TW201430051A - Matt composition for cable sheath and matted cable sheath - Google Patents
Matt composition for cable sheath and matted cable sheath Download PDFInfo
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本發明係關於一種啞光性組成物,特別是關於一種電線包覆用啞光性組成物及電線用啞光性殼層。 The present invention relates to a matte composition, and more particularly to a matte composition for electric wire coating and a matte shell for electric wires.
電線的殼層(sheath)(或者稱為「外皮」),現今廣泛使用熱塑性聚胺甲酸酯(TPU)彈性體,再添加阻燃劑,取代過去普遍使用的聚氯乙烯(PVC)材料。然而,使用熱塑性聚胺甲酸酯樹脂應用於電線及電纜時,需要具備所期望的機械、物理及化學性質,例如耐磨損性、透明度、耐藥性、阻燃性、消光性(或稱為啞光性)、反撥彈性等。 The sheath of the wire (or "skin") is now widely used with thermoplastic polyurethane (TPU) elastomers, and flame retardants are added to replace the commonly used polyvinyl chloride (PVC) materials. However, when thermoplastic polyurethane resin is applied to wires and cables, it is required to have desired mechanical, physical and chemical properties such as abrasion resistance, transparency, chemical resistance, flame retardancy, and matting properties (or For matte), reverse flexibility, etc.
然而,由於電線殼層製造用材料(或稱為「電線殼層製造用組成物」)中包含添加劑,調整機械、物理及化學性質中一特性時,常會有改變其他特性的情況發生,例如添加阻燃劑時,會降低熱塑性彈性體的機械性質等。 However, since the material for manufacturing the wire shell layer (or "the composition for manufacturing a wire shell layer") contains an additive and adjusts one of the mechanical, physical, and chemical properties, there are often cases where other characteristics are changed, such as adding In the case of a flame retardant, the mechanical properties and the like of the thermoplastic elastomer are lowered.
再者,一般彈性體成為啞光性彈性體的方法,例如於材料中添加填充劑、於樹脂中接枝(grafting)類似橡膠之彈性體、樹脂中包含可交聯之乙烯共聚物(參考國專利US 5,508,347的先前技術、日本特開昭59-089346),但是該些材料的成形體的表面有該些填充劑、彈性體或共聚物分散不均造成不均勻消光等的問題。 Furthermore, a method in which a general elastomer becomes a matte elastomer, for example, a filler is added to a material, a rubber-like elastomer is grafted in a resin, and a crosslinkable ethylene copolymer is contained in the resin (reference country The prior art of the U.S. Patent No. 5,508,347, the Japanese Patent Application Laid-Open No. 59-089346, the entire disclosure of which is incorporated herein by reference.
鑒於上述之發明背景,為了符合產業上之要求,本發明之目的之一在於提供一種電線包覆用啞光性組成物及電線用啞光性殼層,藉由熱塑性聚胺甲酸酯樹脂中添加與聚胺甲酸酯樹脂互溶性良好且與聚胺甲酸酯樹脂的線膨脹係數差異大之熱塑性樹脂,達到該組成物的成形體具有光滑且啞光的表面的目的,亦即其成形體的表面粗糙度低且表面霧度高。 In view of the above-described background of the invention, in order to meet the requirements of the industry, it is an object of the present invention to provide a matte composition for electric wire coating and a matte shell for electric wires, which are used in a thermoplastic polyurethane resin. Adding a thermoplastic resin which is excellent in miscibility with the polyurethane resin and has a large difference in linear expansion coefficient from the polyurethane resin, and the molded body of the composition has a smooth and matte surface, that is, it is formed. The surface roughness of the body is low and the surface haze is high.
