TW202206542A - Composition, biodegradable shaped article made therefrom, and method of manufacturing the biodegradable shaped article - Google Patents
Composition, biodegradable shaped article made therefrom, and method of manufacturing the biodegradable shaped article Download PDFInfo
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本發明是有關一種可用以製備生物可分解成形體的組合物,尤其是一種包含聚乳酸的組合物。The present invention relates to a composition that can be used to prepare biodegradable shaped bodies, especially a composition comprising polylactic acid.
傳統塑膠製品因可快速地大量生產,並且方便、衛生,因此廣泛地應用在生活中的各種用品,然而其因一次性使用以及難以分解,也造成環境污染的問題。近來有生物可分解材料的開發,期能替代傳統塑膠並緩解環境汙染。Traditional plastic products can be mass-produced quickly and are convenient and hygienic, so they are widely used in various products in daily life. However, they also cause environmental pollution problems due to one-time use and difficulty in decomposition. Recently, biodegradable materials have been developed, which are expected to replace traditional plastics and alleviate environmental pollution.
聚乳酸即為其中一種生物可分解材料。然而,以聚乳酸製得的成形體通常非晶性,耐熱性不佳,不適合在略高的溫度下使用,因此用途受到很大的限制。為了提高聚乳酸成形體的耐熱性,已知會在聚乳酸中添加成核劑,使其在成形的過程中結晶化。惟在提高結晶性的同時,聚乳酸成形體也失去了原有的透明性,因此用途依然受到限制。此外,一些成核劑的採用則有成核劑分子遷移的情形發生,造成產品品質的不穩定。Polylactic acid is one such biodegradable material. However, the molded body obtained from polylactic acid is usually amorphous, has poor heat resistance, and is not suitable for use at a slightly higher temperature, so its use is greatly limited. In order to improve the heat resistance of a polylactic acid molded body, it is known to add a nucleating agent to polylactic acid to crystallize it during molding. However, while improving the crystallinity, the polylactic acid molded body also loses its original transparency, so the use is still limited. In addition, when some nucleating agents are used, the migration of nucleating agent molecules occurs, resulting in unstable product quality.
有鑑於上述,本發明提供一種組合物,其可用以製成耐熱並具有透明性的生物可分解成形體。In view of the above, the present invention provides a composition which can be used as a heat-resistant and transparent biodegradable molded body.
本發明所提供的組合物包括聚乳酸、有機成核劑以及纖維素奈米纖維,其中有機成核劑佔組合物總重的 0.03 wt %以上,纖維素奈米纖維佔組合物總重的 0.1 wt %以上。The composition provided by the present invention comprises polylactic acid, an organic nucleating agent and cellulose nanofibers, wherein the organic nucleating agent accounts for more than 0.03 wt % of the total weight of the composition, and the cellulose nanofibers account for 0.1% of the total weight of the composition. wt % or more.
在本發明的一實施例中,上述之有機成核劑佔組合物總重的 0.03~9 wt %,纖維素奈米纖維佔組合物總重的0.1~15 wt%。In an embodiment of the present invention, the above-mentioned organic nucleating agent accounts for 0.03-9 wt % of the total weight of the composition, and the cellulose nanofibers account for 0.1-15 wt % of the total weight of the composition.
在本發明的一實施例中,上述之有機成核劑佔組合物總重的 0.05~3 wt %,纖維素奈米纖維佔組合物總重的0.1~5 wt%。In an embodiment of the present invention, the above-mentioned organic nucleating agent accounts for 0.05-3 wt % of the total weight of the composition, and the cellulose nanofibers account for 0.1-5 wt % of the total weight of the composition.
在本發明的一實施例中,上述之纖維素奈米纖維為經改質纖維素奈米纖維。In an embodiment of the present invention, the above-mentioned cellulose nanofibers are modified cellulose nanofibers.
