201117951 六、發明說明： 【發明所屬之技術領域】 種全聚s旨之複 本發明是-種複合材料，尤其是關於一 合材料'其製程方法以及其應用。 【先則技術】 傳統的複合材料具有質輕、高 门湮度寺特性，因此是許 夕特殊需求之場合的不二遠搂 i n 个選擇但目前的複合材料受限於201117951 VI. Description of the invention: [Technical field to which the invention pertains] The present invention is a composite material, particularly a composite material, a process method thereof, and an application thereof. [First-class technology] Traditional composite materials have the characteristics of light weight and high threshold, so it is the best choice for the occasion of special needs. However, the current composite materials are limited by
仏格、無法回收、多屬於埶固性姑 …u r玍材科以及異質材料介面複 合特性不佳等諸多因素，座 又口系便具應用梵到許多的限制。 複材專家pegoretti(2007)於複合材料未來趨勢文章中 特別提出環保節能年代已經來臨，材料之回收與再使用之 方法開發應有更新之思維與做法，而單—高分子複合材料 (Single PQ|y贿CQmpQsite，簡稱spc)則是此—時代趨勢 之中非常重要且特別的材料。 spC係指增強材（Reinf0rcement)與連續相基材 (atrix)均為相同化學成分之高分子材料所組合而成之複合 材料，SPC具有相當多優點與特色。舉例而言，由於增強 材與基材具相同化學結構，因此二者間完全相容，不存在 傳統纖維複合材料之界面問題，並且Spc複合材料中之纖 維材料分子鏈的高度取向使材料具有足夠之初始強度，因 而賦予S P C具備更加優越之比剛性、比強度、低密度等特 性’尤其於衝擊韌性與斷裂伸長率之改善更為顯著。此外 ’熱塑性之單一高分子之製造過程中之廢/邊料或當該產品 生命週期結束後，其可完全藉由熔融方法進行回收，使單 201117951 一面分子複合材料完全符合綠色材料之要求。 目前業界相對發展較為成熟的SPC之開發工作，主要 以廠商 Propex Fabrics Inc.等所提出以聚丙烯 (Polypropylene ’ PP)為主要材質之 spC 產品。PP_SPC 之 增強材（纖維）及連續相基材（樹脂）係均為PP，因此解決傳 統複合材料中因為纖維與基材之異質特性造成的所有問題 ，不僅具備相對低成本之優勢，還可讓PP_SPC具備可後 製加工之特質。 # 然而，前述的全聚丙烯複合材料（PP-SPC)卻有許多仍 待改善的缺點，如後列： 1.機械物性仍不夠強韌，且亦受溫度影響而導致性能 大幅下降。 2·熔點溫度低，耐溫性不足，導致使用受到限制。 3.聚丙烯為非極性物質，表面穩定不易與其他物質反 應。過於穩定的表面不利於聚丙稀高分子片材與其他材料 結合（膠合、黏合）或進行表面塗裝，因此造成難以後製加工 φ 的缺點。 【發明内容】 為了解決前述習用技術的諸多缺點，本發明提出以全 聚酿作為單-高分子複合材料的主成分，解決習用技術之 機械物性不佳、炫點過低、不容易後製加工的技術問題。 配合解決前述技術問題，本發明提供一種 材料的製造方法，其步驟包含： “日複。 將一 t酯纖維布經熱定型製程； 5 201117951 將一聚酿樹脂經過改質以降低溶點並形成膜片狀，改 質後的該聚酯樹脂與該聚酯纖維布之熔點差異形成一工作 溫度視窗；及 疊合該聚酯纖維布與改質後的聚酯樹脂，並於該工作 服度視®内以一熱壓製程將該聚酯纖維布與改質後的該聚 醋樹脂成形為一單層全聚酯複材。 本發明再提供一種單層全聚酯複材，其包含一聚酯纖 維布及緊密包覆該聚酯纖維布之一膜片狀之低熔點聚酯樹 • 脂，該低低熔點聚酯樹脂之熔點低於該聚酯纖維布，其中 該單層聚酯複材之製造方法步驟包含： 將該聚s旨纖維布經熱定型製程； 將一聚醋樹脂經過改質以降低熔點並形成膜片狀之該 低炫點聚酿樹脂’改質後的該低炫點聚醋樹脂與該聚醋纖 維布之熔點差異形成一工作溫度視窗；及 疊合該聚酯纖維布與該低熔點聚酯樹脂，並於該工作 溫度視窗内以一熱壓製程將該聚I纖維布#該低溶點聚酷 Φ 樹脂結合形成該單層全聚酯複材。 本發明進一步提供一種連續型之全聚酯複合材料的製 造方法，其步驟包含： 將經過改質的一聚酯樹脂先形成一連續的聚酯樹酯薄 膜，使该聚酯樹酯薄膜與一連續的聚酯纖維布之熔點差異 形成一工作溫度區間； 使用一熱滾壓手段將該聚酯樹酯薄膜與該聚酯纖維布 疊合並熱融壓合，形成一連續之全聚酯複材片材； 將連續之全聚酯複材片材經過一冷卻手段後捲收完成 201117951 壓合之連續的全聚酯複材片材。 本發明更提供一種具撓曲表面之全聚酯產品，其由一 層以上且相互疊合之聚酯纖維布以一低熔點聚酯樹脂疊合 組成，其中，形成§亥具撓曲表面之全聚酯產品之製造步驟 包含： 將每一該聚酯纖維布經熱定型製程； 將一聚酯樹脂經過改質以降低熔點並形成膜片狀之該 低熔點聚酯樹脂，改質後的該低熔點聚酯樹脂與該聚酯纖 φ 維布之溶點差異形成一工作溫度視窗； 交錯疊合一層以上之該聚酯纖維布與一層以上的該低 熔點聚酯樹脂，並於該工作溫度視窗内以一熱壓製程將該 聚酯纖維布與該低熔點聚酯樹脂結合形成該單層全聚酯複 材； 將複數層單層全聚酯複材疊合並加高溫使每一單層全 聚酯複材之該低熔點聚酯樹脂形成流動後施高壓結合各單 層全聚醋複材而成為一積層全聚酯複材片材； • 以熱衝壓方法將該積層全聚酯複材片材成形為一具撓 曲表面的一全聚酯產品。 藉此，本發明所提出的全聚酯（PET)之單一高分子複合 材料未見於先前技術，其更集合多種不同複合材料或均質 材料的各項優點，如下： 1·相較於習用的PP單一高分子複合材料，本發明全 聚酯（PET)單一高分子複合材料具備成本相對低廉、可回收 、機械特性佳、耐熱性加而應用範疇廣、易於與其他材料 結合而容易加工與簡化產品製程困難度。 201117951 本發月之王1自旨自增強複合材料具有傳統複合材料 所不具備的熱塑性特徵，賦予本發明在成形之後仍可以加 熱加工成形，因此具備高加工靈活度之特性。 【實施方式】 請參考第一圖，其為本發明之全聚酯自增強複合材料 之製程方法步驟包含： 步驟1_織維布及樹脂備製（10):本發明之全聚酯複合 修材料之原料包含一聚酯纖維布及一聚酯樹脂，其中： (1)該聚酯纖維布必須先經過一熱定型步驟，讓後續 需要加溫的製造過程得維持尺寸均一性，換言之，讓選用 ㈣聚醋纖維布經過特定溫度之下的熱定型；驟後，該聚 酯纖維布在爾後的升溫、降溫過程能夠維持穩定且變異量 微小的尺寸範圍； 該聚醋樹脂則必須先經過改質以降低聚酯樹脂# 熔點藉以使選用之該聚酯樹脂與該聚酯纖維布之熔點羞 生溫度差距（約介於10至6〇度），形成一工作溫度視窗。 该聚醋樹脂之改f方式不限定，可以依據需求而選擇不同 的改質方式，例如共聚合、添加不同分子量之材料…等。 本實施例利用共聚合之方式讓該聚㈣脂的溶點降低，使 該聚醋樹醋與該聚酿纖維布產生該工作溫度視窗之溫度差 異0其中，形成該工作溫唐顏窗± α β 度視®主要目的是為了避免製造 全IS旨自增強複合材料過程中因 w U马同/皿熔融狀態之該聚酯 樹西曰導致該聚酯纖維布一併熔 ^ s θ 1幵塔化或導致其分子結構破壞而 -傷良好的機械性能’因此，必須讓㈣纖維布及該 201117951 聚酉曰樹月曰形成具有差異性的熔融狀態形成溫度，作為製造 本較佳實施例之全聚s旨自增強複合材料之製程空間。若該 聚g曰纖維布與該聚酯樹酯之間的熔融狀態溫度差異越大(該 工作溫度視窗溫度越大）’代表該全聚醋自增強複合材料之 製過程的彈性越大，且該聚酯纖維布之結構穩定性越好 Ο 補充說明則述本實施例所使用之共聚合方法如後列。 高分子在熔融的過程中，一般呈現一個較寬的熔融溫度範 圍’即存在一㈤『炫限』；-般將其最後完全縣時的溫 度稱為熔點Tm。一般而言，聚酯（p〇|yethy丨扣❻ terephthalate，聚对笨二甲酸乙二酯，簡稱聚酯（ρΕτ))之 熔點約在255°C〜265t，但為了要在讓本實施例製造全聚 醋自增強複合材料製程中，使基材（Ma㈣與補強材炫點得 到差異化，因而必須對所使用的PET基材做改質，以便得 到較低炫點的PET。材料的炫點通常會受以下幾點所影響 .(I)分子結構對熔點的影響，包含分子間作用力、分子鏈 的剛性、分子鏈的對稱性與完整性；（ji)結晶條件對熔點的 t/響包3曰B片厚度對熔點的關係、結晶溫度與熔點的關 係。其他影響南分子熔點而在實務上經常用來改變熔點的 方法包含分子量的改變、單體共聚或小分子高分子添加、 塑化劑的添加’其中以共聚法較為有效。 使用共聚物法改變聚酯的熔點，通常會添加己二酸、 癸二酸、聚乙二醇、聚丙二醇、丁二醇、間苯二甲酸（丨pA) 、己一酸乙二醇酯（DEA)…等[鄭為等國立中山大學材料科 學研究所碩士論文，2001]，其中以丨PA與DEA熔點改善最 201117951 為有效為例。