593536 五、發明說明（1 ) 技術領域 本發明係關於特定樹脂構成之樹脂組成物，尤指由聚己 內酯和聚乙烯醇構成之樹脂組成物，特定是適於男鞋、女 鞋、童鞋、長靴、運動鞋、休閒鞋、涼鞋、拖鞋等各種鞋 類製造所用前芯、月形芯等鞋類用芯材之樹脂組成物。 背景技術593536 5. Description of the invention (1) Technical Field The present invention relates to a resin composition composed of a specific resin, especially a resin composition composed of polycaprolactone and polyvinyl alcohol, and is particularly suitable for men's shoes, women's shoes, and children's shoes. , Long boots, sports shoes, casual shoes, sandals, slippers and other footwear manufacturing cores used in the core material of the resin composition. Background technique
向來鞋用芯材之使用，旨在對鞋尖和鞋跟部份等賦予保 形性，係將飽浸熱塑性樹脂的織布或不織布，黏著於鞋尖 和鞋跟部份內側使用。Conventionally, the core material for shoes is used to give shape retention to the toe and heel parts. It is a woven or non-woven fabric impregnated with thermoplastic resin, which is adhered to the inside of the toe and heel parts.
向來鞋的芯材，以對鞋的黏著方法言，可分成幾類。第 一類，以溶劑將芯材再活化（在發明中，活化指可以黏着） 而黏著於鞋的預定部位，有例如織布或不織布飽浸於聚乙 烯乳化液、乙烯•丙烯酸共聚合乳化液等熱塑性樹脂乳化 液，經乾燥凝固成片狀。第二類，係利用黏著劑把芯材黏 著於鞋之方法，例如將第一類所用之組成片材，以天然膠 乳形之黏着劑加以黏着。第三類，利用熱再活化把芯材黏 著於鞋之方法，例如在上述組成和方法所製成片材上，以 乙烯•乙酸乙烯酯共聚物系熱熔黏著劑，或以聚己酯爲主 體之熱塑性樹脂組成物，與織布或不織布構成之片材，利 用熱再活化而黏著於鞋。例如特開昭5 6 - 1 4 8 3 0 1號公報記 載重量平均分子量爲1 0,00 0至200,000之聚己內酯爲主體 之鞋用熱塑性芯材。 前述各類鞋用芯材，均留有尙未解決的問題。首先，第 一類芯材及其黏著方法，成本低且黏著時的作業性良好， 五、發明說明（2) 但因黏著時使用有機溶劑，使製鞋步驟之作業環境有問題 和失火等之虞，不合時代要求。第二類的黏著方法，因使 用黏著劑把芯材黏著鞋，增加作業工時，使作業性惡化， 爲其最大困難。第三類的芯材和黏著方法，係藉熱再活化 把芯材黏著於鞋，具備不用有機溶劑，使作業性更優等益 處。可是’此類所用芯材之製造，必須有對織布等飽浸苯 乙烯乳化液等熱塑性樹脂加以乾燥凝固之步驟，以及塗佈 以乙烯•乙酸乙烯酯爲主成份的黏著劑之步驟，以致有製 造成本增加之缺點。此外，在織布或不織布上，係塗佈熱 熔性黏著劑之構造，將切斷面刨削加工時，未塗佈熱熔性 黏著劑的一面有出現黏著面的缺點。又，以聚己內酯爲主 體的熱塑性樹脂組成物與織布或不織布構成的芯材，因熱 塑性樹脂組成物中的增量劑或補強劑係使用聚氯乙烯樹脂 ，故不要的鞋焚燒時，會有發生戴奧辛的問題。 發明槪沭 本發明之目的，在於提供一種樹脂組成物，黏著時不需 有機溶劑，利用熱再活化即可黏著成爲鞋類用芯材（以下 簡稱芯材），且以單一步驟即可製成。又，提供一種樹脂 組成物，即使經刨削加工，新的面不需塗黏著劑，芯材的 黏着面全體藉熱再活化即可黏着，成爲鞋類用芯材，而且 使用後要焚燒時，由於成形體構成組成份，不會發生戴奧 辛。 本發明人等發現在聚己內酯基質中，具有特定粒徑的聚 乙烯醇呈粉粒狀分散之樹脂組成物，及由此成形所得芯材 -4- 593536 五、發明說明（3) ，可以解決上述問題，而完成本發明。 即，本發明第1是提供一種樹脂組成物，係由25〜95 重量％的聚己內酯（A)和5〜75重量％的聚乙烯醇（B)((A)和 (B)合計爲1〇〇重量％)構成’其中該聚乙烯醇（B)以粒徑 2mm以下之粉粒狀分散於聚己內酯（A)基質內者。 本發明第2是提供本發明第1項之樹脂組成物，其中聚 己內醋（A)之數量平均分子量爲1〇,〇〇〇〜150,000者。 本發明第3是提供本發明第1或2項樹脂組成物之製法 ，其中將25〜95重量％的聚己內酯（A)和5〜75重量％的 粒徑2mm以下的粉粒狀聚乙烯醇（B)((A)和（B)合計爲100 重量％)之混合物，於該聚己內酯（A)之熔點以上及該聚乙 烯醇（B)熔點以下之溫度加以捏合者。 本發明第4是提供本發明第3項樹脂組成物之製法，其 中捏合溫度爲80〜200°C者。 本發明第5是提供一種鞋類用芯材，係由本發明第1或 2項之樹脂組成物所成形者。 較佳具體例之詳細說明 茲說明本發明具體例如下。 本發明所用聚己內酯（以下簡稱PCL)(A)，在本發明樹脂 組成物中，基於與後述聚己內酯（以下簡稱PVA)(B)合計 1 0 0重量％，含2 5〜9 5重量％，以3 0〜7 0重量％範圍爲佳 。PCL(A)比率在25重量％以下時，若用作芯材用之成形 體時’無法藉熱再活化獲得充分黏著性。而P C L (A )比率 超過95重量％時，作爲芯材之保形性無法令人滿意，且The core material of shoes has been classified into several types by the method of adhering to shoes. In the first category, the core material is reactivated with a solvent (in the invention, the activation means can be adhered) and adheres to a predetermined part of the shoe. For example, woven or non-woven cloth is saturated with polyethylene emulsion and ethylene-acrylic copolymer emulsion. The thermoplastic resin emulsion is dried and solidified into a sheet. The second type is a method for adhering a core material to a shoe by using an adhesive. For example, the component sheet used in the first type is adhered with a natural latex-shaped adhesive. The third type is the method of using thermal reactivation to adhere the core material to the shoe. For example, on the sheet made of the above composition and method, an