在本發明的一實施例中,上述之纖維素奈米纖維包括多個葡萄糖單體;經改質纖維素奈米纖維為氧化纖維素奈米纖維,且至少部分的這些葡萄糖單體具有羧酸或羧酸鹽的官能基。In an embodiment of the present invention, the above-mentioned cellulose nanofibers include a plurality of glucose monomers; the modified cellulose nanofibers are oxidized cellulose nanofibers, and at least part of the glucose monomers have carboxylic acids or carboxylate functional group.
在本發明的一實施例中,上述之氧化纖維素奈米纖維為TEMPO氧化纖維素奈米纖維,且至少部分的這些葡萄糖單體在C6位置具有羧酸鈉或羧酸鋰的官能基。In an embodiment of the present invention, the oxidized cellulose nanofibers are TEMPO oxidized cellulose nanofibers, and at least part of the glucose monomers have functional groups of sodium carboxylate or lithium carboxylate at C6 position.
在本發明的一實施例中,上述之經改質纖維素奈米纖維有丙交酯、聚乳酸寡聚物,或者丙交酯與聚乳酸寡聚物的接枝。In an embodiment of the present invention, the above-mentioned modified cellulose nanofibers include lactide, polylactic acid oligomer, or grafting of lactide and polylactic acid oligomer.
在本發明的一實施例中,上述之有機成核劑為脂肪族羧酸醯胺類、脂肪族羧酸鹽類、脂肪醇類、脂肪族羧酸酯類成核劑或選自其之組合。In an embodiment of the present invention, the above-mentioned organic nucleating agent is aliphatic carboxylic acid amides, aliphatic carboxylates, aliphatic alcohols, aliphatic carboxylate nucleating agents or a combination thereof .
本發明還提供一種生物可分解成形體,由前述組合物製成,其中所述組合物經混煉製成多個顆粒,這些顆粒再經加熱並成形為成形體。The present invention also provides a biodegradable shaped body made from the aforementioned composition, wherein the composition is kneaded into a plurality of granules which are then heated and shaped into a shaped body.
在本發明的一實施例中,上述之多個顆粒更經加熱並形成板材,且板材經加熱成形為成形體。In an embodiment of the present invention, the above-mentioned plurality of particles are further heated to form a sheet, and the sheet is heated to form a shaped body.
本發明還提供一種生物可分解成形體的製造方法,包括步驟:混合聚乳酸、有機成核劑以及纖維素奈米纖維並製備組合物,其中有機成核劑佔組合物總重的 0.03~9 wt %,纖維素奈米纖維佔組合物總重的 0.1~15 wt %;混煉組合物並形成多個顆粒;加熱這些顆粒並形成成形體。The present invention also provides a method for manufacturing a biodegradable shaped body, comprising the steps of: mixing polylactic acid, an organic nucleating agent and cellulose nanofibers and preparing a composition, wherein the organic nucleating agent accounts for 0.03-9% of the total weight of the composition. wt %, the cellulose nanofibers account for 0.1-15 wt % of the total weight of the composition; the composition is kneaded and formed into a plurality of particles; the particles are heated and formed into a shaped body.
在本發明的一實施例中,上述之加熱這些顆粒並形成成形體的步驟更包括加熱這些顆粒並形成板材,以及加熱板材並形成成形體。In an embodiment of the present invention, the above-mentioned step of heating the particles and forming the shaped body further comprises heating the particles and forming the sheet, and heating the sheet and forming the shaped body.
在本發明的一實施例中,上述之加熱這些顆粒並形成成形體的步驟更包括進行射出成型程序、吸塑成型程序、射出吹氣成型程序、吹膜成型程序、流延法成膜程序而形成成形體。In an embodiment of the present invention, the above-mentioned step of heating the particles to form a formed body further includes performing an injection molding process, a blister molding process, an injection blow molding process, a blown film molding process, and a casting method film forming process. A shaped body is formed.
本發明因採用有機成核劑以及纖維素奈米纖維,因此在幫助成形體結晶之餘,更提高結晶效率、縮短結晶時間,因此有助於提升結晶度以及耐熱度。Because the present invention adopts organic nucleating agent and cellulose nanofibers, in addition to assisting the crystallization of the formed body, the crystallization efficiency is improved and the crystallization time is shortened, thus helping to improve the crystallinity and heat resistance.
