TW200936643A - Polyether polyamide elastomer and multilayer body using the same - Google Patents

Abstract

Disclosed is a polyether polyamide elastomer having good molding processability and excellent transparency, which is free from decrease in melt viscosity accompanying decrease of polyamide units. Specifically disclosed is a polyether polyamide elastomer containing a polyether polyamide elastomer which is characterized by being obtained by polymerizing a polyamide-forming monomer (A) selected from aminocarboxylic acid compounds and lactam compounds, an amine compound (B) containing a triblock polyether diamine compound and a polyether polyamine compound (B2), and a dicarboxylic acid compound (C). Also disclosed is a multilayer body obtained by laminating a layer made of such a polyether polyamide elastomer and a layer made of a thermoplastic polyurethane.

Description

200936643 六、發明說明： C發明所屬之技術領域1 與相關申請案的關係 本發明係主張基於2007年10月31日於日本國特許廳提 5申之特願2007 —284154號的優先權之申請案，且該優先權 申清案的内容係參照並包含於此。 技術領域 本發明係有關於一種將聚醯胺單元作為硬鏈段(hard segment)，並將聚趟單元作為軟鍵段(soft segment)，且透明 10 性、成形加工性良好的聚醚聚醯胺彈性體。更詳而言之， 特別是有關於一種透明性優異，且具有作為熱可塑性彈性 體之實用材料物性重要的熔融成形性、低溫耐衝擊性、低 溫柔軟性、力學物性、強韌性、耐彎曲疲勞性等之特性的 聚醚聚醯胺彈性體。 15 【先前技術】 背景技術 於特開平9 — 118750號公報及特開2000— 7780號公報 中係揭示有由聚醯胺單元、聚氧乙烯單元及二羧酸單元所 形成之聚醚聚醯胺彈性體。 20 然而，由聚醯胺單元、聚氧乙烯單元及二羧酸單元所 形成之聚醚聚醯胺彈性體因吸水性高，而不適合使用作為 在屋外或嚴苛的氣候條件下使用的成形體(例如，運動鞋等 之鞋底、墊子），且透明性亦不足夠。 在特許第3199797號中係揭示有一種由聚醯胺單元、聚 25 氧丁烯單元及二羧酸單元所形成之聚醚聚醯胺彈性體。 由聚醯胺單元、聚氧丁烯單元及二羧酸單元所形成之 200936643 5 10 15 聚㈣醯㈣雜軸吸水性㈣低，但料曲疲勞 之物性容㈣料足夠，且相性亦容錢差，並且 胺基甲酸醋片等樹脂片之接著性亦難含胃非常古 於特開2〇〇4— 161964號公報及特開2_"節93號公 報中，係揭示有—種由聚醯胺單元、聚氧_(X)與聚氧丁 稀00化學性賴結而形成XYX型的㈣單元及二叛 元所形成的聚鰱聚醯胺彈性體。χ，於特開讓—遍Μ 號公報中，係揭示-種由《胺單元、以聚氧丙稀(χ)盘聚 氧丁稀00形成ΧΥΧ型之《與聚氧㈣形成的㈣單元 及一羧酸單元所形成的聚醚聚酿胺彈性體。 由聚醯胺單元、聚氧丙烯(Χ)與聚氧丁烤(γ)化學性地 鍵結而形成ΧΥΧ型的聚鱗元及二魏單元所形成的聚鍵 聚醯胺彈性體，以及由聚醯胺單元、以聚氧丙稀(χ)與聚氧 丁烯⑺形成ΧΥΧ型之親與聚氧⑽形成的㈣單元及 二羧酸單元所形成的聚醚聚醯胺彈性體，雖然吸水性非常 低，耐彎曲疲勞性等之物性亦足夠，且與聚胺基甲酸醋片 等之樹脂片之接著性亦十分優異，但透明性卻難謂足夠。 又，由於熔融黏度會隨著聚醯胺單元之減少而變低，會使 得成形加工範圍變窄而會限制所適用之用途領域。 ❹ 〇 20 於特表2006_503951號公報中，係揭示一種具有聚醯 胺嵌段與聚醚嵌段且可用於製造運動鞋的透明共聚物。 然而，該聚合物係以作為聚謎嵌段之數平均分子量Μη 為200〜4000g/m〇l的PTMG為主所構成之聚醚酯醯胺，而 不同於由作為聚醚嵌段之聚氧丙烯(χ)與聚氧丁烯(γ)化學 性地鍵結而形成ΧΥΧ型的聚醚二胺所構成的本發明之聚醚 聚醯胺彈性體。專利文獻7之聚合物於構成分子的主鏈上具 有酯鍵，因此其耐水性比本發明之聚醚聚醯胺彈性體低。 【發明内容3 4 25 200936643 發明内容 5 ❹ 10 15 Ο 本發明之課題在於提供一種可解決前述問題點，吸水 性非常低，耐彎曲疲勞性等之物性亦足夠，且具有熔融黏 度並不會隨聚醯胺單元之而降低的良好成形加工性，並且 透明性優異的聚醚聚醯胺彈性體。 本發明人為解決前述課題而全力研究，結果發現到藉 由將由胺基羧酸化合物及/或内醯胺化合物形成的聚醯胺 形成性單體、聚氧丙烯(X)與聚氧丁烯(γ)化學性地鍵結而 形成ΧΥΧ型之聚醚二胺化合物、三嵌段聚醚二胺化合物及 二羧酸化合物聚合，可得到吸水性非常低，耐彎曲疲勞性 等之物性亦足夠，且具有熔融黏度並不會隨聚醯胺單元之 減少而降低的良好成形加工性，並且透明性優異的聚醚聚 醯胺彈性體，進而達致本發明。 亦即，本發明係一種聚醚聚醯胺彈性體，係聚合下列 組份而得者： (Α)聚醯胺形成性單體，其係選自於胺基羧酸化合物 (Α1)及内醯胺化合物(Α2); (Β)胺化合物，其係包含以下列式（1)表示的三嵌段聚 醚二胺化合物（Β1)及以下列式（2)表示的聚醚聚胺化合物 (Β2);及 (C)二羧酸化合物。 π CH3 ' Jy" -ch2cho-• · ch3 ~ΟΗ2〇Η—NH2200936643 VI. Description of the invention: The technical field to which the C invention belongs 1 The relationship with the related application The present invention claims the priority application based on the Japanese Patent Office No. 2007-284154 filed on October 31, 2007 in the Japanese Patent Office. The content of the priority claim is referred to and included herein. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyether polybenz which uses a polyamine unit as a hard segment and a polyfluorene unit as a soft segment, and which is transparent and has good formability. Amine elastomer. More specifically, in particular, it is excellent in transparency, and has melt formability, low-temperature impact resistance, low-temperature flexibility, mechanical properties, toughness, and bending fatigue which are important as physical properties of a thermoplastic elastomer. A polyether polyamine elastomer having properties such as sex. [Prior Art] The polyether polyamine formed from a polyamido unit, a polyoxyethylene unit, and a dicarboxylic acid unit is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-118750 and No. 2000-7780. Elastomer. 20 However, polyether polyamine elastomers formed from polyamine units, polyoxyethylene units and dicarboxylic acid units are not suitable for use as molded bodies for use in outdoor or harsh weather conditions due to their high water absorption. (for example, soles and mats for sports shoes, etc.), and transparency is not sufficient. A polyether polyamine elastomer formed from a polyamine unit, a poly 25 oxybutylene unit and a dicarboxylic acid unit is disclosed in Japanese Patent No. 3199797. The 200936643 5 10 15 poly(tetra)phosphonium (tetra) miscellaneous axis formed by the polyamine unit, the polyoxybutylene unit and the dicarboxylic acid unit has low water absorption (four), but the material content of the material is sufficient, and the phase is also sufficient. Poor, and the adhesion of a resin sheet such as a carboxylic acid vinegar sheet is also difficult to contain. The stomach is very different from that of the special publication No. 2〇〇4-161964 and the special opening 2_" Section 93, which reveals that there is a kind of The amine unit, polyoxy-(X) and polyoxybutylene 00 are chemically bonded to form a (4) unit of the XYX type and a polyfluorene polyamine elastomer formed by the two elements. χ, in the special publication, the Μ Μ 公报 , , 系 系 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由A polyether polyamine elastomer formed from a monocarboxylic acid unit. The polyamine unit, the polyoxypropylene (Χ) and the polyoxybutylene (γ) are chemically bonded to form a fluorene-type poly-scale and a poly-bonded polyamide elastomer formed by the di-Wei unit, and a polyamide unit, a polyether polyamine elastomer formed by forming a fluorene type (4) formed by a polyoxypropylene (?) and a polyoxybutylene (7), and a dicarboxylic acid unit, although absorbing water The properties are very low, and the physical properties such as bending fatigue resistance are sufficient, and the adhesion to a resin sheet such as a polyurethane plate is excellent, but transparency is not sufficient. Further, since the melt viscosity becomes lower as the polyamine unit decreases, the range of the forming process is narrowed, which limits the field of application to which it is applied. U.S. Patent Publication No. 2006-503951 discloses a transparent copolymer having a polyamido block and a polyether block and which can be used in the manufacture of sports shoes. However, the polymer is a polyether ester decylamine mainly composed of PTMG having a number average molecular weight Μη of 200 to 4000 g/m〇1 as a polymyster block, and is different from polyoxyl oxide as a polyether block. A polyether polyamine elastomer of the present invention comprising propylene (fluorene) and polyoxybutylene (γ) chemically bonded to form a fluorene-type polyether diamine. The polymer of Patent Document 7 has an ester bond in the main chain constituting the molecule, and therefore its water resistance is lower than that of the polyether polyamine elastomer of the present invention. SUMMARY OF THE INVENTION 3 4 25 200936643 SUMMARY OF THE INVENTION 5 ❹ 10 15 Ο An object of the present invention is to provide a solution to the above problems, which is characterized in that the water absorption is extremely low, the physical properties such as bending fatigue resistance are sufficient, and the melt viscosity does not follow. A polyether polyamine elastomer which is excellent in moldability and which is excellent in transparency and which is excellent in transparency. The present inventors have made intensive studies to solve the above problems, and as a result, it has been found that a polyamine-forming monomer, polyoxypropylene (X), and polyoxybutylene (formed by an aminocarboxylic acid compound and/or an indoleamine compound) γ) chemically bonded to form a fluorene-type polyether diamine compound, a triblock polyether diamine compound, and a dicarboxylic acid compound, and the physical properties such as very low water absorption and bending fatigue resistance are sufficient. Further, the polyether polyamine elastomer having excellent melt formability without deteriorating with the reduction of the polyamide unit and having excellent transparency can achieve the present invention. That is, the present invention is a polyether polyamine elastomer obtained by polymerizing the following components: (Α) a polyamine-forming monomer selected from the group consisting of an aminocarboxylic acid compound (Α1) and a guanamine compound (Α2); an amine compound comprising a triblock polyether diamine compound (Β1) represented by the following formula (1) and a polyether polyamine compound represented by the following formula (2) ( Β2); and (C) a dicarboxylic acid compound. π CH3 ' Jy" -ch2cho-• · ch3 ~ΟΗ2〇Η—NH2

·〒η3 _ η2ν- -chch2o- X ch2ch2ch2ch2o· 20 200936643 (但’分別地’ X係表示1〜20，y係表示4〜50，且z係表 示1〜20。） (但’ η係表示4〜4〇，评係表示1及/或2。） 本發明之較佳態様係如下所舉。 1 :相對於聚醯胺形成性單體(Α)、胺化合物(Β)及二羧酸化 10合物（C)之總量100質量％，係以聚醯胺形成性單體(Α)之比 例為10〜95質量％之量來使用。 2 :相對於聚醯胺形成性單體(a)、胺化合物(Β)及二羧酸化 合物(C)之總量100重量％，係以該聚醯胺形成性單體(Α) 之比例為15〜80質量％，且二胺化合物(β)及二羧酸化合物 15 (C)之合計比例為20〜85質量％之量來使用。 3 :胺基竣酸化合物(Α1)係於破原子數為2〜20之伸烧基的 末端具有胺基與羧基之胺基羧酸。 4 :内醯胺化合物(Α2)係包含碳原子數為2〜20之伸烷基的 内醢胺。 20 5 :分別地，式（1)之X表示2〜6，y表示6〜12，且ζ表示1 6 :分別地，式⑴之X表示2〜10，y表示13〜28,且z表示 200936643 7 :相對於聚醯胺形成性單體(A)、胺化合物(B)及二羧酸化 合物(C)之總量100質量％，係以聚醚聚胺化合物(B2)之比 例為0.5〜20質量％之量來使用。 8 .分別地’式(2)之η表示7〜30，w表示1及/或2。 5 9 : (C)二羧酸化合物為脂肪族二羧酸或脂環式二羧酸。 10 . 一叛酸化合物（C)係於碳原子數為1〜20之伸烧基之兩 末端具有羧基的二羧酸。 11:添加有其他聚合物及/或各種添加劑的彈性體組成物。 本發明聚醚醯胺系彈性體係將聚醯胺作為硬鏈段，且 10將具有當作重複單元之ΧΥΧ型三嵌段聚醚二胺及聚氧基丁 烯的聚醚聚胺作為軟鏈段，且於強韌性、熔融成形加工性、 低柔軟性、低溫对衝擊性、耐彎曲疲勞性、透明性、色 調等優異的聚醯胺系彈性體，並且特別是特徵在於具有隨 聚醯胺單元之減少時常發生的熔融黏度之降低較少的良好 15成形加工性，並且透明性、耐彎曲疲勞性及耐衝擊性等之 特性亦優異。 【實施方式3 實施發明之最佳形態 本發明聚醚聚醯胺彈性體中所包含的聚醚聚酿胺彈性 20 體係聚合 (A) 聚醯胺形成性單體’其係選自於胺基羧酸化合物 (A1)及内醯胺化合物(A2); (B) 胺化合物，其係包含以下列式（1)表示的三嵌段聚 醚二胺化合物（Bl)及以下列式（2)表示的聚醚聚胺化合物 200936643 (B2);及 (C)二羧酸化合物 而得之聚醚聚醯胺彈性體。 於前述聚醚聚醯胺彈性體中，在聚醯胺形成性單體 5 (A)、胺化合物(B)及二羧酸化合物(〇中包含的末端之羧酸 或羧基’與末端之胺基以大致上呈等莫耳的比例為宜。 特別是’聚醯胺形成性單體(A)之一邊的末端為胺基， 而另一邊的末端為羧酸或羧基時，以使胺化合物(B)之胺基 與一幾·酸化合物(C)之叛基調成大致等莫耳的比例為佳。 10 接下來，針對於聚醯胺形成性單體(A)中的胺基羧酸化 合物(A1)及内醯胺化合物(A2)進行說明。 胺基羧酸化合物(A1)係具有胺基與羧基的有機化合 物，雖可廣為使用聚醯胺之合成中所一般使用者，但代表 性地可舉例如為以下列式(3)所表示之化合物。 15 H2N-R1-COOH ........ (3) (但，R1係表示包含烴鏈的連結基。） 於前述胺基羧酸化合物(A1)中，R1以表示碳數2〜2〇的 2〇烴分子鍵或是具有2〜20個碳原子的伸烷基為宜，且以表示 碳數3〜18的烴分子鍵或是具有3〜18個碳原子的伸烷基為 佳，又以表示碳數4〜15的烴分子鏈或是具有4〜15個碳原 子的伸炫基更佳，且特別是以表示碳數10〜15的烴分子鏈 或是具有4〜丨5個碳原子的伸烷基更佳，更特別是以表示碳 200936643 數l〇~ 15的烴分子鏈或是具有10〜15個碳原子的伸烷基最 佳。 前述胺基羧酸化合物(A1)可舉例如6一胺基己酸、7 — 胺基庚酸、8—胺基辛酸、10—胺基癸酸、η一胺基十一酸、 5 12—胺基十二酸等之碳數5〜20之脂肪族ω_胺基叛酸等。 内醯胺化合物係具有内酿胺鍵結的環式有機化合物， 雖可廣為使用聚醯胺之合成中所一般使用者，但代表性地 可舉例如為以下列式(4)所表示之化合物。〒η3 _ η2ν- -chch2o- X ch2ch2ch2ch2o· 20 200936643 (But 'separately' X indicates 1 to 20, y indicates 4 to 50, and z indicates 1 to 20.) (But 'η indicates 4 ~4〇, the rating indicates 1 and/or 2.) The preferred embodiment of the invention is as follows. 1 : 100% by mass based on the total amount of the polyamine forming monomer (Α), the amine compound (Β), and the dicarboxylic acid compound 10 (C), which is a polyamine forming monomer (Α) The ratio is used in an amount of 10 to 95% by mass. 2 : relative to 100% by weight of the total amount of the polyamine-forming monomer (a), the amine compound (Β), and the dicarboxylic acid compound (C), the ratio of the polyamine-forming monomer (Α) The amount is 15 to 80% by mass, and the total ratio of the diamine compound (β) and the dicarboxylic acid compound 15 (C) is 20 to 85% by mass. 3: The amino phthalic acid compound (Α1) is an aminocarboxylic acid having an amine group and a carboxyl group at the terminal of the alkylene group having a broken atomic number of 2 to 20. 4: The indoleamine compound (Α2) is an intrinsic amine containing an alkylene group having 2 to 20 carbon atoms. 20 5 : respectively, X of the formula (1) represents 2 to 6, y represents 6 to 12, and ζ represents 16: respectively, X of the formula (1) represents 2 to 10, y represents 13 to 28, and z represents 200936643 7 : The ratio of the polyether polyamine compound (B2) is 0.5% by mass based on 100% by mass of the total of the polyamine-forming monomer (A), the amine compound (B) and the dicarboxylic acid compound (C). Use ~20% by mass. 8. The η of the formula (2) represents 7 to 30, respectively, and w represents 1 and/or 2. 5 9 : (C) The dicarboxylic acid compound is an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid. 10. A retinoic acid compound (C) is a dicarboxylic acid having a carboxyl group at both terminals of a stretching group having 1 to 20 carbon atoms. 11: An elastomer composition to which other polymers and/or various additives are added. The polyether amide-based elastic system of the present invention uses polydecylamine as a hard segment, and 10 has a polyether polyamine having a fluorene-type triblock polyether diamine as a repeating unit and a polyoxybutylene as a soft chain. a polyamide-based elastomer excellent in toughness, melt moldability, low flexibility, low-temperature impact resistance, bending fatigue resistance, transparency, color tone, and the like, and is particularly characterized by having a polyamine The decrease in the melt viscosity which is often caused by the decrease in the unit is excellent in 15 moldability, and the properties such as transparency, bending fatigue resistance, and impact resistance are also excellent. [Embodiment 3] BEST MODE FOR CARRYING OUT THE INVENTION The polyether polyamine polyamine system 20 polymerized in the polyether polyamine elastomer of the present invention (A) Polyamine forming monomer is selected from an amine group a carboxylic acid compound (A1) and an indoleamine compound (A2); (B) an amine compound comprising a triblock polyether diamine compound (B1) represented by the following formula (1) and having the following formula (2) The polyether polyamine compound 200936643 (B2); and (C) the polyether polyamine elastomer obtained by the dicarboxylic acid compound. In the polyether polyamine elastomer, the polyamine-forming monomer 5 (A), the amine compound (B), and the dicarboxylic acid compound (the terminal carboxylic acid or carboxyl group contained in the oxime and the terminal amine) The base is preferably in a ratio of substantially equimolar. In particular, when the end of one of the polyamine-forming monomers (A) is an amine group and the other end is a carboxylic acid or a carboxyl group, the amine compound is used. The ratio of the amine group of (B) to the thiol group of the acid compound (C) is preferably about a molar ratio. 10 Next, the aminocarboxylic acid in the polyamine-forming monomer (A) is used. The compound (A1) and the indoleamine compound (A2) are described. The aminocarboxylic acid compound (A1) is an organic compound having an amine group and a carboxyl group, and can be widely used as a general user in the synthesis of polyamine. Representatively, for example, a compound represented by the following formula (3): 15 H2N-R1-COOH (3) (However, R1 represents a linking group containing a hydrocarbon chain.) In the above aminocarboxylic acid compound (A1), R1 is preferably a 2-mer hydrocarbon bond having 2 to 2 carbon atoms or an alkylene group having 2 to 20 carbon atoms, and is represented by a carbon number of 3 to 1. a hydrocarbon molecular bond of 8 or an alkylene group having 3 to 18 carbon atoms is preferred, and a hydrocarbon molecular chain having a carbon number of 4 to 15 or a stretching group having 4 to 15 carbon atoms is more preferable, and In particular, it is more preferably a hydrocarbon molecular chain having a carbon number of 10 to 15 or an alkylene group having 4 to 5 carbon atoms, more particularly a hydrocarbon molecular chain having a carbon number of 200936643, or having 10 hydrocarbon chains. The alkyl group having 15 to 15 carbon atoms is most preferably used. The aforementioned aminocarboxylic acid compound (A1) may, for example, be 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid or 10-amino decanoic acid. , η-aminoundecanoic acid, 5 12-aminododecanoic acid, etc., aliphatic ω-amino acid, etc. having a carbon number of 5 to 20, etc. The indoleamine compound is a cyclic organic compound having an internal amine bond. The compound is widely used as a general user in the synthesis of polyamine, and is typically a compound represented by the following formula (4).

