TWI547517B - Bio-plastic - Google Patents
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Description
本發明係關於一種生物可分解塑膠，特別是關於一種包含聚乳酸(polylactic acid，PLA)與聚胺基甲酸酯(polyurethane，PU)之生物可分解塑膠。 The present invention relates to a biodegradable plastic, and more particularly to a biodegradable plastic comprising polylactic acid (PLA) and polyurethane (PU).
生物可分解塑膠(biodegradable plastics)係一在特定環境條件下，其化學結構會發生明顯變化，且用標準測試方式可測定其物質性能變化的塑膠。也就是說，生物可分解塑膠在特定濕度、氧氣與微生物環境下，其化學結構發生變化，促使其力學性能下降，進而發生破裂、粉化等現象，最終完全分解成二氧化碳、水或甲烷。 Biodegradable plastics are plastics whose chemical structure changes significantly under specific environmental conditions and whose physical properties are measured by standard tests. That is to say, in the specific humidity, oxygen and microbial environment, the biodegradable plastic changes its chemical structure, causing its mechanical properties to decline, and then cracking, chalking, etc., and finally completely decomposed into carbon dioxide, water or methane.
生物分解塑膠主要材料包含澱粉、聚乳酸及纖維蛋白質。其中，聚乳酸係為最常使用之生物分解塑膠原料，其利用馬鈴薯或玉米做為原料發酵再聚合而成，因此使用生物分解塑膠可減少石化能源的消耗。 The main materials of biodegradable plastics include starch, polylactic acid and fiber protein. Among them, polylactic acid is the most commonly used biodegradable plastic raw material, which uses potato or corn as raw material for fermentation and polymerization. Therefore, the use of biodegradable plastic can reduce the consumption of petrochemical energy.
美國專利6,852,807揭示了一種可生物分解與水解之樹脂，上述樹脂係藉由混掺熱塑性脂肪族聚酯類樹脂(thermoplastic aliphatic polyester resin)與聚酯型聚氨酯(polyester urethane)而成。並且，此樹脂具有良好物理性質如抗拉伸強度。另外，上述樹脂具有廣泛應用性如可拋式提袋或食物包裝上。 U.S. Patent 6,852,807 discloses a biodegradable and hydrolyzable resin which is obtained by blending a thermoplastic aliphatic polyester resin with a polyester urethane. Also, this resin has good physical properties such as tensile strength. In addition, the above resins have a wide range of applications such as disposable bags or food packaging.
目前生物可分解塑膠正使用在包裝產品、物流條碼等 產品中，但市售之生物可分解塑膠的力學性質與價格表現仍未滿意。有鑑於此，仍有必要發展新的生物可分解塑膠，除了具有材料天然、無毒、可自然分解等特性外，抗張強度、斷裂伸長率的調控或成本降低，係亟欲發展之技術。 Currently biodegradable plastics are being used in packaging products, logistics barcodes, etc. Among the products, the mechanical properties and price performance of commercially available biodegradable plastics are still not satisfactory. In view of this, it is still necessary to develop new biodegradable plastics. In addition to the natural, non-toxic, and naturally decomposable properties of materials, the regulation of tensile strength, elongation at break, or cost reduction is a technique that is desired to develop.
鑒於上述之發明背景中，為了符合產業上之要求，本發明提供一種新的生物可分解塑膠。 In view of the above-described background of the invention, the present invention provides a novel biodegradable plastic in order to meet industrial requirements.
本發明揭露了一種生物可分解塑膠，其包含一聚胺基甲酸酯(thermoplastic polyurethane，TPU)與聚乳酸(polylactic acid，PLA)。其中，聚胺基甲酸酯係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、一二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)，且聚二醇選自下列之一者或其任意組合：PBA、PEA、PCL。 The invention discloses a biodegradable plastic comprising a thermoplastic polyurethane (TPU) and polylactic acid (PLA). Wherein, the polyurethane is formed by reacting: a poly diol, a diisocyanate and a chain extender, and the polyglycol is selected. From one of the following or any combination thereof: PBA, PEA, PCL.