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式,作詳細說明如下。In order to make the above-mentioned and other objects, features and advantages of the present invention more obvious and easy to understand, the following specific embodiments are given and described in detail in conjunction with the accompanying drawings.
本發明提供一種組合物,其可用以製備生物可分解成形體,且所製成的成形體耐熱並具有透明性。The present invention provides a composition which can be used to prepare a biodegradable shaped body which is heat-resistant and transparent.
本發明之組合物包括生物可分解聚合物、成核劑以及纖維素奈米纖維 (Cellulose Nanofiber,CNF)。適用之生物可分解聚合物例如為脂肪族聚酯 (Aliphatic polyesters)、脂肪族-芳香族共聚合物 (Aliphatic-aromatic polyester copolymers)聚乳酸─脂肪族聚酯共聚合物(CPLA, Polylactide aliphatic polyester copolymers)。適用之成核劑為有機成核劑。The composition of the present invention includes a biodegradable polymer, a nucleating agent, and Cellulose Nanofiber (CNF). Suitable biodegradable polymers are, for example, aliphatic polyesters, aliphatic-aromatic polyester copolymers, polylactic acid-aliphatic polyester copolymers (CPLA, Polylactide aliphatic polyester copolymers). ). Suitable nucleating agents are organic nucleating agents.
在本發明一實施例中,組合物包括脂肪族聚酯類的聚乳酸、有機成核劑以及纖維素奈米纖維。聚乳酸可採用例如 NatureWorks 公司的聚乳酸產品。有機成核劑舉例來說,可為脂肪族羧酸醯胺 (aliphatic carboxylic acid amide)、脂肪族羧酸鹽 (aliphatic carboxylic acid salt)、脂肪醇 (aliphatic alcohol)、脂肪族羧酸酯 (aliphatic carboxylic acid ester)等類的成核劑。本發明實施例之有機成核劑的量佔組合物總重的 0.03 wt %以上,惟較佳不超過9 wt%,且可包括前述種類的一種或多種。有機成核劑的量更佳佔組合物總重的0.05~3 wt %。In an embodiment of the present invention, the composition includes polylactic acid of aliphatic polyester, an organic nucleating agent, and cellulose nanofibers. The polylactic acid can be, for example, a polylactic acid product of NatureWorks. For example, the organic nucleating agent can be aliphatic carboxylic acid amide, aliphatic carboxylic acid salt, aliphatic alcohol, aliphatic carboxylic acid acid ester) and other nucleating agents. The amount of the organic nucleating agent in the embodiment of the present invention accounts for more than 0.03 wt % of the total weight of the composition, but preferably not more than 9 wt %, and may include one or more of the aforementioned types. The amount of the organic nucleating agent is preferably 0.05-3 wt % of the total weight of the composition.
本發明實施例之纖維素奈米纖維為經改質的纖維素奈米纖維,且佔組合物總重的 0.1 wt %以上,且較佳不超過15 wt %。纖維素奈米纖維量更佳佔組合物總重的0.1~5 wt%。經改質的纖維素奈米纖維包括氧化纖維素奈米纖維,且纖維素之至少部分的葡萄糖單體具有羧酸或羧酸鹽的官能基。較佳而言,本發明實施例之氧化纖維素奈米纖維是以 TEMPO 氧化法取得的 TEMPO氧化纖維素奈米纖維,且纖維素之至少部分的葡萄糖單體具有羧酸鈉或羧酸鋰的官能基。而除氧化外,纖維素奈米纖維並可經其他改質,例如於 TEMPO氧化纖維素奈米纖維上導入疏水性及/或接枝,從而提高其與聚乳酸的相容性,其中導入疏水性及/或接枝的位置例如是在羧基、羧酸鹽、羥基等官能基。舉例來說,可以馬來酸酐接枝聚乙烯、馬來酸酐接枝聚乳酸、聚苯乙烯作為改質劑,處理纖維素奈米纖維以提升其疏水性;及/或以左旋丙交酯、聚乳酸寡聚物等處理TEMPO纖維素奈米纖維。