分別添加 IDA ·5ηι〇Ι/0、15 m〇r/0、25 mol%之 IHA’可使熔點由純 之252 C降低至分別為2331：、 、與 186t，若添加 dea 比例為 5.5mol%、15 m〇|%There are many factors, such as plague, unrecoverable, and many collaterals, and the poor composite interface characteristics of heterogeneous materials. Composite material expert pegoretti (2007) in the future trend of composite materials article specifically proposed that the era of environmental protection and energy conservation has come, the development of materials recycling and reuse methods should have updated thinking and practices, and single-polymer composite materials (Single PQ| y bribe CQmpQsite, referred to as spc) is this is a very important and special material in the trend of the times. spC refers to a composite material in which a reinforcing material (Reinf0rcement) and a continuous phase substrate (atrix) are the same chemical composition of a polymer material, and SPC has considerable advantages and features. For example, since the reinforcing material has the same chemical structure as the substrate, the two are completely compatible, there is no interface problem of the conventional fiber composite, and the high orientation of the molecular chain of the fiber material in the Spc composite makes the material sufficient. The initial strength gives the SPC a superior ratio of rigidity, specific strength, and low density, especially for impact toughness and elongation at break. In addition, the waste/edge material in the manufacturing process of the thermoplastic single polymer or the end of the product life cycle can be completely recovered by the melting method, so that the single molecular composite material of the 201117951 side fully meets the requirements of the green material. At present, the development of SPC, which is relatively mature in the industry, is mainly based on the propC fabrics Inc., which is made of polypropylene (Polypropylene PTFE). PP_SPC's reinforcement (fiber) and continuous phase substrate (resin) are all PP, so it solves all the problems caused by the heterogeneity of fiber and substrate in traditional composite materials, not only has the advantage of relatively low cost, but also allows PP_SPC has the characteristics of post-processing. # However, the aforementioned all-polypropylene composite (PP-SPC) has many shortcomings that still need to be improved, such as the following: 1. The mechanical properties are still not strong enough, and the performance is also greatly reduced due to temperature. 2. The melting point is low and the temperature resistance is insufficient, resulting in limited use. 3. Polypropylene is a non-polar substance and its surface is not stable enough to react with other substances. An overly stable surface is not conducive to the bonding (gluing, bonding) or surface coating of a polypropylene polymer sheet with other materials, thus causing the disadvantage of being difficult to process φ. SUMMARY OF THE INVENTION In order to solve the many shortcomings of the prior art, the present invention proposes to use full-growth as the main component of the single-polymer composite material, and to solve the problem of poor mechanical properties of the conventional technology, too low a dazzling point, and not easy post-processing. Technical problem. In order to solve the above technical problems, the present invention provides a method for manufacturing a material, the steps of which include: "Daily. A t-ester fiber cloth is subjected to a heat setting process; 5 201117951 A poly-brew resin is modified to reduce the melting point and form a film-like shape, the modified polyester resin and the polyester fiber cloth have a melting point difference to form a working temperature window; and the polyester fiber cloth and the modified polyester resin are laminated, and the working clothes are inspected The polyester fiber cloth and the modified polyester resin are formed into a single-layered all-polyester composite material by a hot pressing process. The present invention