TW201122019A - Copolymerized polyamide - Google Patents
Copolymerized polyamide Download PDFInfo
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- TW201122019A TW201122019A TW99136409A TW99136409A TW201122019A TW 201122019 A TW201122019 A TW 201122019A TW 99136409 A TW99136409 A TW 99136409A TW 99136409 A TW99136409 A TW 99136409A TW 201122019 A TW201122019 A TW 201122019A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
Description
201122019 六、發明說明： 【發明所屬之技術領域】 本發明關於新穎的聚醯胺，其係除了高熔點、低吸水 性，還高度滿足成形性、耐熱老化性及阻汽油性的三個特 性全部。 【先前技術】 就成形用材料、滑動用材料等中所使用的聚醯胺而 言，以往熟知係由己二胺（6)與對苯二甲酸（T)之共縮聚合 反應所合成的6T尼龍》6T尼龍係耐熱性、機械特性、耐 藥品性、滑動性、阻氣性或阻汽油性等的樹脂特性之平衡 優異的聚醯胺’但由於未共聚合的6Τ尼龍具有超過360 °C的熔點’有聚合物的聚合或所得之聚合物的成形係困難 之缺點。 爲了賦予6T尼龍的成形性，目前工業上係藉由共聚 合己內醯胺或己二酸、間苯二甲酸、2-甲基-1,5-戊二胺， 而使熔點降低到290 °C至3 3 0 °C的手段。然而，與己內醯 胺或己二酸共聚合時，有吸水率高、在吸濕下發生物性大 幅降低之問題。另一方面，於共聚合間苯二甲酸或2-甲 基-1,5 -戊二胺時，由於維持著高的玻璃轉移溫度，經由共 聚合而使結晶速度降低，於一般進行的射出成形中，結晶 化不充分進行，有引起脫模不足等的成形困難，或在以後 的使用中，於高溫下進行結晶化而二次收縮導致變形等的 問題。 201122019 爲了一邊活用6T尼龍的特性，一邊賦予其它特性， 亦已知於6Τ尼龍中進而共聚合有其它成分的共聚合聚醒 胺。例如，專利文獻1中揭示使61尼龍（由己二胺與間苯 二甲酸的共縮聚合反應所合成的尼龍）對6Τ尼龍進行共聚 合，再共聚合11尼龍（由十一內醯胺等的碳數11之單體 的聚縮合反應所合成的尼龍）或12尼龍（由月桂內醯胺等 的碳數12之單體的聚縮合反應所合成的尼龍）而成的三元 共聚合聚醯胺。此共聚合聚醯胺係具有透明性優異的優 點，但玻璃轉移溫度變成130 °C以上，有成形性差的缺 點。 又，專利文獻2中揭示使12尼龍對6T尼龍共聚合而 成的二元共聚合聚醯胺。此共聚合聚醯胺具有短時間的耐 熱性、耐衝撃特性及滑動特性優異的優點，但有耐熱老化 性及阻汽油性差的缺點。 還有，專利文獻3中揭示使比較大量的11尼龍或12 尼龍對6T尼龍共聚合而成的二元共聚合聚醯胺。此共聚 合聚醯胺具有低吸水性且機械特性優異的優點，但具有成 形性或耐熱老化性、阻汽油性差的缺點。 如此地，於習知的6T系尼龍中，沒有一邊維持高熔 點、低吸水性，且一邊高度地滿足成形性、耐熱老化性及 阻汽油性的三個特性全部者。 先前技術文獻 專利文獻 £ -4- 201122019 專利文獻1 :特公昭46-24249號公報 專利文獻2 :特開昭62- 1 5 6 1 30號公報 專利文獻3:特開平5-310925號公報 【發明內容】 發明所欲解決的問題 本發明係鑒於相關先前技術之現狀而創作者，其目的 爲提供除了 300°C以上的高熔點、低吸水性，還高度滿足 成形性、耐熱老化性及阻汽油性的三個特性全部之6T系 尼龍。 解決問題的手段 本發明者爲了達成上述目的，對於與6T尼龍共聚合 的成分之種類及其量進行專心致力的檢討，結果發現藉由 以特定的比例共聚合1 1尼龍.，可提供除了 300°C以上的熔 點、低吸水性，還高度滿足成形性、耐熱老化性及阻汽油 性的三個特性全部之6T系尼龍，而達到本發明的完成。 即，若依照本發明，可提供一種共聚合聚醯胺，其特 徵爲由（a) 55〜75莫耳％的由己二胺與對苯二甲酸之等量莫 耳鹽所得之結構單位，及（b)45〜25莫耳％的由11-胺基十 一酸或十一內醯胺所得之結構單位所組成。 若依照本發明的較佳態樣，共聚合聚醯胺含有最大至 20莫耳％爲止的（c)由前述（a)的結構單位以外的二胺與二 羧酸的等量莫耳鹽所得之結構單位 '或由前述（b)的結構 單位以外的胺基羧酸或內醯胺所得之結構單位，共聚合聚 201122019 醯胺的熔點（Tm)爲300〜330 C ’升溫結晶化溫度（Tel)爲 90 〜140〇C。 發明的效果 本發明的共聚合聚醯胺’由於11尼龍以特定的比例 對主成分的6T尼龍進行共聚合’故可一邊活用機械特 性、滑動性等的6T尼龍之特性’―邊除了 300°C以上的 高熔點、低吸水性’還高度滿足成形性、耐熱老化性及阻 汽油性。 . 【實施方式】 實施發明的形態 以下，詳述本發明的共聚合聚醯胺。本發明的共聚合 聚醯胺係以特定的比例含有相當於6 τ尼龍的（a)成分與相 當於11尼龍的（b)成分者’不僅改良6T尼龍之缺點的成 形性、高吸水性’而且具有高度滿足耐熱老化性及阻汽油 性的特徵。 (a)成分係相當於藉由使己二胺（6)與對苯二甲酸（T)以 等量莫耳進行共縮聚合而得之6T尼龍’具體地爲下述式 ⑴所示者。201122019 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel polyamine which has three characteristics of high formability, heat aging resistance and gas barrier resistance in addition to high melting point and low water absorption. . [Prior Art] For the polyamine used in the molding material, the sliding material, and the like, 6T nylon synthesized by the copolycondensation reaction of hexamethylenediamine (6) and terephthalic acid (T) is conventionally known. 》6T nylon is a polyamide which is excellent in balance of resin properties such as heat resistance, mechanical properties, chemical resistance, slidability, gas barrier properties, or gasoline resistance. However, since uncopolymerized 6 Τ nylon has a temperature exceeding 360 °C The melting point 'has a disadvantage of the polymerization of the polymer or the formation of the resulting polymer. In order to impart formability to 6T nylon, it is currently industrially reduced in melting point to 290 ° by copolymerizing caprolactam or adipic acid, isophthalic acid, 2-methyl-1,5-pentanediamine. C to 3 30 °C means. However, when it is copolymerized with caprolactam or adipic acid, there is a problem that the water absorption rate is high and the physical properties are largely lowered under moisture absorption. On the other hand, when copolymerizing isophthalic acid or 2-methyl-1,5-pentanediamine, the crystallization rate is lowered by copolymerization due to the high glass transition temperature, and the injection molding is generally performed. The crystallization is not sufficiently performed, and it may cause difficulty in molding such as insufficient mold release, or may cause problems such as crystallization at a high temperature and secondary shrinkage due to deformation in later use. 201122019 In order to utilize other characteristics of 6T nylon, it is also known that it is copolymerized with 6 Τ nylon and further copolymerized with other components. For example, Patent Document 1 discloses that 61 nylon (a nylon synthesized by a copolycondensation reaction of hexamethylenediamine and isophthalic acid) is copolymerized with 6 nylon, and then copolymerized with 11 nylon (by eleven decylamine or the like). Ternary copolymerization of a nylon synthesized by a polycondensation reaction of a monomer having a carbon number of 11 or 12 nylon (a nylon synthesized by a polycondensation reaction of a monomer having a carbon number of 12 such as laurylamine) amine. This copolymerized polyamine has the advantage of being excellent in transparency, but the glass transition temperature is 130 °C or more, and there is a disadvantage that the formability is poor. Further, Patent Document 2 discloses a binary copolymerized polyamine which is obtained by copolymerizing 12 nylon to 6T nylon. The copolymerized polyamine has the advantages of short heat resistance, impact resistance and sliding properties, but has disadvantages of poor heat aging resistance and poor gasoline resistance. Further, Patent Document 3 discloses a binary copolymerized polyamine which is obtained by copolymerizing a relatively large amount of 11 nylon or 12 nylon to 6T nylon. This copolymerized polyamine has the advantages of low water absorption and excellent mechanical properties, but has the disadvantages of formability, heat aging resistance, and poor gasoline resistance. As described above, in the conventional 6T-based nylon, all of the three characteristics of the moldability, the heat aging resistance, and the gasoline resistance are highly satisfied while maintaining a high melting point and low water absorption. CITATION LIST OF RELATED APPLICATIONS LIST OF RELATED APPLICATIONS LIST OF RELATED APPLICATIONS LIST OF RELATED APPLICATIONS RELATED APPLICATIONS SUMMARY OF THE INVENTION The present invention has been made in view of the status quo of the related prior art, and its object is to provide high melting point and low water absorption in addition to 300 ° C or higher, and also to highly satisfy formability, heat aging resistance, and gasoline resistance. The three characteristics of sex are all 6T nylon. Means for Solving the Problems In order to achieve the above object, the present inventors conducted a review of the types and amounts of the components copolymerized with 6T nylon, and found that by copolymerizing 11 nylon in a specific ratio, it is possible to provide 300. The melting point and the low water absorption of °C or higher, and the 6T-based nylon, which has three characteristics of the moldability, the heat aging resistance and the gasoline resistance, are all highly satisfied, and the completion of the present invention is achieved. That is, according to the present invention, it is possible to provide a copolymerized polyamine which is characterized by (a) 55 to 75 mol% of a structural unit derived from an equivalent amount of a molar salt of hexamethylenediamine and terephthalic acid, and (b) 45 to 25 mol% of a structural unit derived from 11-aminoundecanoic acid or elevenamine. According to a preferred embodiment of the present invention, the copolymerized polyamine contains up to 20 mol%, and (c) an equivalent molar salt of a diamine and a dicarboxylic acid other than the structural unit of the above (a). The structural unit or the structural unit obtained from the aminocarboxylic acid or the indoleamine other than the structural unit of the above (b), the melting point (Tm) of the copolymerized poly 201122019 decylamine is 300 to 330 C 'temperature crystallization temperature ( Tel) is 90 ~ 140 〇 C. Advantageous Effects of Invention The copolymerized polyamine of the present invention is a copolymer of 6T nylon which is a main component in a specific ratio, so that the characteristics of 6T nylon such as mechanical properties and slidability can be utilized. The high melting point and low water absorption of C or more 'highly satisfy the formability, heat aging resistance, and gasoline resistance. [Embodiment] Mode for Carrying Out the Invention Hereinafter, the copolymerized polyamine of the present invention will be described in detail. The copolymerized polyamine of the present invention contains a component (a) corresponding to 6 τ nylon and a component (b) corresponding to 11 nylon in a specific ratio, and is not only improved in formability and high water absorption of the disadvantage of 6T nylon. Moreover, it has the characteristics of highly satisfying heat aging resistance and gasoline resistance. The component (a) corresponds to 6T nylon which is obtained by co-condensation polymerization of hexamethylenediamine (6) and terephthalic acid (T) in an equivalent amount of mol, and is specifically represented by the following formula (1).