ethylene-vinyl acetate copolymer-based hot-melt adhesive or polyhexyl ester is used The thermoplastic resin composition of the main body and a sheet made of woven or non-woven fabric are re-activated by heat to adhere to the shoe. For example, Japanese Unexamined Patent Publication No. 5 6-1 4 8 3 0 1 discloses a thermoplastic core material for footwear mainly composed of polycaprolactone having a weight average molecular weight of 10,000 to 200,000. The aforementioned various types of core materials for shoes still have unresolved problems. First, the first type of core material and its adhesion method have low cost and good workability during adhesion. 5. Description of the invention (2) However, because of the use of organic solvents during adhesion, the working environment of the shoemaking step has problems and misfires. Yu, does not meet the requirements of the times. The second type of adhesion method is the most difficult because the core material is adhered to the shoe with an adhesive, which increases the working hours and deteriorates the workability. The third type of core material and adhesion method is the use of heat to reactivate the core material to adhere to the shoe. It has the advantage of no use of organic solvents and better workability. However, the manufacture of such core materials must include the steps of drying and solidifying thermoplastic resins such as woven fabrics impregnated with styrene emulsion, and the steps of applying an adhesive containing ethylene vinyl acetate as the main component, so that There are disadvantages of increased manufacturing costs. In addition, a woven fabric or a non-woven fabric has a structure in which a hot-melt adhesive is applied. When the cut surface is planed, there is a disadvantage that the side where the hot-melt adhesive is not applied has an adhesive surface. In addition, the core material composed of a thermoplastic resin composition mainly composed of polycaprolactone and a woven or non-woven fabric uses polyvinyl chloride resin as an extender or a reinforcing agent in the thermoplastic resin composition, so when unnecessary shoes are incinerated, There will be problems with dioxin. Invention 目的 The object of the present invention is to provide a resin composition that does not require an organic solvent during adhesion, and can be adhered to become a core material for footwear (hereinafter referred to as a core material) by heat reactivation, and can be made in a single step. . In addition, a resin composition is provided. Even after the planing process, the new surface does not need to be coated with an adhesive. The entire adhesive surface of the core material can be reactivated by heat and can be adhered to become a core material for footwear. Due to the composition of the formed body, dioxin does not occur. The present inventors have found that in a polycaprolactone matrix, a polyvinyl alcohol having a specific particle diameter is dispersed in a powdery and granular resin composition, and a core material obtained by molding -4- 593536 5. Description of the invention (3), The above problems can be solved and the present invention has been completed. That is, the first aspect of the present invention is to provide a resin composition comprising 25 to 95% by weight of polycaprolactone (A) and 5 to 