本發明所揭露之生物可分解塑膠，可隨著聚二醇分子量增加，以提高其機械強度。另外，當生物可分解塑膠未發生相分離時，可增加聚胺基甲酸酯比例，以增加其斷裂伸長率。此外，聚胺基甲酸酯(polyurethane；PU)佔該生物可分解塑膠重量比例小於20%，以使得抗撕裂強度高於低密度聚乙烯(LDPE) The biodegradable plastic disclosed in the present invention can increase the mechanical strength of the polyglycol as the molecular weight thereof increases. In addition, when the biodegradable plastic does not undergo phase separation, the polyurethane ratio can be increased to increase its elongation at break. In addition, polyurethane (PU) accounts for less than 20% by weight of the biodegradable plastic, so that the tear strength is higher than that of low density polyethylene (LDPE).
再者，生物可分解塑膠可更包含一澱粉(starch)作為填充物(filler)，以降低其成本。因此，本發明所揭露之生物可分解塑膠具有良好的應用性。 Furthermore, the biodegradable plastic may further comprise a starch as a filler to reduce its cost. Therefore, the biodegradable plastic disclosed in the present invention has good applicability.
本發明在此揭示一種生物可分解塑膠。為了能徹底地 瞭解本發明，將在下列的描述中提出詳盡的步驟及其組成。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的組成或步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的較佳實施例會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的實施例中，且本發明的範圍不受限定，其以之後的專利範圍為準。 The present invention discloses a biodegradable plastic herein. In order to be thorough In order to understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention are described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the scope of the following patents. .
本發明之一第一實施例揭露一種生物可分解塑膠，一聚乳酸(polylactic acid；PLA)與一聚胺基甲酸酯(polyurethane；PU)，其中，聚胺基甲酸酯係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)，且聚二醇選自下列之一者或其任意組合：(PBA)、(PEA)、(PCL)，。 A first embodiment of the present invention discloses a biodegradable plastic, polylactic acid (PLA) and polyurethane (PU), wherein the polyurethane is reacted by the following The reaction product comprises: a poly diol, a diisocyanate and a chain extender, and the polyglycol is selected from one of the following or any combination thereof: (PBA), (PEA), (PCL),.
其中，聚乳酸(polylactic acid；PLA)較宜者分子量範圍為25,000至300,000。其中，聚胺基甲酸酯(polyurethane；PU)較宜者分子量範圍為25,000至300,000。其中，PBA、PEA與PCL較宜者分子量範圍大於或等於500，而更佳者分子量約為2000。其中，上述之生物可分解塑膠較宜者係由聚 乳酸(polylactic acid；PLA)與聚胺基甲酸酯(polyurethane；PU)混摻而成。其中，鏈延長劑(chain extender)較宜者係丁二醇(1,4-butanediol)。 Among them, polylactic acid (PLA) is preferably in the range of 25,000 to 300,000 molecular weight. Among them, polyurethane (PU) preferably has a molecular weight ranging from 25,000 to 300,000. Among them, the preferred molecular weight range of PBA, PEA and PCL is greater than or equal to 500, and more preferably the molecular weight is about 2,000. Among them, the above biodegradable plastic is more suitable for the poly Polylactic acid (PLA) is mixed with polyurethane (PU). Among them, a chain extender is preferably a 1,4-butanediol.
其中，聚胺基甲酸酯(polyurethane；PU)佔生物可分解塑膠重量比例較宜者小於40%，以減少相分離現象，而更佳者聚胺基甲酸酯(polyurethane；PU)重量比例小於20%，以使得抗撕裂強度高於低密度聚乙烯(LDPE)。 Among them, polyurethane (PU) accounted for less than 40% of the biodegradable plastic weight ratio to reduce phase separation, and more preferred polyurethane (PU) weight ratio Less than 20% so that the tear strength is higher than low density polyethylene (LDPE).
於本實施例之一較佳範例中，隨著上述之聚二醇分子量增加，生物可分解塑膠的機械強度也隨之增高。 In a preferred embodiment of the present embodiment, as the molecular weight of the above polyglycol increases, the mechanical strength of the biodegradable plastic increases.