CMOCMO
(a)成分係本發明的共聚合聚醯胺之主成分’具有對 共聚合聚醯胺賦予優異的耐熱性、機械特性、耐藥品性、 滑動性、阻氣性等之作用。共聚合聚醯胺中的（a)成分之調 201122019 配比例爲55〜75莫耳％ ’較佳爲60〜70莫耳％，更佳爲 62〜68莫耳％。U)成分的調配比例低於上述下限時，結晶 成分的6T尼龍係受到共聚合成分的結晶阻礙，有導致成 形性或高溫特性的降低之虞，另一方面超過上述時，熔點 變過高，加工時有分解之虞而不宜。 (b)成分係相當於藉由使Π-胺基十一酸或十一內醯胺 進行聚縮合而得之11尼龍者，具體而言，爲下述式（II)所 示者。 —NH(CH2)1〇C — (II)The component (a) is a main component of the copolymerized polyamine of the present invention, and has an effect of imparting excellent heat resistance, mechanical properties, chemical resistance, slidability, gas barrier properties, and the like to the copolymerized polyamine. The adjustment of the component (a) in the copolymerized polyamine is 201122019. The ratio is 55 to 75 mol%, preferably 60 to 70 mol%, more preferably 62 to 68 mol%. When the blending ratio of the U) component is less than the above lower limit, the 6T nylon of the crystal component is inhibited by the crystallization of the copolymer component, and the moldability or the high-temperature property is lowered. On the other hand, when the content exceeds the above, the melting point becomes too high. It is not suitable for decomposition when processing. The component (b) is equivalent to 11 nylon obtained by polycondensation of fluorene-aminoundecanoic acid or undecanoin, and specifically, it is represented by the following formula (II). —NH(CH2)1〇C — (II)
II 〇 (b)成分係用於改良（a)成分的缺點者，具有使共聚合 聚醯胺的熔點及升溫結晶化溫度降低而提高成形性之作 用，以及使吸水率減低而改善吸水時的物性變化或尺寸變 化所致的問題之作用。共聚合聚醯胺中的（b)成分之調配 比例爲45〜25莫耳％，較佳爲40〜30莫耳％，更佳38〜 32莫耳％。（b)成分的調配比例低於上述下限時，共聚合聚 醯胺的熔點降低不充分，成形性有不足之虞，同時使所得 之樹脂的吸水率減低的效果係不足，吸水時有導致機械特 性降低等物性的不安定之虞。超過上述上限時，共聚合聚 醯胺的熔點係過度降低，結晶化速度變慢，有成形性反而 變差之虞，同時相當於6T尼龍的（a)成分之量變少，機械 特性或滑動性有不足之虞而不宜。 本發明的共聚合聚醯胺係除了上述（a)成分及（b)成分 201122019 以外，還可共聚合最大20莫耳％的（c)由上述（a)的結構單 位以外的二胺與二羧酸的等量莫耳鹽所得之結構單位、或 由上述（b)的結構單位以外的胺基羧酸或內醯胺所得之結 構單位。（c)成分係具有對於共聚合聚醯胺，賦予由6T尼 龍或1 1尼龍所得不到的其它特性，或進一步改良由6T尼 龍或11尼龍所得之特性的作用者，具體地可舉出如以下 的共聚合成分。就胺成分而言，可舉出如1,2-乙二胺、 1,3-丙二胺、1，4-丁 二胺、1,5-戊二胺、2-甲基-1,5-戊二 胺、1,6-己二胺、1，7-庚二胺、1,8-辛二胺、1.9-壬二胺、 2-甲基-1,8-辛二胺、ι，ι〇-癸二胺、——烷二胺、 1，12-十二烷二胺、1，13-十三烷二胺、1,16-十六烷二胺、 1，18-十八烷二胺、2,2,4(或2,4,4)-三甲基己二胺的脂肪族 二胺、如哌畊、環己二胺、雙（3-甲基-4-胺基己基）甲烷、 雙-(4,4’_胺基環己基）甲烷、異佛爾酮二胺的脂環式二胺、 間苯二甲基二胺、對苯二甲基二胺 '對苯二胺、間苯二胺 等的芳香族二胺及此等的氫化物等。作爲聚醯胺的酸成 分’可使用以下所示的多元羧酸或酸酐。作爲多元羧酸， 例如可舉出對苯二甲酸、間苯二甲酸、鄰苯二甲酸、丨，5_ 萘二羧酸、2,6-萘二羧酸、4,4’-二苯基二羧酸、2,2’-二苯 基二羧酸、4,4、二苯基醚二羧酸.、5-磺酸鈉間苯二甲酸、 5-羥基間苯二甲酸等的芳香族二羧酸、富馬酸、馬來酸、 琥珀酸、伊康酸、己二酸、壬二酸、癸二酸、1，1丨_十一烷 二酸、1，12-十二烷二酸、1，14-十四烷二酸、1，18_十八烷 201122019 二酸、1，4-環己烷二羧酸、ι，3-環己烷二羧酸、1,2-環己烷 二羧酸、4-甲基-1，2-環己烷二羧酸、二聚酸等的脂肪族或 脂環族二羧酸等。又，可舉出ε-己內醯胺、12-月桂內醯胺 等的內醯胺及此等開環的構造之胺基羧酸等。 就具體的（c)成分而言，可舉出聚己醯胺（尼龍6)、聚 十二醯胺（尼龍12)、聚己二醯丁二胺（尼龍46)、聚己二醯 己二胺（尼龍66)、聚己二醯十一烷二胺（尼龍116)、聚間 苯二甲基己二醯胺（尼龍MXD6)、聚對苯二甲基己二醯胺 (尼龍PXD6)、聚癸二醯丁二胺（尼龍410)、聚癸二醯己二 胺（尼龍610)、聚己二醯癸二胺（尼龍106)、聚癸二醯癸二 胺（尼龍1010)、聚十二烷二醯己二胺（尼龍612)、聚十二 烷二醯癸二胺（尼龍1012)、聚間苯二甲醯己二胺（尼龍 61)、聚對苯二甲醯丁二胺（尼龍4Τ)、聚對苯二甲醯戊二 胺（尼龍5Τ)、聚-2·甲基對苯二甲醯戊二胺（尼龍Μ-5Τ)、 聚六氫對苯二甲醯己二胺（尼龍6Τ(Η))、聚對苯二甲醯壬 二胺（尼龍9Τ)、聚對苯二甲醯癸二胺（尼龍.10Τ) '聚對苯 二甲醯十一烷二胺（尼龍11 Τ)、聚對苯二甲醯十二烷二胺 (尼龍12Τ)、聚雙（3-甲基-4-胺基己基）甲烷對苯二甲醯胺 (尼龍PACMT)、聚雙（3-甲基-4·胺基己基）甲烷間苯二甲醯 胺（尼龍PACMI)、聚雙（3-甲基-4_胺基己基）甲烷十二醯胺 (尼龍PACM12)、聚雙（3-甲基-4-胺基己基）甲烷十四醯胺 (尼龍PACM14)等。 於前述結構單位之中，作爲較佳的（c)成分之例，可 201122019 舉出對共聚合聚醯胺賦予高結晶性用的聚己二醯己二胺， 或更賦予低吸水性用的聚對苯二甲醯癸二胺、阻汽油性提 高用的聚間苯二甲基己二醯胺等。共聚合聚醯胺中的（幻成 分之調配比例較佳爲最大至20莫耳％爲止，更佳爲1〇〜 20莫耳％。（c)成分的比例低於上述下限時，成分的效 果有無法充分發揮之虞，超過上述上限時，必要成分的 成分或（b)成分之量變少’本發明的共聚合聚醯胺之本來 意圖的效果有無法充分發揮之虞而不宜。 本發明的共聚合聚醯胺較佳爲具有300〜330。(：的熔 點（T m)及9 0〜1 4 0 °C的升溫結晶化溫度（T c 1)。T m超過上 述上限時’由於藉由射出成形法等將共聚合聚醯胺成形之 際所需要的加工溫度變爲極高，加工時會分解，有時會得 不到目的之物性或外觀。相反地，Tm低於上述下限時， 結晶化速度變慢，成形皆變困難。又，Tel超過上述上限 時’藉由射出成形法等將共聚合聚醯胺成形之際所需要的 模具溫度變高，不僅成形變困難，而且於射出成形的短周 期之中，結晶化會進行不充分，而引起脫模不足等的成形 困難’或在以後的使用中，於高溫下進行結晶化而二次收 縮導致變形等的問題。相反地，Tel低於上述下限時，作 爲樹脂組成，出現必然地使玻璃轉移溫度降低的需求。由 於Tel 一般爲玻璃轉移溫度以上的溫度，故使Tel低於90 亡時，作爲玻璃轉移溫度，要求低的値，但於該情況下， 發生物性的大幅降低，或無法維持吸水後的物性等之問II. The component (b) is used to improve the disadvantage of the component (a), and has a function of lowering the melting point and temperature-increasing crystallization temperature of the copolymerized polyamine to improve the formability, and reducing the water absorption rate to improve the water absorption. The role of problems caused by changes in physical properties or dimensional changes. The blending ratio of the component (b) in the copolymerized polyamine is 45 to 25 mol%, preferably 40 to 30 mol%, more preferably 38 to 32 mol%. When the blending ratio of the component (b) is less than the above lower limit, the melting point of the copolymerized polyamine is insufficiently lowered, and the formability is insufficient, and the effect of reducing the water absorption of the obtained resin is insufficient, and the mechanism is caused by water absorption. Unstable stability of physical properties such as reduced characteristics. When the above upper limit is exceeded, the melting point of the copolymerized polyamine is excessively lowered, the crystallization rate is slow, and the formability is rather deteriorated, and the amount of the component (a) corresponding to 6T nylon is small, and mechanical properties or slidability are obtained. It is not appropriate to have insufficient. The copolymerized polyamine of the present invention may be copolymerized with a maximum of 20 mol% in addition to the above-mentioned (a) component and (b) component 201122019, (c) a diamine and two other than the structural unit of the above (a). A structural unit obtained by equating a molar amount of a carboxylic acid or a structural unit derived from an aminocarboxylic acid or an indoleamine other than the structural unit of the above (b). The component (c) has a function of imparting other properties which are not obtained by 6T nylon or 11 