為了達到上述目的,根據本發明一實施態樣,提供一種電線包覆用啞光性組成物,包括:一第一熱塑性樹脂;以及一第二熱塑性樹脂,其中該第二熱塑性樹脂與該第一熱塑性樹脂不同,且該第二熱塑性樹脂的線膨脹係數與該第一熱塑性樹脂的線膨脹係數之差的絕對值為10%~30%的該第一熱塑性樹脂的線膨脹係數的範圍。 In order to achieve the above object, according to an embodiment of the present invention, a matte composition for wire coating comprising: a first thermoplastic resin; and a second thermoplastic resin, wherein the second thermoplastic resin and the first The thermoplastic resin is different, and the absolute value of the difference between the linear expansion coefficient of the second thermoplastic resin and the linear expansion coefficient of the first thermoplastic resin is in the range of 10% to 30% of the linear expansion coefficient of the first thermoplastic resin.
於一實施例,該第一熱塑性樹脂為熱塑性聚胺基甲酸酯(TPU)樹脂。 In one embodiment, the first thermoplastic resin is a thermoplastic polyurethane (TPU) resin.
於一實施例,該第二熱塑性樹脂為選自乙烯-乙酸乙烯酯共聚物(EVA)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、熱塑性聚酯彈性體(TPEE)所成群之1種或1種以上的樹脂。 In one embodiment, the second thermoplastic resin is selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS), and thermoplastic polyester elastomer (TPEE). One or more resins in groups.
於一實施例,該第二熱塑性樹脂為乙烯-乙酸乙烯酯共聚物與熱塑性聚酯彈性體的混合物較理想。 In one embodiment, the second thermoplastic resin is preferably a mixture of an ethylene-vinyl acetate copolymer and a thermoplastic polyester elastomer.
於一實施例,對該組成物的總重量100%而言,包含5~10%的乙烯-乙酸乙烯酯共聚物,5~10%的熱塑性聚酯彈性體以及60~90%的第一熱塑性樹脂較理想。 In one embodiment, the total weight of the composition is 100%, including 5-10% ethylene-vinyl acetate copolymer, 5-10% thermoplastic polyester elastomer, and 60-90% of the first thermoplastic. The resin is ideal.
於一實施例,對該組成物的總重量100%而言,包含5~20 %的第二熱塑性樹脂,以及60~90%的第一熱塑性樹脂。 In one embodiment, the total weight of the composition is 100%, including 5-20 % of the second thermoplastic resin, and 60 to 90% of the first thermoplastic resin.
於一實施例,該第一熱塑性樹脂包含30~50莫耳%的硬鏈段及50~70莫耳%的軟鏈段,其Shore硬度為80~95A較理想。 In one embodiment, the first thermoplastic resin comprises 30 to 50 mol% of a hard segment and 50 to 70 mol% of a soft segment, and a Shore hardness of 80 to 95 A is preferred.
於一實施例,該熱塑性聚酯彈性體的Shore硬度為35~40D較理想。 In one embodiment, the thermoplastic polyester elastomer preferably has a Shore hardness of 35 to 40 D.
於一實施例,上述電線包覆用啞光性組成物,更包含相溶化劑較理想。該相溶化劑為甲基苯乙烯,對該組成物的總重量100%而言,包含小於1%的甲基苯乙烯較理想。 In one embodiment, the matte composition for wire coating further preferably contains a compatibilizing agent. The compatibilizing agent is methyl styrene, and it is preferable to contain less than 1% of methyl styrene per 100% by weight of the total weight of the composition.
於一實施例,上述電線包覆用啞光性組成物,可更包含顏料、阻燃劑、耐磨劑等添加劑。 In one embodiment, the matte composition for wire coating may further include an additive such as a pigment, a flame retardant, or an anti-wear agent.
再者,根據本發明另一實施態樣,提供一種電線用啞光殼層,其係使用上述電線包覆用啞光性組成物藉由射出或擠壓成形所構成。 Furthermore, according to another embodiment of the present invention, there is provided a matte shell for an electric wire, which is formed by injection or extrusion using the above-mentioned matte composition for electric wire coating.
根據本發明之電線包覆用啞光性組成物及電線用啞光性殼層,可製造表面霧度高且表面光滑的電線用啞光性殼層及射出、擠出或吹製之成形體,除符合產業要求外,可達到製品的美觀性。 According to the matte composition for wire coating of the present invention and the matte shell for electric wires, it is possible to produce a matte shell for electric wires having a high surface haze and a smooth surface, and a molded body which is extruded, extruded or blown. In addition to meeting the industrial requirements, the aesthetics of the product can be achieved.