於本實施例之另一較佳範例中，當生物可分解塑膠未發生相分離時，隨著聚胺基甲酸酯(polyurethane；PU)添加比例增加，斷裂伸長率(elongation at break)也隨之增加。 In another preferred embodiment of the present embodiment, when the biodegradable plastic does not undergo phase separation, as the proportion of the addition of polyurethane (PU) increases, the elongation at break also follows Increase.
於本實施例之又一較佳範例中，上述之生物可分解塑膠可更包含一澱粉(starch)作為填充物(filler)，其中，澱粉較宜者佔生物可分解塑膠重量比例小於30%，而更佳者重量比例小於或等於10%。此填充物可更包含一相容劑以提高聚乳酸(polylactic acid；PLA)與澱粉間的界面作用力。其中，上述之相容劑可包含下列之一者或其任意組合：棕櫚油、甘油、硬酯酸、椰子油、酪梨油、杏仁油、葡萄籽油、榛子油、橄欖油渣、茶油、米糠油、胡桃油、花生油、葵花油、紅花油、亞麻仁油、菜籽油、大豆油、玉米油、橄欖油。 In another preferred embodiment of the present embodiment, the biodegradable plastic may further comprise a starch as a filler, wherein the starch preferably comprises less than 30% by weight of the biodegradable plastic. The better weight ratio is less than or equal to 10%. The filler may further comprise a compatibilizer to enhance the interfacial force between polylactic acid (PLA) and starch. Wherein, the above compatibilizer may comprise one or any combination of the following: palm oil, glycerin, stearic acid, coconut oil, avocado oil, almond oil, grape seed oil, hazelnut oil, olive oil residue, tea oil Rice bran oil, walnut oil, peanut oil, sunflower oil, safflower oil, linseed oil, rapeseed oil, soybean oil, corn oil, olive oil.
本發明之一第二實施例揭露一種生物可分解塑膠，一種生物可分解塑膠，其包含：一聚乳酸(polylactic acid；PLA)與一聚胺基甲酸酯(polyurethane；PU)，其中，聚胺基甲酸酯係由下列反應物進行反應而成，其包含：一聚二醇 (polyol)、一二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)。其中，聚二醇較宜者為(PBA)，其分子量約為2000，且上述之聚胺基甲酸酯(polyurethane；PU)佔生物可分解塑膠重量比例約為10%，以使得生物可分解塑膠的的抗張強度(tensile strength)大於70MPa，潛伏應力(yield strength)大於55MPa。 A second embodiment of the present invention discloses a biodegradable plastic, a biodegradable plastic comprising: polylactic acid (PLA) and polyurethane (PU), wherein The urethane is formed by reacting a polyhydric diol, a diisocyanate, and a chain extender. Among them, polyglycol is more suitable for (PBA), which has a molecular weight of about 2,000, and the above-mentioned polyurethane (PU) accounts for about 10% by weight of the biodegradable plastic, so that the tensile strength of the biodegradable plastic (tensile strength) ) greater than 70 MPa, the yield strength is greater than 55 MPa.
於本實施例之一較佳範例中，上述之生物可分解塑膠可更包含一澱粉(starch)作為填充物(filler)，其中，澱粉較宜者佔生物可分解塑膠重量比例小於30%，而更佳者重量比例小於或等於10%。此填充物可更包含一相容劑以提高聚乳酸(polylactic acid；PLA)與澱粉間的界面作用力。其中，上述之相容劑可包含下列之一者或其任意組合：棕櫚油、甘油、硬酯酸、椰子油、酪梨油、杏仁油、葡萄籽油、榛子油、橄欖油渣、茶油、米糠油、胡桃油、花生油、葵花油、紅花油、亞麻仁油、菜籽油、大豆油、玉米油、橄欖油。 In a preferred embodiment of the present embodiment, the biodegradable plastic may further comprise a starch as a filler, wherein the starch is preferably less than 30% by weight of the biodegradable plastic, and The better weight ratio is less than or equal to 10%. The filler may further comprise a compatibilizer to enhance the interfacial force between polylactic acid (PLA) and starch. Wherein, the above compatibilizer may comprise one or any combination of the following: palm oil, glycerin, stearic acid, coconut oil, avocado oil, almond oil, grape seed oil, hazelnut oil, olive oil residue, tea oil Rice bran oil, walnut oil, peanut oil, sunflower oil, safflower oil, linseed oil, rapeseed oil, soybean oil, corn oil, olive oil.