The cellulose nanofibers of the embodiments of the present invention are modified cellulose nanofibers, and account for more than 0.1 wt % of the total weight of the composition, and preferably not more than 15 wt %. More preferably, the amount of cellulose nanofibers accounts for 0.1-5 wt% of the total weight of the composition. The modified cellulose nanofibers include oxidized cellulose nanofibers, and at least part of the glucose monomers of the cellulose have functional groups of carboxylic acid or carboxylate. Preferably, the oxidized cellulose nanofibers in the embodiment of the present invention are TEMPO oxidized cellulose nanofibers obtained by TEMPO oxidation, and at least part of the glucose monomers in the cellulose has sodium carboxylate or lithium carboxylate. functional group. In addition to oxidation, cellulose nanofibers can be modified by other modifications, such as introducing hydrophobicity and/or grafting on TEMPO oxidized cellulose nanofibers to improve their compatibility with polylactic acid. The sites of sex and/or grafting are, for example, functional groups such as carboxyl, carboxylate, and hydroxyl. For example, cellulose nanofibers can be treated with maleic anhydride grafted polyethylene, maleic anhydride grafted polylactic acid, and polystyrene as modifiers to improve their hydrophobicity; and/or with L-lactide, TEMPO cellulose nanofibers are treated with polylactic acid oligomers, etc.
再者,視製程或應用範圍的需要,本發明實施例之組合物可進一步包括其他成分例如熱安定劑、著色劑、抗靜電劑、防燃劑、發泡劑、抗 UV 安定劑、抗滑劑、塑化劑、無機填充劑、抗氧化劑、潤滑劑等。扣除掉有機成核劑、纖維素奈米纖維以及其他成分的重量,剩下為聚乳酸的重量。Furthermore, depending on the needs of the manufacturing process or the scope of application, the composition of the embodiments of the present invention may further include other components such as heat stabilizers, colorants, antistatic agents, flame retardants, foaming agents, anti-UV stabilizers, anti-slip agents, etc. agents, plasticizers, inorganic fillers, antioxidants, lubricants, etc. After deducting the weight of organic nucleating agent, cellulose nanofibers and other components, the remaining weight is the weight of polylactic acid.
本發明組合物因包括纖維素奈米纖維,而纖維素奈米纖維羥基官能基與有機成核劑易於形成氫鍵,因此纖維素奈米纖維可抓住有機成核劑分子,及纖維素奈米纖維因均勻分散於聚乳酸基體內,形成屏障,有助於抑制有機成核劑遷移,幫助結晶並提高結晶效率、縮短結晶時間。因此一方面可提升結晶度並有助於提高成形體的耐熱度,另一方面可避免結晶粒子太大以及其對於透明性的不良影響。The composition of the present invention includes cellulose nanofibers, and the hydroxyl functional groups of the cellulose nanofibers and the organic nucleating agent are easy to form hydrogen bonds, so the cellulose nanofibers can grasp the molecules of the organic nucleating agent, and the cellulose nanofibers can easily form hydrogen bonds. Because the rice fiber is uniformly dispersed in the polylactic acid matrix, it forms a barrier, which helps to inhibit the migration of organic nucleating agents, helps crystallization, improves the crystallization efficiency, and shortens the crystallization time. Therefore, on the one hand, the degree of crystallinity can be improved and the heat resistance of the formed body can be improved, and on the other hand, the crystal particles that are too large and their adverse effects on transparency can be avoided.