further provides a single-layered all-polyester composite material comprising a poly-polymer. An ester fiber cloth and a low-melting polyester resin which is tightly coated with a film of the polyester fiber cloth, wherein the low-low melting point polyester resin has a lower melting point than the polyester fiber cloth, wherein the single-layer polyester compound The manufacturing method step comprises: subjecting the polystyrene fiber cloth to a heat setting process; modifying the polyacetal resin to lower the melting point and forming a film shape, the low-density polymer resin is low after the modification Hyun dot polyester resin and the polyester cloth The difference in dots forms a working temperature window; and the polyester fiber cloth and the low-melting-point polyester resin are superposed, and the poly-I-fiber cloth is gathered in the working temperature window by a hot pressing process. The resin is combined to form the single-layered all-polyester composite. The invention further provides a method for producing a continuous all-polyester composite, the steps comprising: forming a continuous polyester tree by modifying a polyester resin. The ester film forms a working temperature interval between the polyester resin film and a continuous polyester fiber cloth; the polyester resin film is laminated with the polyester fiber cloth by a hot rolling method Pressing to form a continuous all-polyester composite sheet; the continuous all-polyester composite sheet is subjected to a cooling means and then wound up to complete the continuous all-polyester composite sheet of 201117951. The invention further Provided is a full polyester product having a flexural surface, which is composed of a layer of a plurality of polyester fiber cloths laminated on each other and laminated with a low melting point polyester resin, wherein a full polyester product forming a flexing surface is formed. Manufacturing step package Included: each of the polyester fiber cloth is subjected to a heat setting process; a polyester resin is modified to lower the melting point and form a film-like low-melting point polyester resin, and the modified low-melting point polyester resin is The difference in melting point of the polyester fiber φ wei cloth forms an operating temperature window; interlacing more than one layer of the polyester fiber cloth with more than one layer of the low melting point polyester resin, and heat pressing in the working temperature window The process comprises combining the polyester fiber cloth with the low melting point polyester resin to form the single layer full polyester composite material; stacking a plurality of layers of the single layer full polyester composite material and adding high temperature to make each single layer of the whole polyester composite material The low-melting-point polyester resin forms a flow and then applies a high pressure combined with each single-layer full-polyester composite material to form a laminated all-polyester composite material sheet; • forming the laminated all-polyester composite material sheet into a hot stamping method An all-polyester product having a flexed surface. Accordingly, the single-polymer composite material of the all-polyester (PET) proposed by the present invention is not found in the prior art, and is more advantageous in assembling a plurality of different composite materials or homogeneous materials. , as follows: 1 · Compared to the custom The PP single polymer composite material, the whole polyester (PET) single polymer composite material of the invention has the advantages of relatively low cost, recyclability, good mechanical properties, heat resistance and wide application range, and is easy to be combined with other materials and is easy to process and Simplify product manufacturing difficulties. 