10 L-R2 CON Η10 L-R2 CON Η

(4) (但，R2表示包含烴鏈的連結基。） 於前述内醯胺化合物(A2)中，R2以表示碳數3〜2〇之烴 分子鏈或具有3〜20個碳原子的伸烷基為宜，且以表示碳數 15 3〜18之烴分子鏈或具有3〜18個碳原子的伸烷基為佳，又 以表示碳數4〜15之烴分子鏈或具有4〜15個碳原子的伸烷 基更佳，且特別是以表示碳數10〜15之烴分子鏈或具有4〜 15個碳原子的伸烷基更佳，更特別是以表示碳數1〇〜15之 烴分子鏈或具有10〜15個碳原子的伸烷基最佳。 2〇 前述内醯胺化合物(A2)可舉例如ε —己内醯胺、ω — 庚内醯胺、ω —十一内醯胺、十二内醯胺、2—π比咯啶 嗣等之厌數5〜20之脂肪族内酿胺等。 相對於前述聚醚聚醯胺彈性體全成分之聚醯胺形成性 單體(Α)之比例’係以1〇〜95質量％為宜，且以15〜95質量 9 200936643 %為佳，又以15〜85質量％更佳，特別是以15〜8〇質量％ 最佳。當相對於前述聚醚聚醯胺彈性體全成分之聚醯胺形 成性單體(A)之比例在上述範圍之下限値以上時，因聚酿胺 成分的結晶性高，且強度、彈性率等之機械物性會提升故 5較佳。相對於前述聚醚聚酿胺彈性體全成分之聚酿胺形成 性單體(A)之比例在上述範圍之上限値以上時，因更能確實 地顯現橡膠彈性或柔軟性等之作為彈性體的機能、性能故 較佳。 於前述胺化合物(B)中的以式（1)表示的χγχ型三嵌段 1〇聚醚二胺化合物(Β1)，係可使用藉由於聚（氧基1，4~伸丁基) 一醇等之兩末端附加環氧丙烷而形成聚丙二醇後，使氨等 於此聚丙二醇之末端反應以製造的聚醚二胺等。 於前述ΧΥΧ型三嵌段聚醚二胺化合物(Β1)中，\係1〜 15 20，以1〜18為宜，且以1〜16為佳，又以1〜14更佳，且特 別疋以1〜12更佳，更特別是以3〜12烧基最佳；y係4〜 以5〜45為宜，且以6〜4〇為佳，又以了〜”更佳且特 別是以8〜30更佳’更特別是以9〜19最佳；z ·〜2〇，以 1 18為宜，且以卜16為佳，又以卜14更佳，且特別是以 12’更特別是以2〜11最佳。前述X及y及z可相同亦可 20相異。 、於月mXYX型三喪段聚輕二胺化合物(B1)中，當乂及2 刀别在上述範圍之下限値以上時因所得到的彈性體之特 性中特別是以透明性為優故較佳；而當y在上述範圍之下 限値以上時’因橡勝彈性高故較佳。再者，當X及Z在上述 200936643 範圍之上限値以下時，且當y在上述範圍之上限値以下 時，因與聚酿胺成分之相溶性會變高而可輕易地得到強動 的彈性體故較佳。 5 ❹ 10 15 ❹ 前述XYX型三嵌段聚醚二胺化合物（B1)之具體例，可 使用美國HUNTSMAN公司製XTJ-533(於式（3)中，x約為 12，y約為11，z約為n) 、XTJ_ 536(於式（3)中，χ約為 8.5, y 約為 17, z 約為7.5)、XTJ_542(於式(3)中，χ約為3， y約為9，ζ約為2)以及xtj—559(於式（3)中，χ約為3 , y 約為14，z約為2)等。 再者，XYX型三嵌段聚醚二胺化合物（B1)亦可使用 XYX一 1(於式(3)中，χ約為3、y約為14、ζ約為2)、XYX 一2(於式（3)中’ χ約為5、y約為14、ζ約為2)以及χγχ — 3(於式(3)中，χ約為3、y約為19、z約為2)等。 XYX型三嵌段聚醚二胺化合物（B1)之比例，相對於聚 醯胺形成性單體(A)、聚醚胺化合物(B)及二羧酸化合物(c) 之總量100重量％，以2〜87質量％為宜，且特別是以7〜78 質量％為佳。當XYX型三嵌段聚醚二胺化合物(B1)之比例 在上述範圍之下限値以上時，因可充分顯現應力緩和、彎 曲疲勞性專之作為彈性體之特性，故適於作為聚酿胺系彈 性體。gXYX型二欣段聚峻二胺化合物(B1)之比例在上述 範圍之上限値以下時，因聚醯胺成分較多而可更為確實地 顯現聚醯胺之象徵性的優異力學強度故較佳。 於本發明之胺化合物（B)中以式（2)表示的聚醚聚胺化 合物(B2)，係可使用在相對於聚（氧基14—伸丁基)二醇1莫 20 200936643 耳約1〜300莫耳之氨及0.1〜10莫耳氫的存在下，使聚（氧基 1，4一伸丁基)二醇與鎳、銅、鉬、鉻等之催化劑接觸，而藉 由還原性胺基化反應所得到的聚胺化合物。 於以式(2)表示的前述聚醚聚胺化合物(B2)中，n係表示 5 4〜40,且w係表示1〜2。具體而言，可使用美國huntsman 公司製XTJ—548(於式(2)中’ η約為13，且w為1〜2)等。 聚醚聚胺化合物(Β2)之比例，相對於(a)聚醯胺形成性 早體、胺化合物(Β)及一缓酸化合物(C)之總量1〇〇重量％， 以0.5〜15質量％為宜，且以1〜12質量％為佳。當聚醚聚 10胺化合物（Β2)之比例在上述範圍之下限値以上時，可充分 顯現透明性。當聚醚聚胺化合物(Β2)之比例在上述範圍之 上限値以下時，因源自於聚醯胺形成性單體的結晶性會提 升，而顯現充分的力學強度故較佳。 再者，於前述胺化合物(Β)中亦可包含除三嵌段聚醚二 15 胺化合物（Β1)及聚醚聚胺化合物(Β2)之外的其他二胺化合 物(Β3)。 前述其他二胺化合物(Β3)可舉例如乙二胺、ι，3—丙二 胺、1，4 一丁二胺、1，6—己二胺、1,7 —庚二胺、1，8~ 辛二 胺、1，9一壬二胺、1,10—癸二胺、1，11 —|—烧二胺、1，12 20 ''十二烧二胺、2,2,4—三甲基一1，6—己二胺、2,4,4—三甲 基一1，6—己二胺、3 —甲基一 1，7 —庚二胺等之脂肪族二 胺、雙(4_胺基環己基）甲烷、雙(4—胺基環己基）丙烷、1,3 —雙胺基曱基環己烷、1，4一雙胺基甲基環己烷等之脂環式 二胺、間苯二甲胺、對苯二甲胺等之芳香族二胺等，該等 12 200936643 二胺係可單獨使用，或料適#地組合2_以上來使用。 二叛酸化合物(c)係具有2健基的有機化合物，雖可 廣為使用聚醯胺之合成巾所__般制者，但代表性地可舉 例如為以下列式（5)所表示之化合物。 HOOC_(r3)st-C〇〇h (於此，R表示包含烴鏈的連結基，且111係〇或1。） 於以式（3)表不的前述二羧酸化合物（C)中，R3以表示碳 10數0〜20之分子鏈或具有卜細碳原子的伸絲為宜且 以表示碳數1〜15之烴分子鏈或具有〗〜15個碳原子的伸烷 基為佳，又以表示碳數2〜12之烴分子鏈或具有2〜12個碳 原子的伸烷基更佳，又特別是以表示碳數4〜1〇之烴分子鏈 或具有4〜10個碳原子的伸烧基最佳。m表示〇或2。 15 二叛酸化合物(c)係可使用選自於脂肪族、脂環式及芳 香族二羧酸之至少一種二羧酸或其等之衍生物。 二羧酸化合物（C)之具體例可舉例如草酸、琥珀酸、戊 ❹ ❹ 二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二 烷二酸等之碳數2〜25之直鏈脂肪族二羧酸，或者是，將藉 20 由三酸甘油酯之分館而得到的不飽和脂肪酸進行二聚合之 碳數14〜48之二聚合脂肪族二羧酸（二聚酸)及其等之氫化 物（氫化二聚酸）等之脂肪族二羧酸、1，4 一環己烷二羧酸等 之脂環式二羧酸及對苯二甲酸、間苯二甲酸等之芳香族二 羧酸。二聚酸及氫化二聚酸係可使用「Pripol 1004」、「Pripol 13 200936643 1006」、「Pripol 1009」、「prip〇i ι〇!3」等。 前述聚醚聚醯胺彈性體之硬度（蕭氏硬度D，ShoreD) 係以15〜70之範圍者為宜，又以18〜7〇之範圍者為佳，且 以20〜70之範圍者更佳，又特別是以25〜7〇之範圍者最佳。 前述聚醚聚醯胺彈性體之彎曲強度係以〇 8〜2〇MPa為 宜，又以1〜18MPa為佳’且以1.1〜15Mpa更佳，又特別是 以1.2〜13MPa最佳。藉由使聚醚聚醯胺彈性體之彎曲強度 在上述範圍，因可得到強韌性與橡膠彈性平衡地優異的彈 性體故較佳。 前述聚醚聚醯胺彈性體之彎曲彈性率係以2〇〜 400MPa為宜’又以20〜350MPa為佳，且以2〇〜300MPa更 佳，又特別是以20〜250MPa最佳。藉由使聚醚聚醯胺彈性 體之·彎曲雜率在上㈣圍，目可得㈣減與橡勝彈性 平衡地優異的彈性體故較佳。 前述聚醚聚醯胺彈性體之霧度係以在15以下為宜，又 以在13以下為佳，且以在職下更佳，又制是在以7以下 最佳藉由使霧度低於上述而可得到透明性優異的彈性體。 前述聚趟聚酼胺彈性體之吸水率（％)係以在3%以下 為且又以在2.7%更佳，X特別是以在2 5%以下最佳。 前述聚喊聚醯胺彈性體之製造方法，舉例而言，可使 用由以下步驟所構成的方法：將聚醯胺形成性單體(A)、 XYX型三彼段聚喊二胺化合物(B1)、聚鍵聚胺化合物_ 及二幾酸化合物(C)四成分同時於加壓及/或常壓下進行 熔融聚口’且可因應需要於進一步的減壓下進行熔融聚 14 200936643 合。又’亦可利用先使聚醯胺形成性單體(A)與二羧酸化合 物(C)二成分預先聚合’接著再使χγχ型之三嵌段聚_二胺 (B1)與聚醚聚胺化合物(B2)聚合之方法。 於前述聚醚聚醯胺彈性體之製造中’原料的進料方法 5雖無特別限制，但可以以下方式進料：（A)聚酿胺形成性單 體、XYX型三嵌段聚醚二胺化合物（B1)、聚醚聚胺化合物 (B2)及一叛酸化合物(C)之進料比例，相對於全成分，係以 _ 聚醯胺形成性單體(A)為10〜95質量％之範圍為宜，且特別 是以15〜80質量％之範圍為佳；χγχ型三嵌段聚醚二胺化 10合物(Β1)以2〜87質量％為宜，且特別是以7〜78質量％為 佳·’聚醚聚胺化合物(Β2)以〇_5〜20質量％為宜，且特別是 以1〜15質量％為佳。χγχ型三嵌段聚醚二胺化合物（Β1) 與聚驗^^胺化合物（Β2)與二緩酸化合物（c)較佳係以χγχ 型三嵌段聚醚二胺化合物（B1)與聚醚聚胺化合物(B2)之胺 15基與二羧酸化合物(C)之叛基成為大致等莫耳來進料。 Q 本發明之聚醚聚醯胺彈性體之製造，其聚合溫度係可 較佳以150〜300°C來進行，且更佳以16〇〜28(rc來進行， 又最佳以170〜250°C來進行。當聚合溫度比上述溫度低時 聚合反應遲緩，當比上述溫度高時會容易產生熱分解而會 20 有無法得到良好物性的聚合物之情形。 本發明之聚醚聚醯胺彈性體，於將ω_胺基鲮酸作為 聚醯胺形成性單體(Α)使用時，可以由包含常壓熔融聚合， 或是常壓熔融聚合與該步驟後的減壓熔融聚合之步驟之方 法來製造。 15 200936643 另一方面，將内醯胺作為聚醯胺形成性單體(A)使用 時，可使其與適量的水共存，並於〇.1〜5MPa之加壓下以包 含熔融聚合以及該步驟後的常壓熔融聚合及/或減壓熔融 聚合之方法來製造。 5 本發明之聚醚聚醯胺彈性體，可以一般為〇.5〜30小時 的聚合時間來製造。若聚合時間比上述範圍短，分子量的 上昇會不足，若比上述範圍長則會因熱分解而產生著色 等，該等任一情況皆會有無法得到具有所希望物性的聚醚 聚醯胺彈性體的情形。 10 本發明之聚謎聚酿胺彈性體的製造可以分批式或連續 式來實施’亦可單獨或適當組合使用分批式反應器、一槽 式至多槽式之連續反應裝置、管狀連績反應裝置等。 本發明之聚醚聚醯胺彈性體之相對黏度（β Γ)在丨.2〜 3.5(0.5質量/體積％間甲紛溶液，25°C)之範園内為宜。 15 於本發明之聚醚聚醯胺彈性體之製造中’可因應需要 為了分子量調節或成形加工時的熔融黏度穩定’而添加十 二胺、十八胺、1，6-己二胺、間苯二甲胺等之單胺或二胺； 醋酸、安息香酸、硬脂酸、己二酸、癸二酸、十二烧二酸 等之單羧酸或是二叛酸等。其等之使用量較佳係可適當地 20 添加以使最終得到的彈性體之相對黏度（77 r)在1·2〜3.5(0.5 質量/體積％間甲酚溶液’ 25°C)之範圍内。 於本發明之聚醚聚醯胺彈性體之製造中，上述單胺及 二胺、單羧酸及二羧酸等之添加量係以調成不阻礙所得到 的聚醚聚醯胺彈性體之特性的範圍内為宜。 16 200936643 前述聚醚聚醯胺彈性體之製造中，可因應需要添加磷 酸、焦磷酸、聚磷酸等作為催化劑，或者可以催化劑與耐 熱劑兩者的效果為目的添加亞磷酸、次磷酸及其等之鹼金 屬鹽、鹼土金屬鹽等之無機磷化合物。添加量一般為相對 5 於進料量的50〜3000 ppm。 於前述聚醚聚醯胺彈性體中，可於不阻礙其特性之範 圍内，添加耐熱劑、紫外線吸收劑、光穩定劑、抗氧化劑、 抗靜電劑、潤滑劑、助滑劑、晶核劑、黏著性賦予劑、密 封性改良劑、防暈劑、離型劑、可塑劑、顏料、染料、香 10 料、難燃劑、補強材等。以下，將包含聚醚聚醯胺彈性體 單獨及於同彈性體中添加該等之添加物而得之組成物，皆 單純稱為聚醚聚醯胺彈性體組成物。 本發明之聚醚聚醯胺彈性體組成物吸水性低、熔融成 形性優異、成形加工性優異、強勒性優異、财彎曲疲勞性 15 優異、反彈彈性優異、透明性優異、低比重性、低溫柔軟 性優異，消音特性及橡膠性質等皆優異。 再者，於前述聚醚聚醯胺彈性體中，以耐熱性的觀點 看來，末端胺基濃度比末端羧基濃度大較佳。 本發明之聚醚聚醯胺彈性體組成物可藉由射出成形、 20 擠壓成形、吹製成形、真空成形、壓空成形等之習知之成 形方法而得到成形物。 本發明之聚醚聚醯胺彈性體組成物之射出成形品可舉 例如較佳為強韌性、耐彎曲疲勞性、反彈彈性、低比重的 材料之棒球、足球、陸上競技等領域中的鞋溶膠材料，而 17 200936643 其他射出成形品可舉例如機械、電子精密機器之齒輪、連 接器、密封、汽車用模、密封材等。 本發明之聚醚聚醯胺彈性體組成物之擠壓成形品可舉 例如管、軟管、異形材、片、薄膜、單絲等。 5 本發明之聚醚聚醯胺彈性體組成物之吹製成形品可舉 例如用於汽車的鏡防塵套、等速接頭防塵套等。 本發明之聚醚聚醯胺彈性體組成物，與前述聚醚聚醯 胺彈性體之外的聚酿胺、聚氣乙烯、熱可塑性聚胺基甲酸 酯、ABS樹脂等之熱可塑性樹脂之相溶性佳，而可藉由與 10 該等熱可塑性樹脂作為調合物，而改良該等樹脂之成形 性、耐衝擊性、彈性及柔軟性等。 再者，可做成積層由本發明之聚醚聚醯胺彈性體組成 物所形成之層與由其他熱可塑性樹脂所形成之層之積層 體。 15 積層體係可為將由本發明之聚醚聚醯胺彈性體組成物 所形成之層與由其他熱可塑性樹脂所形成之層積層一層 者，亦可為積層2層以上者。各層的厚度並無特別限制，構 成各層的聚合物的種類、積層體中的全體層數可因應用途 等進行調節。 20 再者，積層體之層數雖為2層以上，於積層體中全體層 數並無特別限制，任一層數皆可。 而由積層體製造裝置之機構來判斷為7層以下為宜，且 以2層〜5層為佳。 前述其他熱可塑性樹脂，可舉例如高密度聚乙烯 18 200936643 (HDPE)、低密度聚乙烯（LDPE)、超高分子量聚乙烯 (UHMWPE)、聚丙烯(PP)、乙烯/丙烯共聚物(EPR)、乙烯 /丁烯共聚物(EBR)、乙烯/醋酸乙烯酯共聚物(EVA)、乙 烯/醋酸乙烯酯共聚物鹸化物(EVOH)、乙烯/丙烯酸共聚 5物(EAA)、乙烯/甲基丙烯酸共聚物(EMAA)、乙烯/丙烯 酸甲酯共聚物（EMA)、乙烯/甲基丙烯酸甲酯共聚物 (EMMA)、乙烯/丙烯酸乙酯（EEA)等之聚烯烴系樹脂，以 及包含羧基及其鹽、酸酐基、乙氧基等官能基的上述聚烯 烴系樹脂、聚對苯二甲酸丙二酯(PBT)、聚對苯二甲酸乙二 10 酯（PET)、聚間苯二甲酸乙二酯(PEI)、PET/PEI共聚物、 聚芳酯(PAR)、聚萘二甲酸丁二酯(PBN)、聚萘二甲酸乙二 酯（PEN)、液晶聚酯（LCP)等之聚酯系樹脂、聚縮醛(POM)、 聚苯醚(PPO)等之聚醚系樹脂、聚颯(PSF)、聚醚諷(PES)等 之聚颯系樹脂、聚苯硫醚(PPS)、聚硫醚颯(polythioether 15 sulfone，PTES)等之聚硫醚系樹脂、聚醚醚酮（PEEK) '聚 芳醚酮(PAEK)等之聚酮系樹脂、聚丙烯腈(PAN)、聚甲基丙 烯腈、丙烯腈/苯乙烯共聚物(AS)、甲基丙烯腈/苯乙烯 共聚物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、甲基丙烯 腈/苯乙烯/丁二烯共聚物(MBS)等之聚腈系樹脂、聚甲基 20丙烯酸曱酯（PMMA)、聚甲基丙烯酸乙酯（ΡΕΜΑ)等之聚曱 基丙烯酸酯系樹脂、聚乙烯醇（PVA)、聚二氯亞乙烯 (PVDC)、聚氯乙烯（PVC)、氣乙烯/二氣亞乙烯共聚物、 二氯亞乙烯/甲基丙烯酸共聚物等之聚乙烯系樹脂、醋酸 纖維素、酪酸纖維素等之纖維素系樹脂、聚二氟亞乙烯 19 200936643 (PVDF)、聚氟&烯(PVF)、聚三氟氯乙烯(PCTFE)、乙烯/ 四氟乙烯共聚物（etfe)、乙烯/三氟氯乙烯共聚物 (ECTFE)、四氟乙烯/六氟丙烯共聚物(TFE/HFP，FEP)、 四氟乙烯/六氟丙烯/氟乙烯共聚物（TFE/HFP/VDF， 5 THV)、四氟乙稀/氟（烧基乙烯醚）共聚物（PFA)等氟系樹 脂、聚碳酸酯（PC)等之聚碳酸酯系樹脂、熱可塑性聚醯亞 胺（PI)、聚醯胺醯亞胺(PAI)、聚醚醯亞胺等之聚醯亞胺系 樹脂、熱可塑性聚胺基甲酸酯樹脂、聚伸乙基己二酸二酿 胺（耐綸26)、聚四伸甲基己二酸二醯胺（耐綸46)、聚六伸甲 10 基己二酸二醯胺（耐綸66)、聚六伸甲基壬二酸二醯胺（耐綸 69)、聚六伸甲基癸二酸二醯胺(耐綸610)、聚六伸甲基十一 烷二酸二醯胺（耐綸611)、聚六伸甲基十二烷二酸二醯胺（耐 綸612)、聚六伸曱基對苯二甲酸二醯胺（耐綸6T)、聚六伸甲 基間苯二甲酸二醯胺（耐綸61)、聚九伸甲基十二烷二酸二醯 15 胺（耐綸912)、聚十伸甲基十二烷二酸二醯胺（耐綸1012)、 聚十二伸甲基十二烷二酸二醯胺(耐綸1212)、聚間二甲苯己 二酸二醯胺（耐綸MXD6)、聚三甲基六伸甲基對苯二甲酸二 醯胺(TMHT)、聚雙(4一胺基環己基）甲烷十二烷二酸二醯胺 (耐綸PACM12)、聚雙(3—甲基一4—胺基環己基）甲烷十二 20 烷二酸二醯胺（耐綸二甲基PACM12)、聚九伸甲基對苯二甲 酸二醯胺（耐綸9T)、聚十伸甲基對苯二甲酸二醯胺（耐綸 10T)、聚十一伸甲基對苯二甲酸二醯胺(耐綸11T)、聚十二 伸甲基對苯二曱酸二醯胺（耐綸12T)或使用數種形成其等 之聚醯胺原料單體之共聚物等之聚醯胺系樹脂。於其等 20 200936643 中’以使用聚烯煙系樹脂、聚酯系樹脂、聚酿胺系樹脂、 聚硫醚系樹脂、氟系樹脂為佳。 本發明之聚謎聚酿胺彈性體組成物可有利地使用於形 成可用於運動鞋溶膠、滑雪鞋等之聚醯胺系彈性體組成物 5 ❹ 10 15 ❹ 20 與熱可塑性聚胺基甲酸酯之積層體。特別是，本發明係有 利於提供與熱可塑性聚胺基甲酸酯接著性優異的聚醯胺系 彈性體組成物，與熱可塑性聚胺基甲酸酯直接積層之積層 體。 以下’將前述由聚醚聚醢胺彈性體組成物形成之層稱 為X層’並將前述由其他熱可塑性樹脂形成之層稱為γ層。 於將聚喊聚醯胺彈性體組成物之層與聚胺基曱酸酯之 層積層而形成的積層體中，相對於前述聚醚聚醯胺彈性體 全成为之聚醯胺形成性單體(A)之比例，以10〜95質量％為 宜，且以15〜95質量％為佳，又以15〜85質量％更佳，而 特別是以15〜8〇質量％最佳。 相對於前述聚醚聚醯胺彈性體全成分之聚醯胺形成性 單體(A)之比例在前述範圍内，特別因X層與γ層之接著性 優異’且強度、彈性率、柔軟性等之作為雜體之機械特 性優異而純。#相對於前述料_轉性體全成分之 聚酿胺^/成性單體(A)之比例比前述範圍少時，X層與Y層 之接著強度會變低’且強度、彈性料之機械物性會降低 而較不適合。當相對於前述聚醚聚醯胺彈性體全成分之聚 酿胺形成性單體(A)之比例比前述範圍多時，因橡膠彈性或 柔軟性等之作為彈性體之機能、性能會較難顯現而較不適 21 200936643 合。可推測到聚醚聚醯胺彈性體之醯胺鍵結與聚胺基甲酸 酯之胺基甲酸酯鍵結間的分子間氫鍵會影響X層與γ層之 接著強度。 X層及/或Y層係可藉由射出成形、擠壓成形、吹製成 5 形、輪壓成形、熱壓縮成形等之成形方法以得到成形物。 成形積層體的方法，係可藉由將包含X層及Y層的各層 同時成形方法、將各層成形再貼合的方法、於層上再一邊 將層成形一邊積層的方法（串接(tandem)法）等，或是其等的 組合而獲得。 ίο 於y層中，聚胺基甲酸酯係可使用：使聚醇與二異氰醆 酯反應而得到的聚胺基甲酸酯、使增鏈劑與二異氰酸酯反 應而得到的聚胺基甲酸酯、使聚醇、二異氰酸酯及增鏈劑 反應而得到的聚胺基甲酸酯等。特別是’聚胺基甲醆酯以 使用熱可塑性之聚胺基甲酸酯為值。 15 於Y層中，聚胺基甲酸酯係<適宜地使用將聚酯二醇及 /或聚醚二醇作為軟鏈段之熱町橥性聚胺基甲酸酯。 聚醇係可使用縮合系聚酯聚鞟、内酯系聚酯聚醇、聚 碳酸酯聚醇等及聚醚聚醇等。縮舍系聚酯聚醇以使用藉由 用1種或2種以上二叛酸與二醇而得到的聚酯二醇為佳。 20 二羧酸可舉例如戊二酸、已>酸、庚二酸、辛二酸、 壬二酸、癸二酸、十二烧二酸等之脂肪族二叛酸；環己燒 二羧酸等之脂環式二羧酸；對笨> 甲酸、間苯二甲酸、臨 苯二甲酸等之芳香族二羧酸或其等之低級烷酯，且其等係 可使用1種或2種以上。於其等中，以己一酸、壬二酸、癸 200936643 二酸等之脂肪族二羧酸或其等之低級烷酯為佳。 5 Ο 10 15 ❹ 20 二醇可舉例如乙二醇、1，2—丙二醇、1，3—丙二醇、1，4 —丁二醇、1,5—戊二醇、3—甲基_1，5—戊二醇、1,6—己 二醇、1，7—庚二醇、1,8—辛二醇、2—甲基一 1,8—辛二醇、 1，9一壬二醇、1,10— 癸二醇、1，11_ 十一烷二醇、1,12—十 二烷二醇等之脂肪族二醇；環己烷二甲烷、環己烷二醇等 之脂環式二醇，其等係可以1種或2種以上使用。其等中， 以使用1,5—戊二醇、3—甲基一 1，5—戊二醇、1,6—己二 醇、2—甲基一1,8—辛二醇、1,9—壬二醇、1,12—十二烷 二醇等之脂肪族二醇為佳。 内酯系聚酯聚醇可舉例如使冷一丙内酯、特戊内酯、 5—戊内酯、ε —己内酯、曱基一ε —己内酯、二甲基一 ε —己内S旨、三甲基一 £ —己内醋等之内S旨化合物，與短 鏈之聚醇等之羥基化合物共同反應者等。 聚碳酸酯二醇可係可藉由低分子二醇與碳酸烷酯、碳 酸伸烷酯、碳酸二芳酯等之碳酸酯化合物之反應而獲得。 聚碳酸酯二醇之製造原料低分子二醇係可使用作為聚酯二 醇製造原料之先前所例示的低分子二醇。再者，碳酸二烷 酯可舉例如碳酸二曱酯、碳酸二乙酯等；碳酸伸烷酯可舉 例如碳酸伸乙酯等；碳酸二芳酯可舉例如碳酸二苯酯等。 聚醚聚醇可舉例如聚乙二醇、聚丙二醇、聚1，4一丁二 醇、聚氧基丙二醇、以甘油為基底的聚伸烷基醚二醇等。 除上述之外，亦可使用眾所皆知的各種聚胺基甲酸酯用聚 醇0 23 200936643 於聚胺基甲酸酯所使用的聚異氰酸酯之種類並無特別 限制，而可使用迄今於聚胺基甲酸酯，較佳為熱可塑性聚 胺基甲酸酯之製造中所使用的聚異氰酸酯之任一者。 聚異氰酸酯係可使用二異氰酸1,4一伸丁酯、二異氰酸 5 1,5 —伸戊酯、二異氰酸1，6 —伸己酯、離胺酸二異氰酸酯、 環己基曱烷二異氰酸酯、二異氰酸2,2,4—或2,4,4一三甲基 1,6 —伸己酯、異亞丙基雙(4一環己基異氰酸酯）、異佛酮二 異氰酸酯等之脂肪族或脂環式二異氰酸酯、2,4一或2,6—甲 苯二異氰酸酯、4,4’ 一二苯基甲烷二異氰酸酯、3_甲基 10 二苯基曱烷_4,4’一二異氰酸酯、m—或p_伸苯基二異氰 酸酯、氣伸苯基2,4 —二異氰酸酯、萘一1,5 —二異氰酸酯、 二甲苯二異氰酸酯、四曱基二甲苯二異氰酸酯等之芳香族 二異氰酸酯等，其等中可使用1種或2種以上的聚異氰酸 酯。於其等中以使用4,4’ 一二苯基甲烷二異氰酸酯為佳。 15 於聚胺基甲酸酯之製造所使用的增鏈劑的種類雖無特 別限制，而雖使用於一般聚胺基甲酸酯之製造中迄今所使 用的增鏈劑的任一者，但以使用於分子中具有2個以上可與 聚異氰酸酯基反應的活性氫原子，且分子量在300以下之低 分子量化合物。 20 增鏈劑可舉例如乙二醇、丙二醇、1，4 — 丁二醇、1,6 一己二醇、1,4—雙（万一羥基乙氧基）苯、1,4一環己烷二醇、 雙一（/5 —羥基乙基）對苯二甲酸酯、二甲苯二醇等之二醇 類；聯胺、乙二胺、丙二胺、二甲苯二胺、異佛酮二胺、 哌畊及其衍生物、苯二胺、曱苯二胺、二甲苯二胺、己二 24 200936643 酸二醯肼、間苯二甲酸二醯肼等之二胺類；胺基乙醇、胺 基丙醇等之醇類等，且其等係可使用1種或2種以上，且於 其等中以使用碳數2〜10之脂肪族二醇為佳，且以使用ι，4 —丁二醇更佳。 5 ❹ 10 15 ❹ 20 增鏈劑係可使用多價醇、多價胺等。市售的具體商品 名可舉例如「Pandex」（大曰本墨水化學工業公司製）、 「Kuramiron」（可樂麗公司製）、「Miractran」（日本 Miractran 公司製）等。 熱可塑性聚胺基曱酸酯（TPU等）係可使用BASF日本公 司製的商品名「Elastolan ET195」、「Elastolan ET690」、 「Elastolan ET890」、大日本墨水化學工業公司製商品名 「Pandex T — 8190U」、日本聚胺基甲酸酯工業公司製 「Miractran E190」、「Miractran E390」、「Miractran E490」、 「Miractran E590」、「Miractran E990」等。 X層在無損及特性之範圍内，與除了聚醚醯胺之外的其 他聚醯胺、聚氣乙烯、熱可塑性聚胺基曱酸酯、ABS樹脂 等之熱可塑性樹脂之相容性佳，而可與該等熱可塑性樹脂 調合使用。X層係以包含70質量％以上的聚醚酿胺為宜，且 以包含80質量％以上的聚醚醯胺為佳，又以包含9〇質量％ 以上的聚醚酿胺更佳，且特別是以包含95質量％以上的聚 醚醯胺最佳。Y層在無損及特性的範圍内，可與除了聚胺基 甲酸酯之外的其他熱可塑性聚合物、彈性體、橡膠等調合 使用。 再者’以使層間接著性提升為目的，亦可設置接著層。 25 200936643 又，亦可積層熱可塑性樹脂之外的任意基材，例如：紙、 金屬系材料、無延伸、一軸或二軸延伸塑膠膜或片、織布、 不織布、金屬綿、木質等。金屬系材料係可舉例如：铭、 鐵、銅、鎳、金、銀、鈦、翻、鎮、猛、錯、錫、絡、皱、 5 鎢、鈷等之金屬或金屬化合物及由其等2種類以上組成之不 鏽鋼等之合金鋼、鋁合金、黄銅、青銅等之剛合金、鎳合 金等之合金類等。 接著層係以使用包含羧基及其鹽、酸酐基、乙氧基之 烯烴系聚合物為宜。烯烴系聚合物係可舉例如聚乙烯、聚 10 丙烯、乙烯一丙稀共聚物、乙烯一丁稀共聚物、聚丁烯、 乙烯一丙烯一二烯共聚物、聚丁二烯、丁二烯一丙烯腈共 聚物、聚異戊二烯、丁烯一異戊二稀共聚物等。再者，於 烯烴系聚合物中，可為使羧酸酯共聚合而成者，而可舉例 如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯 15 酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲 基丙烯酸丁酯等經共聚合之聚合物等，且更具體而言，可 舉例如乙烯一丙烯酸曱酯共聚物、乙烯一丙烯酸乙酯共聚 物、乙稀一丙稀酸丙酷共聚物、乙浠一丙烯酸丁 S旨共聚物、 乙烯一曱基丙烯酸甲酯共聚物、乙烯一甲基丙烯酸乙酯共 20 聚物、乙烯一甲基丙烯酸丙酯共聚物、乙烯一甲基丙烯酸 丁酯共聚物、乙烯一甲基丙烯酸異丁酯共聚物等之烯烴一 (曱基）丙烯酸酯共聚物、丙烯酸甲酯一丙烯腈共聚物、曱 基丙烯酸曱酯一丙烯腈共聚物、丙烯酸丙酯一丙烯腈共聚 物、甲基丙稀酸丙酯一丙烯腈共聚物、丙烯酸丁酯一丙烯 26 200936643 腈共聚物、甲基丙烯酸丁酯一丙烯腈共聚物等之（甲基）丙 烯酸酯_丙烯腈共聚物。 且羧基及其鹽、酸酐基、乙氧基被導入聚烯烴分子中 主鍵上的共聚物，或是被導入側鏈上的接枝聚合物任一者 5 Ο 10 15 ❹ 20 皆可。 羧基及其鹽、酸酐基、乙氧基係可舉例如：丙烯酸、 甲基丙烯酸、順丁烯二酸、反丁烯二酸、伊康酸、丁烯酸、 中康酸、焦檸檬酸、戊烯二酸、順式一4 —環庚烯一1,2 — 二缓酸、内順-雙環〔2.2.1〕庚一5 —婦一2,3 —二叛酸及該 等羧酸之金屬鹽(Na、Zn、K、Ca、Mg)、無水順丁烯二酸、 無水伊康酸、無水焦檸檬酸、無水反丁烯二酸、内雙環一 〔2.2,1〕一 5 —庚烧一2,3 —二羧酸無水物、丙烯酸去水甘 油Θ旨、甲基丙烯酸去水甘油S旨、乙基丙稀酸(ethacrylic acid) 去水甘油酯、伊康酸去水甘油酯、焦檸檬酸去水甘油酯等。 接著層係可使用包含前述記載的羧基及其鹽、酸酐 基、乙氧基等之官能基的上述例示的烯烴系聚合物。 本發明積層體之積層組成之例係可舉例如：X層/Y 層、X層/Y層/X層、Y層/X層/Y層、X層/Y層/基材 層、基材層/X層/Y層、X層/Y層/X層/基材層、Y層 /X層/Y層/基材層、γ層/X層/接著層/基材層、X層 /Y層/接著層/基材層、基材層/接著層/X層/Y層/ X層/接著層/基材層、基材層/接著層/Y層/X層/Y 層/接著層/基材層等。基材層除了 X層及Y層之聚合物之 外’亦可使用由其他聚合物材料得到的薄膜(film)、片、膜 27 200936643 及成形物等；由將天然、合成纖維、玻璃、陶瓷等作為原 料之無機纖維所得到的織物、編物、編帶及不織布等；玻 璃、金屬、陶瓷、塗膜、紙等；皮革等。 接著層係可使用眾所皆知的各接著成分、具有接著性 5 的片或薄膜等，且以使用無損本發明特性者為宜。 本發明之積層體，作為藉由射出成形而形成的二色成 形品，而可用於鞋溶膠材料、滑雪鞋等之鞋材、汽車部件 等，而作為擠壓成形品，可用於使用薄膜積層體的滑雪板 及軟管、管、帶等。 10 本發明之積層體之X層與Y層的剝離強度係以9.5kg · cm以上為宜，且以10.5kg · cm以上為佳。於本發明之積層 體中，當Y層之軟鏈段為聚醚二醇之聚胺基曱酸酯時，本發 明之X層與Y層的剝離強度係以9.5kg · cm以上為宜，且以 10.5kg · cm以上為佳，又特別是以10.8kg · cm以上更佳。 15 於本發明之積層體中，Y層之軟鏈段為聚酯二醇之聚胺基甲 酸S旨時，本發明之X層與Y層的剝離強度係以9.8kg · cm以 上為宜，且以10.2kg. cm以上為佳，有特別是以10.5kg .cm 以上更佳。 20 實施例 以下舉出實施例及比較例以說明本發明，但本發明當 不受該等實施例之限定。 特性値係如下數一般地進行測量。 1)相對黏度（7?r)(0.5質量/體積％間甲酚溶液、25°C): 28 200936643 將試劑特級品之m—曱酚作為溶劑，以5g/d功3之農 度’使用奧士華黏度6十（Ostwald’s Visometer)於25°C進行 量。 仃剛 2) 末端羧基濃度（〔C00H〕）： 5 於聚合物約1g中添加40mL2苯甲醇，並於氮氣氣體壤 境加熱溶解，且於所得之樣品溶液中添加指示劑酚酞，並 以N/20氫氧化鉀一乙醇溶液滴定。 3) 末端胺基濃度（〔NH2〕）： 將聚合物約1 g溶解於4 0 m L之酚/甲醇混合溶劑中（體 10積比：9/1)，於所得到的樣品溶液中添加指示劑瑞香草酚 藍，並以N/20鹽酸滴定。 4) 融點（Tm)及結晶化溫度(tc):(4) (However, R2 represents a linking group containing a hydrocarbon chain.) In the above internal indoleamine compound (A2), R2 represents a hydrocarbon molecular chain having a carbon number of 3 to 2 Å or a stretching having 3 to 20 carbon atoms. An alkyl group is preferred, and is preferably a hydrocarbon molecular chain having a carbon number of 15 3 to 18 or an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having a carbon number of 4 to 15 or having 4 to 15 More preferably, the alkyl group of the carbon atom is more preferably a hydrocarbon chain having a carbon number of 10 to 15 or an alkyl group having 4 to 15 carbon atoms, more particularly a carbon number of 1 to 15 The hydrocarbon molecular chain or alkylene group having 10 to 15 carbon atoms is most preferred. 2 〇 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己 己An aliphatic number of 5 to 20 aliphatic amines and the like. The ratio of the polyamine-forming monomer (Α) to the entire polyether polyamine elastomer is preferably from 1 to 95% by mass, and preferably from 15 to 95, 9 to 200936643%, and It is preferably 15 to 85% by mass, particularly preferably 15 to 8 % by mass. When the ratio of the polyamine-forming monomer (A) to the entire polyether polyamine elastomer is less than or equal to the lower limit of the above range, the crystallinity of the polyamine component is high, and the strength and modulus are high. It is better to increase the mechanical properties of the machine. When the ratio of the polyamine-forming monomer (A) of the entire polyether polystyrene elastomer is more than or equal to the upper limit of the above range, the rubber elasticity or flexibility can be more reliably exhibited as an elastomer. The function and performance are better. The χγχ type triblock 1 〇 polyether diamine compound (Β1) represented by the formula (1) in the above amine compound (B) can be used by poly(oxy 1,4~butylene) A polyether diamine produced by reacting propylene oxide at both ends of an alcohol or the like to form polypropylene glycol, and reacting ammonia at the end of the polypropylene glycol. In the above-mentioned fluorene-type triblock polyether diamine compound (Β1), \ is 1 to 15 20, preferably 1 to 18, preferably 1 to 16, more preferably 1 to 14, and particularly It is preferably 1 to 12, more preferably 3 to 12, and y is 4 to 5 to 45, and preferably 6 to 4, and more preferably ~" 8~30 is better' more especially 9~19 best; z ·~2〇, 1 18 is suitable, and it is better to use Bu 16 and better as Bu 14 , especially especially 12' It is preferably 2 to 11. The above X and y and z may be the same or 20 different. In the mXYX type three-stage poly-light diamine compound (B1), when 乂 and 2 are in the above range When the lower limit is 値 or more, it is preferable that the properties of the obtained elastomer are particularly excellent in transparency; and when y is at least the lower limit of the above range, 'because the rubber is high in elasticity, it is preferable. When Z is not more than the upper limit of the range of the above-mentioned 200936643, and when y is less than or equal to the upper limit of the above range, it is preferable because the compatibility with the polyamine component becomes high and the strong elastic body can be easily obtained. 