有關本發明之前述及其他技術內容、特點與功效,在以下較佳實施例的詳細說明中,將可清楚的呈現。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 above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. In order to thoroughly 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 compositions or steps The details 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. .
根據本發明一實施例,揭露一種電線包覆用啞光性組成物,包括:一第一熱塑性樹脂;以及一第二熱塑性樹脂,其中該第二熱塑性樹脂與該第一熱塑性樹脂不同,且該第二熱塑性樹脂的線膨脹係數與該第一熱塑性樹脂的線膨脹係數之差的絕對值為10%~30%的該第一熱塑性樹脂的線膨脹係數的範圍,。上述第一熱塑性樹脂為熱塑性聚胺基甲酸酯(TPU)樹脂較理想。具體地,例如聚酯型聚胺基甲酸酯樹脂,可藉由二苯基甲烷二異氰酸酯(4,4’-methylenediphenyl diisocyanate;MDI)、擴鏈劑的丁二醇(1,4-butanediol;BG)及/或乙二醇(EG)、二元酸聚多元醇聚酯(分子量約為1000~3000)或二元醇多元醇聚醚(分子量約為1000~3000)反應而得到熱塑性聚胺基甲酸酯樹脂。例如熱塑性聚胺基甲酸酯樹脂包含30~50莫耳%的硬鏈段及50~70莫耳%的軟鏈段,其Shore硬度為80~95A較理想。更理想為具有Shore硬度95A之TPU。 According to an embodiment of the present invention, a matte composition for wire coating is disclosed, comprising: a first thermoplastic resin; and a second thermoplastic resin, wherein the second thermoplastic resin is different from the first thermoplastic resin, and The absolute value of the difference between the linear expansion coefficient of the second thermoplastic resin and the linear expansion coefficient of the first thermoplastic resin is in the range of 10% to 30% of the linear expansion coefficient of the first thermoplastic resin. The above first thermoplastic resin is preferably a thermoplastic polyurethane (TPU) resin. Specifically, for example, a polyester urethane resin, a butylene glycol (1,4-butanediol; a 4,4'-methylenediphenyl diisocyanate; MDI), a chain extender; A thermoplastic polyamine obtained by reacting BG) and/or ethylene glycol (EG), a dibasic acid polypolyol polyester (having a molecular weight of about 1000 to 3000) or a glycol polyol polyether (having a molecular weight of about 1000 to 3000) Carbamate resin. For example, the thermoplastic polyurethane resin comprises 30 to 50 mol% of a hard segment and 50 to 70 mol% of a soft segment, and a Shore hardness of 80 to 95 A is preferred. More preferably, it is a TPU having a Shore hardness of 95A.
於一實施例,上述第二熱塑性樹脂為選自乙烯-乙酸乙烯酯共聚物(EVA)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、熱塑性聚酯彈性體(TPEE)所成群之1種或1種以上的樹脂較理想。EVA與TPU具有良好的互溶性,為了提高成形體的反撥彈性,再添加少量的TPEE於啞光性組成物中較理想。使用TPEE於啞光性組成物中的情況,反撥彈性較佳,又可提高耐低溫性、耐水解性、耐熱性,而使用SBS於啞光性組成物中的情 況,因SBS本質軟,可調節成形體的軟度。 In one embodiment, the second thermoplastic resin is selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS), and thermoplastic polyester elastomer (TPEE). One or more resins in a group are preferred. EVA and TPU have good mutual solubility. In order to improve the rebound elasticity of the molded body, it is preferable to add a small amount of TPEE to the matte composition. When TPEE is used in the matte composition, the rebound elasticity is better, and the low temperature resistance, hydrolysis resistance, and heat resistance are improved, and the use of SBS in the matte composition is used. Moreover, since the SBS is essentially soft, the softness of the formed body can be adjusted.