75% by weight of polyvinyl alcohol (B) ((A) and (B) in total It is 100% by weight), wherein the polyvinyl alcohol (B) is dispersed in a polycaprolactone (A) matrix in a granular form with a particle diameter of 2 mm or less. The second aspect of the present invention provides the resin composition according to the first aspect of the present invention, wherein the number average molecular weight of the polycaprolactone (A) is 10,000 to 150,000. The third aspect of the present invention provides the method for producing the first or second resin composition of the present invention, wherein 25 to 95% by weight of polycaprolactone (A) and 5 to 75% by weight of powdery particles having a particle diameter of 2 mm or less are polymerized. A mixture of vinyl alcohol (B) ((A) and (B) in total 100% by weight)) is kneaded at a temperature above the melting point of the polycaprolactone (A) and below the melting point of the polyvinyl alcohol (B). The fourth aspect of the present invention provides a method for producing the third resin composition of the present invention, wherein the kneading temperature is 80 to 200 ° C. A fifth aspect of the present invention provides a core material for footwear, which is formed from the resin composition of the first or second aspect of the present invention. DETAILED DESCRIPTION OF THE PREFERRED SPECIFIC EXAMPLES Specific examples of the present invention will be described below. The polycaprolactone (hereinafter referred to as PCL) (A) used in the present invention, in the resin composition of the present invention, contains 100% by weight based on a total of 100% by weight with polycaprolactone (hereinafter referred to as PVA) (B) described later, and contains 25% to 95% by weight, preferably in the range of 30 to 70% by weight. When the PCL (A) ratio is 25% by weight or less, if it is used as a molded body for a core material, it cannot be reactivated by heat to obtain sufficient adhesion. When the P C L (A) ratio exceeds 95% by weight, the shape retention of the core material is not satisfactory, and
五、發明說明（4) 原料成本方面不利。 本發明樹脂組成物所用PCL(A)的數量平均分子量’就 本發明樹脂組成物作爲芯材時的耐屈曲性等觀點言，以 10,000 〜150,000 爲佳，而以 30,000 〜130,000 更好。若 PCL(A)的數量平均分子量超過1 50,000時，芯材用成形體 製造時之處理作業性等會惡化。 構成本發明樹脂組成物的PVA(B)，有通常合成纖維用 之PV A，薄膜用之粉粒狀PVA(均爲聚乙酸乙烯酯完全皂 化物），部份皂化物、特殊改質部份皂化物、或其混合物 。本發明樹脂組成物中，PVA(B)係以粒徑2mm以下的粉 粒狀分散於PCL(A)基質中，於樹脂組成物中基於前述 PCL(A)合計100重量％，必須含有5〜75重量％範圍。 PVA顆粒與其他高分子顆粒，例如聚氯乙烯或聚丙烯顆 粒相較，由於PVA本身分子構造，基質與：PCL具有適度 親和性，可安定分散，而且由此樹脂組成物所得芯材表面 存在的顆粒幾無脫落。而且利用捏合即可容易分散於PCL 基質中，一旦分散後，即未見顆粒再凝集。 於此，粉粒狀係粉粒狀製造時的原來狀態，或隨後經粉 碎、破碎、製粒、乾燥、篩選等操作產生的粉狀或粒狀， 即形狀不拘。當然，顆粒表面至少一部份熔化成帶有圓形 、球狀或其近似形態均可。又，「分散於PCL基質中」 係指，將所得樹脂組成物成形爲薄片，以透光目視觀察之 際，實.質上看不出顆粒的偏頗。 PVA(B)無法保持粒徑2mm以下粉粒狀的形狀時，不能 593536 五、發明說明（5)V. Description of the invention (4) The cost of raw materials is disadvantageous. The number-average molecular weight of PCL (A) used in the resin composition of the present invention is preferably 10,000 to 150,000, and more preferably 30,000 to 130,000 in terms of buckling resistance when the resin composition of the present invention is used as a core material. When the number-average molecular weight of PCL (A) exceeds 1 50,000, the workability and the like at the time of manufacturing the formed body for a core material are deteriorated. The PVA (B) constituting the resin composition of the present invention includes PV A for general synthetic fibers, and powdered and granular PVA for films (all are fully saponified by polyvinyl acetate), part of the saponification, and special modified parts Saponification, or mixtures thereof. In the resin composition of the present invention, PVA (B) is dispersed in a PCL (A) matrix as a powder having a particle diameter of 2 mm or less. The resin composition contains 100% by weight based on the aforementioned PCL (A), and must contain 5 to 5%. 