5 ❹ 10 15 ❹ The aforementioned XYX type Specific examples of the block polyether diamine compound (B1) can be XTJ-533 manufactured by HUNTSMAN Co., Ltd. (in the formula (3), x is about 12, y is about 11, z is about n), and XTJ_536 ( In the formula (3), χ is about 8.5, y is about 17, z is about 7.5), XTJ_542 (in the formula (3), χ is about 3, y is about 9, ζ is about 2) and xtj— 559 (in the formula (3), χ is about 3, y is about 14, z is about 2), etc. Further, the XYX type triblock polyether diamine compound (B1) can also use XYX-1 (in In the formula (3), χ is about 3, y is about 14, ζ is about 2), XYX is 2 (in the formula (3), 'χ is about 5, y is about 14, and ζ is about 2) and χγχ — 3 (in the formula (3), χ is about 3, y is about 19, z is about 2), etc. The ratio of the XYX-type triblock polyether diamine compound (B1) is relative to the polyamine forming property. The total amount of the monomer (A), the polyetheramine compound (B) and the dicarboxylic acid compound (c) is preferably from 2 to 87% by mass, particularly preferably from 7 to 78% by mass, based on 100% by weight of the total amount. When the ratio of the XYX-type triblock polyether diamine compound (B1) is at least the lower limit of the above range, the stress relaxation and the bending fatigue property can be sufficiently exhibited as an elastomer. It is suitable as a polyamine-based elastomer. When the ratio of the gXYX-type dixin-stage polydiamine compound (B1) is less than or equal to the upper limit of the above range, the polyamine component can be more reliably expressed. The symbolic excellent mechanical strength of the guanamine is preferred. The polyether polyamine compound (B2) represented by the formula (2) in the amine compound (B) of the present invention can be used in comparison with poly(oxyl 14). - butyl butyl diol 1 Mo 20 200936643 Approximately 1 to 300 moles of ammonia in the ear and 0.1 to 10 moles of hydrogen in the presence of poly(oxy 1,4 butyl butyl) diol with nickel, copper, A polyamine compound obtained by a reductive amination reaction by contacting a catalyst such as molybdenum or chromium. In the polyether polyamine compound (B2) represented by the formula (2), n represents 5 4 to 40, and w represents 1 to 2. Specifically, XTJ-548 manufactured by U.S. Huntsman Co., Ltd. (in the formula (2), η is about 13, and w is 1 to 2) can be used. The ratio of the polyether polyamine compound (Β2) is 0.5% by weight relative to the total amount of (a) polyamine-forming precursor, amine compound (Β) and a slow acid compound (C). The mass % is preferably from 1 to 12% by mass. When the ratio of the polyether polyamine compound (?2) is at least the lower limit of the above range, the transparency can be sufficiently exhibited. When the ratio of the polyether polyamine compound (?2) is at most the upper limit of the above range, the crystallinity derived from the polyamine-forming monomer is increased, and sufficient mechanical strength is exhibited, which is preferable. Further, other diamine compounds (Β3) other than the triblock polyether hexaamine compound (Β1) and the polyether polyamine compound (Β2) may be contained in the above amine compound (Β). The other diamine compound (Β3) may, for example, be ethylenediamine, iota, propylenediamine, 1,4-butyleneamine, hexamethylenediamine, 1,7-heptanediamine, 1,8. ~ Octodiamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-|-diamine, 1,12 20 ''dodecyl diamine, 2,2,4-three Aliphatic diamines such as methyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 3-methyl-1,7-heptanediamine, etc. Alicyclic of 4_aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, 1,3-diaminodecylcyclohexane, 1,4-diaminomethylcyclohexane, etc. An aromatic diamine such as a diamine, m-xylylenediamine or p-xylylenediamine may be used alone or in combination of two or more. The second oxic acid compound (c) is an organic compound having two octyl groups, and can be widely used as a synthetic smear of polyamido, but representatively, for example, represented by the following formula (5) Compound. HOOC_(r3)st-C〇〇h (wherein R represents a linking group containing a hydrocarbon chain, and 111 is hydrazine or 1). In the aforementioned dicarboxylic acid compound (C) represented by the formula (3), R3 is preferably a molecular chain having a carbon number of 0 to 20 or a stretched carbon having a fine carbon atom, and preferably a hydrocarbon molecular chain having a carbon number of 1 to 15 or an alkylene group having from 1 to 15 carbon atoms. Further, it is more preferably a hydrocarbon molecular chain having a carbon number of 2 to 12 or an alkylene group having 2 to 12 carbon atoms, and particularly a hydrocarbon molecular chain having a carbon number of 4 to 1 fluorene or having 4 to 10 carbon atoms. The best base for stretching. m means 〇 or 2. Further, as the dibasic acid compound (c), at least one dicarboxylic acid selected from the group consisting of aliphatic, alicyclic and aromatic dicarboxylic acids or a derivative thereof can be used. Specific examples of the dicarboxylic acid compound (C) include oxalic acid, succinic acid, amyl phthalic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, dodecanedioic acid, and the like. a linear aliphatic dicarboxylic acid having a carbon number of 2 to 25, or a polymerized aliphatic dicarboxylic acid having a carbon number of 14 to 48 dimerized by an unsaturated fatty acid obtained by a branch of triglyceride An aliphatic dicarboxylic acid such as an acid (dimer acid) or a hydride thereof (hydrogenated dimer acid), an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, or a terephthalic acid, An aromatic dicarboxylic acid such as phthalic acid. As the dimer acid and the hydrogenated dimer acid, "Pripol 1004", "Pripol 13 200936643 1006", "Pripol 1009", "prip〇i ι〇! 3", or the like can be used. The hardness of the polyether polyamine elastomer (Shore hardness D, ShoreD) is preferably in the range of 15 to 70, and preferably in the range of 18 to 7 Å, and more preferably in the range of 20 to 70. Good, especially in the range of 25~7〇 is the best. The flexural strength of the polyether polyamine elastomer is preferably 〇 8 to 2 MPa, more preferably 1 to 18 MPa, and more preferably 1.1 to 15 MPa, and particularly preferably 1.2 to 13 MPa. When the flexural strength of the polyether polyamine elastomer is in the above range, an elastic body excellent in balance between toughness and rubber elasticity can be obtained. The flexural modulus of the polyether polyamine elastomer is preferably from 2 Torr to 400 MPa, and further preferably from 20 to 350 MPa, more preferably from 2 Torr to 300 MPa, particularly preferably from 20 to 250 MPa. By making the bending polystyrene of the polyether polyamine elastomer in the upper (four) range, it is preferable to obtain (4) an elastomer excellent in balance with the rubber elastic balance. The haze of the polyether polyamine elastomer is preferably 15 or less, more preferably 13 or less, and more preferably in the service, and the method is preferably 7 or less to make the haze lower than As described above, an elastomer excellent in transparency can be obtained. The water absorption ratio (%) of the polyfluorene polyimide elastomer is preferably 3% or less and more preferably 2.7%, and particularly preferably X is 25% or less. For the method for producing the polyacrylamide elastomer, for example, a method comprising the steps of: polyamine-forming monomer (A), XYX-type polypyramidine compound (B1) can be used. The poly-bonded polyamine compound _ and the di-acid compound (C) are simultaneously melt-polymerized under pressure and/or atmospheric pressure, and may be melt-polymerized under further reduced pressure as needed. Further, it is also possible to use a prepolymerization of the polyamine-forming monomer (A) and the dicarboxylic acid compound (C), and then to polymerize the triblock poly-diamine (B1) and the polyether of the χγχ type. A method of polymerizing an amine compound (B2). In the production of the polyether polyamide elastomer, the raw material feeding method 5 is not particularly limited, but may be fed in the following manner: (A) polyamine forming monomer, XYX type triblock polyether 2 The feed ratio of the amine compound (B1), the polyether polyamine compound (B2), and the oleic acid compound (C) is 10 to 95 by mass based on the total composition of the polyamine-forming monomer (A). The range of % is preferably, and particularly preferably in the range of 15 to 80% by mass; the χγχ type triblock polyether diamined 10 compound (Β1) is preferably 2 to 87% by mass, and particularly 7 ～78% by mass is preferably a polyether polyamine compound (Β2), preferably 〇5 to 20% by mass, and particularly preferably 1 to 15% by mass. The χγχ type triblock polyether diamine compound (Β1) and the polyamine compound (Β2) and the bis-acid compound (c) are preferably χγχ type triblock polyether diamine compound (B1) and poly The amine 15 group of the ether polyamine compound (B2) and the thiol group of the dicarboxylic acid compound (C) are fed in substantially the same molar amount. Q The polyether polyamine elastomer of the present invention is preferably produced at a polymerization temperature of 150 to 300 ° C, more preferably 16 to 28 (rc, and most preferably 170 to 250). When the polymerization temperature is lower than the above temperature, the polymerization reaction is sluggish, and when it is higher than the above temperature, thermal decomposition is likely to occur, and 20 polymers having good physical properties cannot be obtained. The elastomer, when the ω-amino phthalic acid is used as the polyamine forming monomer (Α), may be a step comprising melt polymerization at atmospheric pressure, or atmospheric pressure melt polymerization and vacuum melt polymerization after the step. 15 200936643 On the other hand, when the indoleamine is used as the polyamine-forming monomer (A), it can be coexisted with an appropriate amount of water and pressurized under the pressure of 〜1 to 5 MPa. The method comprises the steps of melt polymerization and atmospheric pressure melt polymerization and/or vacuum melt polymerization after the step. 5 The polyether polyamine elastomer of the present invention can be produced by a polymerization time of generally 5 to 30 hours. If the polymerization time is shorter than the above range, the molecular weight will rise. When the length is longer than the above range, coloring or the like may occur due to thermal decomposition, and in any of the cases, a polyether polyamine elastomer having desired physical properties may not be obtained. The production of the amine elastomer can be carried out in batch or continuous mode. A batch reactor, a tank-to-multi-tank continuous reaction apparatus, a tubular continuous reaction apparatus, etc. can also be used singly or in appropriate combination. The relative viscosity (β Γ) of the ether polyimine elastomer is preferably in the range of 2.2 to 3.5 (0.5 mass/vol% solution, 25 ° C). 15 The polyether polyamine of the present invention In the manufacture of an elastomer, a monoamine or a diamine such as dodecylamine, octadecylamine, 1,6-hexanediamine or m-xylylenediamine may be added for the purpose of determining the molecular weight adjustment or the melt viscosity during the forming process. An amine; a monocarboxylic acid such as acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid or dodecamic acid; or a dicarboxylic acid; etc., preferably used in an amount of 20 The relative viscosity (77 r) of the finally obtained elastomer is between 1.2 and 3.5 (0.5 mass/body) In the range of the % cresol solution '25 ° C). In the manufacture of the polyether polyamine elastomer of the present invention, the above-mentioned monoamine and diamine, monocarboxylic acid and dicarboxylic acid are added in an amount of It is preferable to adjust to the range which does not inhibit the characteristics of the obtained polyether polyamide elastomer. 16 200936643 In the manufacture of the said polyether polyamide elastomer, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. can be added as a catalyst as needed. Or an inorganic phosphorus compound such as an alkali metal salt or an alkaline earth metal salt such as phosphorous acid, hypophosphorous acid or the like may be added for the purpose of the effect of both the catalyst and the heat-resistant agent. The amount of addition is generally 50 to 3000 relative to the amount of the feed. In the above polyether polyamine elastomer, a heat-resistant agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, and a crystal may be added within a range not inhibiting the properties thereof. Nucleating agents, adhesion imparting agents, sealability improvers, antihalation agents, release agents, plasticizers, pigments, dyes, fragrances, flame retardants, reinforcing materials, and the like. Hereinafter, the composition comprising the polyether polyamine elastomer alone and the addition of the additives to the same elastomer is simply referred to as a polyether polyamine elastomer composition. The polyether polyamine elastomer composition of the present invention has low water absorbability, excellent melt moldability, excellent moldability, excellent strong drawability, excellent financial bending fatigue property 15, excellent rebound elasticity, excellent transparency, and low specific gravity. Excellent in low temperature flexibility, excellent in sound absorbing properties and rubber properties. Further, in the polyether polyamide elastomer, the terminal amine group concentration is preferably larger than the terminal carboxyl group concentration from the viewpoint of heat resistance. The polyether polyamine elastomer composition of the present invention can be obtained by a conventional molding method such as injection molding, 20 extrusion molding, blow molding, vacuum molding, or pressure forming. The injection-molded article of the polyether polyamine elastomer composition of the present invention may, for example, be a shoe sol which is preferably in the fields of baseball, soccer, and land sports, such as toughness, bending fatigue resistance, rebound resilience, and low specific gravity. Materials, and 17 200936643 Other injection molded articles include, for example, gears for mechanical and electronic precision machines, connectors, seals, automobile molds, and sealing materials. The extruded product of the polyether polyamine elastomer composition of the present invention may, for example, be a tube, a hose, a profiled material, a sheet, a film, a monofilament or the like. 5 The blow molded article of the polyether polyamine elastomer composition of the present invention may be, for example, a mirror dust cover for an automobile, a constant velocity joint boot, and the like. The polyether polyamine elastomer composition of the present invention is a thermoplastic resin other than the polyether polyamine elastomer, such as polyamide, polyethylene oxide, thermoplastic polyurethane, or ABS resin. The compatibility is good, and the thermoplastic resin can be used as a blend with 10 to improve the moldability, impact resistance, elasticity, flexibility, and the like of the resins. Further, it is possible to form a laminate in which a layer formed of the polyether polyamine elastomer composition of the present invention and a layer formed of another thermoplastic resin are laminated. The layered system may be one layer formed of the polyether polyamine elastomer composition of the present invention and one layer formed of another thermoplastic resin, or two or more layers. The thickness of each layer is not particularly limited, and the type of the polymer constituting each layer and the total number of layers in the laminate can be adjusted depending on the application and the like. Further, although the number of layers of the laminate is two or more, the total number of layers in the laminate is not particularly limited, and any number of layers may be used. Further, it is preferable that the structure of the laminated body manufacturing apparatus is 7 or less layers, and it is preferable to use 2 to 5 layers. Other thermoplastic resins mentioned above include, for example, high density polyethylene 18 200936643 (HDPE), low density polyethylene (LDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), and ethylene/propylene copolymer (EPR). , ethylene/butene copolymer (EBR), ethylene/vinyl acetate copolymer (EVA), ethylene/vinyl acetate copolymer telluride (EVOH), ethylene/acrylic copolymer 5 (EAA), ethylene/methacrylic acid Copolymer (EMAA), ethylene/methyl acrylate copolymer (EMA), ethylene/methyl methacrylate copolymer (EMMA), ethylene/ethyl acrylate (EEA), and the like, and carboxyl groups and The above polyolefin-based resin having a functional group such as a salt, an acid anhydride group or an ethoxy group, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and poly(ethylene isophthalate) Polyesters such as ester (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystal polyester (LCP), etc. Polyether resin such as resin, polyacetal (POM) or polyphenylene ether (PPO), polyfluorene resin such as polyfluorene (PSF) or polyether (PES), Polysulfone-based resin such as phenyl sulfide (PPS), polythioether 15 sulfone (PTES), polyetheretherketone (PEEK) polyketone resin such as polyaryletherketone (PAEK), polypropylene Nitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer (ABS), methacryl a polyacrylonitrile resin such as a nitrile/styrene/butadiene copolymer (MBS), a polymethyl acrylate such as polymethyl 20 acrylate (PMMA) or polyethyl methacrylate (ΡΕΜΑ); Polyethylene resin (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), ethylene/diethylene vinylene copolymer, polyethylene chloride/methacrylic acid copolymer, etc. Cellulose resin such as cellulose acetate or cellulose butyrate, polydifluoroethylene ethylene 19 200936643 (PVDF), polyfluoro olefin (PVF), polychlorotrifluoroethylene (PCTFE), ethylene/tetrafluoroethylene copolymer (etfe), ethylene/chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene/hexafluoropropylene copolymer (TFE/HFP, FEP), tetrafluoroethylene/hexafluoropropylene/fluorine a fluororesin such as an olefin copolymer (TFE/HFP/VDF, 5 THV), a tetrafluoroethylene/fluoro (alkylene ether) copolymer (PFA), or a polycarbonate resin such as polycarbonate (PC). Thermoplastic polyimine (PI), polyamidimide (PAI), polyetherimine, and the like, polyimide resin, thermoplastic polyurethane resin, polyethylidene Acid diamine (Nylon 26), polytetramethylammonium adipate (Nylon 46), polyhexamethylene adipamide (Nylon 66), polyhexamethylenemethyl Didecyl sebacate (Nylon 69), polyhexamethylenediamine diamine (Nylon 610), polyhexamethylenemethyl undecanedioate (Nylon 611), poly six Methyldodecanedioic acid diamine (Nylon 612), polyhexamethylenediamine terephthalate (Nylon 6T), polyhexamethylene diisophthalate diamine (Nylon) 61), poly-nine methyl dodecanedioic acid dioxane 15 amine (Nylon 912), poly-dodecylmethyldodecanedioic acid diamine (Nylon 1012), poly-twelve methyl 12 Diammonium alkanoate (Nylon 1212), polymethylene diamine adipate (Nylon MXD6), poly three Dihexylmethyldimethylene terephthalate (TMHT), polybis(4-aminocyclohexyl)methanedodecanoic acid diamine (Nylon PACM12), poly-bis(3-methyl-4) -Aminocyclohexyl)methane dodecylamine didecylamine (Nylon dimethyl PACM12), poly-nine methyldi-terephthalate (Nylon 9T), poly-methyl-p-phenylene Diammonium dicarboxylate (Nylon 10T), polydecylmethyldi-terephthalate (Nylon 11T), polydodemethyl-terephthalate diamine (Nylon 12T) or A polyammonium-based resin or the like which forms a copolymer of a polyamine raw material monomer or the like is used. In the Japanese Patent Publication No. 2009 200943, it is preferable to use a polyene-based resin, a polyester resin, a polyamine resin, a polysulfide resin, or a fluorine resin. The polymygular amine elastomer composition of the present invention can be advantageously used to form a polyamide-based elastomer composition which can be used for sports shoe sols, ski shoes, etc. 5 ❹ 10 15 ❹ 20 and thermoplastic polyamic acid. An ester laminate. In particular, the present invention is advantageous in that it provides a laminate in which a polyamidoquinone elastomer composition excellent in adhesion to a thermoplastic polyurethane and a thermoplastic polyurethane directly laminated. Hereinafter, the layer formed of the polyether polyamine elastomer composition described above is referred to as an X layer, and the layer formed of the other thermoplastic resin described above is referred to as a γ layer. a polyamine-forming monomer which is formed by laminating a layer of a polyamine phthalic acid ester layer and a layer of a polyamino phthalic acid ester. The ratio of (A) is preferably 10 to 95% by mass, more preferably 15 to 95% by mass, still more preferably 15 to 85% by mass, and particularly preferably 15 to 8 % by mass. The ratio of the polyamine-forming monomer (A) to the entire polyether polyamine elastomer is in the above range, particularly because the adhesion between the X layer and the γ layer is excellent, and the strength, the modulus, and the flexibility are It is excellent and pure as a mechanical property of a hybrid. When the ratio of the poly-branched amine/complex monomer (A) of the above-mentioned material-transfer body is less than the above range, the bonding strength of the X layer and the Y layer becomes lower, and the strength and the elastic material are Mechanical properties are reduced and less suitable. When the ratio of the polyamine-forming monomer (A) to the entire polyether polyamine elastomer is more than the above range, the function and performance of the elastomer as rubber elasticity or flexibility may be difficult. Appeared and more uncomfortable 21 200936643. It is speculated that the intermolecular hydrogen bond between the indole bond of the polyether polyamine elastomer and the urethane bond of the polyurethane affects the subsequent strength of the X layer and the γ layer. The X layer and/or the Y layer can be obtained by a molding method such as injection molding, extrusion molding, or blowing into a 5-shape, a roll forming, or a thermocompression molding. The method of forming a laminate is a method in which a layer including the X layer and the Y layer is simultaneously molded, a method of forming and laminating each layer, and a layer is formed on the layer while forming a layer (tandem). Law), etc., or a combination of them, etc. In the y layer, a polyurethane may be used: a polyurethane obtained by reacting a polyalcohol with diisocyanate, and a polyamine obtained by reacting a chain extender with a diisocyanate. A formic acid ester, a polyurethane obtained by reacting a polyhydric alcohol, a diisocyanate, and a chain extender. In particular, 'polyaminoformate' is based on the use of a thermoplastic polyurethane. 15 in the Y layer, polyurethane system <Hot oxime-type polyurethane having a polyester diol and/or a polyether diol as a soft segment is suitably used. As the polyhydric alcohol, a condensed polyester polyfluorene, a lactone polyester polyol, a polycarbonate polyol, a polyether polyol, or the like can be used. It is preferred to use a polyester diol which is obtained by using one or two or more kinds of di-reactive acid and a diol. The dicarboxylic acid may, for example, be an aliphatic diteric acid such as glutaric acid, gt; acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid; An alicyclic dicarboxylic acid such as an acid; an aromatic dicarboxylic acid such as a benzoic acid, an isophthalic acid or a phthalic acid or a lower alkyl ester thereof; and one or two of them may be used. More than one species. Among them, an aliphatic dicarboxylic acid such as a peric acid, azelaic acid or hydrazine 200936643 diacid or a lower alkyl ester thereof is preferred. 5 Ο 10 15 ❹ 20 The diol may, for example, be ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and other aliphatic diols; cyclohexane dimethane, cyclohexanediol, etc. The diol may be used alone or in combination of two or more. And the like, using 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1, An aliphatic diol such as 9-nonanediol or 1,12-dodecanediol is preferred. The lactone polyester polyol may, for example, be cold propiolactone, pivalolactone, 5-valerolactone, ε-caprolactone, fluorenyl-ε-caprolactone, dimethyl-ε-hexane. In the case of S, a compound such as a trimethyl group, an internal vinegar, or the like, and a hydroxy compound such as a short-chain polyalcohol are reacted. The polycarbonate diol can be obtained by a reaction of a low molecular diol with a carbonate compound such as an alkyl carbonate, an alkylene carbonate or a diaryl carbonate. Raw material for producing polycarbonate diol The low molecular diol system can be used as a low molecular diol exemplified as a raw material for producing a polyester diol. Further, examples of the dialkyl carbonate include dinonyl carbonate and diethyl carbonate; and the alkyl carbonate may, for example, be an ethyl carbonate; and the diaryl carbonate may, for example, be diphenyl carbonate. The polyether polyol may, for example, be polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glycol or polyalkylene glycol glycol based on glycerin. In addition to the above, various kinds of polyisocyanates used for various polyurethanes can be used. The type of polyisocyanate used in the polyurethane is not particularly limited, and it can be used up to now. The polyurethane is preferably any of the polyisocyanates used in the manufacture of the thermoplastic polyurethane. As the polyisocyanate, 1,4 - butyl diisocyanate, 1,5 -5 - pentyl diisocyanate, 1,6 - hexyl hexyl diisocyanate, diisocyanate diisocyanate, cyclohexyl hydrazine can be used. Alkane diisocyanate, diisocyanate 2,2,4- or 2,4,4-trimethyl 1,6-extended hexyl ester, isopropylidene bis(4-cyclohexyl isocyanate), isophorone diisocyanate, etc. Aliphatic or alicyclic diisocyanate, 2,4 or 2,6-toluene diisocyanate, 4,4' diphenylmethane diisocyanate, 3-methyl 10 diphenyl decane _4,4' Aromatic diisocyanate, m- or p_phenylene diisocyanate, gas-extended phenyl 2,4-diisocyanate, naphthalene-1,5-diisocyanate, xylene diisocyanate, tetradecyl xylene diisocyanate A diisocyanate or the like may be used, and one or two or more kinds of polyisocyanates may be used. Among them, 4,4'-diphenylmethane diisocyanate is preferably used. The type of the chain extender used in the production of the polyurethane is not particularly limited, and is used in any of the chain extenders used in the production of general polyurethanes. It is used as a low molecular weight compound having two or more active hydrogen atoms reactive with a polyisocyanate group in the molecule and having a molecular weight of 300 or less. The chain extender may, for example, be ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis(tenhydroxyethoxy)benzene, 1,4-cyclohexane. Alcohol, bis(/5-hydroxyethyl)terephthalate, glycol such as xylene glycol; hydrazine, ethylenediamine, propylenediamine, xylenediamine, isophoronediamine , piperene and its derivatives, phenylenediamine, indolediamine, xylene diamine, hexamethylene 24 200936643 diamines, diammonium isophthalate and other diamines; aminoethanol, amine An alcohol or the like, such as a propanol, may be used alone or in combination of two or more, and it is preferred to use an aliphatic diol having 2 to 10 carbon atoms, and to use ι, 4 - butyl Alcohol is better. 5 ❹ 10 15 ❹ 20 Chain extenders can use polyvalent alcohols, polyvalent amines, and the like. For example, "Pandex" (manufactured by Otsuka Ink Chemical Industries Co., Ltd.), "Kuramiron" (manufactured by Kuraray Co., Ltd.), "Miractran" (manufactured by Japan Miractran Co., Ltd.), and the like are exemplified. For the thermoplastic polyamine phthalate (TPU, etc.), the trade name "Elastolan ET195", "Elastolan ET690", "Elastolan ET890" manufactured by BASF Japan, and the brand name "Pandex T" manufactured by Dainippon Ink Chemical Industry Co., Ltd. can be used. 8190U", "Miractran E190", "Miractran E390", "Miractran E490", "Miractran E590", "Miractran E990", etc. manufactured by Japan Polyurethane Industry Co., Ltd. The X layer has good compatibility with thermoplastic resins such as polyamine, polystyrene, thermoplastic polyamine phthalate, ABS resin, etc., other than polyether decyl, in the range of non-destructive properties. It can be used in combination with these thermoplastic resins. The X layer is preferably contained in an amount of 70% by mass or more of polyetherenamine, more preferably 80% by mass or more of polyether decylamine, and more preferably 8% by mass or more of polyether amide, and particularly It is preferably the polyether amide containing 95% by mass or more. The Y layer can be used in combination with other thermoplastic polymers, elastomers, rubbers, and the like other than the polyurethane in the range of non-destructive properties. Further, for the purpose of improving the adhesion between the layers, an adhesive layer may be provided. 25 200936643 Also, any substrate other than thermoplastic resin may be laminated, such as paper, metal-based materials, non-extension, one- or two-axis extended plastic film or sheet, woven fabric, non-woven fabric, metal wool, wood, and the like. The metal-based material may, for example, be a metal or a metal compound such as ing, iron, copper, nickel, gold, silver, titanium, turn, town, smash, smear, tin, ruthenium, wrinkle, 5 tungsten, cobalt, etc. Alloy steel such as stainless steel of two or more types, alloys such as aluminum alloy, brass, and bronze, and alloys such as nickel alloy. Next, it is preferred to use an olefin-based polymer containing a carboxyl group, a salt thereof, an acid anhydride group or an ethoxy group. Examples of the olefin-based polymer include polyethylene, poly 10 propylene, ethylene-propylene copolymer, ethylene-butylene copolymer, polybutene, ethylene-propylene-diene copolymer, polybutadiene, and butadiene. An acrylonitrile copolymer, polyisoprene, butene-isopentadiene copolymer, and the like. Further, in the olefin-based polymer, a carboxylic acid ester may be copolymerized, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid ethyl acrylate, and acrylic acid acrylate. a copolymerized polymer such as ester, propyl methacrylate, butyl acrylate or butyl methacrylate, and more specifically, for example, an ethylene methacrylate copolymer or an ethylene ethyl acrylate copolymer , Ethylene-acrylic acid propylene copolymer, acetonitrile-acrylic acid butyl S copolymer, ethylene methyl methacrylate copolymer, ethylene monoethyl methacrylate total 20 polymer, ethylene monomethacrylate Olefin-(meth) acrylate copolymer, methyl acrylate-acrylonitrile copolymer, bismuth methacrylate, etc., ester copolymer, ethylene-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer Ester-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl propyl acrylate-acrylonitrile copolymer, butyl acrylate-propylene 26 200936643 Nitrile copolymer, butyl methacrylate-acrylonitrile Dimer, etc. (meth) acrylate-acrylonitrile copolymer _. Further, the carboxyl group and its salt, the acid anhydride group, the ethoxy group may be introduced into the copolymer of the primary bond of the polyolefin molecule, or the graft polymer introduced into the side chain may be any of 5 Ο 10 15 ❹ 20 . Examples of the carboxyl group, the salt thereof, the acid anhydride group, and the ethoxy group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, and pyroic acid. Pentenoic acid, cis-4-cycloheptene-1,2-di-hypo-acid, endo-bicyclo[2.2.1]g- 5,- 2,3-di-retensive acid and the carboxylic acid Metal salt (Na, Zn, K, Ca, Mg), anhydrous maleic acid, anhydrous itaconic acid, anhydrous pyroic acid citrate, anhydrous fumaric acid, internal bicyclo-[2.2,1]-5-g Burning a 2,3-dicarboxylic acid anhydride, acrylic acid dehydrating glycerol, methacrylic acid dehydrating glycerol, ethacrylic acid deglycidyl ester, and itaconic acid dehydroglyceryl ester, Pyrogallol dehydroglyceryl ester and the like. The above-exemplified olefin-based polymer containing a functional group such as a carboxyl group, a salt thereof, an acid anhydride group or an ethoxy group described above can be used as the layer. Examples of the laminated composition of the laminated body of the present invention include, for example, an X layer/Y layer, an X layer/Y layer/X layer, a Y layer/X layer/Y layer, an X layer/Y layer/substrate layer, and a substrate. Layer/X layer/Y layer, X layer/Y layer/X layer/substrate layer, Y layer/X layer/Y layer/substrate layer, γ layer/X layer/Bottom layer/Substrate layer, X layer/ Y layer / adhesive layer / substrate layer, substrate layer / bonding layer / X layer / Y layer / X layer / bonding layer / substrate layer, substrate layer / bonding layer / Y layer / X layer / Y layer / then Layer/substrate layer, etc. In addition to the polymer of the X layer and the Y layer, a substrate, a film, a film 27 200936643 and a molded article obtained from other polymer materials may be used; natural, synthetic fibers, glass, ceramics, etc.; Fabrics, braids, braids, and non-woven fabrics obtained from inorganic fibers as raw materials; glass, metal, ceramics, coating film, paper, etc.; leather, and the like. Next, it is preferable to use a well-known respective components, a sheet or film having an adhesiveness 5, and the like, and it is preferable to use the characteristics of the present invention. The laminated body of the present invention can be used as a two-color molded article formed by injection molding, and can be used for a shoe material such as a shoe sol material or a ski shoe, an automobile part, or the like, and can be used as an extrusion molded article for using a film laminate. Snowboards and hoses, tubes, belts, etc. The peel strength of the X layer and the Y layer of the laminate of the present invention is preferably 9.5 kg·cm or more, and more preferably 10.5 kg·cm or more. In the laminate of the present invention, when the soft segment of the Y layer is a polyamine phthalate of a polyether diol, the peel strength of the X layer and the Y layer of the present invention is preferably 9.5 kg·cm or more. Further, it is preferably 10.5 kg·cm or more, and particularly preferably 10.8 kg·cm or more. In the laminate of the present invention, when the soft segment of the Y layer is a polyaminocarbamic acid S of a polyester diol, the peel strength of the X layer and the Y layer of the present invention is preferably 9.8 kg·cm or more. Further, it is preferably 10.2 kg.cm or more, and more preferably 10.5 kg.cm or more. 20 EXAMPLES Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited by the examples. The characteristics are generally measured as follows. 1) Relative viscosity (7?r) (0.5 mass/vol% m-cresol solution, 25 °C): 28 200936643 The m-nonylphenol of the reagent grade product is used as a solvent, and the agricultural degree of 5 g/d work 3 is used. Ostwald's Visometer was taken at 25 °C.仃2) End carboxyl group concentration ([C00H]): 5 Add 40 mL of 2 benzyl alcohol to about 1 g of the polymer, heat-dissolve in a nitrogen gas field, and add the indicator phenolphthalein to the obtained sample solution, and add N/ 20 titration of potassium hydroxide-ethanol solution. 3) Terminal amine group concentration ([NH2]): Dissolve about 1 g of the polymer in a 40 mM phenol/methanol mixed solvent (body 10 ratio: 9/1), and add it to the obtained sample solution. The indicator thymol blue was titrated with N/20 hydrochloric acid. 4) Melting point (Tm) and crystallization temperature (tc):