nylon to the copolymerized polyamine, or further improving the properties obtained by 6T nylon or 11 nylon, and specifically, for example, The following copolymerization ingredients. The amine component may, for example, be 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5. -pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1.9-decanediamine, 2-methyl-1,8-octanediamine, ι, 〇〇-癸 diamine, —alkyl diamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,16-hexadecyldiamine, 1,18-octadecane Aliphatic diamines of diamines, 2,2,4 (or 2,4,4)-trimethylhexamethylenediamine, such as piperene, cyclohexanediamine, bis(3-methyl-4-aminohexyl) Methane, bis-(4,4'-aminocyclohexyl)methane, alicyclic diamine of isophoronediamine, m-xylylenediamine, p-xylylenediamine 'p-phenylene An aromatic diamine such as an amine or m-phenylenediamine, or a hydride or the like. As the acid component of the polyamine, the polyvalent carboxylic acid or acid anhydride shown below can be used. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, anthracene, 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-diphenyl group. Aromatic carboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4, diphenyl ether dicarboxylic acid, sodium 5-sulfonate isophthalic acid, 5-hydroxyisophthalic acid, etc. Carboxylic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,1 丨-undecanedioic acid, 1,12-dodecanedioic acid 1,14-tetradecanedioic acid, 1,18-octadecane 201122019 diacid, 1,4-cyclohexanedicarboxylic acid, iota, cyclohexanedicarboxylic acid, 1,2-cyclohexane An aliphatic or alicyclic dicarboxylic acid such as an alkyl dicarboxylic acid, 4-methyl-1,2-cyclohexane dicarboxylic acid or a dimer acid. Further, examples thereof include an indoleamine such as ε-caprolactam or 12-lauric acid and an aminocarboxylic acid having such a ring-opening structure. Specific examples of the component (c) include polyhexylamine (nylon 6), polydodesylamine (nylon 12), polyhexamethylenediamine (nylon 46), and polyhexamethylene dichloride. Amine (nylon 66), polyhexamethylene undecanediamine (nylon 116), poly-m-xylylene hexamethylenediamine (nylon MXD6), polyparaxyl dimethyl decylamine (nylon PXD6), Polyfluorene diamine diamine (nylon 410), polyfluorene dimercaptodiamine (nylon 610), polyhexamethylene diamine (nylon 106), polyfluorene diamine (nylon 1010), poly ten Dioxane hexamethylenediamine (nylon 612), polydodecanediamine diamine (nylon 1012), poly-m-xylylenediamine (nylon 61), poly(p-xylylenediamine) Nylon 4Τ), polyparaphenylene pentanediamine (nylon 5Τ), poly-2·methyl-p-xylylene pentanediamine (nylon Μ-5Τ), polyhexahydroterephthyl hexamethylenediamine (Nylon 6Τ(Η)), Poly(p-xylylenediamine) (Nylon 9Τ), Poly(p-xylylenediamine) (Nylon.10Τ) 'Polyphenylene terephthalate (Nylon) 11 Τ), polyparaxyl dodecane diamine (nylon 12 Τ), poly bis (3-methyl-4-amine) Hexyl) methane terephthalamide (nylon PACMT), polybis(3-methyl-4.aminohexyl)methane meta-xylamine (nylon PACMI), poly-bis(3-methyl-4_ Aminohexyl)methane dodecylamine (nylon PACM12), polybis(3-methyl-4-aminohexyl)methanetetradecylamine (nylon PACM14), and the like. Among the above-mentioned structural units, as an example of the preferable component (c), it is possible to use polyhexamethylene diamine for imparting high crystallinity to the copolymerized polyamine, or to impart low water absorbability to 201122019. Poly-p-xylylenediamine, poly(m-xylylene hexamethyleneamine) for improving gasoline resistance. In the copolymerized polyamine, the blending ratio of the magic component is preferably up to 20 mol%, more preferably 1 to 20 mol%. When the ratio of the component (c) is lower than the lower limit, the effect of the component In the case where the above-mentioned upper limit is exceeded, the amount of the component of the essential component or the amount of the component (b) is small. The original intended effect of the copolymerized polyamine of the present invention may not be sufficiently exhibited. The copolymerized polyamine preferably has a melting point (T m) of from 300 to 330 (T m) and a temperature rising crystallization temperature (T c 1) of from 90 to 140 ° C. When T m exceeds the above upper limit, The processing temperature required for molding the copolymerized polyamine by the injection molding method or the like is extremely high, and it is decomposed during processing, and the desired physical properties or appearance may not be obtained. Conversely, when Tm is lower than the lower limit When the crystallization rate is slow, the molding becomes difficult. When the Tel exceeds the above upper limit, the temperature of the mold required for forming the copolymerized polyamine by the injection molding method or the like is increased, which makes it difficult to form the mold. Crystallization will occur during the short cycle of injection molding If it is insufficient, it may cause difficulty in molding such as insufficient mold release, or in the subsequent use, crystallization is performed at a high temperature, and secondary shrinkage causes deformation or the like. Conversely, when Tel is lower than the lower limit, it is used as a resin composition. There is a demand that the glass transition temperature is inevitably lowered. Since Tel is generally a temperature higher than the glass transition temperature, when Tel is less than 90, a low enthalpy is required as the glass transition temperature, but in this case, physical properties occur. Drastically reduced, or unable to maintain physical properties after water absorption, etc.
