201109148 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種環保型發泡複合鞋材及其製備 方法，特別是有關於一種利用乙烯-醋酸乙烯共聚物、聚 己内酯及玉米殿粉來製備之方法。 【先前技術】201109148 VI. Description of the Invention: [Technical Field] The invention relates to an environment-friendly foam composite shoe material and a preparation method thereof, in particular to an ethylene-vinyl acetate copolymer, polycaprolactone and corn The method of preparing the temple powder. [Prior Art]
目前，塑膠具有價格低廉、質量輕、性質優異及加 工容易的優點，使得塑膠已經成為人類日常生活上不可 或缺的材料，主要的產品包括聚氣乙烯（pvc)、聚乙烯 (PE)、聚丙烯（PP)、聚苯乙烯(ps)、聚酯、尼龍和其他工 程塑膠等。 這些塑膠製品帶來人們生活上許多便利和舒適，但 是塑膠不像鐵、木材、紙張等材f在土射會腐钱、分 解。大部分的塑膠都極為安定’經過相當長的時間也不 會分解，不管是在陸地上或海洋上，都已形成嚴重的環 保問題’其中，錢有光分解性塑膠及部分生物可 性塑膠被研發出來。 另外，塑膠應用在鞋底材質方面，大都是以橡膠之 材質製成’而利用橡膠製成之鞋子，其回收過程複雜， 回收成本高，絕大部份讓其自然老化，但分解時間很長， 造成垃圾掩埋之困擾，如作為廢棄物以焚燒處理，亦衍 生各種空氣5染之間題。因此大部分的鞋子在不堪使用 時就會丢棄’因而對環境造成破壞與垃圾量的增加。 此外，亦有利用完全可分解性塑膠做為鞋材，但苴 年内；乎完全分解，但-般鞋子之使用壽命常； ^ ，可兀全生物分解性塑膠的分解可能造成鞋子結 201109148 構上的缺陷，導致無法使用而造成浪費。 因此如何製作出對環境不造成影響之鞋材，且能避 免垃圾量增加之問題，並能兼顧耐用性，實是一個亟待 解決的問題。 有鑑於習知技藝之各項問題，為了能夠兼顧解決 之，本發明人基於多年研究開發與諸多實務經驗，提出 一種環保型發泡複合鞋材及其製備方法，以作為改善上 述缺點之實現方式與依據。 【發明内容】 有鑑於此，本發明之目的就是在提供一種環保型發 泡複合鞋材及其製備方法，以解決前述橡膠鞋材無法回 收對環境造成破壞、造成垃圾量增加及耐用性不佳之問 題。 本發明之環保型發泡複合鞋材，其包含有： 乙烯-醋酸乙烯共聚物（Ethylene-Vinyl Acetate Copolymers，E.V.A.)，此乙稀-醋酸乙稀共聚物之重量係 佔複合鞋材之重量65wt%〜85wt% ; 聚己内酯，此聚己内酯之重量係佔複合鞋材之重量 15wt%〜35wt% ; 有機填充物，此有機填充物之重量係佔複合鞋材之 重量 10wt%〜25wt% ; 發泡助劑，此發泡助劑之重量係佔複合鞋材之重量 0.5wt%〜1.5wt% ; 分散劑，此分散劑之重量係佔複合鞋材之重量 4wt%〜7wt% ;以及 201109148 之重 硬脂酸st，此硬脂酸ST之重量係佔複合 量 0.6wt%〜l.Owt%。 此外，本發明更提出一種環保型發泡複合鞋材 備方法，步驟為先添加硬脂酸ST於乙烯-醋酸乙此 物及聚己内醋之混練過程中以得一合成樹脂，利二= 劑使有機填充物進行改質程序，再與合成樹脂混合均^ 以得一混合物，利用發泡助劑使混合物進行發泡 最^，固化成型後即得環保型發泡複合鞋材之母粒或成 型品。 兹為使貴審查委員對本發明之技術特徵及所 之功效有更進-步之瞭解與認識，謹佐以較佳 及配合詳細之說明如後。 【實施方式】 以下將參照相關式，說明依本發日驗佳實施例之 φ環保型發泡複合㈣及其製備方法，為使便於理解，下 述實施例中之相同元件係以相同之符號標示來說明。 凊參閲第1圖，其係為本發明之環保型發泡複合鞋 ^備方法之步驟流程圖。圖中，此方法將以下列步驟 步驟S1:添加硬脂酸ST於乙烯-醋酸乙烯共聚物及 聚己内酯之混練過程中以得一合成樹脂。 其中’乙烯-醋酸乙烯共聚物中之醋酸乙烯（Vinyl 201109148At present, plastics have the advantages of low price, light weight, excellent properties and easy processing, making plastics an indispensable material in daily life. The main products include polystyrene (PVC), polyethylene (PE), and poly. Propylene (PP), polystyrene (ps), polyester, nylon and other engineering plastics. These plastic products bring a lot of convenience and comfort to people's lives, but plastics do not like iron, wood, paper and other materials. Most of the plastics are extremely stable. After a long period of time, they will not decompose. Whether on land or in the sea, serious environmental problems have been formed. Among them, money has photodegradable plastics and some bio-plastics have been Developed. In addition, the application of plastic in the sole material is mostly made of rubber material, and the shoes made of rubber have complicated recycling process and high recycling cost. Most of them are naturally aged, but the decomposition time is long. Caused by the problem of landfill, such as waste treatment by incineration, also derived from various air 5 dyeing issues. Therefore, most of the shoes will be discarded when they are unusable, thus causing damage to the environment and an increase in the amount of garbage. In addition, there is also the use of fully decomposable plastic as a shoe material, but in the next year; it is completely decomposed, but the life of the shoes is often; ^, the decomposition of the whole biodegradable plastic may cause the shoe knot 201109148 Defects that cause unusable and waste. Therefore, how to make a shoe material that does not affect the environment, and to avoid the problem of increasing the amount of garbage, and to take into account durability, is an urgent problem to be solved. In view of the problems of the prior art, in order to be able to solve the problem, the inventors have proposed an environmentally-friendly foam composite shoe material and a preparation method thereof based on years of research and development and many practical experiences, as an implementation method for improving the above disadvantages. And basis. SUMMARY OF THE INVENTION In view of the above, the object of the present invention is to provide an environment-friendly foam composite shoe material and a preparation method thereof, so as to solve the problem that the rubber shoe material cannot be recovered and the environment is damaged, the amount of garbage is increased, and the durability is poor. problem. The environment-friendly foam composite shoe material of the invention comprises: Ethylene-Vinyl Acetate Copolymers (EVA), and the weight of the ethylene-vinyl acetate copolymer accounts for 65wt of the weight of the composite shoe material. %〜85wt%; polycaprolactone, the weight of the polycaprolactone accounts for 15wt%~35wt% of the weight of the composite shoe material; the organic filler, the weight of the organic filler accounts for 10wt% of the weight of the composite shoe material~ 25wt%; foaming aid, the weight of the foaming aid is 0.5wt%~1.5wt% of the weight of the composite shoe material; the dispersing agent, the weight of the dispersing agent is 4wt%~7wt% of the weight of the composite shoe material And the heavy stearic acid st of 201109148, the weight of the stearic acid ST is 0.6% by weight to 1.0% by weight of the compound. In addition, the present invention further provides an environmentally-friendly foaming composite shoe material preparation method, the first step is to add stearic acid ST in the process of mixing ethylene-acetic acid B and poly-caprol vinegar to obtain a synthetic resin, Li 2 = The organic filler is subjected to a modification procedure, and then mixed with the synthetic resin to obtain a mixture, and the mixture is foamed by the foaming assistant, and the masterbatch of the environmentally-friendly foam composite shoe material is obtained after the solidification molding. Or molded products. In order to give your reviewers a better understanding and understanding of the technical features and effects of the present invention, please refer to the better and detailed descriptions. [Embodiment] Hereinafter, the φ environment-friendly foam composite (IV) according to the present embodiment will be described with reference to the relevant formula, and a preparation method thereof. For the sake of easy understanding, the same components in the following embodiments have the same symbols. Mark to illustrate. Referring to Fig. 1, it is a flow chart of the steps of the environmentally friendly foam composite shoe preparation method of the present invention. In the figure, the method will be as follows: Step S1: Adding stearic acid ST to a mixing process of ethylene-vinyl acetate copolymer and polycaprolactone to obtain a synthetic resin. Among them, vinyl acetate in ethylene-vinyl acetate copolymer (Vinyl 201109148)
Acetate，V.A.)含量範圍為 16wt%〜26wt%。 其中，混練程序更可利用布斯混合器、萬馬力混合 器、雙螺桿押出機、力拿混合器、加壓混合器、滾輪或 反應槽等之混練器具。 步驟S2 :利用分散劑使有機填充物進行改質程序， 再與合成樹脂混合均勻以得一混合物。 其中，改質程序係利用分散劑接枝有機填充物以使 有機填充物與乙烯-醋酸乙烯共聚物及聚己内酯之相容性 提南。 而有機填充物係可為植物性澱粉，其可為玉米澱粉 來實施。而分散劑可為丙浠酸。 此外，乙烯-醋酸乙烯共聚物亦可以聚乙烯醇 (PolyVinyl Alcohol, P.V.A.)來實施。 其中，硬脂酸ST係可為一具有親水端及疏水端特性 之化合物，而由於有機填充物具有親水性，硬脂酸ST之 親水端係可接枝於有機填充物，而合成樹脂具有舒水 性，硬脂酸ST之疏水端係可接枝於合成樹脂。 步驟S3 :利用發泡助劑使混合物進行發泡程序。 而發泡助劑可為交聯劑（AK-3)。 其中，發泡程序可為物理發泡、化學押出發泡、吹 出成型發泡、射出成型發泡及旋轉成型發泡。 步驟S4 :固化成型後即得環保型發泡複合鞋材之母 粒或成型品。 其中，此環保型發泡複合鞋材包含有： 201109148 乙稀-醋酸乙稀共聚物（Ethylene-Vinyl Acetate Copolymers, E.V.A.)，此乙烯-醋酸乙烯共聚物之重量係 佔複合鞋材之重量65wt%〜85wt% ; 聚己内酯，此聚己内酯之重量係佔複合鞋材之重量 15wt%〜35wt%; 有機填充物，此有機填充物之重量係佔複合鞋材之 重量 10wt%〜25wt% ; 發泡助劑，此發泡助劑之重量係佔複合鞋材之重i 0.5wt%〜1.5wt% ; 分散劑，此分散劑之重量係佔複合鞋材之重旦 4wt%~7wt% ;以及 硬脂酸ST，此硬脂酸ST之重量係佔複合鞋材之重 量 0.6wt%〜l.Owt%。 本發明之環保型發泡複合鞋材在一對複材之&彳生 試中，利用對環境及人體均無毒無害之乙烯-醋酸乙 2 聚物（E.V.A.)以及混練可完全分解之聚己内g旨及—、 入· 有機: 填充物以玉米澱粉來實施，而分散劑以丙締酸來實施， 相容劑則以交聯劑AK-3來實施，利用分散技術及添力3相 容劑來使上述組成能均勻混合，添加同時含親水$ 水端之化合物可使親水性的有機填充物能與疏水性# ^ 膠能有較佳之相容性，本發明以硬脂酸ST來實施，纟里^ 對添加不同含量的相容劑或分散劑的研究發j見相容^ ^由 分散劑及發泡助劑之間的含量必須恰當落在特$ ^ ' 内，才可以使本發明之複合鞋材達到較高之發、;包^率 201109148 上述所製得之材料在本發明之含量範圍中的三組實 施例之成份含量表如下： 成份 成份之含量(％) 實施例一 實施例二 實施例三 EVA 75 82 75 聚己内酯 25 18 24 玉米澱粉 18 18 15 硬脂酸ST 1.2 1.2 1.2 交聯劑AK-3 1 1.2 1.2 丙烯酸 6 6 6 TOTAL 126.2 126.4 123.4 上表中實施例一及實施例二以EVA及聚己内酯之含 量不同，而實施例一及實施例三則以添加玉米澱粉及交 聯劑AK-3含量不同來做比較。 201109148 而在經由相同發泡條件下，將此三組實施例之混合物 進行發泡程序後，之後便使用射出機及進行ASTM標準試 片之射出試片，之後進行各項物性測試，測試結果如下 表： 性質 測試結果 第一組 第二組 第三組 標準值 硬度(Asker C) 55 56 55 55 士 3 比重(g/cm2) 0.206 0.201 0.203 0.2±0.03 彈性(％) 53 47 46 40(min) 壓縮率(％) 55.3 58.2 59.1 60 (max) 剝離強度(N/cm) 27.2 28.5 28.8 27(min) 抗拉強度(Mpa) 2.2 2.62 2.73 2(min) 而在與業界對鞋材物性之公開標準值比較中，硬度 之標準值為52〜58 Asker C，而三組實施例之硬度測試結 果均落在標準值範圍中。 比重之標準值為0.17〜0.23 g/cm3,三組實施例之比重 測試結果亦均落在標準值範圍中。 參 彈性之最低標準值需為40%，而三組實施例之彈性測 試結果分別為53%、47%及46%，均高於最低標準值。 壓縮率之最高標準值為6 0 %，三組實施例之壓縮率測 試結果分別為55.3%、58.2%及59.1%，均低於最高標準值。 剝離強度之最低標準值為27 N/cm，三組實施例之剝 離強度測試結果分別為27.2 N/cm、28.5 N/cm及28.8 N/cm，均高於最低標準值。 抗拉強度之最低標準值為2 Mpa，三組實施例之抗拉 強度測試結果分別為2.2 Mpa、2.62 Mpa及2.73 Mpa，均 高於最低標準值。 201109148 綜上所述，本發明夕pa & 的三組實施例之物‘ 泡複合鞋材含量範圍t 之特性，而玉米塑膠，對人體有無毒無害 = : =作=材料亦可降低成本，所 可一可自 離本舉例性’而非為限制性者。任何未脫 之精神與範.，而對其 更，均應包含於後附之中請專利範圍中。 201109148 【圖式簡單說明】 ' 第1圖係為本發明之環保型發泡複合鞋材之製備方法之 步驟流程圖。 【主要元件符號說明】 S1〜S4 :步驟流程。The content of Acetate, V.A.) ranges from 16 wt% to 26 wt%. Among them, the kneading program can utilize a mixing device such as a Buss mixer, a 10,000-horse mixer, a twin-screw extruder, a force mixer, a pressure mixer, a roller or a reaction tank. Step S2: The organic filler is subjected to a upgrading procedure using a dispersing agent, and then uniformly mixed with the synthetic resin to obtain a mixture. Among them, the upgrading procedure is to graft the organic filler with a dispersing agent to make the compatibility of the organic filler with the ethylene-vinyl acetate copolymer and the polycaprolactone. The organic filler may be a vegetable starch which may be carried out as corn starch. The dispersing agent can be propionic acid. Further, the ethylene-vinyl acetate copolymer can also be carried out by polyvinyl alcohol (PolyVinyl Alcohol, P.V.A.). Wherein, the stearic acid ST system can be a compound having a hydrophilic end and a hydrophobic end characteristic, and since the organic filler has hydrophilicity, the hydrophilic end of the stearic acid ST can be grafted to the organic filler, and the synthetic resin has a comfortable The aqueous, stearic acid ST hydrophobic end can be grafted to a synthetic resin. Step S3: The mixture is subjected to a foaming process using a foaming aid. The foaming aid may be a crosslinking agent (AK-3). Among them, the foaming process may be physical foaming, chemical extrusion foaming, blow molding foaming, injection molding foaming, and rotational molding foaming. Step S4: After solidification molding, the mother material or molded product of the environmentally-friendly foam composite shoe material is obtained. Among them, the environmentally-friendly foam composite shoe material comprises: 201109148 Ethylene-Vinyl Acetate Copolymers (EVA), the weight of the ethylene-vinyl acetate copolymer accounts for 65 wt% of the weight of the composite shoe material. ~85wt%; polycaprolactone, the weight of the polycaprolactone accounts for 15wt%~35wt% of the weight of the composite shoe material; the organic filler, the weight of the organic filler accounts for 10wt%~25wt of the weight of the composite shoe material %; foaming aid, the weight of the foaming aid is 0.5 to 5% by weight of the composite shoe material; dispersing agent, the weight of the dispersing agent is 4wt% to 7wt of the weight of the composite shoe material And stearic acid ST, the weight of the stearic acid ST is 0.6% by weight to 1.0% by weight of the composite shoe material. The environmentally-friendly foamed composite shoe material of the present invention utilizes ethylene-acetic acid ethylene glycol (EVA) which is non-toxic and harmless to the environment and the human body, and the self-disintegration which can be completely decomposed in a pair of composite materials & Ingredients: -, organic: the filling is carried out with corn starch, the dispersing agent is carried out with propionic acid, and the compatibilizing agent is carried out with the cross-linking agent AK-3, using dispersion technology and adding 3 phases The agent can uniformly mix the above components, and the compound containing the hydrophilic water at the same time can make the hydrophilic organic filler have better compatibility with the hydrophobic rubber. The present invention uses stearic acid ST. Implementation, 纟里^ For the study of adding different levels of compatibilizers or dispersants, the compatibility between the dispersant and the foaming auxiliaries must be properly within the special ^^'. The composite shoe material of the invention achieves higher hair; the compounding rate 201109148 The content of the components of the three groups of the materials prepared in the above-mentioned content range is as follows: Content of the component (%) Example Embodiment 2 Embodiment 3 EVA 75 82 75 Polycaprolactone 25 18 24 Cornstarch 18 18 15 Stearic acid ST 1.2 1.2 1.2 Crosslinker AK-3 1 1.2 1.2 Acrylic 6 6 6 TOTAL 126.2 126.4 123.4 In the above table, Example 1 and Example 2 differ in the content of EVA and polycaprolactone. In the first embodiment and the third embodiment, the content of the corn starch and the cross-linking agent AK-3 are compared for comparison. 