Tm及Tc係使用（股）島津製作所製造的示差掃描熱析儀 DSC—50，且於氮氣氣體環境下進行測量。以1〇〇c/分鐘 15的速度從室溫昇溫至230。〇（稱為昇溫首輪），並於230°C保持 ίο分鐘後，以io°c/分鐘的速度降溫至—10(rc(稱為降溫 首輪），接下來以io°c/分鐘的速度昇溫至23(rc(稱為昇溫 第二輪）。自將所得到的DSC圖表的降溫首輪之發熱峰值溫 度定為Tc，將昇溫第二輪之吸熱峰值溫度定為丁瓜。 20 5)彎曲試驗(彎曲彈性率、彎曲強度） 使用尺寸為6.35mmxl2.7mmxl27mm之試驗片，以 ASTM D790為基準，於23°c測量。 6)壓縮永久變形(Cs ):Tm and Tc were measured by a differential scanning calorimeter DSC-50 manufactured by Shimadzu Corporation and measured under a nitrogen gas atmosphere. The temperature was raised from room temperature to 230 at a rate of 1 〇〇c/min. 〇 (called the first round of warming), and after maintaining ίο minutes at 230 ° C, cool down to _ 10 (rc (called the first round of cooling) at io ° c / minute, then heat up at io ° c / minute To 23 (rc (referred to as the second round of heating). Since the peak temperature of the first round of cooling of the obtained DSC chart is set to Tc, the peak endothermic temperature of the second round of temperature rise is set to began. 20 5) Bending test (Bending Elasticity, Bending Strength) A test piece having a size of 6.35 mm x 2.7 mm x 27 mm was used, measured at 23 ° C based on ASTM D790. 6) Compression set (Cs ):