對該組成物的總重量100%而言,包含5~20%的第二熱塑性樹脂,以及60~95%的第一熱塑性樹脂較理想,藉由添加添加與聚胺甲酸酯樹脂(此處為第一熱塑性樹脂)互溶性良好且與聚胺甲酸酯樹脂的線膨脹係數差異大之第二熱塑性樹脂,使成形體具有啞光性,且維持表面光滑。 For the total weight of 100% of the composition, 5 to 20% of the second thermoplastic resin, and 60 to 95% of the first thermoplastic resin is preferable, by adding and adding a polyurethane resin (here) The second thermoplastic resin which is a first thermoplastic resin and which has a good mutual solubility and a large difference in linear expansion coefficient from the polyurethane resin has a matte property and maintains a smooth surface.
再者,第二熱塑性樹脂為乙烯-乙酸乙烯酯共聚物(EVA)與熱塑性聚酯彈性體(TPEE)的混合物較理想,具體地例如TPEE與EVA的比例,以重量比為1:2添加於組成物中。TPEE可使用市售品,例如杜邦製Hytrel製品,可選擇Shore硬度為35~40D者較理想,選擇Shore硬度為38D者更理想,此時,對該組成物的總重量100%而言,包含5~20%的第二熱塑性樹脂更理想,15%的第二熱塑性樹脂更加理想。 Furthermore, the second thermoplastic resin is preferably a mixture of an ethylene-vinyl acetate copolymer (EVA) and a thermoplastic polyester elastomer (TPEE), specifically, for example, a ratio of TPEE to EVA, added in a weight ratio of 1:2. In the composition. TPEE can use commercially available products, such as DuPont's Hytrel products. It is preferable to select a Shore hardness of 35 to 40D, and it is more preferable to select a Shore hardness of 38D. In this case, 100% of the total weight of the composition is included. 5 to 20% of the second thermoplastic resin is more desirable, and 15% of the second thermoplastic resin is more desirable.
此外,於一實施例,對該組成物的總重量100%而言,包含5~10%的乙烯-乙酸乙烯酯共聚物,5~10%的熱塑性聚酯彈性體以及60~90%的第一熱塑性樹脂較理想。 Further, in one embodiment, the total weight of the composition is 100%, comprising 5 to 10% of an ethylene-vinyl acetate copolymer, 5 to 10% of a thermoplastic polyester elastomer, and 60 to 90% of the first A thermoplastic resin is preferred.
上述電線包覆用啞光性組成物,可更包含相溶化劑較理想。該相溶化劑為甲基苯乙烯,對該組成物的總重量100%而言,包含小於1%的甲基苯乙烯較理想。 The above matte composition for wire coating may further contain a compatibilizing agent. The compatibilizing agent is methyl styrene, and it is preferable to contain less than 1% of methyl styrene per 100% by weight of the total weight of the composition.
於一實施例,上述電線包覆用啞光性組成物,可更包含顏料、耐磨劑、阻燃劑等的添加劑。上述阻燃劑的含量,在不影響本發明的效果之範圍內較理想,例如為30重量%以下。顏料的添加量,例如為5重量%以下。耐磨劑,例如為矽酮(silicone)等,添加量例如為15重量%以 下,較理想為1~12重量%。 In one embodiment, the matte composition for wire coating may further include an additive such as a pigment, an anti-wear agent, or a flame retardant. The content of the above flame retardant is preferably within a range that does not impair the effects of the present invention, and is, for example, 30% by weight or less. The amount of the pigment added is, for example, 5% by weight or less. The anti-wear agent, for example, silicone or the like, is added in an amount of, for example, 15% by weight. Next, it is preferably 1 to 12% by weight.
再者,根據本發明另一實施例,揭露一種電線用啞光殼層,其係使用上述電線包覆用啞光性組成物藉由射出或擠壓成形所構成。 Furthermore, according to another embodiment of the present invention, a matte shell for an electric wire is disclosed which is formed by injection or extrusion using the above-mentioned matte composition for electric wire coating.