本發明還提供一種生物可分解成形體,其並且是由前述之組合物製成。所述生物可分解成形體耐熱並具有透明性。在本發明一實施例中,如圖1所示,製造生物可分解成形體可包括步驟S100:混合聚乳酸、有機成核劑以及纖維素奈米纖維並製備組合物,其中有機成核劑佔組合物總重的 0.03~9 wt %,纖維素奈米纖維佔組合物總重的 0.1~15 wt %;以及步驟S200:混煉組合物並形成多個顆粒。這些顆粒可以是半成品。步驟S200後可對顆粒半成品進一步加工並製成成形體及/或終成品。The present invention also provides a biodegradable shaped body made from the aforementioned composition. The biodegradable shaped body is heat-resistant and transparent. In an embodiment of the present invention, as shown in FIG. 1 , manufacturing a biodegradable shaped body may include step S100 : mixing polylactic acid, an organic nucleating agent and cellulose nanofibers to prepare a composition, wherein the organic nucleating agent accounts for 0.03-9 wt % of the total weight of the composition, cellulose nanofibers account for 0.1-15 wt % of the total weight of the composition; and step S200: kneading the composition and forming a plurality of particles. These granules can be semi-finished products. After step S200, the semi-finished pellets can be further processed and formed into shaped bodies and/or final products.
本發明實施例更包括步驟S300:加熱多個顆粒並形成成形體。本文中之成形體可即為終成品,亦可再經加工以產出終成品。所述加工可為射出成型 (Injection molding)、吸塑成型 (Thermoforming)、射出吹氣成型 (Injection blown)、吹膜成型 (Film by blown)以及流延法成膜 (Film by casting)等程序,但不以此為限。舉例來說,多個顆粒可先形成為板材的成形體,接著板材經加熱以及模具成形的加工而產出終成品。The embodiment of the present invention further includes step S300: heating a plurality of particles to form a shaped body. The shaped body herein can be the final product, or it can be further processed to produce the final product. The processing can be injection molding, thermoforming, injection blown, film by blown, and film by casting, etc. But not limited to this. For example, a plurality of particles can be formed into a shaped body of a sheet, and then the sheet is heated and moulded to produce the final product.
步驟S300可更包括射出成型、吸塑成型、射出吹氣成型、吹膜成型、流延法成膜等程序,而步驟S200之顆粒經所述程序形成成形體。Step S300 may further include procedures such as injection molding, blister molding, injection blow molding, film blowing, and casting film forming, and the particles in step S200 are formed into a molded body through the procedures.
本發明還在步驟S200或S300進行當中或結束時對顆粒或成形體作結晶速率、結晶度、耐熱度、霧度等之測試。The present invention also tests the crystallization rate, crystallinity, heat resistance, haze, etc. of the particles or formed bodies during or at the end of step S200 or S300.
以下透過實施例例示說明本發明實施例生物可分解成形體的製造方法及測試方法。The following examples illustrate the manufacturing method and testing method of the biodegradable shaped body according to the embodiment of the present invention.
實施例:Example:
1. 材料及設備 (1) 聚乳酸 (PLA):來自 Nature Works 或 Total Corbion。 (2) 有機成核劑:選自 ethylene bislauramide (Mitsubishi Chemical) 的脂肪族羧酸酰胺,zinc stearate (Dainichi Chemical Industry) 的脂肪族羧酸鹽、stearyl alcohol (Kao Japan) 及 pentanol (Tokyo Chemical Industry) 的脂肪醇。 (3) 纖維素奈米纖維: (3-1) TEMPO氧化纖維素奈米纖維,其可以直接購入或以如下方式準備: 使用2,2,6,6-四甲基哌啶-1-氧基(2,2,6,6-tetramethylpiperidine-1-oxyl;TEMPO)作為催化劑,次氯酸鈉 (NaOCl)為主要氧化劑,氯酸鈉 (NaBr)為活化劑,於水溶液內 (去離子水)將纖維素(來自紙漿(中華紙漿))的羥基氧化成羧基,製備成TEMPO氧化纖維素奈米纖維 (TOCNs),且至少部分的這些葡萄糖單體在C6位置具有羧酸鈉的官能基。進一步可將羧酸鈉取代成羧酸鋰。 (3-2) TOCN-g-PLA,其可以直接購入或以如下方式準備: 將(3-1)的TEMPO氧化纖維素奈米纖維與左旋丙交酯溶於四氫呋喃(Tetrahydrofuran;THF),並將左旋丙交酯開環 (ring-opening)後聚合接枝(grafted)於TEMPO氧化纖維素奈米纖維的羧基上,接著使用聚乳酸寡聚物聚合,增加接枝於TEMPO氧化纖維素奈米纖維的聚乳酸的分子量與立體障礙。 (4) 其他成分: 左旋丙交酯 (L-lactide):Puralact® L (Total Corbion),用於TEMPO氧化纖維素奈米纖維的丙交酯接枝。 聚乳酸寡聚物 (PLA oligomer):Futerro,用於TEMPO氧化纖維素奈米纖維的聚乳酸寡聚物接枝。 (5) 雙螺桿混鍊機:LabTech Twin Screw Extruder,用於步驟 S200。 (6) 單螺桿流延機 (Film casting):用於步驟 S300。 (7) 吸塑機:用於步驟S300。 (8) 熱示差掃描量熱儀:TA Instruments DSC 250,用於量測結晶速率與結晶度。 (9) 熱變形溫度儀器:Instron CEAST HV500 (ASTM D648),用於量測耐熱度(即熱變形溫度 (Heat Deflection Temperature,HDT))。 (10) 霧度量測儀:BYK Haze guard i (ASTM D1003),用於量測透明度。1. Materials and Equipment (1) Polylactic acid (PLA): from Nature Works or Total Corbion. (2) Organic nucleating agent: selected from aliphatic carboxylic acid amides of ethylene bislauramide (Mitsubishi Chemical), aliphatic carboxylic acid salts of zinc stearate (Dainichi Chemical Industry), stearyl alcohol (Kao Japan) and pentanol (Tokyo Chemical Industry) of fatty alcohols. (3) Cellulose nanofibers: (3-1) TEMPO oxidized cellulose nanofibers, which can be purchased directly or prepared as follows: Using 2,2,6,6-tetramethylpiperidine-1-oxyl (2,2,6,6-tetramethylpiperidine-1-oxyl; TEMPO) as catalyst, sodium hypochlorite (NaOCl) as main oxidant, sodium chlorate (NaBr) is an activator that oxidizes hydroxyl groups of cellulose (from pulp (Chinese pulp) to carboxyl groups in an aqueous solution (deionized water) to prepare TEMPO oxidized cellulose nanofibers (TOCNs), and at least part of these The glucose monomer has a functional group of sodium carboxylate at the C6 position. Further, sodium carboxylate can be substituted into lithium carboxylate. (3-2) TOCN-g-PLA, which can be purchased directly or prepared as follows: (3-1) TEMPO oxidized cellulose nanofibers and L-lactide were dissolved in tetrahydrofuran (Tetrahydrofuran; THF), and L-lactide was ring-opened and then polymerized and grafted on TEMPO. The carboxyl groups of oxidized cellulose nanofibers were then polymerized with polylactic acid oligomers to increase the molecular weight and steric barriers of polylactic acid grafted on TEMPO oxidized cellulose nanofibers. (4) Other ingredients: L-lactide: Puralact® L (Total Corbion) for lactide grafting of TEMPO oxidized cellulose nanofibers. PLA oligomer: Futerro, PLA oligomer grafting for TEMPO oxidized cellulose nanofibers. (5) Twin Screw Mixer: LabTech Twin Screw Extruder, used in step S200. (6) Single-screw casting machine (Film casting): used in step S300. (7) Blister machine: used in step S300. (8) Thermal Differential Scanning Calorimeter: TA Instruments DSC 250, used to measure the crystallization rate and crystallinity. (9) Heat Deflection Temperature Instrument: Instron CEAST HV500 (ASTM D648), used to measure heat resistance (ie Heat Deflection Temperature (HDT)). (10) Haze meter: BYK Haze guard i (ASTM D1003), for measuring transparency.
2. 步驟2. Steps
步驟S100~S200:混合重量百分比92~99.85 % 的聚乳酸、0.05~3 % 的有機成核劑以及0.1~5 % 的TOCN-g-PLA,供給至雙螺桿混鍊機。雙螺桿混鍊機將纖維素奈米纖維均勻分散於聚乳酸高分子內,將其以160℃~220℃的溫度熔融混煉並擠壓成束狀,再切割製成多個顆粒。例示如下(實施例一~三)。Steps S100-S200: mixing 92-99.85% by weight of polylactic acid, 0.05-3% organic nucleating agent and 0.1-5% TOCN-g-PLA, and supplying them to a twin-screw chain mixer. The twin-screw chain mixer uniformly disperses the cellulose nanofibers in the polylactic acid polymer, melts and kneads them at a temperature of 160°C to 220°C, extrudes them into bundles, and then cuts them into multiple pellets. Examples are as follows (Examples 1 to 3).
實施例一:將聚乳酸 (Ingeo 2003D (Nature Works))、TOCN-g-PLA與成核劑 (stearyl alcohol (Kao Japan))以96.5 wt%、3 wt%和0.5 wt%的比例混合,使用雙螺桿混鍊機將TOCN-g-PLA均勻分散於聚乳酸高分子基體(PLA polymer matrix),溫度設定於160℃~220℃之間。將所得的顆粒 (pellet)以烘箱除水,溫度設定為70℃,將含水率控制在250 ppm以下。Example 1: Polylactic acid (Ingeo 2003D (Nature Works)), TOCN-g-PLA and nucleating agent (stearyl alcohol (Kao Japan)) were mixed in the proportions of 96.5 wt%, 3 wt% and 0.5 wt%, using The twin-screw chain mixer uniformly disperses TOCN-g-PLA in the PLA polymer matrix, and the temperature is set between 160°C and 220°C. The resulting pellets were dewatered in an oven, the temperature was set to 70°C, and the water content was controlled to be 250 ppm or less.
實施例二:將聚乳酸 (Ingeo 2003D (Nature Works))、TOCN-g-PLA與成核劑 (stearyl alcohol (Kao Japan))以96 wt%、3 wt%和1 wt%的比例混合。之後的步驟同實施例一。Example 2: Polylactic acid (Ingeo 2003D (Nature Works)), TOCN-g-PLA and a nucleating agent (stearyl alcohol (Kao Japan)) were mixed at a ratio of 96 wt%, 3 wt% and 1 wt%. The subsequent steps are the same as those in the first embodiment.
實施例三:將聚乳酸 (Ingeo 2003D (Nature Works))、TOCN-g-PLA與成核劑 (stearyl alcohol (Kao Japan))以94 wt%、3 wt%和3 wt%的比例混合。之後的步驟同實施例一。Example 3: Polylactic acid (Ingeo 2003D (Nature Works)), TOCN-g-PLA and a nucleating agent (stearyl alcohol (Kao Japan)) were mixed at a ratio of 94 wt%, 3 wt% and 3 wt%. The subsequent steps are the same as those in the first embodiment.
步驟S300:加熱多個顆粒並形成成形體。步驟S300可更包括吸塑成型的程序,例示如下(實施例四)。Step S300: Heating a plurality of particles and forming a shaped body. Step S300 may further include a process of blister molding, which is exemplified as follows (Embodiment 4).
實施例四:取實施例一、二或三烘乾後之顆粒,使用單螺桿流延機製備板材 (sheet)。板材厚度為0.5 mm。使用具備上下兩個加熱板 (platen heater)的實驗室級 (labscale)吸塑機,溫度設定為100℃,加熱板材30秒。接著,以空壓 (air pressure)和真空 (vacuum)方式,模具溫度設定為40℃,將板材成形為模具的形狀。Embodiment four: get the particles after embodiment one, two or three drying, use single screw casting machine to prepare sheet (sheet). The sheet thickness is 0.5 mm. A labscale blister machine with upper and lower platen heaters was used, the temperature was set to 100°C, and the plates were heated for 30 seconds. Next, the plate was molded into the shape of the mold by air pressure and vacuum, and the mold temperature was set to 40°C.
3. 測試方法 (A) 結晶度與結晶速率:取步驟S300的成形體進行測試,以熱示差掃描量熱儀量測其結晶度與結晶速率。結晶度(%) = ΔHm +ΔHc /ΔHf ,其中ΔHm 為測得的熔化之熱焓(正值),ΔHc 為測得的結晶化之熱焓(負值),ΔHf 為聚乳酸完全結晶之熱焓(ΔHf = 93 J/g)。結晶速率是指結晶半生期,亦即達到 50% 結晶度所需的時間。本發明實施例之成形體的結晶度較佳為25%~50%,結晶半生期不超過30秒。 (B) 耐熱度 (HDT):以步驟S300的成形體進行測試。本發明實施例之成形體的耐熱度為高於100℃。 (C) 霧度 (Haze):以步驟S300的成形體進行測試。本發明實施例之成形體的霧度小於80%,且較佳小於10%。3. Test method (A) Crystallinity and crystallization rate: Take the formed body in step S300 for testing, and measure its crystallinity and crystallization rate with a thermal differential scanning calorimeter. Crystallinity (%) = ΔH m +ΔH c /ΔH f , where ΔH m is the measured enthalpy of fusion (positive value), ΔH c is the measured enthalpy of crystallization (negative value), and ΔH f is Enthalpy of complete crystallization of polylactic acid (ΔH f = 93 J/g). Crystallization rate refers to the crystallization half-life, ie the time required to reach 50% crystallinity. The crystallinity of the formed body in the embodiment of the present invention is preferably 25% to 50%, and the crystallization half-life is not more than 30 seconds. (B) Heat resistance (HDT): Tested with the molded body of step S300. The heat resistance of the molded body of the embodiment of the present invention is higher than 100°C. (C) Haze: the test was carried out with the molded body of step S300. The haze of the formed body of the embodiment of the present invention is less than 80%, and preferably less than 10%.
實施例四之成形體所測得之結晶度、耐熱度、霧度如表一。
表一
以上實施例僅為例示,本發明不限制製造成形體所用的設備以及測試所用的儀器。The above embodiments are only examples, and the present invention does not limit the equipment used for manufacturing the formed body and the equipment used for testing.
本發明實施例因混合使用纖維素奈米纖維,其不但有成核助劑的作用,還可與有機成核劑的形成氫鍵,因此抓住有機成核劑分子而抑制有機成核劑的遷移,從而幫助結晶並提高結晶效率、縮短結晶時間。因此,一方面可提升結晶度並有助於提高成形體的耐熱度,另一方面可避免結晶粒子太大以及其對於透明性的不良影響,從而生物可分解成形體還兼備耐熱性及透明性,適於作為食品容器如耐熱透明飲料杯。Due to the mixed use of cellulose nanofibers in the embodiment of the present invention, it not only functions as a nucleating aid, but also forms hydrogen bonds with the organic nucleating agent, so the molecules of the organic nucleating agent are seized and the nucleation of the organic nucleating agent is inhibited. migration, thereby helping crystallization and improving crystallization efficiency and shortening crystallization time. Therefore, on the one hand, the degree of crystallinity can be increased and the heat resistance of the molded body can be improved, and on the other hand, the crystal particles are too large and their adverse effects on transparency can be avoided, so that the biodegradable molded body has both heat resistance and transparency. , suitable for food containers such as heat-resistant transparent drink cups.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,本發明所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the appended patent application.
S100:混合聚乳酸、有機成核劑以及纖維素奈米纖維並製備組合物,其中有機成核劑佔組合物總重的 0.03~9 wt %,纖維素奈米纖維佔組合物總重的 0.1~15 wt % S200:混煉組合物並形成多個顆粒 S300:加熱這些顆粒並形成成形體S100: mix polylactic acid, organic nucleating agent and cellulose nanofibers and prepare a composition, wherein the organic nucleating agent accounts for 0.03-9 wt % of the total weight of the composition, and the cellulose nanofibers account for 0.1% of the total weight of the composition ~15 wt % S200: Compounding the composition and forming a plurality of granules S300: Heating the particles and forming shaped bodies
圖1所示為本發明一實施例之生物可分解成形體的製造方法的流程示意圖。FIG. 1 is a schematic flowchart of a method for manufacturing a biodegradable molded body according to an embodiment of the present invention.
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