-10- S 201122019 題。由於必須將Tg保持在比較高，故就Tc 1而言，必須 使其成爲至少9(TC以上。 於本發明的共聚合聚醯胺中，由於特定量的11尼龍 成分對6T尼龍進行共聚合，故不僅得到高熔點或低吸水 性等的特性，而且得到成形性或耐熱老化性、阻汽油性的 平衡優異之樹脂。於電子零件的成形中，除了 300°C以上 的高熔點、低吸水，還要求薄壁、高周期的成型。於對苯 二甲醯己二胺/聚己二醯己二胺共聚物（PA6T/66)中，雖然 成形性良好，但吸水率極高。因此，於表面安裝等所進行 廻焊處理中，在成型品發生起泡等問題。另一方面，於聚 對苯二甲醯壬二胺中，雖然低吸水，但有Tel成爲15(TC 以上的情況，由於成型時的模具溫度必須成爲1 50 °C以 上，故成型加工性係有困難。即使以低溫模具可成型，但 使用時的結晶化進行所致的二次收縮係成爲問題。基於如 上述的背景，要求具有300 °C以上的高熔點及低吸水、易 成形性的樹脂，於本發明的共聚合聚醯胺中，藉由使特定 量的1 1尼龍對6T尼龍進行共聚合，不僅可爲高熔點、低 吸水，而且可壓低Tc 1，大幅改善射出成形的加工性。 又，考慮6T尼龍對汽車零件的延展時，不僅要求成型加 工性或低吸水，而且耐受引擎室內的溫度之耐熱老化性， 或爲了防止燃料的揮發之汽油等的障壁性係成爲重要。目 前，雖然有報告使12尼龍對6T尼龍進行共聚合之例，但 與11尼龍比較，1 2尼龍係醯胺鍵量少，若考慮醯胺鍵間-10- S 201122019 Question. Since Tg must be kept relatively high, it is necessary to make Tc 1 at least 9 (TC or more. In the copolymerized polyamine of the present invention, 6T nylon is copolymerized due to a specific amount of 11 nylon component. Therefore, it is not only a resin having a high melting point or a low water absorption property, but also a resin having excellent balance between moldability, heat aging resistance, and gasoline resistance. In the molding of electronic parts, high melting point and low water absorption in addition to 300 ° C or higher. Thin-walled, high-cycle molding is also required. In the phthalic acid hexamethylenediamine/polyhexamethylene adipamide copolymer (PA6T/66), although the formability is good, the water absorption rate is extremely high. In the case of the surface soldering or the like, the problem of foaming occurs in the molded article. On the other hand, in the case of polyparathylenediamine, the amount of Tel is 15 (TC or more). Since the mold temperature at the time of molding must be 1 50 ° C or more, molding processability is difficult. Even if it can be molded by a low temperature mold, secondary shrinkage due to crystallization during use becomes a problem. Background, want A resin having a high melting point of 300 ° C or higher and a low water absorption and formability, in the copolymerized polyamine of the present invention, not only a high melting point but also a specific amount of 1 1 nylon to 6T nylon is copolymerized. Low water absorption, and can reduce Tc 1, can greatly improve the processability of injection molding. Also, considering the extension of 6T nylon to automotive parts, it requires not only molding processability or low water absorption, but also resistance to heat aging in the engine room. Or, in order to prevent the volatilization of fuel, the barrier property of gasoline or the like is important. At present, although there are reports of the copolymerization of 12 nylon to 6T nylon, the amount of the 12 nylon nylon amine bond is smaller than that of the 11 nylon. If you consider the indole bond
-11- S 201122019 的氫鍵賦予氣體成分的遮蔽效果’則不利於阻汽油性。 又，於11尼龍採取鋸齒形構造之際，係比12尼龍容易取 得氫鍵之構造’容易有效率地形成氫鍵’相對於此’ 12 尼龍係難以取得氫鍵而氫鍵性變弱。氫鍵性的提高’由於 會提高玻璃轉移溫度或提高汽油成分的遮蔽效果，從耐熱 老化性及阻汽油性的觀點係較佳。根據以上，儘管 Π尼 龍成分係比12尼龍成分優異的共聚合成分，且是具有優 異特性的樹脂，但是迄今爲止，使11尼龍對6T尼龍進行 共聚合，而具有熔點3 00 °C的具體共聚合聚醯胺尙未被報 告。 於製造本發明的共聚合聚醯胺之際，作爲所使用的觸 媒，可舉出磷酸、亞磷酸、次磷酸或其金屬鹽或銨鹽、 酯。就金屬鹽的金屬種而言，具體地可舉出鉀、鈉、鎂、 釩、鈣、鋅、鈷、錳、錫、鎢、鍺、鈦、銻等。就酯而 言，可添加乙酯、異丙酯、丁酯、己酯、異癸酯、十八 酯、癸酯、十八酯、苯酯等。又，從熔融滞留安定性提高 的觀點來看，較佳爲添加氫氧化鈉。 本發明的共聚合聚醯胺在96%濃硫酸中20°C所測定 的相對黏度（RV)爲0.4〜4.0，較佳爲1.0〜3.5，更佳爲1.5 -〜3.0。就使聚醯胺的相對黏度在一定範圍內的方法而 胃’可舉出調整分子量的手段。 本發明的共聚合聚醯胺，係可藉由調整胺基量與羧基 的莫耳比以進行聚縮合的方法或添加封端劑的方法，而調The shielding effect of the hydrogen bond imparted to the gas component by the hydrogen bond of -11-S 201122019 is not conducive to the resistance to gasoline. In addition, when the nylon has a zigzag structure, it is easier to obtain a hydrogen bond than the structure of the 12 nylon. The hydrogen bond is easily formed. The hydrogen bond is difficult to obtain hydrogen bonds and the hydrogen bond property is weak. The improvement in hydrogen bonding property is preferable from the viewpoint of heat aging resistance and gas barrier resistance because the glass transition temperature is increased or the shielding effect of the gasoline component is improved. According to the above, although the yttrium nylon component is a copolymer component superior to the 12 nylon component and is a resin having excellent characteristics, a nylon resin has been copolymerized with 6T nylon so far, and has a specific melting point of 300 ° C. Polymeric polyamidoxime has not been reported. In the production of the copolymerized polyamine of the present invention, phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt thereof, an ammonium salt or an ester thereof may be mentioned as the catalyst to be used. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, rhenium, titanium, ruthenium and the like. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, stearyl ester, decyl ester, octadecyl ester, phenyl ester or the like can be added. Further, from the viewpoint of improving the stability of the melt retention, it is preferred to add sodium hydroxide. The relative viscosity (RV) of the copolymerized polyamine of the present invention measured at 20 ° C in 96% concentrated sulfuric acid is from 0.4 to 4.0, preferably from 1.0 to 3.5, more preferably from 1.5 to 3.0. In the method of making the relative viscosity of polyamine into a certain range, the stomach can be exemplified by adjusting the molecular weight. The copolymerized polyamine of the present invention can be adjusted by adjusting the molar ratio of the amine group to the molar ratio of the carboxyl group to carry out the polycondensation method or the method of adding the blocking agent.
-12- S 201122019 整聚醯胺的末端基量及分子量。當將胺基量與羧基的莫耳 比以一定比率進行聚縮合時，較佳爲將所使用的全部二胺 與全部二羧酸之莫耳比調整至二胺/二羧酸= 1.00/1.05至 1.10/1.00 的範圍。 就添加封端劑的時期而言，可舉出原料投入時、聚合 開始時、聚合後期或聚合結束時。就封端劑而言，只要是 具有與聚醯胺末端的胺基或羧基的反應性的單官能性化合 物，則沒有特別的限制，可使用單羧酸或單胺、鄰苯二甲 酸酐等的酸酐、單異氰酸酯、單酸鹵化物、單酯類、單醇 類等。作爲封端劑，例如可舉出乙酸、丙酸、丁酸、戊 酸、己酸、辛酸、十二酸、十三酸、十四酸、十六酸、十 八酸、三甲基乙酸、異丁酸等的脂肪族單羧酸、環己烷羧 酸等的脂環式單羧酸、苯甲酸、苯乙酸、〇：-萘羧酸、 萘羧酸、甲基萘羧酸、苯基乙酸等的芳香族單羧酸、馬來 酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐等的酸酐、甲基 胺、乙胺、丙胺'丁胺 '己胺、辛胺、癸胺、十八胺、二 甲胺、二乙胺、二丙胺、二丁胺等的脂肪族單胺、環己 胺、二環己胺等的脂環式單胺；苯胺、甲苯胺、二.苯基 胺、萘胺等的芳香族單胺等。 本發明的共聚合聚醯胺之酸價及胺價分別較佳爲〇〜 200eQ/ton、0 〜lOOeq/ton。末端官能基若爲 200eq/ton 以 上，則不僅在熔融滯留時會促進膠化或劣化，而且在使用 環境下，亦會發生著色或水解等的問題。另一方面，將玻 5 -13- 201122019 璃纖維或馬來酸改性聚烯烴等的反應性化合物複合之際’ 配合反應性及反應基，酸價及/或胺價較佳爲5〜 1 00eq/ton 〇 於本發明的共聚合聚醯胺中’可使用以往的聚醯胺用 之各種添加劑。就添加劑而言’可舉出纖維狀強化材•塡 充材、安定劑、衝撃改良材、難燃劑、脫模劑、滑動性改 良材、著色劑、可塑劑、結晶核劑、與本發明共聚合聚醯 胺不同的聚醯胺、聚醯胺以外的熱塑性樹脂等。 就纖維狀強化材而言，可舉出玻璃纖維、碳纖維、金 屬纖維、陶瓷纖維、有機纖維、晶鬚等，其中較佳爲玻璃 纖維。此等纖維狀強化材不僅可只單獨使用1種，也可組 合數種使用。就此處所用的玻璃纖維而言，可使用具有 0.1mm〜100mm的長度之短切纖維或連續單絲纖維。就玻 璃纖維的截面形狀而言，可使用圓形截面及非圓形截面的 玻璃纖維。就玻璃纖維的截面形狀而言，從物性面來看， 較佳爲非圓形截面的玻璃纖維。就非圓形截面的玻璃纖維 而言，亦包含在對於纖維長的長度方向呈垂直的截面中略 橢圓系、略長圓系、略蠶繭形系者，偏平度較佳爲1.5〜 8。此處所謂的偏平度，就是假想在對於玻璃纖維的長度 方向呈垂直的截面所外接的最小面積之長方形，將此長方 形的長邊之長度當作長徑、短邊的長度當作短徑時的長徑 /短徑之比。玻璃纖維的粗度係沒有特別的限定，短徑爲1 〜50μιη，長徑爲2〜ΙΟΟμιη左右。