上述啞光性的標準,係根據物體表面的光反射率(0度角反射率)判定,以透明玻璃表面的光反射率為4%為基準,由本發明的電線包覆用啞光性組成物形成之電線用啞光殼層的光反射率為3%以下,較理想為2.5%以下。 The matteness criterion is determined based on the light reflectance (0 degree angular reflectance) of the surface of the object, and the matte composition for wire coating of the present invention is based on a light reflectance of 4% on the surface of the transparent glass. The light reflectance of the matte shell layer for the formed electric wire is 3% or less, preferably 2.5% or less.
上述線膨脹係數(linear thermal expansion coefficient),TPU的線膨脹係數為50~200×10-6 mm/mm/℃,TPEE的線膨脹係數為81~90×10-6 mm/mm/℃,EVA的線膨脹係數為10~20×10-6 mm/mm/℃,SBS的線膨脹係數為50~89×10-6 mm/mm/℃。具體地,第二熱塑性樹脂的線膨脹係數為70%~90%的該第一熱塑性樹脂的線膨脹係數或1.1~1.3倍的該第一熱塑性樹脂的線膨脹係數。該第二熱塑性樹脂的線膨脹係數與該第一熱塑性樹脂的線膨脹係數之差的絕對值為10%~30%的該第一熱塑性樹脂的線膨脹係數的範圍。 The above linear thermal expansion coefficient, the linear expansion coefficient of TPU is 50~200×10 -6 mm/mm/°C, and the linear expansion coefficient of TPEE is 81~90×10 -6 mm/mm/°C, EVA The linear expansion coefficient is 10~20×10 -6 mm/mm/°C, and the linear expansion coefficient of SBS is 50~89×10 -6 mm/mm/°C. Specifically, the linear expansion coefficient of the second thermoplastic resin is 70% to 90% of the linear expansion coefficient of the first thermoplastic resin or 1.1 to 1.3 times the linear expansion coefficient of the first thermoplastic resin. The absolute value of the difference between the linear expansion coefficient of the second thermoplastic resin and the linear expansion coefficient of the first thermoplastic resin is in the range of 10% to 30% of the linear expansion coefficient of the first thermoplastic resin.
上述第一熱塑性樹脂與第二熱塑性樹脂的互溶性,一般根據溶解度參數(solubility parameter)進行評價,而於本發明,以下述實驗為基準,將樹脂壓成薄片,以透明或不透明判斷互溶性是否良好,如果為透明時,可判斷相容性良好;若為不透明時則進一步藉由撕開該薄片時是否分離,判斷互溶性是否良好,亦即如果撕開時分離成2片,判斷互溶性不佳,如果無法撕開仍保持完整,沒有分離,判斷互溶性良好。 The mutual solubility of the first thermoplastic resin and the second thermoplastic resin is generally evaluated according to a solubility parameter. In the present invention, the resin is pressed into a sheet based on the following experiment, and whether the mutual solubility is determined by transparency or opacity is Good, if it is transparent, it can be judged that the compatibility is good; if it is opaque, it is further separated by tearing the sheet, and it is judged whether the mutual solubility is good, that is, if it is separated into two pieces when it is torn, the mutual solubility is judged. Poor, if it can not be torn, it remains intact, there is no separation, and the mutual solubility is judged to be good.
TPU的製作:使用MDI、1,4-丁二醇(1,4-BG)及己二酸聚多元醇聚酯(分子量約為2000),進行合成反應,得到TPU。 Preparation of TPU: A synthesis reaction was carried out using MDI, 1,4-butanediol (1,4-BG) and adipic acid polypolyol polyester (molecular weight of about 2,000) to obtain TPU.
將硬度38D的TPEE 15重量份及TPU 48.4重量份,摻合混練後,以單螺桿抽粒,得到A料。將A料與EVA 10重量份、SEBS(苯乙烯-乙烯-丁二烯嵌段共聚物)1.2重量份、黑色顏料2.5重量份、矽酮(耐磨劑)1.3重量份、TPU 21.6重量份摻合混練後,以單螺桿抽粒,得到電線包覆用啞光性組成物1。 15 parts by weight of TPEE having a hardness of 38D and 48.4 parts by weight of TPU were blended and kneaded, and then single-screwed to obtain a material A. 10 parts by weight of A material and EVA, 1.2 parts by weight of SEBS (styrene-ethylene-butadiene block copolymer), 2.5 parts by weight of black pigment, 1.3 parts by weight of anthrone (anti-wear agent), and 21.6 parts by weight of TPU After the kneading, the single-screw was used to obtain a matte composition 1 for wire coating.