本發明之一第三實施例揭露一種生物可分解塑膠，一種生物可分解塑膠，其包含：一聚乳酸(polylactic acid；PLA)與一聚胺基甲酸酯(polyurethane；PU)，其中，聚胺基甲酸酯係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、一二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)。其中，聚二醇較宜者為 (PBA)，其分子量約為2000，且上述之聚胺基甲酸酯(polyurethane；PU)佔生物可分解塑膠重量比例約為30%，以使得生物可分解塑膠的的斷裂伸長率大於180%。 A third embodiment of the present invention discloses a biodegradable plastic, a biodegradable plastic comprising: a polylactic acid (PLA) and a polyurethane (PU), wherein The urethane is formed by reacting a polyhydric diol, a diisocyanate, and a chain extender. Among them, polyglycol is more suitable for (PBA), which has a molecular weight of about 2,000, and the above-mentioned polyurethane (PU) accounts for about 30% by weight of the biodegradable plastic, so that the elongation at break of the biodegradable plastic is greater than 180%. .
於本實施例之一較佳範例中，上述之生物可分解塑膠可更包含一澱粉(starch)作為填充物(filler)，其中，澱粉較宜者佔生物可分解塑膠重量比例小於30%，而更佳者重量比例小於或等於10%。此填充物可更包含一相容劑以提高聚乳酸(polylactic acid；PLA)與澱粉間的界面作用力。其中，上述之相容劑可包含下列之一者或其任意組合：棕櫚油、甘油、硬酯酸、椰子油、酪梨油、杏仁油、葡萄籽油、榛子油、橄欖油渣、茶油、米糠油、胡桃油、花生油、葵花油、紅花油、亞麻仁油、菜籽油、大豆油、玉米油、橄欖油。 In a preferred embodiment of the present embodiment, the biodegradable plastic may further comprise a starch as a filler, wherein the starch is preferably less than 30% by weight of the biodegradable plastic, and The better weight ratio is less than or equal to 10%. The filler may further comprise a compatibilizer to enhance the interfacial force between polylactic acid (PLA) and starch. Wherein, the above compatibilizer may comprise one or any combination of the following: palm oil, glycerin, stearic acid, coconut oil, avocado oil, almond oil, grape seed oil, hazelnut oil, olive oil residue, tea oil Rice bran oil, walnut oil, peanut oil, sunflower oil, safflower oil, linseed oil, rapeseed oil, soybean oil, corn oil, olive oil.
參考上表所示之生物可分解塑膠所含之聚胺基甲酸酯(polyurethane；PU)比例與其抗張強度(tensile strength)、潛伏應力(yield strength)、斷裂伸張率(elongation at break)之對照表。其中，聚胺基甲酸酯(polyurethane；PU)係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)，且聚二醇為(PBA)，其中分子量分別為2000或1000。 Refer to the ratio of polyurethane (PU) contained in the biodegradable plastic shown in the above table and its tensile strength, yield strength, and elongation at break. Chart. Wherein, polyurethane (PU) is formed by reacting: a poly diol, a diisocyanate and a chain extender, and Polyglycol (PBA) wherein the molecular weight is 2000 or 1000, respectively.