75% by weight. Compared with other polymer particles, such as polyvinyl chloride or polypropylene particles, PVA particles have a moderate affinity with PCL due to the molecular structure of PVA itself, which can be stably dispersed, and the core material obtained from the resin composition is present on the surface of the core material. Few particles fall off. Moreover, it can be easily dispersed in the PCL matrix by kneading. Once dispersed, no re-aggregation of particles is seen. Here, the powder or granule is in the original state when the powder or granule is manufactured, or the powder or granule produced by operations such as crushing, crushing, granulating, drying, and screening, that is, the shape is not restrictive. Of course, at least a part of the surface of the particles can be melted to have a round shape, a spherical shape or an approximate shape. In addition, "dispersed in a PCL matrix" means that the obtained resin composition is formed into a thin sheet, and when observed with a light-transmitting visual observation, no particle bias is actually observed. When PVA (B) cannot maintain a powdery shape with a particle size of 2mm or less, it cannot be 593536 V. Description of the invention (5)
呈現本發明效果。即PCL(A)和微粒狀PVA(B)加熱混合時 ，若在PVA熔點以上混合，PVA(B)會熔化，與PCL(A)熔 態混拌，形成均勻熔體。此時，即使經冷卻，在組成物藉 目視看不出微粒狀PVA。形成如此樹脂組成物所得芯材， 利用熱再活化黏著於鞋預定部位時，黏著強度會降低。而 粉粒狀PVA(B)保持其形狀愈偏在於PCL中時，大多情形 無法滿足作爲芯材之保形性或機械強度，即時暫時滿足， 其參差亦大。而且利用熱再活化、黏著於鞋預定部位時， 黏著強度降低。樹脂組成物所含PVA(B)比率在5重量％ 以下時，作爲芯材用成形體的保形性或機械強度無法令人 滿足。又，PVA(B)比率超過75重量％時，由樹脂組成物 -成形所得材料，經熱再活化黏着於鞋之預定部位時的黏着 強度無法令人滿意。The effect of the present invention is exhibited. That is, when PCL (A) and particulate PVA (B) are heated and mixed, if they are mixed above the melting point of PVA, PVA (B) will melt and mix with PCL (A) in a molten state to form a homogeneous melt. At this time, even after cooling, particulate PVA was not visually recognized in the composition. When the core material obtained by forming such a resin composition is reactivated and adhered to a predetermined portion of a shoe by heat, the adhesion strength is reduced. When the powder and granular PVA (B) keeps its shape more in the PCL, in most cases, it cannot meet the shape retention or mechanical strength of the core material, and it is satisfied temporarily and its variation is also large. In addition, when it is reactivated by heat and adheres to a predetermined part of a shoe, the adhesive strength is reduced. When the ratio of PVA (B) contained in the resin composition is 5% by weight or less, the shape retention or mechanical strength as a molded article for a core material cannot be satisfied. In addition, when the PVA (B) ratio exceeds 75% by weight, the adhesion strength when the resin composition-molded material is re-activated and adhered to a predetermined portion of the shoe by heat is not satisfactory.
分散的PVA(B)顆粒粒徑在2mm以下，以1.5〜0.1mm 爲佳。PVA(B)粒徑比2mm大時，PVA顆粒會突出於芯材 I 的黏著表面，或PVA顆粒容易從芯材表面外露，所得芯 材經熱再活化黏著於鞋預定部位時，黏著強度會降低。 本發明樹脂組成物可視需要添加各種添加劑。此種添加 ί物雖無特別限制，惟例如作爲芯材的成形體利用熱再活化 黏著於靴的預定部位之際，爲調節開放時間，無妨添加少 量松香及其衍生物、萜烯化合物、烴系化合物、石蠟、低 分子量聚乙烯蠟。又，在樹脂組成物熱熔混合時或由所得 芯材熱熔加工時，或芯材藉熱再活化之際，爲提高熱安定 性，亦可添加少量抗氧化劑（氧化防止劑）。此外，爲改良 五、發明說明（6 ) 芯材的耐寒性、柔軟性、耐衝擊性、表面高度等目的，在 不妨碍本發明效果的範圍內，亦可隨意添加烯烴系樹脂、 苯乙烯系樹脂、胺酯系樹脂及酯系共聚物，或玻纖、玻粒 、碳酸鈣、硫酸鋇、氧化鈦、黏土、滑粉等塡料。 本發明樹脂組成物製造時，不必使用特定方法和裝置。 一般是將PCL九粒，粉粒狀PVA，再任意添加之添加劑 ’經加熱捏合成爲混拌物。可例如利用單軸或雙軸擠壓機 混拌，此時，爲了不使PVA(B)熔化，加熱捏合溫度必須 設定在PVA(B)熔點（軟化點）以下，PCL熔點以上，以80 〜2 00°C範圍爲佳。加熱捏合之前，亦可將本發明樹脂組 成物的構成原料預先乾拌。本發明樹脂組成物一旦成爲九 粒取出，或在樹脂組成物製造中接續投入芯材成形用片材 成形機或射出成形機，在PVA(B)熔點更低溫度，可得作· 爲芯材之成形體。 實施例 兹以實施例更具體說明本發明，惟本發明不受此等實施 例之限制。 實施例1〜1 0和比較例1〜4 製造表1所示組成份（捏合溫度以外，混配以重量份表 示）之樹脂組成物。此樹脂組成物是預先將各構成成份原 料按預定比率乾拌後，一次投入東洋精機公司製造之拿伯 卜拉司特軋機（混合部R-60)，在表1所示捏合溫度、捏合 轉數50rPm、捏合時間3分鐘的捏合條件捏合，得組成物 。除比較例1之外，捏合溫度均設定在比所用PV A熔點 五、發明說明（7) 低的溫度（l〇〇°C)。 將調製之組成物（實施例1〜1 〇和比較例1〜4)，於加熱 至110°C之加壓成形機於一次壓力l〇kg/cm2加壓3分鐘， 在二次壓l〇〇kg/cm2加壓2分鐘，由此製成厚1.2mm的片 材。就此等片材進行評估，確認作爲芯材用成形體之特性 ，結果如表2所示。 又，比較例2的成形體在成形爲片材之際，由於脆性高 ，加以屈曲時，片材會破裂，若判斷未具芯材用成形體之 耐屈曲性或韌性時，即無法進行各項評估。而在比較例1 的組成物中，製造組成物時是在捏合溫度較PVA熔點 (2 17t)更高的溫度捏合，故PVA熔化，且無法保持溶入 PCL的PVA顆粒形狀，其他實施例和比較例都可保持 PVA顆粒形狀。又，在保持PVA顆粒形狀的組成物中， 藉上述片材透射光目視觀察結果，並無顆粒偏集或成塊’ 可知爲均勻分散。 物性等測量方法說明如下。 PCL之數量平均分子量··利用GPC測量，由聚苯乙烯 換算而得之分子量。GPC的管柱是使用昭和電工公司製造 Shodex GPC KF-6 > KF - 8 0 4、KF _ 8 0 2 5、KF - 8 0 卜檢測器 使用島津製作所製造RID-6A，溶離液使用四氫呋喃’在 管柱溫度50°C，流速l.〇ml/min測量。 黏著性，於實施例1〜1 〇和比較例1、3、4所製成片材 ，調製成縱7cmx橫2.5cmx厚1.2mm大小。將此等長方 形片材放置在150°C乾燥器中水平設置的不銹鋼板上’經 593536 五、發明說明（8) 40秒後，立即從乾燥器中取出，自然放置3 0秒，然後把 此等長方形片材放在壓機板內設置之聚酯製織布上，以調 溫至30°C的壓機，在壓力lkg/cm2進行冷壓10秒鐘，使 此等長方形片材和聚酯製織布黏着。此時，長方形片材縱 2cm爲T形剝離試驗用的夾頭，不與夾持鋁箔的織布黏着 。黏著性是用Orientec公司製品的Tensilon以剝離速度 lOOmm/min進行T形剝離試驗。以平均剝離強度評估。 耐屈曲性：將實施例1〜1 〇和比較例1、3、4的片材， 調製成縱14cmx橫3.0cmx厚l.2mm大小。此等長方形片 材以可在縱向屈曲的方式設定在耐屈曲試驗機，對此等長 方形片材實施縱寬10.5cm，衝程4.7cm的重複屈曲。此 時重複屈曲速度設定在300次（1次爲1往回）/分鐘。以長 方形片材斷裂時的屈曲次數來評估。 -10- 593536 五、發明說明（9) 騰丨J4 -47,91 1 56.3 1 10.4 41:7 ο tW娜 LZLU | 28.6 | | 10.0 | cn 寸· 1 28.6 1 100 t(J娜 」1A」 | 28.6 | 10.0 rn 1 28.6 1 100 ttf娜 ,21.1., | 28.6 | | lo.o 1 cn 寸· 1 28.6 1 230 實施例10 | 66.7 1 [33.3 1 O 寸· 1 16.0 1 ο i | 66.7 | [33.3 | L ij:3」 ο 寸· 1 16.0 1 ο 勣_8 137^1 [25.0 1 [ -37,5 J oo 00 oo rn [_ι2」ί 100 i L.71.4_1 | 28.6 | 10.0 ] ΟΊ — 1 28.6 1 100 v〇 1 R [82.4 1 1 17.6」 00 r—t On 100 in i 0Ί oo 100 寸 I * o s 100 m 義 m o s 1 26-7J 卜 \ό ο fN i 71.4 28.6 10.0 rn 寸 1 28.6 J ο i 00 ο PCL-A* 丨 PCL-B*2 PCL-C*3 PVA-A*4 PVA-B*5 PVA-C*6 ST系共聚物^ 〇L系共聚物A# OL系共聚物B# 烴系化合物*m 玻璃纖維 捏合溫度/°c Goo^i ^ ooo^s^f § ^ ^ nnn^isi^em^ - i,d^ - ^—SI ΗΊ-svssiM趨 H:III，ngiKfiff<4#^ffi阳柃m" I 鬆4ΠΛ3Ι恢a >w ^ ^ Jo^ —«si ^ nnaiism .· OOOSHi - - nnn^w^i .