又，玻璃纖維係成爲纖-12- S 201122019 The terminal amount and molecular weight of the polypeptamide. When the molar ratio of the amine group to the molar ratio of the carboxyl group is polycondensed at a certain ratio, it is preferred to adjust the molar ratio of all the diamines used to all the dicarboxylic acids to the diamine/dicarboxylic acid = 1.00/1.05. To the range of 1.10.10.00. The period in which the terminal blocking agent is added may be, for example, when the raw material is charged, at the start of polymerization, at the later stage of polymerization, or at the end of polymerization. The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amine group or a carboxyl group at the terminal of polyamine, and a monocarboxylic acid, a monoamine, a phthalic anhydride, or the like can be used. Anhydride, monoisocyanate, monoacid halide, monoester, monool, and the like. Examples of the terminal blocking agent include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, palmitic acid, octadecanoic acid, and trimethylacetic acid. Aliphatic monocarboxylic acid such as isobutyric acid, alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid, benzoic acid, phenylacetic acid, fluorene-naphthalenecarboxylic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenyl An aromatic monocarboxylic acid such as acetic acid, an anhydride such as maleic anhydride, phthalic anhydride or hexahydrophthalic anhydride, methylamine, ethylamine, propylamine 'butylamine' hexylamine, octylamine, decylamine An alicyclic monoamine such as octadecylamine, dimethylamine, diethylamine, dipropylamine or dibutylamine, an alicyclic monoamine such as cyclohexylamine or dicyclohexylamine; aniline, toluidine or diphenyl An aromatic monoamine such as a base amine or naphthylamine. The acid value and the amine value of the copolymerized polyamine of the present invention are preferably 〇~200eQ/ton and 0 to 100 eq/ton, respectively. When the terminal functional group is 200 eq/ton or more, not only gelation or deterioration is promoted during melt retention, but also problems such as coloring or hydrolysis occur in the use environment. On the other hand, when the reactive compound such as glass 5-13-201122019 glass fiber or maleic acid-modified polyolefin is compounded, the acidity and/or the amine value are preferably 5 to 1 in combination with the reactivity and the reactive group. 00 eq/ton 〇 In the copolymerized polyamine of the present invention, various additives for the conventional polyamine can be used. Examples of the additive include a fibrous reinforcing material, a cerium filling material, a stabilizer, a scouring improving material, a flame retardant, a releasing agent, a slidability improving material, a coloring agent, a plasticizer, a crystal nucleating agent, and the present invention. A poly-polyamine or a thermoplastic resin other than polyamine is copolymerized. The fibrous reinforcing material may, for example, be glass fiber, carbon fiber, metal fiber, ceramic fiber, organic fiber or whisker, and among them, glass fiber is preferred. These fibrous reinforcing materials may be used alone or in combination of several types. As the glass fiber used herein, chopped fibers or continuous monofilament fibers having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a circular cross section and a non-circular cross section can be used. The cross-sectional shape of the glass fiber is preferably a glass fiber having a non-circular cross section from the viewpoint of the physical property. The glass fiber having a non-circular cross section is also included in the cross section which is perpendicular to the longitudinal direction of the fiber length, and is slightly elliptical, slightly round, or slightly silkworm, and the degree of flatness is preferably 1.5 to 8. The degree of flatness referred to herein is a rectangle having a minimum area circumscribing a section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of the rectangle is regarded as the length of the long diameter and the short side as the short diameter. The ratio of long diameter to short diameter. The thickness of the glass fiber is not particularly limited, and the short diameter is 1 to 50 μm, and the long diameter is about 2 to ΙΟΟμηη. Also, the glass fiber becomes a fiber
S -14- 201122019 維束，較佳使用被切斷成纖維長1 維狀者。纖維狀強化材的添加量只 相對於100重量份而言，可添加（ 20〜150重量份。 就塡充材（塡料）而言，按照目 塡料或導電性塡料、磁性塡料、難 具體地可舉出玻璃珠、玻璃薄片 石、高嶺土、砂灰石、雲母、氧化 羥基磷灰石、石墨、碳奈米管、1 銦、氧化錫、氧化鐵、氧化鈦、氧 化鎂、紅磷、碳酸鈣、鈦酸鉀、鈦 化鋁、氮化硼、硼酸鋅、硼酸鋁、 鋅、鐵、鋁、銅、銀等。此等塡充 也可組合數種使用。形狀係沒有1 狀、球狀、板狀、不定形等。塡充 合適量即可，相對於100重量份的 添加250重量份以下、較佳爲20〜 又，爲了提高與聚醯胺樹脂的親和 充材較佳爲經偶合劑處理者，或與 而言，可使用矽烷系偶合劑、鈦酸 劑的任一者，其中特佳爲胺基矽烷 劑。 作爲安定劑，可舉出受阻酚系 〜20mm左右的短絲纖 要選擇最合適量即可， ί〜M .0重量份，較佳爲 的分別，可舉出強化用 燃塡料、導熱塡料等， 、玻璃氣球、矽石、滑 鋁、水滑石、蒙脫石、 霧樂烯、氧化鋅、氧化 化鎂、氫氧化銘、氫氧 酸鉻酸鉛、鈦酸鋇、氮 硫酸鋇、硫酸鎂、硫化 材可僅單獨使用1種， 穿別的限定，可使甩針 材的添加量只要選擇最 共聚合聚醯胺而言，可 / 150重量份的塡充材。 性，纖維狀強化材、塡 偶合劑倂用，就偶合劑 酯系偶合劑、鋁系偶合 偶合劑、環氧矽烷偶合 抗氧化劑、硫系抗氧化S -14- 201122019 Dimensional bundle, preferably used to be cut into fiber length 1 dimension. The amount of the fibrous reinforcing material to be added may be (20 to 150 parts by weight) per 100 parts by weight. For the ceramium filling material, the target material or conductive material, magnetic material, Specifically, glass beads, glass flakes, kaolin, sandstone, mica, oxidized hydroxyapatite, graphite, carbon nanotubes, indium, tin oxide, iron oxide, titanium oxide, magnesium oxide, red are exemplified. Phosphorus, calcium carbonate, potassium titanate, aluminum titanate, boron nitride, zinc borate, aluminum borate, zinc, iron, aluminum, copper, silver, etc. These can also be used in combination with several types. And a spherical shape, a plate shape, an amorphous shape, etc., may be appropriately added in an amount of 250 parts by weight or less, preferably 20% to 100 parts by weight, in order to improve the affinity filling material with the polyamide resin. Any one of a decane-based coupling agent and a titanic acid agent may be used as the coupler-treated agent, and particularly preferably an amino-based decane agent. Examples of the stabilizer include a hindered phenol system of about 20 mm. The shortest fiber should be selected in an optimum amount, ί~M.0 parts by weight, preferably Respectively, for example, refractory materials, thermal conductive materials, etc., glass balloons, vermiculite, sliding aluminum, hydrotalcite, montmorillonite, haloene, zinc oxide, magnesium oxide, hydroxide, hydrogen and oxygen Lead acid chromate, barium titanate, barium strontium sulphate, magnesium sulphate, and vulcanized material can be used alone or in combination, and the amount of enamel needle can be added as long as the most copolymerized polyamine is selected. / 150 parts by weight of enamel filler. Properties, fibrous reinforcing materials, bismuth coupling agents, coupling agent ester coupling agents, aluminum coupling coupling agents, epoxy decane coupling antioxidants, sulfur-based antioxidants