其中，100% PLA之抗張強度為57.9MPa，其斷裂伸長率僅有7%，顯示PLA為硬且脆之性質。加入PUPBA後有明顯的增韌效果，當PBA分子量約為2000，且上述之聚胺基甲酸酯(polyurethane；PU)佔該生物可分解塑膠重量比例約為10%，以使得該生物可分解塑膠的抗張強度(tensile strength)大於70MPa，潛伏應力(yield strength)大於55MPa。 Among them, 100% PLA has a tensile strength of 57.9 MPa and an elongation at break of only 7%, indicating that PLA is hard and brittle. After adding PU PBA , there is obvious toughening effect. When the molecular weight of PBA is about 2000, and the above-mentioned polyurethane (PU) accounts for about 10% by weight of the biodegradable plastic, the bio-available The tensile strength of the decomposed plastic is greater than 70 MPa, and the yield strength is greater than 55 MPa.
另外，當上述之PBA分子量約為2000，且上述之聚胺基甲酸酯(polyurethane；PU)佔該生物可分解塑膠重量比例約為30%，以使得該生物可分解塑膠的的斷裂伸長率大 於180%。 In addition, when the above PBA has a molecular weight of about 2,000, and the above-mentioned polyurethane (PU) accounts for about 30% by weight of the biodegradable plastic, the elongation at break of the biodegradable plastic is made. Big At 180%.
參考上表所示之生物可分解塑膠所含之聚胺基甲酸酯(polyurethane；PU)比例與其抗張強度(tensile strength)、潛伏應力(yield strength)、斷裂伸張率(elongation at break)之對照表。其中，聚胺基甲酸酯(polyurethane；PU)係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)，且聚二醇為(PEA)，其中分子量分別為2000或1000。 Refer to the ratio of polyurethane (PU) contained in the biodegradable plastic shown in the above table and its tensile strength, yield strength, and elongation at break. Chart. Wherein, polyurethane (PU) is formed by reacting: a poly diol, a diisocyanate and a chain extender, and Polyglycol (PEA) wherein the molecular weight is 2000 or 1000, respectively.
結果顯示PLA中加入PUPEA2000亦具有增韌效果，但其機械性質不如PUPBA系列，其最高抗張強度為62MPa(90% PLA與10% PUPEA 2000)，且發生在潛伏點處而非斷裂處；而最高斷裂伸長率為114.8%(80% PLA與20% PUPEA2000)。另外，加入30% PUPEA 2000時則同樣有巨觀相分離現象使機械性質開始下降。 The results show that the addition of PU PEA2000 to PLA also has a toughening effect, but its mechanical properties are not as good as the PU PBA series. Its highest tensile strength is 62 MPa (90% PLA and 10% PU PEA 2000 ), and it occurs at the latent point rather than the fracture. The highest elongation at break was 114.8% (80% PLA and 20% PU PEA2000 ). In addition, when 30% PU PEA 2000 is added, there is also a phenomenon of macroscopic phase separation which causes the mechanical properties to start to decrease.
參考上表所示之生物可分解塑膠所含之聚胺基甲酸酯(polyurethane；PU)比例與其抗張強度(tensile strength)、潛伏應力(yield strength)、斷裂伸張率(elongation at break)之對照表。其中，聚胺基甲酸酯(polyurethane；PU)係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)， 且(PCL)，，且分子量分別為2000或1000。 Refer to the ratio of polyurethane (PU) contained in the biodegradable plastic shown in the above table and its tensile strength, yield strength, and elongation at break. Chart. Wherein, polyurethane (PU) is formed by reacting: a poly diol, a diisocyanate and a chain extender, and (PCL), and the molecular weight is 2000 or 1000, respectively.
90% PLA/10% PUPCL2000與PLA/PUPBA2000系列結果類似，在拉伸過程中會出現明顯之潛伏點與頸縮現象。並在拉伸末端會有很明顯的應變硬化與應力白化的現象，說明了PLA/PUPCL2000在拉伸過程中出現再結晶，因此機械性質大幅提升至79.1MPa，斷裂伸長率亦可達106%。另外，PLA/PUPCL1000系列與PLA/PUPCL2000相比，其抗張強度有明顯下降。 90% PLA/10% PU PCL2000 is similar to the PLA/PU PBA2000 series in that it exhibits significant latent and necking during stretching. At the end of the stretching, there will be obvious strain hardening and stress whitening, which indicates that PLA/PU PCL2000 recrystallizes during the stretching process, so the mechanical properties are greatly improved to 79.1 MPa, and the elongation at break can reach 106%. . In addition, the PLA/PU PCL1000 series has a significant decrease in tensile strength compared to PLA/PU PCL2000 .