· s fE^IS— ^ ^ ^ - h,^s§l.oi ^ oo^^i ^ sffi ^(®niq-zii<Ng5:Toh(N51l^二二-VAd极Hlffi:鉍阮<4鼸歜I?)stiK)骹吳盡：，*v-v>d P09?ii5l· 00096ϊΗ-φίιί1^_«· dIHd，ng^IM<4·^朦面_)餵£旧酸：e*u-ddGoo^i ^ §^s s^f s« ^ sd^ . s^$s§0§0 ..The particle size of the dispersed PVA (B) particles is 2 mm or less, preferably 1.5 to 0.1 mm. When the particle size of PVA (B) is larger than 2mm, the PVA particles will protrude from the adhesion surface of the core material I, or the PVA particles are easily exposed from the surface of the core material. When the obtained core material is reactivated and adhered to a predetermined part of the shoe, the adhesion strength will be reduce. Various additives can be added to the resin composition of the present invention as needed. Although this kind of additive is not particularly limited, for example, when the shaped body as a core material is adhered to a predetermined part of the boot by heat reactivation, in order to adjust the opening time, it may be possible to add a small amount of rosin and its derivative, terpene compound, and hydrocarbon. Series compounds, paraffin wax, low molecular weight polyethylene wax. In addition, when the resin composition is hot-melt mixed or hot-melted from the obtained core material, or when the core material is reactivated by heat, a small amount of an antioxidant (oxidation preventing agent) may be added to improve thermal stability. In addition, for the purpose of improving the cold resistance, softness, impact resistance, and surface height of the core material of the fifth and fifth aspect of the invention (6), an olefin-based resin and a styrene-based resin may be optionally added as long as the effects of the present invention are not hindered. Resin, amine ester resin and ester copolymer, or glass fiber, glass particles, calcium carbonate, barium sulfate, titanium oxide, clay, slip powder and other materials. When manufacturing the resin composition of the present invention, it is not necessary to use a specific method and apparatus. Generally, nine PCL, powdered PVA, and any additive ’added’ are heated and kneaded to form a mixture. For example, it can be mixed with a uniaxial or biaxial extruder. At this time, in order not to melt PVA (B), the heating and kneading temperature must be set below the melting point (softening point) of PVA (B), above the melting point of PCL, and 80 ~ A range of 2 00 ° C is preferred. Before heating and kneading, the constituent materials of the resin composition of the present invention may be dry-mixed in advance. Once the resin composition of the present invention is taken out of nine pellets, or is successively put into a sheet molding machine or an injection molding machine for core material molding in the manufacture of the resin composition, it can be used as a core material at a lower melting point of PVA (B). Of formed body. Examples The present invention will be described more specifically with reference to the examples, but the present invention is not limited by these examples. Examples 1 to 10 and Comparative Examples 1 to 4 Resin compositions having the composition shown in Table 1 (except for kneading temperature and expressed in parts by weight) were prepared. This resin composition is prepared by dry-mixing each component raw material at a predetermined ratio in advance, and once put it into a Nabobrast mill (mixing section R-60) manufactured by Toyo Seiki Co., Ltd. at the kneading temperature and kneading temperature shown in Table 1. The composition was obtained by kneading under a kneading condition of 50 rPm and a kneading time of 3 minutes. Except for Comparative Example 1, the kneading temperature was set to a temperature (100 ° C) lower than the melting point of PV A used. 5. Description of the Invention (7). The prepared compositions (Examples 1 to 10 and Comparative Examples 1 to 4) were pressed in a pressure molding machine heated to 110 ° C for 3 minutes at a primary pressure of 10 kg / cm2, and at a secondary pressure of 10 0 kg / cm2 was pressed for 2 minutes, thereby producing a sheet having a thickness of 1.2 mm. These sheets were evaluated to confirm the characteristics of the formed bodies for core materials. The results are shown in Table 2. In addition, when the formed article of Comparative Example 2 was formed into a sheet, the sheet was cracked when buckled due to its high brittleness. If it is judged that the formed article for core material does not have the buckling resistance or toughness of the formed article, it is impossible to perform each Evaluation. In the composition of Comparative Example 1, when the composition was manufactured, the kneading temperature was higher than the melting point of PVA (2 17t), so PVA was melted, and the shape of PVA particles dissolved in PCL could not be maintained. In other examples and In the comparative examples, the shape of the PVA particles was maintained. Further, in the composition maintaining the shape of the PVA particles, it was found that the particles were uniformly dispersed by no visual observation of the particles through the light transmission of the sheet, as shown in FIG. The measurement methods such as physical properties are described below. The number average molecular weight of PCL .. The molecular weight measured by GPC and converted from polystyrene. The GPC column used Shodex GPC KF-6 > KF-8 0 4, KF _ 8 0 2 5, KF-8 0 manufactured by Showa Denko Corporation. The detector used RID-6A manufactured by Shimadzu Corporation, and tetrahydrofuran was used as the eluent. Measured at a column temperature of 50 ° C and a flow rate of 1.0 ml / min. Adhesiveness was prepared in the sheets of Examples 1 to 10 and Comparative Examples 1, 3, and 4 to a size of 7 cm in length, 2.5 cm in width, and 1.2 mm in thickness. Place these rectangular sheets on a stainless steel plate set horizontally in a 150 ° C dryer. After 593536 V. Description of the invention (8) After 40 seconds, immediately remove from the dryer, leave it for 30 seconds naturally, and then place this The rectangular sheet is placed on a polyester woven cloth set in a press plate, and the temperature is adjusted to 30 ° C, and the sheet is cold-pressed at a pressure of 1 kg / cm2 for 10 seconds to make the rectangular sheet Ester woven fabric is stuck. At this time, the rectangular sheet 2 cm in length is a chuck for a T-peel test, and does not adhere to the woven fabric holding the aluminum foil. The T-shaped peel test was performed using Tensilon manufactured by Orientec Corporation at a peeling speed of 100 mm / min. Assessed by average peel strength. Buckling resistance: The sheets of Examples 1 to 10 and Comparative Examples 1, 3, and 4 were prepared to have a size of 14 cm in length, 3.0 cm in width, and 1.2 mm in thickness. These rectangular sheets were set in a buckling tester so as to be able to flex in the longitudinal direction. Repeated flexion of the rectangular sheet with a length of 10.5 cm and a stroke of 4.7 cm was performed. At this time, the repetitive buckling speed is set to 300 times (one time is 1 back) / minute. The number of bucklings when the rectangular sheet was broken was evaluated. -10- 593536 V. Description of the invention (9) Teng 丨 J4 -47,91 1 56.3 1 10.4 41: 7 ο tWNa LZLU | 28.6 | | 10.0 | cn inch · 1 28.6 1 100 t (J 娜 「1A」 | 28.6 | 10.0 rn 1 28.6 1 100 ttfna, 21.1., | 28.6 | | lo.o 1 cn inch · 1 28.6 1 230 Example 10 | 66.7 1 [33.3 1 O inch · 1 16.0 1 ο i | 66.7 | [ 33.3 | L ij: 3 ″ ο inch · 1 16.0 1 ο product_8 137 ^ 1 [25.0 1 [-37,5 J oo 00 oo rn [_ι2 ″ ί 100 i L.71.4_1 | 28.6 | 10.0] ΟΊ — 1 28.6 1 100 v〇1 R [82.4 1 1 17.6 ″ 00 r—t On 100 in i 0Ί oo 100 inch I * os 100 m meaning mos 1 26-7J BU \ ό ο fN i 71.4 28.6 10.0 rn inch 1 28.6 J ο i 00 ο PCL-A * 丨 PCL-B * 2 PCL-C * 3 PVA-A * 4 PVA-B * 5 PVA-C * 6 ST-based copolymer ^ 〇L-based copolymer A # OL-based copolymer B # Hydrocarbon compound * m Glass fiber kneading temperature / ° c Goo ^ i ^ ooo ^ s ^ f § ^ ^ nnn ^ isi ^ em ^-i, d ^-^ —SI ΗΊ-svssiM trend H: III, ngiKfiff < 4 # ^ ffi 阳 柃 m " I 松 4ΠΛ3Ι 恢 a > w ^ ^ Jo ^ — «si ^ nna iism. · OOOSHi--nnn ^ w ^ i. · s fE ^ IS— ^ ^ ^-h, ^ s§l.oi ^ oo ^^ i ^ sffi ^ (®niq-zii < Ng5: Toh (N51l ^ 22-VAd pole Hlffi: Bi Ruan < 4 鼸 歜 I?) StiK) 骹 Wu Jin :, * v-v > d P09? Ii5l · 00096ϊΗ-φίιί1 ^ _ «· dIHd, ng ^ IM < 4 · ^ Matte _) Hey old acid: e * u-ddGoo ^ i ^ § ^ ss ^ fs «^ sd ^. S ^ $ s§0§0 ...
593536 五、發明說明（1〇) ___ 表 2 黏着性： 平均剝離強度 (kgf/cm) 耐屈曲性： 發生折斷的次數 (回） 實施例1 3.25 7200 實施例2 2.30 3 100 實施例3 1.26 2800 實施例4 1.32 7000 實施例5 3.56 6800 實施例6 3.12 7700 實施例7 2.08 2900 實施例8 2.16 3 900 實施例9 1.96 4600 實施例1 0 2.04 5200 比較例1 0.86 4800 比較例3 0.98 800 比較例4 0.72 600593536 5. Description of the invention (1〇) ___ Table 2 Adhesiveness: Average peel strength (kgf / cm) Buckling resistance: Number of breaks (back) Example 1 3.25 7200 Example 2 2.30 3 100 Example 3 1.26 2800 Example 4 1.32 7000 Example 5 3.56 6800 Example 6 3.12 7700 Example 7 2.08 2900 Example 8 2.16 3 900 Example 9 1.96 4600 Example 1 0 2.04 5200 Comparative Example 1 0.86 4800 Comparative Example 3 0.98 800 Comparative Example 4 0.72 600
產業上利用丨曹丨[g ί安照本發明，提供一種鞋類芯材，藉熱活化的黏着良好 ’ f乍爲芯材之必要物性（例如耐屈曲性）良好，不用鹵系化 η % ’燃燒時無發生戴奧辛的問題，並提供其所用樹脂組 成物。 -12-Industrial use 丨 Cao 丨 [g ί An according to the present invention, to provide a core material for footwear, good adhesion activated by heat 'f is necessary for the core material (such as buckling resistance) is good, not halogenated η% 'Diocin did not occur during combustion, and the resin composition used was provided. -12-