S -15- 201122019 劑、磷系抗氧化劑等的有機系抗氧化劑或熱安定劑、受阻 胺系、二苯甲酮系、咪唑系等的光安定劑或紫外線吸收 劑、金屬惰性化劑、銅化合物等。就銅化合物而言，可使 用氯化亞銅、溴化亞銅、碘化亞銅、氯化銅、溴化銅、碘 化銅、磷酸銅 '焦磷酸銅、硫化銅、硝酸銅、乙酸銅等的 有機羧酸之銅鹽等。再者，就銅化合物以外的構成成分而 言’較佳爲含有鹵化鹼金屬化合物，就鹵化鹼金屬化合物 而言，可舉出氯化鋰、溴化鋰、碘化鋰、氟化鈉、氯化 鈉、溴化鈉、碘化鈉、氟化鉀、氯化鉀、溴化鉀、碘化鉀 等。此等添加劑可僅單獨使用1種，也可組合數種使用。 安定劑的添加量只要選擇最合適量即可，相對於100重量 份的共聚合聚醯胺而言，可添加0〜5重量份。 又，本發明的共聚合聚醯胺亦可聚合摻合與本發明的 共聚合聚醯胺不同組成的聚醯胺。就與本發明的共聚合聚 醯胺不同組成的聚醯胺而言，並沒有特別的限制，可使用 單獨或二種以上的聚己醯胺（尼龍6)、聚十一醯胺（尼龍 11)、聚十二醯胺（尼龍12)、聚己二醯丁二胺（尼龍46)、 聚己二醯己二胺（尼龍66)、聚間苯二甲基己二醯胺（尼龍 MXD6)、聚對苯二甲基己二醯胺（尼龍PXD6)'聚癸二醯丁 二胺（尼龍410)、聚癸二醯己二胺（尼龍610)、.聚己二醯癸 二胺（尼龍106)、聚癸二醯癸二胺（尼龍1010)、聚十二烷 二醯己二胺（尼龍 612)、聚十二烷二醯癸二胺（尼龍 1012)、聚對苯二甲醯己二胺（尼龍6T)、聚聚間苯二甲醯S -15- 201122019 Organic anti-oxidant or thermal stabilizer such as phosphorus-based antioxidant, hindered amine-based, benzophenone-based, imidazole-based light stabilizer, ultraviolet absorber, metal inerting agent, copper Compounds, etc. As the copper compound, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, copper bromide, copper iodide, copper phosphate 'copper pyrophosphate, copper sulfide, copper nitrate, copper acetate can be used. Etching of copper salts of organic carboxylic acids, and the like. Further, the constituent component other than the copper compound is preferably a halogenated alkali metal compound, and examples of the halogenated alkali metal compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, and sodium chloride. , sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, and the like. These additives may be used alone or in combination of several kinds. The amount of the stabilizer to be added may be selected in an optimum amount, and may be added in an amount of from 0 to 5 parts by weight based on 100 parts by weight of the copolymerized polyamine. Further, the copolymerized polyamine of the present invention may also polymerize a polyamine which is different in composition from the copolymerized polyamine of the present invention. The polyamine which has a different composition from the copolymerized polyamine of the present invention is not particularly limited, and two or more kinds of polyhexylamine (nylon 6) and polyundecamide (nylon 11) may be used alone or in combination. ), polydodecylamine (nylon 12), polyhexamethylene diamine (nylon 46), polyhexamethylenediamine (nylon 66), poly-m-xylylene hexanediamine (nylon MXD6) , poly-p-dimethyl dimethyl hexamethylenediamine (nylon PXD6) 'poly phthalocyanine diamine (nylon 410), polyfluorene dimercaptoamine (nylon 610), polyhexamethylene diamine (nylon 106), polydecyl diamine (nylon 1010), polydodecane dimercaptodiamine (nylon 612), polydodecandioxane diamine (nylon 1012), polyparaphenylene benzoate Diamine (nylon 6T), poly(m-xylylene phthalate)
S -16 - 201122019 己二胺（尼龍61)、聚對苯二甲醯丁二胺（尼龍4Τ)、聚對苯 二甲醯戊二胺（尼龍5Τ)、聚-2-甲基對苯二甲醯戊二胺（尼 龍Μ-5Τ)、聚六氫對苯二甲醯己二胺（尼龍6Τ(Η))、聚2· 甲基對苯二甲醯辛二胺、聚對苯二甲醯壬二胺（尼龍9Τ)、 聚對苯二甲醯癸二胺（尼龍10Τ)、聚對苯二甲醯十—烷二 胺（尼龍11Τ)、聚對苯二甲醯十二烷二胺（尼龍12Τ)、聚雙 (3-甲基-4-胺基己基）甲烷對苯二甲醯胺（尼龍PACMT)、聚 雙（3-甲基-4-胺基己基）甲烷間苯二甲醯胺（尼龍pACMI)、 聚雙（3-甲基-4-胺基己基）甲烷十二醯胺（尼龍p ACM 12)、 聚雙（3-甲基-4-胺基己基）甲烷十四醯胺（尼龍p ACM 14)、 聚烷基醚共聚合聚醯胺等的單體、或此等的共聚合聚醯 胺。於此等之中，爲了提高結晶速度，亦可聚合摻合尼龍 66或尼龍6T66等。與本發明的共聚合聚醯胺不同組成的 聚醯胺之添加量只要選擇最合適量即可，相對於1〇〇重量 份的共聚合聚醯胺而言，可添加0〜50重量份。 於本發明的共聚合聚醯胺中，亦可添加與本發明的共 聚合聚醯胺不同組成的聚醯胺以外之熱塑性樹脂。就聚醯 胺以外的聚合物而言，可舉出聚苯硫（PPS)、液晶聚合物 (LCP)、芳香族聚醯胺樹脂、聚醚醚酮（peek)、聚醚酮 (PEK)、聚醚醯亞胺（PEI)、熱塑性聚醯亞胺、聚醯胺醯亞 胺（PAI)、聚醚酮酮（PEKK)、聚苯醚（ppE)、聚醚楓（PES)、 聚颯（PSU)、聚芳酯（PAR)、聚對苯二甲酸乙二酯、聚對苯 二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、S -16 - 201122019 Hexamethylenediamine (nylon 61), poly(p-xylylenediamine diamine (nylon 4Τ), polyparaphenylene pentanediamine (nylon 5Τ), poly-2-methyl-p-phenylene Indole pentanediamine (nylon Μ-5Τ), polyhexahydrophthalic acid hexamethylenediamine (nylon 6 Τ (Η)), poly 2·methyl-p-xylylene diamine, polyparaphenylene Terpene diamine (nylon 9 Τ), polyparaphenylene diamine (nylon 10 Τ), polyparaphenylene decene dialkyl diamine (nylon 11 Τ), polyparaphenylene decyl dodecane diamine (Nylon 12Τ), polybis(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalate Indoleamine (nylon pACMI), polybis(3-methyl-4-aminohexyl)methane dodecylamine (nylon p ACM 12), poly-bis(3-methyl-4-aminohexyl)methane A monomer such as decylamine (nylon p ACM 14), a polyalkyl ether copolymerized polyamine or the like, or a copolymerized polyamine. Among these, in order to increase the crystallization rate, it is also possible to polymerize and blend nylon 66 or nylon 6T66. The amount of the polyamine to be added to the copolymerized polyamine of the present invention may be an optimum amount, and may be added in an amount of 0 to 50 parts by weight based on 1 part by weight of the copolymerized polyamine. Further, in the copolymerized polyamine of the present invention, a thermoplastic resin other than polyamine which has a different composition from the copolymerized polyamine of the present invention may be added. Examples of the polymer other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aromatic polyamine resin, polyetheretherketone (peek), polyetherketone (PEK), Polyetherimine (PEI), thermoplastic polyimide, polyamidimide (PAI), polyetherketoneketone (PEKK), polyphenylene ether (ppE), polyether maple (PES), polyfluorene (PES) PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate,
-17- S 201122019 聚碳酸酯（PC)、聚甲醛（POM)、聚丙烯（PP)、聚乙烯（PE)、 聚甲基戊烯（TPX)、聚苯乙烯（PS)、聚甲基丙烯酸甲酯、 丙烯腈-苯乙烯共聚物（AS)、丙烯腈-丁二烯-苯乙烯共聚物 (ABS)，於相溶性差時，添加反應性化合物或嵌段聚合物 等的相溶化劑或將聚醯胺以外的聚合物改性（特佳爲酸改 性）係重要。此等熱塑性樹脂係可藉由熔融混煉而以熔融 狀態摻合，也可使熱塑性樹脂成爲纖維狀、粒子狀，而分 散於本發明的共聚合聚醯胺中。熱塑性樹脂的添加量只要 選擇最合適量即可，相對於100重量份的共聚合聚醯胺而 言，可添加0〜50重量份。 就衝撃改良材而言，可舉出乙烯-丙烯橡膠（EPM)、乙 烯-丙烯-二烯橡膠（EPDM)、乙烯-丙烯酸共聚物、乙烯_丙 烯酸酯共聚物 '乙烯-甲基丙烯酸共聚物 '乙烯-甲基丙烯 酸酯共聚物、乙烯乙酸乙烯酯共聚物等的聚烯烴系樹脂、 苯乙烯-丁二烯·苯乙烯嵌段共聚物（SBS)、苯乙烯·乙烯-丁 烯-苯乙烯嵌段共聚物（SEBS)、苯乙烯-異戊二烯-苯乙烯共 聚物（SIS)、丙烯酸酯共聚物等的乙烯基聚合物系樹脂，以 聚對苯二甲酸丁二酯或聚萘二甲酸丁二酯當作硬鏈段、以 聚丁二醇或聚己內酯或聚碳酸酯二醇當作軟鏈段的聚酯嵌 段共聚物’ '尼龍彈性體、胺甲酸酯彈性體、聚较氧橡膠、 氟系橡膠、具有由不同2種的聚合物所構成的芯殻構造之 聚合物粒子等。衝撃改良材的添加量只要選擇最合適量即 可’相對於100重量份的共聚合聚醯胺而言，可添加◦〜-17- S 201122019 Polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), polymethacrylic acid a methyl ester, an acrylonitrile-styrene copolymer (AS), or an acrylonitrile-butadiene-styrene copolymer (ABS), when a poor compatibility is added, a compatibilizing agent such as a reactive compound or a block polymer is added or It is important to modify a polymer other than polyamine (preferably acid-modified). These thermoplastic resins may be blended in a molten state by melt-kneading, or may be dispersed in the copolymerized polyamine of the present invention by forming a thermoplastic resin into a fibrous form or a particulate form. The amount of the thermoplastic resin to be added may be selected in an optimum amount, and may be added in an amount of from 0 to 50 parts by weight based on 100 parts by weight of the copolymerized polyamine. Examples of the modified material include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, and ethylene-acrylate copolymer 'ethylene-methacrylic acid copolymer'. Polyolefin resin such as ethylene-methacrylate copolymer or ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene·ethylene-butylene-styrene embedded Vinyl polymer resin such as segment copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS), acrylate copolymer, etc., with polybutylene terephthalate or polynaphthalene dicarboxylic acid a polyester block copolymer of a butadiene ester as a hard segment, a polybutylene glycol or a polycaprolactone or a polycarbonate diol as a soft segment, a nylon elastomer, a urethane elastomer, Polyoxyethylene rubber, fluorine-based rubber, polymer particles having a core-shell structure composed of two different polymers, and the like. The amount of the mashing modified material to be added may be selected as the optimum amount, and may be added with respect to 100 parts by weight of the copolymerized polyamine.