參考上表所示之生物可分解塑膠所含之聚胺基甲酸酯(polyurethane；PU)比例與其抗張強度(tensile strength)、潛伏應力(yield strength)、斷裂伸張率(elongation at break)、撕裂強度(tear strength)之對照表。其中，聚胺基甲酸酯(polyurethane；PU)係由下列反應物進行反應而成，其包含：一聚二醇(polyol)、二異氰酸酯(diisocyanate)與一鏈延長劑(chain extender)，且聚二醇為(PBA)，且分子量為2000。 Refer to the ratio of polyurethane (PU) contained in the biodegradable plastic shown in the above table and its tensile strength, yield strength, elongation at break, A comparison table of tear strength. Wherein, polyurethane (PU) is formed by reacting: a poly diol, a diisocyanate and a chain extender, and Polyglycol (PBA) with a molecular weight of 2000.
本發明固定PLA/PUPBA比例為9/1及8/1，並以這兩組再與10%至30%不等之澱粉進行混摻。結果顯示，加入10%澱粉後使機械性質有些為下降。加入超過20%澱粉後，斷裂伸長率皆降至未混摻澱粉前之三分之一以下，加入30%澱粉時其斷裂伸長率更降低至20%澱粉時之一半，顯示澱粉僅為填充物角色，且澱粉與PLA/PUPBA作用力小。 The ratio of fixed PLA/PU PBA of the present invention is 9/1 and 8/1, and the two groups are further mixed with 10% to 30% of starch. The results showed that the mechanical properties were somewhat reduced after the addition of 10% starch. After adding more than 20% starch, the elongation at break is reduced to less than one third of that before unmixed starch. When 30% starch is added, the elongation at break is reduced to one-half of that of 20% starch, indicating that the starch is only filler. Role, and the starch and PLA / PU PBA have a small force.
純PLA之抗撕裂強度為46.09kN/m，而加入10%PU後，抗撕裂強度皆有些許提升約為50kN/m，差異並不明顯。隨著PU添加量增加巨觀相分離現象明顯，分子間作用力下降，促使抗撕裂強度降低。因此，抗撕裂強度可作為PLA與不同PU間混摻相容性之參考指標之一。其中，PU佔總重量30%之PLA/PU生物可分解塑膠，其抗撕裂強度明顯下降。 The tear strength of pure PLA is 46.09kN/m, and after adding 10% PU, the tear strength is slightly increased by about 50kN/m, and the difference is not obvious. As the amount of PU added increases, the phenomenon of macroscopic phase separation is obvious, and the intermolecular force decreases, which causes the tear strength to decrease. Therefore, the tear strength can be used as one of the reference indicators for compatibility between PLA and different PUs. Among them, PU/PU biodegradable plastics with a PU content of 30% of total weight have a significant decrease in tear strength.
市售塑膠袋原料(LDPE)的抗撕裂強度為28.13kN/m，而PU佔總重量低於20%之PLA/PU生物可分解塑膠，其抗撕裂強度優於市售塑膠袋原料。 Commercially available plastic bag material (LDPE) has a tear strength of 28.13 kN/m, while PU has a total weight of less than 20% of PLA/PU biodegradable plastic, and its tear strength is superior to that of commercially available plastic bag materials.
顯然地，依照上面實施例中的描述，本發明可能有許多的修正與差異。因此需要在其附加的權利要求項之範圍內加以理解，除了上述詳細的描述外，本發明還可以廣泛地在其他的實施例中施行。上述僅為本發明之較佳實施例而已，並非用以限定本發明之申請專利範圍；凡其它未脫離本發明所揭示之精神下所完成的等效改變或修飾，均應包含在下述申請專利範圍內。 Obviously, many modifications and differences may be made to the invention in light of the above description. It is therefore to be understood that within the scope of the appended claims, the invention may be The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following claims. Within the scope.
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