Cs係以JIS K 6262為基準進行測量。從厚度為5〜 29 200936643 6mm的片切割出直徑29mm的試驗片，將其2片重疊(厚度： t 〇)配置在專用的機架上，壓縮至9.5mm( t J，以此狀態於 70°C加熱12小時後，以23°C、55%RH冷卻2小時。其後， 將試驗片從機架取下並測量30分鐘後的厚度（t2)，且藉由 5 下列式求得CS (單元為％)。 C s = { (t 〇~ t 2)/(t 〇— t i)} xlOO 7)永久延伸度 從厚度約1mm的片切割出啞鈴型jis 3號試驗片，將 標線間的距離定為20mm ’並將此試驗片以5〇〇mm/分鐘的 10速度使標線間延伸至120mm。以施加此應力的狀態保持1〇 分鐘後，以1000mm/分鐘的速度解放應力。於此1〇分鐘後 測量標線間距離(L )，並藉由下列式求得永久延伸度（單元為 %)。The Cs is measured based on JIS K 6262. A test piece having a diameter of 29 mm was cut out from a sheet having a thickness of 5 to 29 200936643 6 mm, and two sheets of overlap (thickness: t 〇) were placed on a dedicated frame and compressed to 9.5 mm (t J, in this state at 70 After heating at ° C for 12 hours, it was cooled at 23 ° C, 55% RH for 2 hours. Thereafter, the test piece was taken out from the frame and the thickness (t2) after 30 minutes was measured, and CS was obtained by the following formula: (Unit is %) C s = { (t 〇~ t 2)/(t 〇 — ti)} xlOO 7) Permanent elongation Cut out the dumbbell type jis No. 3 test piece from the sheet with a thickness of about 1 mm, and mark the line The distance between the two was set to 20 mm' and the test piece was extended to 120 mm between the marking lines at a speed of 10 〇〇mm/min. After maintaining this stress for 1 minute, the stress was released at a rate of 1000 mm/min. After 1 minute, the distance between the lines (L) was measured, and the permanent elongation (unit is %) was obtained by the following formula.

永久延伸度={(L—20)/20 } xlOO 15 8)硬度： 使用尺寸為6.35mmxl2.7mmxl27mm之試驗片，並以 ASTM D2240為基準測量蕭氏硬度D。測量係於23°C進行。 再者，藉由重疊6片壓縮成形作成的厚度約1mm之片來 測量蕭氏硬度D。測量係於23°C進行。 20 9)霧度(haze): 使用60mmx60mmx厚度1mm之片，以HS K7105為基 準，並使用須贺試驗機(股)製直接讀取式霧度電腦HGM〜 2DP進行測量。 10)剝離強度： 30 200936643 將聚胺基甲酸酯藉由樹脂溫度21(TC之壓縮成形法成 形成尺寸為：80mmx80mmx厚度imm(Y層）。將成形物以層） 之下方覆以尺寸為：80mmx25mmx厚度15"m2鋁箔對 其將聚酿胺以樹脂溫度240〇c之條件壓縮成开》，而將聚酿胺 5與聚胺基甲酸醋作成直接積層的積層體。為了從此積層體 作成剝離強度測量用樣品，於鋁箔的長邊方向垂直地將片 以10mm寬進行切割’而得到8〇mmxi〇mmx厚度2mm之條。 從該條剝除鋁箔而作成剝離強度測量用試驗片。接著部及 剥離试驗時之試驗機夾頭抓取部之尺寸分別為55jnmx 10 l〇mm及25mmxl〇mm 〇 剝離強度係藉由T剥離試驗進行測量。裝置係使用東方 科技公司（Orientec)製TENSILON 2500，測量係以夾頭間距 離5mm、拉伸速度2〇mm/分鐘進行。剝離強度係丨樣品測 量5次，並取其平均。 15 〔實施例1〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 口、壓力調整裝置及聚合物取出口的5公升壓力容器中進料 入宇部興產（股）製12—胺基十二酸652.8g、己二酸222.5g、 20 XYX型之三嵌段聚醚二胺(HUNTSMAN公司製XTJ —542， 胺價：1.94meq/g)1543.7g、聚醚聚胺化合物(HUNTSMAN 公司製XTJ—548)88.3g、苯膦酸1.53g及财熱劑（三乙二醇一 N—雙一3 —(3—第三丁基一4一羥基一5 —甲基苯基）丙酸 酯；吉富製藥製Tominox 917)6.25g。將容器内置換充分的 31 200936643 氮後，一邊以500毫升/分鐘供給氮氣一般緩緩地進行加 熱。授拌係以速度50rpm進行。花1小時從室溫昇溫至19〇 °C ’並於190°C進行聚合1小時。其後，花丨小時昇溫至225 。(：，並於225°C進行聚合10小時，而得到聚合物。聚合結束 5後，停止攪拌，並從聚合物取出口拉出帶狀的熔融狀態的 無色透明聚合物，且以水冷卻後，使其片狀沉澱，而得到 約1.5kg之片狀沉澱物。 所得到的片狀沉澱物係白色且透明性佳並富有強勤橡 膠彈性的聚合物，且 7?r=2.06、〔CO〇H〕=2.11x10—5eq/ 10 g、〔 NH2〕= 3.60xl0_5eq/g、Tm= 124°C。 將所得到的聚醚聚醯胺彈性體藉由射出成形，而成形 成厚度2mm之片，並與同様經由射出成形成形成厚度2mm 之片的熱可塑性胺基甲酸酯（TPU;BASF日本公司製，商品 名「Elastolan ET690」）藉由熱壓縮成形，而作成積層體試 15 驗片。測量所得到的積層體試驗片之硬度、彎曲彈性率、 彎曲強度、壓縮永久變形、霧度及與TPU的剝離強度。將 結果示於表1。 再者，熱壓縮成形係於溫度230°C、l〇MPa進行。 20 〔實施例2〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 口、壓力調整裝置及聚合物取出口的5公升壓力容器中進料 入宇部興產(股）製12—胺基十二酸653.lg、己二酸221.8g、 XYX型之三嵌段聚醚二胺(HUNTSMAN公司製XT J - 542， 32 200936643 胺價：1.94meq/g)1462.4g、聚醚聚胺化合物(HUNTSMAN 公司製XTJ —548)162.5g、苯膦酸1.50g及耐熱劑（吉富製藥 製Tominox 917)6.25g。將容器内置換充分的氮後，一邊以 500毫升/分鐘供給氮氣一邊緩緩地進行加熱。攪拌係以速 5 度50rpm進行。花1小時從室溫昇溫至190°C，並於190°C進 行聚合1小時。其後，花1小時昇溫至225°C，並於225°C進 行聚合10小時，而得到聚合物。聚合結束後，停止攪拌， 並從聚合物取出口拉出帶狀的熔融狀態的無色透明聚合 物，以水冷卻後，使其片狀沉澱而得到約1.5kg之片狀沉澱 10 物。 所得到的片狀沉澱物係白色且透明性佳並富有強韌橡 膠彈性的聚合物，T/r=2.28、〔COOH〕=3.18xl0_5eq/g、 [NH2 ] = 4.26xl0~5eq//g ' Tm= 125°C 0 使用所得到的聚醚聚酿胺彈性體，與實施例1相同様地 15 作成積層體試驗片，測量硬度、彎曲彈性率、彎曲強度、 壓縮永久變形、霧度及與TPU的剝離強度。將結果示於表1。 〔實施例3〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 20 口、壓力調整裝置及聚合物取出口的5公升壓力容器中進料 入宇部興產（股)製12—胺基十二酸793.0g、己二酸207.1g、 XYX型之三嵌段聚醚二胺(HUNTSMAN公司製XTJ—542， 胺價：1.94meq/g)1425.0g、聚醚聚胺化合物(HUNTSMAN 公司製XTJ—548)75.0g、苯膦酸1.50g及耐熱劑（吉富製藥製 33 200936643 T〇min〇X917)6.25g。將容器内置換充分的氮後，一邊以5〇〇 毫升/分鐘供給氮氣一般緩緩地進行加熱。攪拌係以速度 5〇rpin進行。花1小時從室溫昇溫至19〇。(：，並於190。(：進行 聚合1小時。其後，花1小時昇溫至225°C，並於225。(：進行 5聚合10小時，而得到聚合物。聚合結束後，停止攪拌，並 從聚合物取出口拉出帶狀的熔融狀態的無色透明聚合物， 以水冷卻後’使其片狀沉澱而得到約15]^之片狀沉澱物。 所得到的片狀沉澱物係白色且透明性佳並富有強韌橡 膠彈性的聚合物，7^=2 08、〔C〇〇H〕=2.60xl0_5eq/g、 10 〔 NH2〕= 3.48xl〇-5eq/g、Tm= ΠΟΧ；。 使用所得到的聚醚聚醯胺彈性體，與實施例丨相同様地 作成積層體試驗片，測量硬度、彎曲彈性率、彎曲強度、 壓縮永久變形、霧度及與TPU的剝離強度。將結果示於表1<5 15 〔比較例1〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 口、壓力調整裝置及聚合物取出口的5公升壓力容器中進料 入宇部興產（股)製12-胺基十二酸664.6g、己二酸230.4g、 XYX型之三嵌段聚醚二胺(HUNTSMAN公司製XTJ-542，Permanent elongation = {(L - 20) / 20 } xlOO 15 8) Hardness: A test piece having a size of 6.35 mm x 2.7 mm x 27 mm was used, and the Shore D hardness was measured based on ASTM D2240. The measurement was carried out at 23 °C. Further, the Shore D hardness was measured by superimposing six sheets of compression-molded sheets having a thickness of about 1 mm. The measurement was carried out at 23 °C. 20 9) Haze: A 60 mm x 60 mm x 1 mm piece was used, based on HS K7105, and measured using a direct reading haze computer HGM ~ 2DP manufactured by a Suga test machine. 10) Peel strength: 30 200936643 The polyurethane was formed by a resin temperature of 21 (compression molding method of TC to a size of 80 mm x 80 mm x thickness imm (Y layer). The molded article was layered under the layer). : 80mm x 25mmx thickness 15 " m2 aluminum foil to compress the polyamine to a temperature of 240 〇c at a resin temperature, and the polyamine 5 and the polyurethane urethane are directly laminated. In order to form a sample for peel strength measurement from the laminated body, the sheet was cut perpendicularly in the longitudinal direction of the aluminum foil by 10 mm to obtain a strip having a thickness of 2 mm of 8 mmφxi〇mmx. The aluminum foil was peeled off from this strip to prepare a test piece for peel strength measurement. The dimensions of the gripper gripping portion of the tester and the peeling test were 55jnm x 10 l〇mm and 25mmxl〇mm 〇 respectively. The peel strength was measured by the T peel test. The apparatus was a TENSILON 2500 manufactured by Orientec, and the measurement was carried out at a crosshead distance of 5 mm and a stretching speed of 2 〇mm/min. The peel strength was measured five times and the average was taken. 15 [Example 1] In a 5 liter pressure vessel equipped with a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen inlet, a pressure adjusting device, and a polymer outlet, a 12-amine product was introduced into Ube Industries Co., Ltd. 652.8 g of dicodoic acid, 222.5 g of adipic acid, and triblock polyether diamine of 20 XYX type (XTJ-542, manufactured by HUNTSMAN Co., Ltd., amine price: 1.94 meq/g) 1543.7 g, polyether polyamine compound (HUNTSMAN) Company XTJ-548) 88.3g, phenylphosphonic acid 1.53g and financial agent (triethylene glycol-N-bis-3-(3-t-butyl-4-hydroxy- 5-methylphenyl)-propyl Acid ester; Tominox 917 by Jifu Pharmaceutical Co., Ltd.) 6.25g. After the inside of the vessel was replaced with a sufficient amount of nitrogen, the nitrogen gas was gradually heated at 500 ml/min. The mixing system was carried out at a speed of 50 rpm. The temperature was raised from room temperature to 19 ° C for 1 hour and polymerization was carried out at 190 ° C for 1 hour. Thereafter, the flowering temperature increased to 225 hours. (:, and polymerization was carried out at 225 ° C for 10 hours to obtain a polymer. After the end of the polymerization 5, the stirring was stopped, and the ribbon-like molten colorless transparent polymer was pulled out from the polymer outlet and cooled with water. The pellet was precipitated to obtain a sheet-like precipitate of about 1.5 kg. The obtained pellet was white and had good transparency and a strong rubber-elastic polymer, and 7?r=2.06, [CO 〇H]=2.11x10—5 eq/ 10 g, [NH2]= 3.60×10 −5 eq/g, Tm=124° C. The obtained polyether polyamine elastomer was formed by injection molding to form a sheet having a thickness of 2 mm. And a thermoplastic urethane (TPU; manufactured by BASF Japan Co., Ltd., trade name "Elastolan ET690") which was formed into a sheet having a thickness of 2 mm by injection to form a laminate test piece by thermal compression molding. The hardness, flexural modulus, flexural strength, compression set, haze, and peel strength with TPU of the obtained laminated test piece were measured. The results are shown in Table 1. Further, the thermocompression molding was carried out at a temperature of 230°. C, l 〇 MPa. 20 [Example 2] with stirring , a thermometer, a torque meter, a pressure gauge, a nitrogen inlet, a pressure adjusting device, and a 5 liter pressure vessel for the polymer outlet to be fed into the U-product of the production of 12-aminododecanoic acid 653.lg, 221.8 g of diacid, triblock polyether diamine of XYX type (XT J-542, 32 200936643, amine price: 1.94 meq/g, manufactured by HUNTSMAN Co., Ltd.) 1462.4 g, polyether polyamine compound (XTJ-548, manufactured by HUNTSMAN Co., Ltd.) 162.5 g, 1.50 g of phenylphosphonic acid, and 6.25 g of a heat-resistant agent (Tominox 917 manufactured by Jifu Pharmaceutical Co., Ltd.). After replacing the inside of the container with sufficient nitrogen, the mixture was gradually heated while supplying nitrogen gas at 500 ml/min. The temperature was raised at 50 rpm, and the temperature was raised from room temperature to 190 ° C for 1 hour, and polymerization was carried out at 190 ° C for 1 hour. Thereafter, the temperature was raised to 225 ° C for 1 hour, and polymerization was carried out at 225 ° C for 10 hours to obtain After the completion of the polymerization, the stirring was stopped, and the ribbon-like molten colorless transparent polymer was pulled out from the polymer outlet, and after cooling with water, it was precipitated in a sheet form to obtain a sheet-like precipitate of about 1.5 kg. The resulting flaky precipitate is white and transparent and has a strong oak Gel-elastic polymer, T/r=2.28, [COOH]=3.18x10_5eq/g, [NH2] = 4.26xl0~5eq//g 'Tm= 125°C 0 The obtained polyether polyamine elastomer A laminate test piece was prepared in the same manner as in Example 1 to measure hardness, flexural modulus, flexural strength, compression set, haze, and peel strength with TPU. The results are shown in Table 1. [Example 3] In a 5 liter pressure vessel having a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas introduction port 20, a pressure adjusting device, and a polymer outlet, a 12-amine product was introduced into Ube Industries Co., Ltd. 793.0 g of dicodoic acid, 207.1 g of adipic acid, triblock polyether diamine of XYX type (XTJ-542 manufactured by HUNTSMAN Co., Ltd., amine price: 1.94 meq/g) 1425.0 g, polyether polyamine compound (HUNTSMAN company) 7Xg of XTJ-548), 1.50g of phenylphosphonic acid and 6.25g of heat-resistant agent (33 200936643 T〇min〇X917 made by Jifu Pharmaceutical Co., Ltd.). After the inside of the vessel was replaced with a sufficient amount of nitrogen, the nitrogen gas was gradually supplied while being supplied with nitrogen at 5 Torr/min. The stirring was carried out at a speed of 5 〇rpin. The temperature was raised from room temperature to 19 1 in 1 hour. (:, and 190. (: Polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 225 ° C for 1 hour, and at 225. (: 5 polymerization was carried out for 10 hours to obtain a polymer. After the completion of the polymerization, the stirring was stopped. The ribbon-like molten colorless transparent polymer was pulled out from the polymer outlet, and after cooling with water, it was precipitated in a sheet form to obtain a sheet-like precipitate of about 15%. The obtained pellet was white. The polymer having good transparency and strong rubber elasticity, 7^=2 08, [C〇〇H]=2.60x10_5eq/g, 10[NH2]= 3.48xl〇-5eq/g, Tm=ΠΟΧ; Using the obtained polyether polyamine elastomer, a laminate test piece was prepared in the same manner as in Example ,, and hardness, flexural modulus, bending strength, compression set, haze, and peel strength with TPU were measured. Table 1 <5 15 [Comparative Example 1] was fed into Ube Industries (5 liters) in a 5 liter pressure vessel equipped with a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure regulating device, and a polymer outlet. Co., Ltd. made 12-amino-dodecanoic acid 664.6g, adipic acid 230.4g, XYX type Polyether diamine (manufactured by HUNTSMAN XTJ-542,