-18- S 201122019 30重量份》 對於本發明的共聚合聚醯胺，添加本發明中的聚醯胺 樹脂以外之熱塑性樹脂及耐衝撃改良材時，較佳爲共聚合 可與聚酿胺反應的反應性基，反應性基係聚醯胺樹脂的末 端基之胺基、羧基及與主鏈醯胺基可反應的基。具體地， 可例示羧酸基、酸酐基、環氧基、曙唑啉基、胺基、異氰 酸酯基等，於該等之中，酸酐基係反應性最優異。亦有報 告稱如此地，具有與聚醯胺樹脂反應的反應性基之熱塑性 樹脂，係在聚醯胺中微分散，因微分散而粒子間的距離變 短，大幅改良耐衝撃性[S，Wu: Polymer 26，1855(1985)]。 就難燃劑而言，可爲鹵素系難燃劑與難燃助劑之組 合’就鹵素系難燃劑而言，較佳爲溴化聚苯乙烯、溴化聚 苯醚、溴化雙酚型環氧系聚合物、溴化苯乙烯馬來酸酐聚 合物、溴化環氧樹脂.、溴化苯氧樹脂、十溴二苯基醚、十 溴聯苯、溴化聚碳酸酯、全氯環十五烷及溴化交聯芳香族 聚合物等，就難燃助劑而言，較佳爲三氧化銻、五氧化 錄、銻酸鈉等的銻化合物或錫酸鋅等。其中，從熱安定性 之面來看，較佳爲二溴聚苯乙烯與銻酸鈉及/或錫酸鋅的 組合。又，就非鹵素系難燃劑而言，可舉出蜜胺三聚氰酸 酯、紅磷、次膦酸的金屬鹽.、含氮磷酸系的化合物。特別 地’較佳爲次膦酸金屬鹽與含氮磷酸系化合物之組合，就 含氮磷酸系化合物而言’包含蜜胺或如蜜白胺（melame)、 六聚氰胺（mellon)的蜜胺之縮合物與聚磷酸的反應性生成-18-S 201122019 30 parts by weight. In the case of adding the thermoplastic resin other than the polyamide resin of the present invention and the impact-resistant improving material to the copolymerized polyamine of the present invention, it is preferred that the copolymerization can be reacted with the polyamine. The reactive group, the reactive group is an amine group of a terminal group of a polyamide resin, a carboxyl group, and a group reactive with a main chain amide group. Specifically, a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amine group, an isocyanate group or the like can be exemplified, and among these, the acid anhydride group-based reactivity is the most excellent. It has also been reported that a thermoplastic resin having a reactive group reactive with a polyamide resin is finely dispersed in polyamine, and the distance between particles is shortened due to microdispersion, and the impact resistance is greatly improved [S, Wu: Polymer 26, 1855 (1985)]. In the case of a flame retardant, it may be a combination of a halogen-based flame retardant and a flame retardant. In the case of a halogen-based flame retardant, brominated polystyrene, brominated polyphenylene ether, and brominated bisphenol are preferred. Epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorine The cyclopentadecane and the brominated crosslinked aromatic polymer are preferably a ruthenium compound such as antimony trioxide, pentoxide or sodium citrate or zinc stannate. Among them, from the viewpoint of heat stability, a combination of dibromopolystyrene and sodium citrate and/or zinc stannate is preferred. Further, examples of the non-halogen-based flame retardant include melamine cyanurate, red phosphorus, a metal salt of phosphinic acid, and a nitrogen-containing phosphate-based compound. In particular, it is preferred that the combination of a metal phosphinate and a nitrogen-containing phosphate compound contains melamine or honey such as melame or mellon in the case of a nitrogen-containing phosphate compound. Reactivity formation of amine condensate and polyphosphoric acid
S -19- 201122019 物或該等的混合物。於該情況下，爲了防止模具等的金屬 腐鈾，水滑石系化合物的添加係較佳。又，就其它難燃 劑、難燃助劑而言，可舉出硼酸鋅、硫化鋅、鉬化合物、 氧化鐵、氫氧化鋁、氫氧化鎂、聚矽氧樹脂、氟樹脂、蒙 脫石、矽石、碳酸金屬鹽等》難燃劑的添加量只要選擇最 合適量即可’相對於100重量份的共聚合聚醯胺而言，可 添加0〜50重量份。 就脫模劑而S，可舉出長鏈脂肪酸或其酯或金屬鹽、 醯胺系化合物、聚乙烯蠟、聚矽氧、聚環氧乙烷等。就長 鏈脂肪酸而言’特佳爲碳數12以上，例如可舉出硬脂 酸、12-羥基硬脂酸、二十二酸、褐煤酸等，部分或全部 的羧酸亦可被單二醇或聚二醇所酯化，或也可形成金屬 鹽。就醯胺系化合物而言，可舉出伸乙基雙對苯二甲醯 胺、亞甲基雙硬脂醯胺等。此等脫模劑可爲單獨或當作混 合物使用。脫模劑的添加量只要選擇最合適量即可，相對 於100重量份的共聚合聚醯胺而言，可添加〇〜5重量 份。 就滑動性改良材而言，可舉出高分子量聚乙烯、酸改 性高分子量聚乙烯、氟樹脂粉末、二硫化鉬、聚矽氧樹 脂、聚矽氧油、鋅、石墨、礦物油等。.於不損害本發明的 特性之範圍內’可添加樹脂滑動性改良材，例如0.05〜3 重量份的範圔。 本發明的共聚合聚醯胺係可藉由習知的方法來製造， -20- s .201122019 例如可藉由使（a)成分的原料單體之己二胺、對苯二 及（b)成分的原料單體之11-胺基十一酸或十一內醯 及視需要的（c)由前述（a)的結構單位以外之二胺與 之等量莫耳鹽所得之結構單位、由前述（b)的結構 外的胺基羧酸或內醯胺進行共縮合反應而容易合成 聚合反應的順序係沒有特別的限定，可一次使全部 單體進行反應，也可先使一部分的原料單體進行反 著使剩餘的原料單體進行反應。又，聚合方法係沒 的限定，可以連續的步驟由原料投入開始進行到聚 作爲止，也可使用一次製作寡聚物後，在另一步驟 擠壓機等進行聚合，或藉由將寡聚物固相聚合而高 化等之方法。藉由調整原料單體的投入比率，可控 成的共聚合聚醯胺中.之各結構單位的比例。 實施例 以下藉由實施例來更具體說明本發明，惟本發 此等實施例所限定。再者，實施例中所記載的測定 由以下的方法進行測定者。 (1) 相對黏度 使0.25g聚醯胺樹脂溶解於25ml的96 %硫酸中 奧斯特瓦爾德黏度計在20°C測定。 (2) 末端胺基量 使 〇.2g聚醯胺樹脂溶解於 20ml的間甲酚 0.1 mol/1鹽酸乙醇溶液進行滴定。指示劑係使用甲 甲酸、 胺、以 二羧酸 單位以 。共縮 的原料 應，接 有特別 合物製 中藉由 分子量 制所合 明不受 値係藉 ，使用 中，以 酚紅。S -19- 201122019 The substance or a mixture of these. In this case, in order to prevent metal humusum such as a mold, the addition of the hydrotalcite-based compound is preferred. Further, examples of other flame retardants and flame retardant aids include zinc borate, zinc sulfide, molybdenum compounds, iron oxide, aluminum hydroxide, magnesium hydroxide, polyoxyxylene resins, fluororesins, and montmorillonite. The amount of the flame retardant added to the vermiculite, the metal carbonate, or the like can be 0 to 50 parts by weight with respect to 100 parts by weight of the copolymerized polyamine, as long as the optimum amount is selected. Examples of the mold release agent S include long-chain fatty acids or esters or metal salts thereof, guanamine-based compounds, polyethylene waxes, polyfluorene oxides, and polyethylene oxides. The long-chain fatty acid is particularly preferably a carbon number of 12 or more, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, etc., and some or all of the carboxylic acid may be monodiol. Alternatively, the polyglycol may be esterified or a metal salt may also be formed. The guanamine-based compound may, for example, be ethyl bis-p-xylyleneamine or methylenebisstearylamine. These release agents can be used singly or as a mixture. The amount of the releasing agent to be added may be selected in an optimum amount, and may be added in an amount of 〇 5 parts by weight based on 100 parts by weight of the copolymerized polyamine. The slidability improving material may, for example, be a high molecular weight polyethylene, an acid modified high molecular weight polyethylene, a fluororesin powder, a molybdenum disulfide, a polyoxyxide resin, a polyoxyxylene oil, zinc, graphite or mineral oil. The resin slidability improving material may be added within a range not impairing the characteristics of the present invention, for example, 0.05 to 3 parts by weight. The copolymerized polyamine of the present invention can be produced by a conventional method, -20-s. 201122019, for example, by making the raw material monomers of the component (a) hexamethylenediamine, p-benzoic acid and (b) a structural unit of 11-aminoundecanoic acid or eleven internal hydrazine as a raw material monomer of the component and optionally (c) an equivalent amount of a molar salt other than the structural unit of the above (a) The order in which the aminocarboxylic acid or the indoleamine other than the above-mentioned structure (b) is subjected to a co-condensation reaction to facilitate the synthesis of the polymerization reaction is not particularly limited, and all of the monomers may be reacted at once, or a part of the raw materials may be first The body is reversed to cause the remaining raw material monomers to react. Further, the polymerization method is not limited, and the continuous step may be carried out from the start of the raw material to the polymerization, or the oligomer may be produced once, or the polymerization may be carried out in another step, or by oligomerization. A method in which a solid phase polymerization is carried out and the like is advanced. The ratio of each structural unit in the copolymerized polyamine can be controlled by adjusting the input ratio of the raw material monomers. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, which are defined by the examples. Further, the measurement described in the examples was carried out by the following method. (1) Relative viscosity 0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid. The Ostwald viscometer was measured at 20 °C. (2) Amount of terminal amine group 〇. 2 g of polyamine resin was dissolved in 20 ml of m-cresol 0.1 mol/1 hydrochloric acid ethanol solution for titration. The indicator is a formic acid, an amine, or a dicarboxylic acid unit. The raw material of the co-shrinkage should be borrowed from the molecular weight system by the molecular weight system, and the phenol red is used.