TPU的製作:與上述範例一的TPU的製作相同地,製作TPU。 Production of TPU: A TPU is produced in the same manner as the production of the TPU of the first example described above.
將硬度38D的TPEE 13重量份及TPU 50.4重量份,摻合混練後,以單螺桿抽粒,得到A料。將A料與EVA 10重量份、SBS 1.2重量份、黑色顏料2.5重量份、矽酮(耐磨劑)1.3重量份、TPU 21.6重量份摻合混練後,以單螺桿抽粒,得到電線包覆用啞光性組成物2。 13 parts by weight of TPEE having a hardness of 38D and 50.4 parts by weight of TPU were blended and kneaded, and then single-screwed to obtain a material A. The material A was blended with 10 parts by weight of EVA, 1.2 parts by weight of SBS, 2.5 parts by weight of black pigment, 1.3 parts by weight of anthrone (anti-wear agent), and 21.6 parts by weight of TPU, and then subjected to single-screw granulation to obtain a wire coating. Matte composition 2 was used.
TPU的製作:與上述範例一的TPU的製作相同地,製作TPU。 Production of TPU: A TPU is produced in the same manner as the production of the TPU of the first example described above.
將硬度38D的TPEE 20重量份及TPU 43.4重量份,摻合混練後,以單螺桿抽粒,得到A料。將A料與EVA 10重量份、SBS 0.6重量份、SEBS 0.6重量份、黑色顏料2.5重量份、矽酮(耐磨劑)1.3重量份、TPU 21.6重量份摻合混練後,以單螺桿抽粒,得到電線包覆用啞光性組成物3。 20 parts by weight of TPEE having a hardness of 38D and 43.4 parts by weight of TPU were blended and kneaded, and then single-screwed to obtain a material A. A material was blended with 10 parts by weight of EVA, 0.6 parts by weight of SBS, 0.6 parts by weight of SEBS, 2.5 parts by weight of black pigment, 1.3 parts by weight of anthrone (anti-wear agent), and 21.6 parts by weight of TPU. A matte composition 3 for wire coating is obtained.
使用範例一、二或三所得之電線包覆用啞光性組成物1、2或3,藉由擠出成形機,製造電線用啞光殼層。 Using the matte composition 1, 2 or 3 of the wire coating obtained in Example 1, 2 or 3, a matte shell for electric wires was produced by an extrusion molding machine.
綜上所述,根據本發明之電線包覆用啞光性組成物及電線用啞光性殼層,可製造表面霧度高且表面光滑的電線用啞光性殼層及射出、擠出或吹製之成形體,除符合產業要求外,可達到製品的美觀性。 As described above, according to the matte composition for electric wire coating of the present invention and the matte shell for electric wires, it is possible to produce a matte shell for electric wires having high surface haze and a smooth surface, and to eject, extrude or The blown molded body can meet the requirements of the industry and can achieve the aesthetic appearance of the product.
以上雖以特定實施例說明本發明,但並不因此限定本發明之範圍,只要不脫離本發明之要旨,熟悉本技藝者瞭解在不脫離本發明的意圖及範圍下可進行各種變形或變更。另外本發明的任一實施例或申請專利範圍不須達成本發明所揭露之全部目的或優點或特點。此外,摘要部分和標題僅是用來輔助專利文件搜尋之用,並非用來限制本發明之權利範圍。 The present invention has been described in detail with reference to the preferred embodiments of the present invention, and the scope of the invention is not limited thereto, and it is understood that various modifications and changes can be made without departing from the spirit and scope of the invention. In addition, any of the objects or advantages or features of the present invention are not required to be achieved by any embodiment or application of the invention. In addition, the abstract sections and headings are only used to assist in the search of patent documents and are not intended to limit the scope of the invention.
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