20胺價：i.Mmeq/gHQS.lg、苯膦酸i.53g及耐熱劑（吉富製 藥製Tominox 917)6.25g。將容器内置換充分的氮後，一邊 以500毫升/分鐘供給氮氣一般緩緩地進行加熱。攪拌係以 速度50rpm進行。花1小時從室溫昇溫至19〇<^，並於19〇°c 進行聚合1小時。其後，花1小時昇溫至225。(：，並於225°C 200936643 進行聚合ίο小時，而得到聚合物。聚合結束後，停止攪拌， 並從聚合物取出口拉出帶狀的熔融狀態的無色透明聚合 物，以水冷卻後，使其片狀沉澱而得到約1.5kg之片狀沉澱 物。 5 所得到的片狀沉澱物係幾乎透明並富有強韌橡膠彈性 的聚合物，？？ r=2.00、〔COOH〕=1.72x10—5eq/g、〔NH2 〕=2.88x10 —5eq/g、Tm=128°C。20 amine price: i.Mmeq/gHQS.lg, phenylphosphonic acid i.53g and heat-resistant agent (Tominox 917 made by Jifu Pharmaceutical Co., Ltd.) 6.25g. After replacing the inside of the vessel with sufficient nitrogen, the mixture was gradually heated while supplying nitrogen gas at 500 ml/min. The stirring was carried out at a speed of 50 rpm. The temperature was raised from room temperature to 19 Torr in 1 hour, and polymerization was carried out at 19 ° C for 1 hour. Thereafter, the temperature was raised to 225 in one hour. (:, and polymerization was carried out at 225 ° C 200936643 to obtain a polymer. After the completion of the polymerization, the stirring was stopped, and the ribbon-like molten colorless transparent polymer was pulled out from the polymer outlet to be cooled by water. It was precipitated in a sheet form to obtain a sheet-like precipitate of about 1.5 kg. 5 The obtained sheet-like precipitate was a polymer which was almost transparent and rich in tough rubber elasticity, ??r = 2.00, [COOH] = 1.72 x 10 - 5 eq/g, [NH2] = 2.88 x 10 - 5 eq/g, and Tm = 128 °C.

使用所得到的聚醚聚醯胺彈性體，與實施例1相同様地 作成積層體試驗片，測量硬度、彎曲彈性率、彎曲強度、 10 壓縮永久變形、霧度及與TPU的剝離強度。將結果示於表1。 表1 \ 進料成分 ηΓ 物性 胺基十二 酸 己二酸 XTJ-542 XTJ-548 (D-規 模） 彎曲 彈性 率 變曲 強度 1縮永 久 變形 霧度 剝離 強度 重量％ — 一 MPa MPa % % eg or 實施 例1 26.0 8.9 61.6 3.5 2.06 34 53 3.2 82 2.6 11.5 實施 例2 26.1 8.9 58.5 6.5 2.28 34 54 3.2 82 2.3 11.8 比較 例1 26.4 9.1 64.5 0 2.00 32 56 3.1 73 3.1 11.2 實施 例3 31.7 8.3 57.0 3.0 2.08 37 60 3.5 81 2.2 11.6 可知實施例1〜3之本發明的聚醚醯胺彈性體，相較於 比較例1之聚醚醯胺彈性體，霧度低、透明性優異，且剝離 15 強度高。 35 200936643 〔實施例4〕 於具有攪拌機、氮氣導入口、縮合水排出口之體積約 130毫升的反應容器中進料入宇部興產(股)製12一胺基十二 5酸(ADA)6.138g、己二酸(AA)2.867g、XYX型之三嵌段聚醚 二胺（HUNTSMAN公司製XTJ — 542，胺價：1.94meq/ g)l9.950g、聚醚聚胺化合物（HUNTSMAN公司製XTJ — 548)1.067g、苯膦酸〇.〇l7g及耐熱劑（吉富製藥製Tominox 917)0.076g。將容器内置換充分的氮後，一邊以流速5〇毫升 10 /分鐘供給氮氣，一邊以19(TC加熱1小時，接著花1小時昇 溫至225°C，並於225°C進行聚合10小時，而得到聚合物。 所得到的片狀沉澱物係白色且透明性佳且強韌富有橡 膠彈性的聚合物，7? r=2.25、〔COOH〕= 1.58x10 —5eq/g、 〔NH2〕=4.40xl〇_5eq/g。 15 將所得到的聚醚聚醯胺彈性體以溫度230°C、lOMPa壓 縮成形，而作成厚度約1mm之片。使用此片評定硬度及永 久延伸度。將結果示於表2。 〔實施例5〕 20 於具有攪拌機、氮氣導入口、縮合水排出口之體積約 130毫升的反應容器中進料入宇部興產（股)製12—胺基十二 酸(ADA)6.166g、己二酸(AA)2.838g、XYX型之三嵌段聚醚 二胺（HUNTSMAN公司製XTJ- 542，胺價：1.94meq/ g)18.898g、聚醚聚胺化合物（HUNTSMAN公司製XTJ — 36 200936643 548)2.100g、苯膦酸〇.〇16g及耐熱劑（吉富製藥製Tomin〇x 917)0.077g。將容器内置換充分的氮後，一邊以流速5〇毫升 /分鐘供給氮氣，一邊以190°C加熱1小時，接著花1小時昇 溫至225°C，並於225°C進行聚合1〇小時，而得到聚合物。 5 所得到的片狀沉澱物係白色且透明性佳且強韌富有橡 膠彈性的聚合物，？^=2.35、〔(：0011〕=2.76xl〇-5eq/g、 〔NH2〕=4.15xl〇_5eq/g。 將所得到的聚醚聚酿胺彈性體以溫度230°C、lOMPa壓 縮成形，而作成厚度約1mm之片。使用此片評定硬度及永 10 久延伸度。將結果示於表2。 〔實施例6〕 於具有擅:拌機、氮氣導入口、縮合水排出口之體積約 130毫升的反應容器中進料入宇部興產（股）製π—胺基十二 15 酸(ADA)6.197g、己二酸(AA)2.804g、XYX型之三嵌段聚醚 二胺（HUNTSMAN公司製 XTJ- 542，胺價：i.94meq/ g)18.847g、聚醚聚胺化合物（HUNTSMAN公司製XTJ — 548)3.151g、苯膦酸〇.〇15g及耐熱劑（吉富製藥製Tominox 917)0.079g。將容器内置換充分的氮後，一邊以流速5〇毫升 20 /分鐘供給氮氣，一邊以190°C加熱1小時，接著花1小時昇 溫至225°C，並於225°C進行聚合10小時，而得到聚合物。 所得到的片狀沉澱物係白色且透明性佳且強勃富有橡 膠彈性的聚合物，77 r=2.54、〔COOH〕=4.00x10-5eq/g、 〔NH2〕=0.24x10 一 5eq/g。 37 200936643 將所得到的聚醚聚醯胺彈性體以溫度230°C、10MPa壓 縮成形，而作成厚度約1mm之片。使用此片評定硬度及永 久延伸度。將結果示於表2。 5 〔比較例2〕 於具有攪拌機、氮氣導入口、縮合水排出口之體積約 130毫升的反應容器中進料入宇部興產（股)製12—胺基十二 酸(ADA)6.100g、己二酸(AA)2.908g、XYX型之三嵌段聚喊 二胺（HUNTSMAN公司製 XTJ- 542，胺價：1.94meq/ 10 g)21.〇〇4g、苯膦酸〇.〇i8g及耐熱劑（吉富製藥製T〇min〇x 917)0.073g。將容器内置換充分的氮後，一邊以流速5〇毫升 /分鐘供給氮氣，一邊以19(TC加熱1小時，接著花1小時昇 溫至225°C ’並於225°C進行聚合10小時，而得到聚趟聚酿 胺彈性體。 15 所得到的片狀沉澱物係白色且透明性佳且強韌富有橡 膠彈性的聚合物，^=1.77、〔COOH〕=2.95x10 —5eq/g、 〔NH2〕=3.95x10-5eq/g。 將所得到的聚醚聚醯胺彈性體以溫度230°C、lOMPa壓 縮成形’而作成厚度約1mm之片。使用此片評定硬度及永 20久延伸度。將結果示於表2。 200936643 表2Using the obtained polyether polyamine elastomer, a laminate test piece was produced in the same manner as in Example 1, and the hardness, bending elastic modulus, bending strength, 10 compression set, haze, and peel strength with TPU were measured. The results are shown in Table 1. Table 1 \ Feed composition ηΓ Physical amine dodecanoic acid adipic acid XTJ-542 XTJ-548 (D-scale) Flexural modulus of flexural strength 1 shrinkage permanent deformation haze peel strength % by weight — MPa MPa % % eg Or Example 1 26.0 8.9 61.6 3.5 2.06 34 53 3.2 82 2.6 11.5 Example 2 26.1 8.9 58.5 6.5 2.28 34 54 3.2 82 2.3 11.8 Comparative Example 1 26.4 9.1 64.5 0 2.00 32 56 3.1 73 3.1 11.2 Example 3 31.7 8.3 57.0 3.0 2.08 37 60 3.5 81 2.2 11.6 It is understood that the polyether amide elastomer of the present invention of Examples 1 to 3 has a lower haze, excellent transparency, and peeling strength compared to the polyether phthalamide elastomer of Comparative Example 1. high. 35 200936643 [Example 4] In a reaction vessel having a volume of about 130 ml with a stirrer, a nitrogen gas inlet, and a condensation water discharge port, it was fed into a 12-amino 12-acid (ADA) 6.138 manufactured by Ube Industries. g, adipic acid (AA) 2.867 g, XYX type triblock polyether diamine (XTJ-542, manufactured by HUNTSMAN Co., Ltd., amine price: 1.94 meq/g), l9.950 g, polyether polyamine compound (manufactured by HUNTSMAN Co., Ltd.) XTJ — 548) 1.067 g, phenylphosphonium hydride, 〇l7 g, and heat-resistant agent (Tominox 917, manufactured by Jifu Pharmaceutical Co., Ltd.) 0.076 g. After replacing the inside of the vessel with sufficient nitrogen, the mixture was heated at 19 °C for 1 hour, then heated to 225 ° C for 1 hour, and polymerized at 225 ° C for 10 hours while supplying nitrogen gas at a flow rate of 5 〇 10 10 /min. The resulting pellet was white and highly transparent and toughened with a rubbery elastomeric polymer, 7? r = 2.25, [COOH] = 1.58 x 10 - 5 eq/g, [NH2] = 4.40. Xl〇_5 eq/g. 15 The obtained polyether polyamine elastomer was compression-molded at a temperature of 230 ° C and 10 MPa to prepare a sheet having a thickness of about 1 mm. The sheet was used to evaluate hardness and permanent elongation. [Table 5] [Example 5] 20 In a reaction vessel having a volume of about 130 ml with a stirrer, a nitrogen gas inlet, and a condensation water discharge port, 12-aminododecanoic acid (ADA) was fed into Ube Industries Co., Ltd. 6.166 g, adipic acid (AA) 2.838 g, XYX-type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN Co., Ltd., amine price: 1.94 meq/g), 18.88 g, polyether polyamine compound (HUNTSMAN Co., Ltd.) XTJ — 36 200936643 548) 2.100 g, phenylphosphonium hydride, 〇16 g, and heat-resistant agent (Tomin® x 917 manufactured by Jifu Pharmaceutical Co., Ltd.) 0.077 g. After replacing the inside of the vessel with sufficient nitrogen, the mixture was heated at 190 ° C for 1 hour while supplying nitrogen gas at a flow rate of 5 〇 ml / min, and then heated to 225 ° C for 1 hour, and polymerization was carried out at 225 ° C for 1 hour. The polymer obtained is obtained. The obtained pellet is white and has good transparency and is tough and rubber-elastic polymer, ^^=2.35, [(:0011]=2.76xl〇-5eq/g, [NH2 ]=4.15xl〇_5eq/g The obtained polyether polyamine elastomer was compression-molded at a temperature of 230 ° C and 10 MPa to prepare a sheet having a thickness of about 1 mm. The sheet was used to evaluate hardness and permanent elongation. The results are shown in Table 2. [Example 6] A π-amine manufactured by Ube Industries Co., Ltd. was fed into a reaction vessel having a volume of about 130 ml with a mixer, a nitrogen inlet, and a condensation water discharge port. Base 12 15 acid (ADA) 6.197 g, adipic acid (AA) 2.804 g, XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN Co., Ltd., amine price: i.94 meq/g) 18.847 g, Polyether polyamine compound (XTJ-548, manufactured by HUNTSMAN Co., Ltd.) 3.151 g, phenylphosphonium hydride, ruthenium 15 g, and heat-resistant agent (Tominox 917, manufactured by Jifu Pharmaceutical Co., Ltd.) 0.079 g. After replacing a sufficient amount of nitrogen, the mixture was heated at 190 ° C for 1 hour while supplying nitrogen gas at a flow rate of 5 〇 20 /min, and then heated to 225 ° C for 1 hour, and polymerization was carried out at 225 ° C for 10 hours. polymer. The obtained sheet-like precipitate was a white polymer having good transparency and a strong rubber-elasticity, 77 r = 2.54, [COOH] = 4.00 x 10-5 eq/g, [NH2] = 0.24 x 10 - 5 eq/g. 37 200936643 The obtained polyether polyamine elastomer was compression-molded at a temperature of 230 ° C and 10 MPa to prepare a sheet having a thickness of about 1 mm. Use this piece to assess hardness and permanent elongation. The results are shown in Table 2. 5 [Comparative Example 2] In a reaction vessel having a volume of about 130 ml with a stirrer, a nitrogen gas inlet, and a condensed water discharge port, it was fed into Utsuka Kogyo Co., Ltd. to produce 12.10 g of 12-aminododecanoic acid (ADA). 2.98 g of adipic acid (AA), triblock polydiamine of XYX type (XTJ-542 manufactured by HUNTSMAN Co., Ltd., amine price: 1.94 meq/10 g) 21. 〇〇4 g, phenylphosphonate 〇i8g and A heat-resistant agent (T〇min〇x 917 manufactured by Jifu Pharmaceutical Co., Ltd.) was 0.073 g. After replacing the inside of the vessel with sufficient nitrogen, nitrogen gas was supplied at a flow rate of 5 〇ml/min, and the mixture was heated at 19 °C for 1 hour, then heated to 225 ° C for 1 hour, and polymerized at 225 ° C for 10 hours. The polyylidene polyamine elastomer was obtained. 15 The obtained pellet was white and transparent and strong and rubbery polymer, ^=1.77, [COOH]=2.95x10-5eq/g, [NH2 ???=3.95x10-5 eq/g The obtained polyether polyamine elastomer was compression-molded at a temperature of 230 ° C and 10 MPa to prepare a sheet having a thickness of about 1 mm. The sheet was used to evaluate hardness and permanent elongation for 20 minutes. The results are shown in Table 2. 200936643 Table 2