201117951 The King of the Moon 1 self-reinforced composite material has the thermoplastic characteristics not possessed by the conventional composite material, and the invention can be heated and formed after forming, so that it has high processing flexibility. [Embodiment] Please refer to the first figure, which is a process for preparing the all-polyester self-reinforced composite material of the present invention. The steps include: Step 1_Weaving cloth and resin preparation (10): The all-polyester composite repair of the present invention The material of the material comprises a polyester fiber cloth and a polyester resin, wherein: (1) the polyester fiber cloth must first undergo a heat setting step to maintain the dimensional uniformity of the subsequent manufacturing process requiring heating, in other words, (4) The heat setting of the polyester fiber cloth under a certain temperature is selected; after the step, the temperature and temperature of the polyester fiber cloth can be maintained stably and the variation amount is small; the polyester resin must be modified first. The temperature is lowered to lower the melting point of the polyester resin to thereby make the temperature difference between the polyester resin and the polyester fiber cloth (about 10 to 6 degrees) to form a working temperature window. The method of changing the polyester resin is not limited, and various modifications such as copolymerization, addition of materials having different molecular weights, and the like can be selected depending on the demand. In this embodiment, the melting point of the poly(tetra) lipid is lowered by means of copolymerization, and the temperature difference between the polystyrene vinegar and the polystyrene fiber cloth is generated in the working temperature window, wherein the working temperature window is formed by ±αβ degrees. The main purpose of Vision® is to avoid the manufacture of the full-IS self-reinforced composite material during the process of the polyester fiber, which causes the polyester fiber cloth to melt together or s θ 1幵Resulting in the destruction of its molecular structure - good mechanical properties of injury - Therefore, it is necessary to make the (four) fiber cloth and the 201117951 eucalyptus eucalyptus form a different molten state forming temperature as the total poly s of the preferred embodiment. Designed to enhance the process space of composite materials. If the temperature difference between the molten state of the polyg-fiber fabric and the polyester resin is greater (the operating window temperature is higher), the elasticity of the process of the full-polylactic self-reinforced composite material is greater, and The structural stability of the polyester fiber cloth is better. Supplementary explanation The copolymerization method used in the present embodiment is as follows. In the process of melting, the polymer generally exhibits a wide range of melting temperatures, that is, there is one (five) "hyun limit"; the temperature of the last full county is generally referred to as the melting point Tm. In general, the melting point of polyester (p〇|yethy丨 terephthalate, polyethylene terephthalate, abbreviated as polyester (ρΕτ)) is about 255 ° C ~ 265 t, but in order to let this embodiment In the process of manufacturing a full-poly vinegar self-reinforced composite material, the substrate (Ma(4) and the reinforcing material are differentiated, so the PET substrate used must be modified to obtain a lower scent of PET. The point is usually affected by the following points: (I) the influence of the molecular structure on the melting point, including the intermolecular force, the rigidity of the molecular chain, the symmetry and integrity of the molecular chain; (ji) the crystallization condition to the melting point t/ The relationship between the thickness of the B sheet and the melting point, the relationship between the crystallization temperature and the melting point. Other methods that affect the melting point of the south molecule and are often used to change the melting point in practice include molecular weight change, monomer copolymerization or small molecule polymer addition, The addition of plasticizers is more effective in the copolymerization method. The copolymer method is used to change the melting point of the polyester, usually adding adipic acid, sebacic acid, polyethylene glycol, polypropylene glycol, butanediol, isophthalic acid. (丨pA), one Ethylene glycol ester (DEA)...etc. [Zheng Wei et al., Master's thesis, Institute of Materials Science, National Sun Yat-Sen University, 2001], which is based on the improvement of the melting point of 丨PA and DEA, 201117951. Add IDA ·5ηι〇Ι/0 respectively. , 15 m〇r / 0, 25 mol% of IHA' can reduce the melting point from pure 252 C to 2331:, and 186t, respectively, if the ratio of dea added is 5.5mol%, 15 m〇|%
、mGU ’可使溶點由純PET < 252°C分別降至233°C, mGU ’ can reduce the melting point from pure PET < 252 ° C to 233 ° C
C與185<：[唐詩，&京服裝學院碩士學位論文I ^U03] 〇 &加劑㈣點的影響對各料㈣料都略有不同，若 在PET中添加無機粒子如二氧化石夕⑹〇2)或二氧化欽⑽2) 鲁 無機粒子可破壞聚s旨分子排列之規整性，但不同的無機 ;;子對炫體成核結晶作用不同，有的起阻礙作用，有的起 促進作用’端看添加量的多少，而溶點隨著無機組份含量 的增加而下降[馬權強，21 ’ 5，合成技術及應用，2006]。 另外，塑化劑（Plastjcjzer)的添加是將相容的低分子量 塑化劑或溶劑加入聚合體中，聚合體分子能吸引這些低分 子物質而產生較無規則的構造，以便降低熔點，常用的塑 化劑例如丙三醇、三氧化砷、鍺酸鈉…等，但由於在混摻 _的過程中塑化劑的熱穩^性不佳，容易因為高溫導致揮 發或裂解而消散，因而低溫改質效果並不穩定。 共混方法是指對聚酯進行物理改質，即在聚酯基材中 混入助劑或其它組份，在pET熔體中添加低分子助劑或分 子量低的齊聚物也會使PET熔點降低。例如在聚酯熔體中 ’加入低分子阻燃劑或阻燃體系，聚酯熔點一般降低1 〇°C 〜20 C [羅海林，浙江理工大學碩士學位論文，2〇〇5】，這是 由於低分子添加劑與PET熔體均勻混合後經急冷切粒，鏈 段被凉·結使之成為無定形態，當緩慢升溫至玻璃轉化溫度 201117951 (Tg)以上鏈段開始運動，結晶溫度附近分子鏈將進入結晶 晶格，此時由於低分子物質的存在，使晶格缺陷增加，結 晶不完善增加，進而降低PET之熔點。共混方法目前研究 較多的是PET/PBT共混體系熔點下降行為。相容的高聚物 溶體中，若其中-個組份能夠結晶，就可以觀察溶點降低 的現象。PBT是PET的同系物，兩者在無定形態完全相同 ，同為結晶線性飽和聚酯，PBT的分子鏈比PET多兩個亞 甲基’其熔點和玻璃轉化溫度低於PET，因而pbt分子鏈 • 段活動能力較PET強，其結晶速率比PET快1 〇倍。 由前述可知，降低聚酯基材或樹酯的方式很多種，可 藉由前述的方式讓聚酯基材與聚酯纖維產生熔點的溫度區 間，形成該工作溫度視窗。本實施例所使用之改質ρ樹 脂是透過共聚合改質，藉以得到PET共聚物，將原本熔點 由一般PET樹酯的265〇C降低至所使用之改質PET樹脂的 198.071，採用改質後PET作為本實施例之樹脂基材。第 二圖列舉改質後的聚酯樹脂的特性，顯示改質後的聚酯樹 •脂熔點可以達到約200度，而其流動溫度可於22〇<t下降 至100Pa.s之低粘度。 (3)當聚|旨樹脂改質以降低熔點之後，將改質後的聚醋 樹脂形成膜片狀。成形的方式可以是將聚酯樹脂加溫呈流 動狀態後’置於模具或機具平台後降溫，使其形成一片狀 聚酯樹脂，以作為本實施例之聚酯基材。 步称2.疊合熱麽形成單層全聚酯複材《2〇) 將片以上之片狀聚酯樹脂與一片以上之熱定型之後 的聚酯纖維布疊合後，以一熱壓方法，係加溫加壓讓聚酯 201117951 樹脂形成流動狀態後促使聚酯樹脂流動進入聚酯纖維布之 間的網格孔隙内，形成一单層全聚g旨複材。 步驟3.積層（30> 取複數個單層全聚醋複材予以疊合後，以前述的熱壓 方法再讓各層之單層全聚酯複材之聚酯樹脂呈流動狀態， 並予以熱壓後降溫形成一積層全聚酯複材片材。 步驟4.產品製造（40) 配合製造品之規格要求，可以選擇厚度、層數適當的 • 積層全聚酯複材片材利用一熱衝壓方法予以成形而為一挽 曲面全聚酯成品。 產品應用開發實例如特殊功能硬質鞋底，利用全聚醋 自增強複合材料之質輕強韌特性，用以取代目前常用之玻 璃纖維複合材料，除提供此功能鞋具有剛硬之鞋底支承功 能外’更重要的是以較低密度之聚酯纖維取代高密度之玻 璃纖維之使用而可獲致產品減重功能，此外，熱塑性複材 快速與簡便之加工特點更有助提升此產品之生產效率；由 • 於成品外型簡單且薄’近似平板，因此可選擇由原材料進 行薄膜堆疊入模具中直接成型β 相較於目前商品化之全ΡΡ自增強材料如CurV(B，本實 施例以全聚酯自增強複合材料製造的鞋底材料具備優異的 異質結合相容性，因此更便於製造廠商後製加工，大為鬥 化製程與製造成本。由於此鞋底材料上需再與其他鞋材相 黏合以組合一完整鞋底，然由於非極性之pp材料表面黏著 性較差，常易導致黏合失效，甚至於鞋底射出製程時即有 脫膠之現象，所以，本實施例全聚酯自增強複合材料因表 12 『 201117951 面具有極性讓異質黏著特性較為優異，而可有效克服加工 黏合問題。 在製程溫度及時間的控制方面，如第一圖所示，在聚 酯纖維布之熱定型、單層全聚酯複材之熱壓成形係採以相 對之高溫短時間的方式進行，舉例而言，假設所選之材料 賦予工作溫度視窗介於210〜235°C之間，進行熱定型的溫 度與時間可設定於235°C，1min。 相對於聚酯纖維布熱定型與單層全聚酯複材之熱壓成 形，積層步騾所需的溫度與時間參數則屬於相對低溫及長 時間，例如215°C，2-6min。而在產品製造過程中，由於 其僅需要讓積層全聚酯複材之聚酯樹脂軟化即可進行成形 加工，因此，所需的製程溫度最低，約介於1 50〜200°C。 前述的溫度與時間參數，係可配合選擇不同特性的聚酯纖 維布及聚酯樹脂而可能略有變動。 表一 代號 耐衝擊強度 (J/m) 拉伸模數 (Mpa) 拉伸強數 (Mpa) 彎曲模數 (Mpa) 彎曲強數 (Mpa) 均質PET 13_5±1_6 1873±64 20.48士7.05 2010±101 54.6±2.7 BB15-6 647.5±35.9 3218±67 84.92±6.26 4400±126 73.4±2.5 BB25-3 448.2±28.6 3263±42 75.52±2.06 4514±18 72_4±0_7 BB25-6 360.5±28.8 3316±159 73.55±2.78 4441±154 72.5±2.0 BB25-10 4〇5.0±69.4 3402±66 95.50士4.47 4299±204 71.2±1.0 BB35-6 531.1±53.5 3416±79 66.13±2.82 4650±94 78.0±2.7 在結果方面，本實施例依據前述的步驟所完成多種積 層全聚酯複材片材之機械特性量測結果如表一。結果顯示 相較於均質聚酯片材，本實施例提供的複合材料具備優異 13 201117951 的機械特性’其拉伸、彎曲及耐衝擊性質皆有極明顯的提 升，尤其耐衝擊強度可提升高達647.5J/m以上，較純 PET(均質PET)提升高達6〇倍左右。 此外’本實施例係採用PET纖維布，而PET纖維布可 以選擇回收PET作為材料來源’故可進一步的節省材料成 本，並達到環保之功效。另外，回收pE丁與pET纖維組合 體系’一為性能經降解、熱性能較差、流動較快之材料， 而另一為經高順向延伸、高結晶性材料，本實施例之ΡΕτ • 材料之差異化組合恰可提供有效、更為寬廣的加工視窗， 對於製造便利性更有幫助。 進一步地’該片狀聚酯樹脂不僅可以利用前揭技術生 產’也可以略做改良而為可連續生產型態。如第三圖所示 ，將經過共聚合改質的聚酯樹脂先形成一連續的聚酯樹酯 薄膜（51)，配合一熱滾壓手段將該聚酯樹酯薄膜（51)與一連 續的聚醋纖維布（52)疊合並熱融壓合，其中，所謂的熱滚 壓手段係將該聚酯樹酯薄膜（51)以及該聚酯纖維布（52)一起 ®疊合捲入一加熱滾輪組（60)内，該加熱滾輪組（60)之高溫、 南壓先使該聚酯樹酯薄膜（51)成溶融流動態後擠壓進入該 聚醋纖維布（52)内’形成連續型態的全聚酯複材片材之輸 出。由該熱壓滚輪組（60)輸出之連續的全聚酯複材片材經 過一冷卻手段（70)後，由一收料捲軸（80)則持續捲收完成壓 合的全聚酯複材片材》其中，該冷卻手段（7〇)可以是一冷 風產生裝置、氮氣降溫裝置等。因此，利用本實施例所提 出的製程’全聚酯複合材料可以達到大量且快速的量產， 突破傳統技術之批量生產的限制。 201117951 【圖式簡單說明】 第一圖為本發明較佳實施例之流程示意圖。 第二圖為本發明較佳實施例之共聚合聚酯樹酯之粘度 特性圖。 第三圖為本發明較佳實施例之一連續生產製程示意圖 • 【主要元件符號說明】 (51) 聚酯樹酯薄膜 (52) 聚酯纖維布 (6 0)加熱滾輪組 (70)冷卻手段 (80)收料捲軸 15C and 185 <: [Tang Shi, & Beijing Institute of Fashion Master's Thesis I ^ U03] 〇 & Additives (four) points of the impact of the material (four) materials are slightly different, if the addition of inorganic particles such as dioxide in PET夕(6)〇2) or Dioxin (10)2) Lu inorganic particles can destroy the regularity of the arrangement of the molecules of the polys, but different inorganic; the nucleation of the nucleus is different, some hinder, some The promotion role 'looks at the amount of addition, and the melting point decreases with the increase of inorganic component content [Ma Quanqiang, 21 '5, Synthesis Technology and Application, 2006]. In addition, the addition of a plasticizer (Plastjcjzer) is to add a compatible low molecular weight plasticizer or solvent to the polymer, the polymer molecules can attract these low molecular substances to produce a more irregular structure, in order to lower the melting point, commonly used Plasticizers such as glycerol, arsenic trioxide, sodium citrate, etc., but because of the poor thermal stability of the plasticizer during the process of mixing, it is easy to dissipate due to volatilization or cracking due to high temperature, thus low temperature The effect of the modification is not stable. The blending method refers to the physical modification of the polyester, that is, the addition of an auxiliary agent or other components to the polyester substrate, and the addition of a low molecular auxiliary or a low molecular weight oligomer to the pET melt also causes the melting point of the PET. reduce. For example, in the polyester melt, 'adding a low molecular flame retardant or a flame retardant system, the melting point of the polyester is generally lowered by 1 〇 ° C ~ 20 C [Luo Hailin, Zhejiang University of Technology, Master's thesis, 2〇〇5], which is due to The low molecular additive is uniformly mixed with the PET melt and then quenched by quenching. The segment is cooled and knotted to become amorphous. When the temperature is slowly increased to the glass transition temperature of 201117951 (Tg), the chain begins to move, and the molecular chain is near the crystallization temperature. Will enter the crystal lattice, at this time due to the presence of low molecular substances, the lattice defects increase, the crystal is imperfect to increase, and thus the melting point of PET. The blending method currently studies more of the melting point degradation behavior of PET/PBT blends. In a compatible polymer solution, if one of the components can be crystallized, the decrease in the melting point can be observed. PBT is a homologue of PET. The two are identical in amorphous form. They are crystalline linear saturated polyester. The molecular chain of PBT is more than two methylene groups than PET. Its melting point and glass transition temperature are lower than PET, so pbt molecule Chain and segment activity is stronger than PET, and its crystallization rate is 1 time faster than PET. As described above, there are many ways to reduce the polyester base material or the resin, and the working temperature window can be formed by the temperature range in which the polyester base material and the polyester fiber have a melting point by the above-described manner. The modified ρ resin used in this embodiment is modified by copolymerization to obtain a PET copolymer, and the original melting point is lowered from 265 〇C of the general PET resin to 197.071 of the modified PET resin used, and the modification is carried out. Post PET was used as the resin substrate of this example. The second figure lists the characteristics of the modified polyester resin, showing that the modified polyester tree fat can reach a melting point of about 200 degrees, and its flow temperature can be lowered from 22 〇 < t to a low viscosity of 100 Pa.s. . (3) When the resin is modified to lower the melting point, the modified polyester resin is formed into a sheet shape. The molding may be carried out by heating the polyester resin in a flowing state and then placing it on a mold or a machine platform to cool it to form a sheet-like polyester resin as the polyester substrate of the present embodiment. Step 2: Laminating heat to form a single-layered all-polyester composite material "2") After laminating the sheet-like polyester resin above the sheet with more than one heat-set polyester fiber cloth, a hot pressing method is used. The heating and pressurization causes the polyester 201117951 resin to form a flowing state, and then the polyester resin is caused to flow into the mesh pores between the polyester fiber cloths to form a single-layer full-polymerization material. Step 3. Lamination (30> After laminating a plurality of single-layered full-polyester composite materials, the polyester resin of the single-layered all-polyester composite material of each layer is flowed by the above-mentioned hot pressing method, and is heated. After the pressure is lowered, a laminated polyester sheet is formed. Step 4. Product manufacturing (40) According to the specifications of the manufactured product, the thickness and the number of layers can be selected. • The laminated polyester sheet is coated with a hot stamping. The method is formed into a full-polyester finished product with a curved surface. The product application development example is a special function hard sole, which utilizes the light and tough characteristics of the full-poly vine self-reinforced composite material to replace the currently used glass fiber composite material. This shoe has the function of rigid sole support. What's more important is that the use of low-density polyester fiber instead of high-density glass fiber can achieve weight reduction. In addition, thermoplastic composite is fast and simple. The processing characteristics are more helpful to improve the production efficiency of this product; from the simple and thin 'approximate flat plate' of the finished product, it is possible to choose the raw material for film stacking directly into the mold. Compared with the current commercialized self-reinforced materials such as CurV (B, the sole material made of the all-polyester self-reinforced composite material in this embodiment has excellent heterogeneous bonding compatibility, so it is easier for the manufacturer to manufacture. Processing, great process and manufacturing cost. Because this sole material needs to be bonded with other shoe materials to combine a complete sole, due to the poor adhesion of non-polar pp materials, it often leads to adhesive failure, even When the sole is shot, the degumming phenomenon occurs. Therefore, the all-polyester self-reinforcing composite material of the present embodiment has the polarity of the heterogeneous adhesive property of Table 12 『201117951, which can effectively overcome the processing adhesion problem. In the process temperature and time In terms of control, as shown in the first figure, the hot-press forming of the polyester fiber cloth and the single-layer all-polyester composite material are carried out in a relatively high-temperature and short-time manner, for example, assuming that The material is given a working temperature window between 210 and 235 ° C, and the temperature and time for heat setting can be set at 235 ° C for 1 min. Hot-forming and heat-forming of single-layered all-polyester composites, the temperature and time parameters required for the lamination step are relatively low temperature and long time, such as 215 ° C, 2-6 min. It only needs to soften the polyester resin of the laminated all-polyester composite material, so the required processing temperature is the lowest, about 150 to 200 ° C. The aforementioned temperature and time parameters can be matched. Select polyester fiber cloth and polyester resin with different characteristics and may change slightly. Table 1 code impact strength (J/m) tensile modulus (Mpa) tensile strength (Mpa) bending modulus (Mpa) bending Strong number (Mpa) Homogeneous PET 13_5±1_6 1873±64 20.48±7.05 2010±101 54.6±2.7 BB15-6 647.5±35.9 3218±67 84.92±6.26 4400±126 73.4±2.5 BB25-3 448.2±28.6 3263±42 75.52 ±2.06 4514±18 72_4±0_7 BB25-6 360.5±28.8 3316±159 73.55±2.78 4441±154 72.5±2.0 BB25-10 4〇5.0±69.4 3402±66 95.50士4.47 4299±204 71.2±1.0 BB35-6 531.1 ±53.5 3416±79 66.13±2.82 4650±94 78.0±2.7 In terms of results, this embodiment is based on the aforementioned steps To complete the whole measuring mechanical properties of the polyester-composite sheet of the laminate results in Table a plurality. The results show that the composite material provided by the present embodiment has excellent mechanical properties of 13 201117951 compared with the homogeneous polyester sheet. The tensile, bending and impact resistance properties of the composite material are extremely improved, especially the impact strength can be improved up to 647.5. Above J/m, it is up to 6 times higher than pure PET (homogeneous PET). In addition, the present embodiment employs a PET fiber cloth, and the PET fiber cloth can selectively recycle PET as a material source, thereby further saving material cost and achieving environmental protection. In addition, the combination of pE and pET fiber is recovered as a material whose performance is degraded, poor in thermal performance and fast in flow, and the other is a material which is highly oriented and highly crystalline, and the material of the present embodiment is ΡΕτ. The differentiated combination provides an effective and wider processing window, which is more helpful for manufacturing convenience. Further, the sheet-like polyester resin can be produced not only by the prior art, but also by a slight improvement in a continuously production form. As shown in the third figure, the copolymerized modified polyester resin is first formed into a continuous polyester resin film (51), and the polyester resin film (51) is continuously continuous with a hot rolling method. The polyester fiber cloth (52) is laminated and combined with hot melt pressing, wherein the so-called hot rolling method is to roll the polyester resin film (51) and the polyester fiber cloth (52) together into one. In the heating roller group (60), the high temperature and the south pressure of the heating roller group (60) first melt the polyester resin film (51) into a melt flow and then press it into the polyester fiber cloth (52) to form The output of a continuous type of all-polyester composite sheet. The continuous all-polyester composite sheet outputted by the hot-pressing roller set (60) is subjected to a cooling means (70), and is continuously wound up by a receiving reel (80) to complete the pressed all-polyester composite material. In the sheet, the cooling means (7 〇) may be a cold air generating device, a nitrogen cooling device, or the like. Therefore, the process of the whole polyester composite material proposed in the present embodiment can achieve a large amount and rapid mass production, breaking the limitation of mass production of the conventional technology. 201117951 [Simplified description of the drawings] The first figure is a schematic flow chart of a preferred embodiment of the present invention. The second figure is a graph showing the viscosity characteristics of the copolymerized polyester resin of the preferred embodiment of the present invention. The third drawing is a schematic diagram of a continuous production process according to a preferred embodiment of the present invention. [Description of main components] (51) Polyester resin film (52) Polyester fiber cloth (60) Heating roller set (70) Cooling means (80) Receiving reel 15