201122043 ' 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種具有阻氣性之材料，特別是指一 種具有高阻氣性之生物可分解材料。 【先前技術】 ，具有a氣性之包裝㈣容器自熱塑性高分子與阻 氣材料共押出成型或共射出成型所製得。目前較廣泛使用 之阻氣材料有奈米黏土、乙稀_乙稀醇(EVOH)及聚醯胺等。 由於一般具有阻氣性之包裝材或容器是以共押出成型或共 射出成型’内層由熱塑性高分子所構成，外層則由阻氣材 料所構成，因而常以多層形式存在。在上述製造過程中， 需分別製備内層及外層之材料，再利用特殊機台進行共押 出成型或共射出成型，致使製備過程較為繁雜，外層材料 的機械性質較不佳且使用上多層間可能產生分離，以及高 阻氣產品需要3層以上共押出而導致材料生產成本過高， 1不利於回收或易造成環境污染，因此尚需進—步改進。 隨著環境保護的需求増加，包裝材及容器也希望朝著 易於分解或回收的目標進行改進。由上述說明可知，如能 6又计一配方，同時配合簡單且連續自動化的製程，進而製 得兼具高阻氣性、生物可分解性及機械性質之單層包裝材 料或容器，應可有效解決目前業界所面臨之問題。 【發明内容】 因此，本發明之目的，即在提供一種可有效降低氧氣 及水氣通過率之具有高阻氣性之生物可分解材料。 、 201122043 本發明之另-目是在提供上述之生物可分解材料之製 法。 於是，本發明具有高阻氣性之生物可分解材料是由一 混合物進行溶融混煉及押出所製成，該混合物包含一基質 及二甲苯二胺與己二酸之共聚物(即市售之MXD6，以下簡 稱為『MXD6』）。該基f含有—高分子組份及—填充劑。 該高分子組份含有一熱塑性高分子以及一生物可分解高分 子。 本發明製法包含之步驟為：使一高分子組份、一填充 劑與MXD6進行熔融混煉並押出，以獲得一具有高阻氣性 之生物可分解材料。 本發明之具有高阻氣性之生物可分解材料是經由熔融 混煉及押出製程所製得，也就是該混合物中所含之各個組 份皆會熔融並充分混合，在押出成型後將會形成具備高阻 氣性、生物可分解性及包裝材或容器所需之機械性質等優 點之單層材料。本發明之製法則具備高效能且可有效降低 製作成本。 【實施方式】 該熱塑性高分子主要是指一般用於包裝材料或容器等 之南分子。較佳地’該熱塑性高分子是選自於聚醋類、聚 烯類、含有聚烯類之共聚物或此等之一組合。更佳地，該 熱塑性高分子是選自於聚碳酸酯、聚芳香酯、聚丙烯酸醋 、丙烯腈-丁二烯-苯乙烯共聚物、聚苯乙烯、含有聚烯類之 共聚物或此等之一組合。又更佳地，該熱塑性高分子是選 201122043 自於聚碳酸酯、聚甲基丙烯酸甲酯、聚丙烯、聚芳香酯或 此等之一組合。而於本發明之具體例中，該熱塑性高分子 為聚碳酸醋。 較佳地’該生物可分解高分子是選自於聚乳酸、聚己 内醋、生物可分解共聚酯或此等之一組合。於本發明之具 體例中’該生物可分解高分子是聚乳酸。 較佳地’該填充劑是選自於滑石粉、碳酸每、奈米黏201122043 ' VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a material having gas barrier properties, and more particularly to a biodegradable material having high gas barrier properties. [Prior Art] A package having a gas content (4) is obtained by co-extrusion molding or co-injection molding of a thermoplastic polymer and a gas barrier material. At present, the gas barrier materials widely used include nano clay, ethylene glycol (EVOH) and polyamine. Since the packaging material or container which generally has gas barrier properties is formed by co-extrusion molding or co-molding, the inner layer is composed of a thermoplastic polymer, and the outer layer is composed of a gas barrier material, and thus is often present in a multi-layered form. In the above manufacturing process, the inner layer and the outer layer materials are separately prepared, and then the special machine is used for co-extrusion molding or co-injection molding, which results in a complicated preparation process, and the outer layer material has poor mechanical properties and may be produced in multiple layers. Separation, as well as high-resistance products require more than 3 layers of co-extrusion, resulting in excessive material production costs, 1 is not conducive to recycling or easy to cause environmental pollution, so further improvements are needed. As the demand for environmental protection increases, packaging materials and containers also hope to improve toward the goal of easy decomposition or recycling. It can be seen from the above description that if the formula 6 and the formula are combined with a simple and continuous automated process, a single-layer packaging material or container having high gas barrier properties, biodegradability and mechanical properties can be obtained. Solve the problems facing the industry. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a biodegradable material having high gas barrier properties which can effectively reduce oxygen and water vapor transmission rates. , 201122043 Another object of the invention is to provide a method of providing the biodegradable material described above. Thus, the biodegradable material having high gas barrier property of the present invention is prepared by melt-kneading and extruding a mixture comprising a matrix and a copolymer of xylene diamine and adipic acid (ie, commercially available). MXD6, hereinafter referred to as "MXD6"). The base f contains a polymer component and a filler. The polymer component contains a thermoplastic polymer and a biodegradable polymer. The method of the present invention comprises the steps of: melt-kneading a polymer component and a filler with MXD6 and extruding it to obtain a biodegradable material having high gas barrier properties. The biodegradable material with high gas barrier property of the present invention is obtained through a melt-kneading and extrusion process, that is, each component contained in the mixture is melted and thoroughly mixed, and will be formed after extrusion molding. A single layer of material that has the advantages of high gas barrier properties, biodegradability, and mechanical properties required for packaging materials or containers. The method of the present invention is highly efficient and can effectively reduce the manufacturing cost. [Embodiment] The thermoplastic polymer mainly refers to a south molecule generally used for packaging materials, containers, and the like. Preferably, the thermoplastic polymer is selected from the group consisting of polyacetates, polyolefins, copolymers containing polyolefins or a combination thereof. More preferably, the thermoplastic polymer is selected from the group consisting of polycarbonate, polyarylate, polyacrylic acid vinegar, acrylonitrile-butadiene-styrene copolymer, polystyrene, copolymer containing polyene or such One combination. More preferably, the thermoplastic polymer is selected from 201122043 from polycarbonate, polymethyl methacrylate, polypropylene, polyaryl ester or a combination thereof. In a specific example of the present invention, the thermoplastic polymer is polycarbonate. Preferably, the biodegradable polymer is selected from the group consisting of polylactic acid, polycaprolactone, biodegradable copolyester or a combination thereof. In the specific embodiment of the present invention, the biodegradable polymer is polylactic acid. Preferably, the filler is selected from the group consisting of talc, carbonic acid, and nano-stick.
土或此等之一組合。於本發明之具體例中，該填充劑是滑 石粉。 該基質與MXD6的重量比例可依據所需之阻氣性及機 械性質進行調整。另值得—提的是，# mxd6 @用量增加 時’阻氣性質也可隨著增加。較佳地，該基質與Μ·的 重量比例範圍為30 : 70〜50 : 50。 較佳地，以該高分子組份之總重為1〇〇重量份計算， 該填充劑的用量範圍為1〜2〇重量份。 在該高分子組份中，該熱塑性高分子與該生物可分解 Μ子的含量比例只要可讓後續產品具備業界所需之機械 性質及生物可分解性即可，因此可依據後續用途進行調整 及變化。 该基質可依據實際需要添加其他組份，較佳地，該基 質還包含一加工助劑。該加工助劑例如，但不限於白蠘油 由較佳地’以該向分子組份之總重為⑽重量份計 开’該加工助劑的用量範圍為重量份。 本發月之W疋先製造該基f ,接著再將基質及以職 201122043 進行溶融混煉及押出成型。 較佳地，該製法還包含一乾燥步驟，該步驟是在熔融 混煉前，使該基質與MXD6進行乾燥，接著再進行熔融混 煉及押出成型。 在本發明之具體例中，該基質的製備是利用單螺桿混 煉押出機，而後續之熔融混煉及押出成型步驟則是使用搭 配有單螺桿押出機之塑譜儀。上述所使用之機器可依據實 際需要進行調整及變化。 本贅明具有高阻氣性之生物可分解材料可用於製作各 種包裝材或容器、揮發性有機溶液氣體阻絕容器、汽車用 燃料箱。值得一提的是，當本發明之生物可分解材料用於 製作包裝材或容器時，除了可具備高阻氣性、生物可分解 性及機械性質之外，更具備輕、薄且透明之優點。 本發明將就以下實施例來作進一步說明，但應瞭解的 是，該實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 <實施例> [實施例1】（EX1) 將50重量份之聚碳酸酯、5〇重量份之聚乳酸及18重 置份之滑石粉混合均勻後，再倒入塑膠加工用之雙螺桿混 煉押出機，並將混煉製程條件設定如下：混煉轉速為1〇〇 rPm、溫度為21〇〇c〜23〇〇c、模頭溫度為21〇。匸及下料速 度為80 rpm，接著進行熔融混煉並押出呈條狀後經水槽冷 部’接著再進入造粒機中製成基質。 201122043 將上述之基質、MXD6放入烘箱進行乾燥（溫度為 c及時間為4小時）。將烘乾後之so wt%的基質及5〇 Wt/。的MXD6倒入塑譜儀（其與單螺桿押出機搭配）中並設 定製程條件：溫度為24〇γ及螺桿轉速為6〇 ，接著進 行熔融混煉並押出，再“鏡面輪引取機中形成膜厚小於 1mm之片材，即為實施例丨之生物可分解材料。 [實施例2] (EX2) 除了將滑石粉之添加量改變為2〇重量份、將基質用 量改變為40 wt%以及將MXD6用量改變為6〇加％之外， 其餘流程及條件皆與實施们相同，最後製得實施例2之 生物可分解材料。 [實施例3] (EX3) 除了將滑石粉之添加量改變為2〇重量份、將基質用 量改變為30 wt%以及將MXD6用量改變為7〇加％之外， 其餘流程及條件冑與實_丨_，最後製得實施例3之 生物可分解材料。 [比較例1】（CX1) 將1〇0 wt%之MXD6放入烘箱中進行乾燥（溫度為 100 C及時間4 4小時）’接著再倒人塑譜儀（其與單螺桿 押出機搭配)中並設定製程條件：溫度為24〇〇c及螺桿轉速 為70啊，接著進行炼融混煉並押出，再引人鏡面輪引取 機中形成膜厚小於1 mm之片材，即為比較例丄之片材。 [比較例2] (CX2) 將50重量份之聚碳酸醋、5〇 ^量份之聚乳酸及18重 201122043 滑石粉混合均勻後，再倒人塑膠加工用之雙螺桿混 ’甲機’並將混煉製程條件設定如τ :混煉轉速為1〇〇 ρ /皿度為210 c〜2300c、模頭溫度4 21〇〇c及下料速 ，又為80 rpm ’接著進行熔融混煉並押出呈條狀後經水槽冷 卻:接著再進人造粒機中製成基f。將基f放人烘箱進行 乾燥（溫度為100〇C及時間為4小時）。將烘乾後之基質倒 入塑譜儀（其與單螺桿押出機搭配）中並設定製程條件：溫 度為23G°C及螺桿轉速為7〇 rpm，接著進行溶融混煉並押 出，再引入鏡面輪引取機中形成膜厚小於丨mm之片材， 即為比較例2之片材。 【測試】分別使上述實施例1〜3(EX1〜3)以及比較例 1〜2(CX1〜2)進行以下測試，結果如下表1所示： L 氧氣通過率測試：依據ASTM D-3985及使用氧氣滲透 測試儀（美國MOCON公司製造，型號為〇x_tran) 進行測试’早位為cc/m2.atin.day。 2. 水氣通過率測試：依據ASTM F-1249及使用氧氣渗透 測试儀進行測試’單位為g/m2· atm .day。Earth or a combination of these. In a specific embodiment of the invention, the filler is talc. The weight ratio of the substrate to MXD6 can be adjusted depending on the desired gas barrier properties and mechanical properties. It is also worth mentioning that # mxd6 @ when the amount is increased, the gas barrier property can also increase. Preferably, the weight ratio of the substrate to the ruthenium ranges from 30:70 to 50:50. Preferably, the filler is used in an amount ranging from 1 to 2 parts by weight based on the total weight of the polymer component of 1 part by weight. In the polymer component, the ratio of the thermoplastic polymer to the biodegradable scorpion can be adjusted according to the subsequent use as long as the subsequent product has the mechanical properties and biodegradability required by the industry. Variety. The substrate may be added with other components as needed, and preferably the substrate further comprises a processing aid. The processing aids such as, but not limited to, chalk oil are preferably > (10) parts by weight based on the total weight of the molecular component. The amount of the processing aid is in parts by weight. The base of this month is manufactured by first preparing the base f, and then the matrix and the service 201122043 are melted and kneaded and extruded. Preferably, the process further comprises a drying step of drying the substrate with MXD6 prior to melt-kneading, followed by melt-kneading and extrusion molding. In a specific embodiment of the invention, the substrate is prepared using a single-screw blending extruder, and the subsequent melt-kneading and extrusion molding steps are performed using a spectrometer equipped with a single-screw extruder. The machines used above can be adjusted and changed according to actual needs. Benton's biodegradable materials with high gas barrier properties can be used to make a variety of packaging materials or containers, volatile organic solution gas barrier containers, and automotive fuel tanks. It is worth mentioning that when the biodegradable material of the present invention is used for making packaging materials or containers, in addition to having high gas barrier properties, biodegradability and mechanical properties, it is also light, thin and transparent. . The invention is further illustrated by the following examples, which are to be construed as illustrative and not restrictive. <Examples> [Example 1] (EX1) 50 parts by weight of polycarbonate, 5 parts by weight of polylactic acid, and 18 parts of talc powder were uniformly mixed, and then poured into a double for plastic processing. The screw kneading extruder was set up and the mixing process conditions were set as follows: the kneading speed was 1 〇〇 rPm, the temperature was 21 〇〇 c 23 〇〇 c, and the die temperature was 21 〇. The crucible and the unloading speed were 80 rpm, followed by melt-kneading and extruding in a strip shape, followed by a cold portion of the water tank and then into the granulator to form a matrix. 201122043 The above substrate and MXD6 were placed in an oven for drying (temperature c and time 4 hours). The so wt% matrix and 5 〇 Wt/ will be dried. The MXD6 is poured into a plastic spectrometer (which is matched with a single-screw extruder) and the process conditions are set: the temperature is 24 〇 γ and the screw speed is 6 〇, then melt-kneaded and extruded, and then formed in the mirror wheel extractor. The sheet having a film thickness of less than 1 mm is the biodegradable material of the example. [Example 2] (EX2) The amount of the talc powder was changed to 2 parts by weight, the amount of the substrate was changed to 40% by weight, and The amount of MXD6 