5 優異。 • 〔實施例7〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 口、壓力調整裝置及聚合物取出口之丨公升的壓力容器中進 0 10料入宇部Ems公司製月桂内醯胺（LLc)2〇3 5g、己二酸 (AA)29.5g、水31.1g。將容器内置換充分的氮後，以密封狀 態進行加熱。花約2小時從室溫昇溫至27〇°c，於27〇°c進行 聚合3小時。於270°C之壓力為3.iMPa。於昇溫途中溫度成 為200°C時開始攪拌。攪拌係以速度50rpm進行。其後，花i 15小時使溫度降溫至190°C ’其間壓力係回到常壓。接著於190 °C拉出而得到末端羧基之耐綸12預聚合物。 接著，於具有攪拌機、氮氣導入口、縮合水排出口之 體積約130毫升的反應容器中進料入上述耐綸12預聚合物 39 200936643 15_840g、XYX型之三嵌段聚醚二胺（HUNTSMAN公司製 XTJ—542，胺價：1.94meq/g)14.160g、聚醚聚胺化合物 (HUNTSMAN公司製XTJ—548)1.573g、次磷酸鈉之35質量 %水溶液0.090g及耐熱劑（吉富製藥製Tominox 5 917)0.095g。將容器内置換充分的氮後，一邊以流速50毫升 /分鐘供給氮氣，一邊以190°C加熱1小時，接著花1小時昇 溫至225°C，再於225°C進行聚合6小時，而得到聚合物。 所得到的片狀沉澱物係白色且透明性佳且強韌富有橡 膠彈性的聚合物，7； r=2.13、〔 COOH〕=2.16x10—5eq/g、 10 〔 NH2〕=4.37x10-5eq/g。 所得到的聚醚聚醯胺彈性體係於溫度23(TC、lOMPa壓 縮成形，而作成厚度約lmm之片。使用此片測量硬度（蕭氏 硬度D)及永久延伸度。硬度（蕭氏硬度〇)係48，而永久延伸 度則為168%。 15 〔實施例8〕 於具有攪拌機、溫度計、轉矩計、壓力計、氮氣導入 口、壓力調整裝置及聚合物取出口之丨公升的壓力容器中進 料入宇部Ems公司製月桂内醯胺（LLc)221.〇g、己二酸 20 0A)13.〇g、水3Uge將容器内置換充分的氮後以密封狀 態進行加熱。花約2小時從室溫昇溫至27(Γ(：，於27〇。匸進行 聚合H、時。於27代之壓力為3 1MPa。於昇溫途中溫度成 為2〇(TC時開始授拌。授拌係以速度5〇rpm進行。其後，花i 小時使溫度降溫至190t，其間壓力係回到常壓。接著於i9〇 40 200936643 °C拉出而得到末端羧基之耐綸12預聚合物。 接著’於具有攪拌機、氮氣導入口、縮合水排出口之 體積約130毫升的反應容器中進料入上述耐綸12預聚合物 19.350g、XYX型之三嵌段聚醚二胺（HUNTSMAN公司製 5 XTJ —559、胺價：UWmeq/gWOWOg、聚醚聚胺化合物 (HUNTSMAN公司製XTJ—548)1.880g、次磷酸鈉之35質量 %水溶液0.060g及封熱劑（吉富製藥製T〇min〇x 917)0.095g。將容器内置換充分的氮後，一邊以流速5〇毫升 /分鐘供給氮氣，一邊以190°C加熱1小時，接著花丨小時昇 10 溫至225°C ’再於225°C進行聚合6小時，而得到聚合物。 所得到的聚醚聚醯胺彈性體係白色且強動富橡膠彈性 的聚合物，77r=2.45、〔CO〇H〕=2.09xl(T5eq/g、〔NH2 〕=1.98xl0_5eq/g。 所得到的聚合物係於溫度230°C、lOMPa壓縮成形，而 15作成厚度約lmm之片。使用此片測量硬度(蕭氏硬度D)及永 久延伸度。硬度（蕭氏硬度D)係56、永久延伸度則為173%。 〔實施例9〕 於具有攪拌機、氮氣導入口、縮合水排出口之體積約 20 130毫升的反應容器中進料入宇部興產（股)製12 —胺基十二 酸(ADA)6.138g、十二烷二酸(DDA)4.518g、XYX型之三嵌 段聚醚二胺(HUNTSMAN公司製xTj — 542，胺價：194meq /g)19.950g、聚醚聚胺化合物(HUNTSMAN公司製XTJ-548)1.067g、次磷酸納之35質量％水溶液〇 〇9叫及耐熱劑（吉 41 2009366435 Excellent. • [Example 7] In a pressure vessel with a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure adjusting device, and a polymer outlet, the material is fed into the U.S. Amine (LLc) 2〇3 5g, adipic acid (AA) 29.5g, and water 31.1g. After replacing the inside of the vessel with sufficient nitrogen, the mixture was heated in a sealed state. The temperature was raised from room temperature to 27 ° C for about 2 hours, and polymerization was carried out at 27 ° C for 3 hours. The pressure at 270 ° C was 3. iMPa. Stirring was started when the temperature during the heating was 200 °C. The stirring was carried out at a speed of 50 rpm. Thereafter, it took 15 hours to cool the temperature to 190 ° C. During which the pressure returned to normal pressure. Then, it was pulled out at 190 ° C to obtain a nylon 12 prepolymer having a terminal carboxyl group. Next, the above-mentioned nylon 12 prepolymer 39 200936643 15_840 g, XYX type triblock polyether diamine (HUNTSMAN company) was fed into a reaction vessel having a volume of about 130 ml with a stirrer, a nitrogen gas inlet, and a condensation water discharge port. XTJ-542, amine price: 1.94 meq/g) 14.160 g, polyether polyamine compound (XTJ-548 manufactured by HUNTSMAN Co., Ltd.) 1.573 g, 35 mass% aqueous solution of sodium hypophosphite 0.090 g, and heat-resistant agent (Tominox manufactured by Jifu Pharmaceutical Co., Ltd.) 5 917) 0.095g. After replacing the inside of the vessel with sufficient nitrogen, the mixture was heated at 190 ° C for 1 hour while supplying nitrogen gas at a flow rate of 50 ml/min, and then heated to 225 ° C for 1 hour, and further polymerized at 225 ° C for 6 hours. polymer. The obtained flake precipitate was white and had good transparency and tough rubbery elastic polymer, 7; r = 2.13, [COOH] = 2.16 x 10 - 5 eq/g, 10 [NH2] = 4.37 x 10 -5 eq / g. The obtained polyether polyamine elastic system was compression-molded at a temperature of 23 (TC, 10 MPa to form a sheet having a thickness of about 1 mm. The sheet was used to measure hardness (Shore hardness D) and permanent elongation. Hardness (Shore hardness 〇 ) 48, and the permanent elongation is 168%. 15 [Example 8] A pressure vessel having a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure adjusting device, and a polymer outlet. In the middle of the feed into the Um company Ems company laurel melamine (LLc) 221. 〇 g, adipic acid 20 0A) 13. 〇 g, water 3Uge after the container is replaced with sufficient nitrogen, and then heated in a sealed state. It takes about 2 hours to raise the temperature from room temperature to 27 (Γ(:, at 27 〇. 聚合, polymerization H, when the pressure is 3 1 MPa in the 27th generation. The temperature becomes 2 于 during the heating process. The mixing system was carried out at a speed of 5 rpm. Thereafter, the temperature was lowered to 190 t for 1 hour, during which the pressure was returned to normal pressure, and then pulled out at i9〇40 200936643 °C to obtain a terminal carboxyl group of nylon 12 prepolymer. Then, the above-mentioned nylon 12 prepolymer 19.350g, XYX type triblock polyether diamine (HUNTSMAN company) was fed into a reaction vessel having a volume of about 130 ml with a stirrer, a nitrogen gas inlet, and a condensation water discharge port. 5 XTJ-559, amine price: UWmeq/gWOWOg, polyether polyamine compound (XTJ-548 manufactured by HUNTSMAN Co., Ltd.) 1.880 g, 35 mass% aqueous solution of sodium hypophosphite 0.060 g, and heat sealing agent (T〇min manufactured by Jifu Pharmaceutical Co., Ltd.) 〇x 917)0.095g. After replacing the inside of the vessel with sufficient nitrogen, the nitrogen gas was supplied at a flow rate of 5 〇ml/min, and heated at 190 °C for 1 hour, followed by a flowering hour, 10 liters to 225 °C. Polymerization was carried out at 225 ° C for 6 hours to obtain a polymer. The obtained polyether polyamine elastomer A white and strong rubber-elastic polymer, 77r = 2.45, [CO〇H] = 2.09xl (T5eq/g, [NH2] = 1.98xl_5eq/g. The obtained polymer is at a temperature of 230 ° C, lOMPa was compression-molded, and 15 was formed into a sheet having a thickness of about 1 mm. The sheet was used to measure hardness (Shore hardness D) and permanent elongation. The hardness (Shore hardness D) was 56, and the permanent elongation was 173%. 9] In a reaction vessel with a volume of about 20 130 ml with a stirrer, a nitrogen inlet, and a condensed water discharge port, it is fed into Ube Industries Co., Ltd. 12-aminododecanoic acid (ADA) 6.138 g, dodecane Dicarboxylic acid (DDA) 4.518 g, XYX type triblock polyether diamine (xTj-542 manufactured by HUNTSMAN Co., Ltd., amine price: 194 meq / g) 19.950 g, polyether polyamine compound (XTJ-548 manufactured by HUNTSMAN Co., Ltd.) 1.067 g, 35 mass% aqueous solution of sodium hypophosphite, 〇〇9 and heat-resistant agent (Ji 41 200936643

時’接著花1小時昇溫至225°C， 時，而得到聚合物。 1容II内置換充分的氣後， >氮氣’ 一邊以19(rc加熱w、 "，並於225°C進行聚合1〇小 5 所得到的片狀沉澱物係白色且透明性佳且強韌富有橡 膠彈性的聚合物，；yr=2.17、〔CO〇H〕=2.3lxl0-5eq/g、 〔NH2〕=3.99xl0-5eq/g。 所得到的聚醚聚醯胺彈性體係於溫度230t：、lOMPa壓 縮成形，而作成厚度約1mm之片。使用此片測量硬度（蕭氏 10 硬度D)及永久延伸度。硬度(蕭氏硬度D)係36、永久延伸度 則為149%。 將實施例7〜9之結果整理並示於表3。 42 200936643 表3 \ 進料成分 性質 月桂内醯胺/胺基十 己二酸 XTJ-542 XTJ-548 Φ-mm 永久 延伸 度 重量％ — % 實施例7 43.8 6.4 44.8 5.0 48 168 實施例8 60.2 3.5 33.3 3.0 56 173 實施例9 19.4 14.3 63.0 3.4 36 149 © 產業上的可利用性 本發明之聚醚聚醯胺彈性體因吸水性低、透明性優 5 異、熔融成形性優異、並且具有低溫耐衝擊性、低溫柔軟 ^ 性、力學物性、強韌性、耐彎曲疲勞性等之作為可塑性彈 性體上實用的材料物性，而可用於棒球、足球、陸上競技 等之領域中的鞋溶膠材料；機械、電子精密機器之齒輪、 連接器、密封、汽車用模、密封材等；管、軟管、異形材、 10 片、薄膜、單絲等；用於汽車的鏡防塵套、等速接頭防塵 〇 套等。又，積層由本發明之聚醚聚醯胺彈性體形成之層與 由其他熱可塑性樹脂形成之層的積層體，於鞋溶膠材料、 滑雪鞋等之鞋材料、汽車部件、滑雪板以及軟管、管、帶 等特別有用。 15 【圖式簡單說明】 無 【主要元件符號說明】 無 43Then, when the temperature was raised to 225 ° C for 1 hour, a polymer was obtained. After replacing the sufficient gas in the volume II, >nitrogen' is obtained by heating 19, rc, and polymerizing at 225 ° C. The sheet-like precipitate obtained is white and transparent. Strong rubber-elastic polymer; yr=2.17, [CO〇H]=2.3lxl0-5eq/g, [NH2]=3.99xl0-5eq/g. The obtained polyether polyamine elastic system is at temperature 230t: lOMPa compression molding, and a sheet having a thickness of about 1 mm. The sheet was used to measure hardness (Shore 10 hardness D) and permanent elongation. The hardness (Shore hardness D) was 36, and the permanent elongation was 149%. The results of Examples 7 to 9 were collated and shown in Table 3. 42 200936643 Table 3 \ Feed composition properties Laurel decylamine/aminododecanoic acid XTJ-542 XTJ-548 Φ-mm Permanent elongation wt% - % Example 7 43.8 6.4 44.8 5.0 48 168 Example 8 60.2 3.5 33.3 3.0 56 173 Example 9 19.4 14.3 63.0 3.4 36 149 © Industrial Applicability The polyether polyamine elastomer of the present invention has low water absorption, Excellent transparency, excellent melt formability, low temperature impact resistance, low temperature flexibility, and mechanical properties , toughness, bending fatigue resistance, etc. as a practical material property of plastic elastomer, and can be used for shoe sol materials in the fields of baseball, soccer, land sports, etc.; gears, connectors, seals of mechanical and electronic precision machines , automotive molds, sealing materials, etc.; tubes, hoses, profiled materials, 10 pieces, films, monofilaments, etc.; for the car's mirror dust jacket, constant velocity joint dust jacket, etc. Also, laminated by the polyether of the present invention A laminate of a layer formed of a polyamide elastomer and a layer formed of another thermoplastic resin is particularly useful for a shoe material such as a shoe sol material, a ski shoe, an automobile part, a snowboard, and a hose, a tube, a belt, and the like. Simple description of the schema] No [Main component symbol description] No 43

Claims (1)

200936643 七、申請專利範圍·· L ~種聚鍵聚醯胺彈性體，係聚合下列組份而得： (A) 聚酿胺形成性單體，其係選自於胺基羧酸化合 物(A1)及内醯胺化合物(A2); (B) 胺化合物，其係包含以下列式（1)表示的三嵌段 聚_二胺化合物（B1)及以下列式（2)表示的聚醚聚胺化 合物(B2);及 (C)二羧酸化合物， h2n- CH, 1 1 _ a ch3 ' -chch2o- X -ch2ch2ch2ch2o- y -ch2cho- ch3 -ch2ch-nh2 (但，X係表示1〜20，y係表示4〜50，且Z係表示1〜 20) ❹ (0 2_〇j~CH2CH2CH2CH2—NH2 : (2) Η2Ν-|^〇Η2〇Η2〇Η2〇Η2-〇|-〇η2〇Η2〇Η2〇Η2-Ν·-^ΟΗ2〇Η2〇Η2〇Η (但，η係表示4〜40，W係表示1〜2)。 2. 如申請專利範圍第1項之聚醚聚醯胺彈性體，其中，相 ❹ 對於聚醯胺形成性單體(Α)、胺化合物（Β)及二羧酸化合 物(C)之總量1〇〇質量％，該聚醯胺形成性單體(Α)之比 例為10〜95質量％。 3. 如申請專利範圍第1項之聚醚聚醯胺彈性體，其中，相 對於聚醯胺形成性單體(Α)、胺化合物(Β)及二羧酸化合 物（C)之總量1〇〇質量％，該聚醯胺形成性單體(Α)之比 例為15〜60質量％。 4.如申請專利範圍第1項之聚醚聚醯胺彈性體，其中前述 44 200936643 胺基羧酸化合物(A1)係於碳原子數為2〜20之伸烷基的 末端具有胺基與羧基之胺基羧酸。 5.如申請專利範圍第1項之聚醚聚醯胺彈性體，其中内醯 胺化合物(A2)係包含碳原子數為2〜20之伸烷基的内醢 胺化合物。 6.如申請專利範圍第1項之聚謎聚醯胺彈性體，其中，相 對於聚醯胺形成性單體(A)、胺化合物(b)及二羧酸化合200936643 VII. Patent Application Scope·· L ~ Kind of poly-bonded polyamide elastomer, which is obtained by polymerizing the following components: (A) Polyamine-forming monomer selected from aminocarboxylic acid compound (A1) And an indoleamine compound (A2); (B) an amine compound comprising a triblock poly-diamine compound (B1) represented by the following formula (1) and a polyether polymer represented by the following formula (2) Amine compound (B2); and (C) dicarboxylic acid compound, h2n-CH, 1 1 _ a ch3 ' -chch2o- X -ch2ch2ch2ch2o- y -ch2cho-ch3 -ch2ch-nh2 (However, X system represents 1 to 20 , y represents 4~50, and Z represents 1~20) ❹ (0 2_〇j~CH2CH2CH2CH2-NH2 : (2) Η2Ν-|^〇Η2〇Η2〇Η2〇Η2-〇|-〇η2〇 Η2〇Η2〇Η2-Ν·-^ΟΗ2〇Η2〇Η2〇Η (However, η represents 4 to 40, and W represents 1 to 2). 2. Polyether polyamine as claimed in claim 1 Elastomer, wherein, relative to the total amount of the polyamine-forming monomer (Α), the amine compound (Β), and the dicarboxylic acid compound (C), the polyamine-forming monomer ( Α) The ratio is 10 to 95% by mass. The polyether polyamine elastomer, wherein the polyamine is present in an amount of 1% by mass based on the total amount of the polyamine forming monomer (Α), the amine compound (Β), and the dicarboxylic acid compound (C) The ratio of the forming monomer (Α) is from 15 to 60% by mass. 4. The polyether polyamine elastomer according to claim 1, wherein the aforementioned 44 200936643 aminocarboxylic acid compound (A1) is bonded to a carbon atom. The polyether polyamine elastomer having the amine group and the carboxyl group at the terminal of the alkyl group of 2 to 20, wherein the indoleamine compound (A2) is contained in the polyether polyamine elastomer of the first aspect of the invention. An indoleamine compound having an alkylene group having 2 to 20 carbon atoms. 6. The polymygular polyamide elastomer according to the first aspect of the invention, wherein the polyamine-forming monomer (A), Amine compound (b) and dicarboxylic acid combination 物(C)之總量1〇〇質量％，以式(句表示的聚醚聚胺化合物 (B2)之比例為3〜15質量％。 7. 如申請專利範圍第丨項之聚醚聚醯胺彈性體，其中，於 式(2)中’ η係7〜30 ’且w係1〜2。 8. 如U利範圍^項之聚喊聚醯胺彈性體，其中二叛 酸化合物（C)為脂肪族二羧酸。 申餘專和圍第1項之聚喊聚醯胺彈性體，其中二緩 酸化合物(W碳原子數為卜2G之㈣基之兩末端 具有羧基的二羧酸。 1〇·如申凊專利範圍第1項之聚_聚_彈性體，其中該聚 醚聚酿胺彈性體之末端胺基濃度比聚醚聚醯胺彈性體 之末^0竣基濃度大。 11. 一種彈性體組成物，係於如申請專利範圍第UK)項中 1一 Γ㈣聚醯轉㈣中含有其他聚合物及/或 添加劑。 12· —種積層體， 任一項之聚醚 係積層有由如巾請專利範圍第1至10項中 聚酿胺彈性體或如中請專利範圍第11項 45 200936643 之彈性體組成物所形成之層、與由其他熱可塑性樹脂所 形成之層而形成者。 13. 如申請專利範圍第12項之積層體，其中其他熱可塑性樹 脂係聚胺基甲酸酯。 14. 如申請專利範圍第13項之積層體，其中聚胺基甲酸酯為 熱可塑性聚胺基曱酸酯。 15. 如申請專利範圍第14項之積層體，其中熱可塑性聚胺基 曱酸酯具有作為軟鏈段(soft segment)之聚酯二醇及/ 或聚醚二醇及/或聚碳酸酯二醇及/或聚己内酯二醇 qp 一 早兀。 46 200936643 四、指定代表圖： (一) 本案指定代表圖為：第（無）圖。 (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：The total amount of the substance (C) is 1% by mass, and the ratio of the polyether polyamine compound (B2) represented by the formula is 3 to 15% by mass. 7. The polyether polyether as claimed in the scope of the patent application An amine elastomer, wherein, in the formula (2), 'η is 7 to 30' and w is 1 to 2. 8. As in the U range, the poly-polyamine elastomer, wherein the two are acid-reducing compounds (C) ) is an aliphatic dicarboxylic acid. Shen Yu and the first paragraph of the poly-polyamine elastomer, wherein the two acid-lowering compounds (W carbon number of the 2G (b) base of the two ends of the dicarboxylic acid having a carboxyl group 1. The poly-poly-elastomer of claim 1, wherein the polyether polyamine elastomer has a terminal amine concentration greater than that of the polyether polyamine elastomer. 11. An elastomer composition which is contained in the first paragraph (4) of the patent application (UK), and contains other polymers and/or additives. 12· a layered body, any of the polyethers The tie layer has a layer formed by the elastomeric composition of the patented range 1 to 10 of the patent or the elastomer composition of the patent scope 11th, 2009 200943 And a layer formed of another thermoplastic resin. 13. The laminate according to claim 12, wherein the other thermoplastic resin is a polyurethane. 14. In the scope of claim 13 The laminate, wherein the polyurethane is a thermoplastic polyamine phthalate. 15. The laminate according to claim 14, wherein the thermoplastic polyamine phthalate has a soft segment (soft segment) Polyester diol and / or polyether diol and / or polycarbonate diol and / or polycaprolactone diol qp early morning. 46 200936643 Fourth, the designated representative map: (a) The representative representative of the case is : (None) Figure (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: