,當大量生產如利用於製作鞋組件中的本揭示案之生物可降解且工業上可合成之可撓性發泡體時,當與SCF二氧化碳相比時,大大地降低的SCF氮水平要求確保最佳材料節約及時間節約。In the embodiment discussed above, where the
雖然二氧化碳為較重的,但其在某些應用中可為合適的發泡劑,諸如當黏度降低為製程之目標時,及/或當終端產品不能忍受SCF氮之更侵略性的發泡動作或在半可撓性發泡體中時。例如,當方法600用來生產家具及汽車產品時,SCF 510包含呈臨界狀態的二氧化碳,因為二氧化碳生產大得多的氣孔結構,即使處於較大的大小及/或重量處。在具有物理發泡劑之物理發泡製程期間,看到玻璃轉變中之凹陷。Although carbon dioxide is heavier, it can be a suitable blowing agent in certain applications, such as when viscosity reduction is the goal of the process, and/or when the end product cannot tolerate the more aggressive foaming action of SCF nitrogen Or when in semi-flexible foam. For example, when
如以上簡要地論述,當生產零件所需要的氮量低至使得不可能一致地處理零件時,超臨界狀態中之二氧化碳可經利用為物理發泡劑。因為二氧化碳為侵略性較小的發泡劑,所以在一些應用中,較容易運行低水平的二氧化碳。例如,0.15%或0.2%的二氧化碳(與小於0.05%處的氮水平相比)可經利用來生產具有厚橫截面的軟材料及零件。As discussed briefly above, carbon dioxide in the supercritical state can be utilized as a physical blowing agent when the amount of nitrogen required to produce parts is so low that it is impossible to treat the parts consistently. Because carbon dioxide is a less aggressive blowing agent, it is easier to run low levels of carbon dioxide in some applications. For example, 0.15% or 0.2% carbon dioxide (compared to nitrogen levels less than 0.05%) can be utilized to produce soft materials and parts with thick cross-sections.
儘管以上已詳細描述少數實施例,但其他修改為可能的。其他實施例可在以下申請專利範圍之範疇內。Although a few embodiments have been described in detail above, other modifications are possible. Other embodiments may be within the scope of the following patent applications.
100:鞋中底 102:可撓性發泡體 200:裝置 202:生物聚合物母料 204:漏斗 206:射出模製成形機 208:射出模製成形機螺桿 210:氮或CO2 氣體 212:生物聚合物熔體 214:模製成形工具 216:氣體反壓力系統 218:計量氮或CO2 氣體 220:氣體控制閥 222:動態模具溫度控制系統(DMTC) 300、600、700:方法 302~316、602~614、702~716:步驟 400:可回收微氣孔可撓性發泡體鞋中底 402:可撓性發泡體 500:圖示 502:熱塑性聚合物 503:控制器 504:漏斗 505:溫度及壓力量測裝置 506:射出模製成形機 507:桶 508:柱塞 509:氣體配料系統 510:流體(SCF) 511:噴射器 512:計量單元 514:模具 515:氣體泵 516:氣體反壓力系統(GCP)系統 517:壓縮機 518:氣體儲器 519:壓力感測器 520:氣體控制閥 522:動態模具溫度控制(DMTC) 526:閥交換裝置 532:冷卻塔 534:水加熱單元100: shoe midsole 102: flexible foam 200: device 202: biopolymer master batch 204: funnel 206: injection molding machine 208: injection molding machine screw 210: nitrogen or CO 2 gas 212: Biopolymer melt 214: Molding tool 216: Gas back pressure system 218: Metering nitrogen or CO 2 gas 220: Gas control valve 222: Dynamic mold temperature control system (DMTC) 300, 600, 700: Methods 302-316 602~614,702~716: Step 400: Recyclable micro-pore flexible foam shoe midsole 402: Flexible foam 500: Graphic 502: Thermoplastic polymer 503: Controller 504: Funnel 505 : Temperature and pressure measuring device 506: Injection molding machine 507: Barrel 508: Plunger 509: Gas batching system 510: Fluid (SCF) 511: Ejector 512: Metering unit 514: Mold 515: Gas pump 516: Gas Back pressure system (GCP) system 517: compressor 518: gas reservoir 519: pressure sensor 520: gas control valve 522: dynamic mold temperature control (DMTC) 526: valve exchange device 532: cooling tower 534: water heating unit
現將參看以下圖式詳細地描述此等及其他態樣。These and other aspects will now be described in detail with reference to the following drawings.
圖1示出發泡鞋類組件,亦即根據本揭示案之一實行方案之鞋中底。Figure 1 shows a foamed footwear component, that is, a shoe midsole according to one implementation of the present disclosure.
圖2例示用於生產適合於鞋類的生物可降解且工業上可合成之可撓性發泡體之射出模製成形的微氣孔可撓性發泡體系統的示意圖。Fig. 2 illustrates a schematic diagram of a microporous flexible foam system used to produce a biodegradable and industrially synthesizable flexible foam suitable for footwear.
圖3為用於製造生物可降解且工業上可合成之射出模製成形的微氣孔可撓性發泡體之方法的流程圖。Fig. 3 is a flow chart of a method for manufacturing a biodegradable and industrially synthesizable injection-molded flexible foam.
圖4示出射出模製成形以產生用於運動鞋之中底的根據本揭示案之可回收可撓性發泡體。Figure 4 shows injection molding to produce a recyclable flexible foam according to the present disclosure for use in a midsole of a sports shoe.
圖5示出用於生產圖4中所描繪之可回收可撓性發泡體之射出模製成形機的示意圖。Fig. 5 shows a schematic diagram of an injection molding machine used to produce the recyclable flexible foam depicted in Fig. 4.
圖6為用於製造圖4之可回收微氣孔可撓性發泡體之方法的流程圖Fig. 6 is a flow chart of a method for manufacturing the recyclable micro-pore flexible foam of Fig. 4
圖7為示出與圖6之用於製造可回收微氣孔可撓性發泡體之方法之實施例相結合回收可撓性發泡體之步驟的流程圖。FIG. 7 is a flowchart showing the steps of recovering flexible foam in combination with the embodiment of the method for manufacturing the recoverable micro-pore flexible foam of FIG. 6.
在各個圖中,相同參考符號指示相同元件。In the various figures, the same reference symbols indicate the same elements.
200:裝置200: device
202:生物聚合物母料202: Biopolymer masterbatch
204:漏斗204: Funnel
206:射出模製成形機206: Injection molding machine
208:射出模製成形機螺桿208: Injection molding machine screw
210:氮或CO2 氣體210: Nitrogen or CO 2 gas
212:生物聚合物熔體212: Biopolymer melt
214:模製成形工具214: Molding tools
216:氣體反壓力系統216: Gas Back Pressure System
218:計量氮或CO2 氣體218: Measuring nitrogen or CO 2 gas
220:氣體控制閥220: Gas control valve
222:動態模具溫度控制系統/DMTC222: Dynamic mold temperature control system/DMTC
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