201109148 After the foaming process of the mixture of the three groups of examples was carried out under the same foaming conditions, the injection tester and the test piece of the ASTM standard test piece were used, and then the physical properties test was carried out, and the test results were as follows: Table: Property test results Group 1 Group 2 Group 3 Standard value hardness (Asker C) 55 56 55 55 ± 3 Specific gravity (g/cm2) 0.206 0.201 0.203 0.2 ± 0.03 Elasticity (%) 53 47 46 40 (min) Compression ratio (%) 55.3 58.2 59.1 60 (max) Peel strength (N/cm) 27.2 28.5 28.8 27 (min) Tensile strength (Mpa) 2.2 2.62 2.73 2 (min) and in the industry open standards for the physical properties of shoe materials In the value comparison, the standard value of hardness is 52 to 58 Asker C, and the hardness test results of the three sets of examples all fall within the standard value range. The specific gravity of the specific gravity is 0.17~0.23 g/cm3, and the test results of the three groups of examples also fall within the standard value range. The minimum standard value of the participation elasticity is 40%, and the elastic test results of the three sets of examples are 53%, 47% and 46%, respectively, which are higher than the minimum standard value. The highest standard value of compression ratio is 60%, and the compression ratio test results of the three groups of examples are 55.3%, 58.2%, and 59.1%, respectively, which are lower than the highest standard value. The minimum standard value of peel strength was 27 N/cm, and the peeling strength test results of the three groups of examples were 27.2 N/cm, 28.5 N/cm, and 28.8 N/cm, respectively, both higher than the minimum standard value. The minimum standard value of tensile strength is 2 Mpa, and the tensile strength test results of the three sets of examples are 2.2 Mpa, 2.62 Mpa and 2.73 Mpa, respectively, which are higher than the minimum standard value. 201109148 In summary, the three sets of embodiments of the present invention are characterized by the content of the composite material of the foam composite shoe material, and the corn plastic is non-toxic and harmless to the human body = : = = = material can also reduce costs, It is to be understood that the invention is not intended to be limiting. Any spirit and scope that are not removed, and more, should be included in the scope of the patents attached. 201109148 [Simple description of the drawings] 'The first figure is a flow chart of the steps for preparing the environmentally-friendly foam composite shoe material of the present invention. [Description of main component symbols] S1~S4: Step flow.
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