was changed to 6 〇 plus %, and the other procedures and conditions were the same as those of the implementers. Finally, the biodegradable material of Example 2 was obtained. [Example 3] (EX3) In addition to changing the amount of talc added The biodegradable material of Example 3 was prepared by adding 2 parts by weight, changing the amount of the substrate to 30 wt%, and changing the amount of MXD6 to 7 〇 plus %, and the remaining procedures and conditions. [Comparative Example 1] (CX1) 1 〇 0 wt% of MXD6 was placed in an oven for drying (temperature was 100 C and time 4 4 hours), and then the plastic spectrometer was replaced (which was matched with a single screw extruder) And set the process conditions: temperature is 24〇〇c and screw speed is 70 Then, the smelting and kneading is carried out, and the sheet having a film thickness of less than 1 mm is formed in the mirror wheel picker, which is a sheet of the comparative example. [Comparative Example 2] (CX2) 50 parts by weight Polycarbonate, 5〇^ parts of polylactic acid and 18 weight 201122043 talcum powder are mixed evenly, then pour the double-screw mixing 'machine> for plastic processing and set the mixing process conditions as τ: mixing speed is 1〇〇ρ / dish degree is 210 c~2300c, die temperature is 4 21〇〇c and the feed speed is 80 rpm'. Then it is melt-kneaded and extruded into strips and then cooled by the sink: then enters again The base is prepared in a granulator. The base f is placed in an oven for drying (temperature is 100 ° C and time is 4 hours). The dried substrate is poured into a plastic spectrometer (which is matched with a single screw extruder) The process conditions are set: the temperature is 23G ° C and the screw rotation speed is 7 rpm, and then melt-mixed and extruded, and then introduced into the mirror wheel extractor to form a sheet having a film thickness of less than 丨 mm, which is the comparative example 2 [Test] The above Examples 1 to 3 (EX1 to 3) and Comparative Examples 1 to 2 (CX1 to 2) were respectively subjected to the following. The results are shown in Table 1 below: L Oxygen Pass Rate Test: Tested according to ASTM D-3985 and using an oxygen permeation tester (manufactured by MOCON, USA, model 〇x_tran) 'early position cc/m2.atin. 2. Water Vapor Pass Rate Test: Tested in accordance with ASTM F-1249 and using an oxygen permeation tester in g/m2·atm.day.
201122043 在表1中’相較於CX1及CX2，EX1〜EX3的氧氣通 過率及水氣通過率皆較低，證明本發明之生物可分解材料 確，具有高阻氣性。此外，另可發現當MXD6及滑石粉的 用量增加時，將可有效的改善阻氧氣性及阻水氣性。 、、示上所述，本發明具有高阻氣性之生物可分解材料藉 由將冋刀子組伤、MXD6及填充劑進行熔融混煉及押出所製 得故本毛明之生物可分解材料為單層材料，且具備極低 之氧氣通過率及水氣通過率，同時具備業界所要求之機 性質。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請^利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 無201122043 In Table 1, the oxygen permeation rate and the water vapor permeation rate of EX1 to EX3 are lower than those of CX1 and CX2, which proves that the biodegradable material of the present invention has high gas barrier properties. In addition, it can be found that when the amount of MXD6 and talc is increased, the oxygen barrier property and water vapor barrier property can be effectively improved. As described above, the biodegradable material having high gas barrier property of the present invention is obtained by melt-kneading and extruding a scorpion knife group, MXD6 and a filler, so that the biodegradable material of the present invention is single. The layer material has extremely low oxygen passage rate and water vapor transmission rate, and has the machine properties required by the industry. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made in accordance with the scope of the invention and the description of the invention. All remain within the scope of the invention patent. [Simple description of the diagram]
【主要元件符號說明】[Main component symbol description]