-21- S 201122019 以1噸樹脂中的當量（eq/ton)表示。 (3) 熔點（Tm)及升溫結晶化溫度（Tel) 於鋁製盤（ΤΑ Instruments公司製，品號900793.90 1 ) 中秤量10mg經105t減壓乾燥15小時的聚醯胺，用鋁製 蓋（TA Instruments公司製，品號900794.901)使其成爲密封 狀態，調製測定試料後，使用差示掃描熱量計 DSCQ100(TA INSTRUMENTS 製），由室溫以 20°C/分鐘進行 升溫，在3 50°C保持3分鐘後，取出測定試料盤，浸入液 態氮中以使急冷。然後，由液態氮中取出樣品，於室溫放 置30分鐘後，再使用差示掃描熱量計 DSCQ100(TA INSTRUMENTS製），由室溫以20°C /分鐘進行升溫’在350 t保持3分鐘。於該情況下，將升溫時的結晶化之發熱尖 峰溫度當作升溫時結晶化溫度（Tc 1 )，將熔解所致的吸熱 之尖峰溫度當作熔點（Tm)。 (4) 成形性 使用東芝機械.製射出成形機EC-100，料筒溫度係設 定在樹脂的熔點+ 20 °C 。模具係使用縱l〇〇mm、橫 100mm、厚度lmmt的平板作成用模具。模具溫度係設定 在140°C，以射出速度50mm/sec、保壓30MPa、射出時間 10秒、冷卻時間1 0秒進行成型，成形性的好壞係實施如 以下的評價。 〇：未看到顯著的樹脂分解，而且得到無問題的成型品。 X :成形時伴隨分解所致的發泡’或脫模性係不充分’而-21- S 201122019 is expressed in equivalents (eq/ton) of 1 ton of resin. (3) Melting point (Tm) and temperature rising crystallization temperature (Tel) Polyacrylamide was weighed and dried in an aluminum pan (manufactured by Sigma Instruments, product number 900793.90 1 ) under reduced pressure of 105 t for 15 hours, and covered with aluminum ( TA Instruments, product number 900794.901) was placed in a sealed state, and after the measurement sample was prepared, a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) was used, and the temperature was raised from room temperature at 20 ° C / min, at 3 50 ° C. After holding for 3 minutes, the test tray was taken out and immersed in liquid nitrogen to quench. Then, the sample was taken out from the liquid nitrogen, and left at room temperature for 30 minutes, and then subjected to a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS), and the temperature was raised from room temperature at 20 ° C /min, and held at 350 t for 3 minutes. In this case, the heat-generating peak temperature at the time of temperature rise is regarded as the crystallization temperature (Tc 1 ) at the time of temperature rise, and the peak temperature of the endotherm due to the melting is taken as the melting point (Tm). (4) Formability Using Toshiba Machine Co., Ltd., the injection molding machine EC-100 was used, and the barrel temperature was set at the melting point of the resin + 20 °C. The mold was formed into a mold using a flat plate having a length of l〇〇mm, a width of 100 mm, and a thickness of lmmt. The mold temperature was set at 140 ° C, and the molding was carried out at an injection speed of 50 mm/sec, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 10 seconds. The moldability was evaluated as follows. 〇: No significant resin decomposition was observed, and a problem-free molded article was obtained. X: foaming or dismantling due to decomposition during molding is insufficient
-22- S 201122019 成型品黏貼於模具或變形》 (5) 耐熱老化性 於耐熱老化性試驗用中，使用對於1〇〇份的聚醯胺， 複合有0.02份的溴化銅、0.15份的碘化鉀者，藉由射出 成形機，根據ISO來製作啞鈴狀試片。成型品係在16(TC geer式烘箱中實施1 000小時的熱老化試驗，拉伸試驗係 按照IS ◦ 5 2 7進行。耐熱老化性的好壞係藉由如以下的基 準進行評價。 〇：160 °C 10 00小時後的拉伸強度或拉伸降伏強度的保持 率爲9 0 %以上 X : 160°C 1 000小時後的拉伸強度或拉伸降伏強度的保持率 低於90% (6) 阻汽油性 於阻汽油性的評價中，實施杯法的燃料透過性試驗。 於杯中添加4.6g由異辛垸/甲本/乙醇以45/45/10vol%所構 成的燃料。於燃料透過率測定中，使用以熱壓機將本發明 的聚醯胺製作成100 μιη厚度的薄膜者。所得之薄膜係設置 於加有剛才的燃料之杯上，但不接觸燃料（氣相法）。除了 自薄膜的透過以外，不使燃料揮發而維持氣密性。測定係 以1.1 3 3 x 1 0 3m2的透過面積、60°C的試驗溫度進行240小 時的試驗時間，測量測定前後的重量變化量。又，由於考 慮試料的吸放水特性，進行空白實驗，進行校正而算出燃 料透過量。阻汽油性的好壞係藉由如以下的基準進行評-22- S 201122019 Molded product adhered to mold or deformation" (5) Heat aging resistance in heat aging test, using 0.02 parts of copper bromide and 0.15 parts for 1 part of polyamide In the case of potassium iodide, a dumbbell-shaped test piece was produced according to ISO by an injection molding machine. The molded product was subjected to a heat aging test of 1 000 hours in a 16 (TC geer type oven), and the tensile test was carried out in accordance with IS ◦ 5 2 7. The heat aging resistance was evaluated by the following criteria. The retention of tensile strength or tensile strength after 100 ° C for 100 ° C is more than 90%. X : The retention of tensile strength or tensile strength after 1 000 hours at 160 ° C is less than 90% ( 6) In the evaluation of gasoline resistance, the fuel permeability test of the cup method was carried out. 4.6 g of fuel consisting of 45/45/10 vol% of isoxin/benben/ethanol was added to the cup. In the measurement of the fuel permeability, a polyacetamide of the present invention was formed into a film having a thickness of 100 μm by a hot press. The obtained film was placed on a cup to which the fuel was added, but was not in contact with the fuel (gas phase method). In addition to the permeation of the film, the fuel was not volatilized and the airtightness was maintained. The measurement was carried out for a test time of 240 hours at a test area of 1.13 3 x 1 3 3 m 2 and a test temperature of 60 ° C. The amount of change in weight. Also, due to the characteristics of the water absorption and discharge of the sample A blank test, is calculated by correcting the fuel permeation amount. The quality of the gasoline barrier properties as described below by reference lines for Comments
S -23- 201122019 價。 〇：重量減少量低於l〇〇mg X:重量減少量爲lOOmg以上 (7)飽和吸水率 於飽和吸水率的評價中，製作縱100mm、橫l〇Omm、 厚度1mm的平板，將此浸漬在80°C熱水中’藉由下式來 求得。 飽和吸水率（％ )=(飽和吸水時的重量-乾燥時重量）/乾 燥時重量X 1 〇〇 <實施例1 > 將 7.54kg 己二胺、l〇.79kg 對苯二甲酸、7.〇4kg 11·胺 基十一酸、9g當作觸媒的二亞磷酸鈉、40g當作末端調整 劑的乙酸及17.52kg離子交換水投入50升的高壓釜中，用 N2由常壓加壓到0.05MPa爲止，降壓，而回到常壓。進行 3次此操作’進行置換後，於攪拌下在135°C、0.3MPa 使其均勻溶解。然後，藉由送液泵來連續供給溶解液，以 加熱配管使升溫到240°C爲止，加熱1小時。然後，將反 應混合物供給至加壓反應罐，加熱到290°C，而將罐內壓 維持在3MPa ’餾出水的一部分，得到低度縮合物。然 後’將此低度縮合物維持著熔融狀態，而直接供給至二軸 擠壓機（螺桿直徑37mm, L/D = 60)，使樹脂溫度爲3 30°C， 一邊由3個地方的通氣口來去除水，—邊在熔融下進行聚 縮合’而得到共聚合聚醯胺。表1中顯示原料單體的投入S -23- 201122019 Price. 〇: the weight loss is less than 10 mg X: the weight loss is 100 mg or more. (7) The saturated water absorption rate is evaluated in the saturated water absorption rate, and a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm is prepared and impregnated. It is obtained by the following formula in hot water at 80 °C. Saturated water absorption (%) = (weight at saturated water absorption - weight at drying) / weight at drying X 1 〇〇 <Example 1 > 7.54 kg of hexamethylenediamine, 1 〇.79 kg of terephthalic acid, 7 〇4kg 11·aminoundecanoic acid, 9g sodium diphosphite as a catalyst, 40g acetic acid as a terminal regulator, and 17.52kg ion-exchanged water are put into a 50-liter autoclave, and N2 is added by atmospheric pressure. Pressurize to 0.05 MPa, reduce the pressure, and return to normal pressure. This operation was carried out three times. After the replacement, the mixture was uniformly dissolved at 135 ° C and 0.3 MPa with stirring. Then, the solution was continuously supplied by a liquid supply pump, and the tube was heated to a temperature of 240 ° C and heated for 1 hour. Then, the reaction mixture was supplied to a pressurized reaction tank, heated to 290 ° C, and the internal pressure of the tank was maintained at a portion of 3 MPa' of distilled water to obtain a low condensate. Then, the low-condensation product was maintained in a molten state, and was directly supplied to a two-axis extruder (screw diameter: 37 mm, L/D = 60), so that the resin temperature was 3 30 ° C, and ventilation was performed by three places. The mouth is used to remove water, and polycondensation is carried out under melting to obtain a copolymerized polyamine. Table 1 shows the input of raw material monomers
S -24- 201122019 比率及所得之共聚合聚醯胺的特性。 <實施例2 > 除了將己二胺之量變更爲8.12kg，將對苯二甲酸之量 變更爲11.62kg’將1丨_胺基十一酸之量變更爲6‘03kg，將 二軸擠壓機的樹脂溫度變更爲335 〇c。此等以外係與實施 例1同樣’而合成共聚合聚醯胺。表1中顯示原料單體的 投入比率及所得之共聚合聚醯胺的特性。 <實施例3 > 除了將己二胺之量變更爲6.96kg，將對苯二申酸之量 變更爲9.96kg’將11-胺基十一酸之量變更爲8.〇4kg以 外，與實施例1同樣地合成共聚合聚醯胺。表1中顯示原 料單體的投入比率及所得之共聚合聚醯胺的特性。 <實施例4 > 除了將己二胺之量變更爲8_1 2kg，將對苯二甲酸之量 變更爲9.9 6kg，將11-胺基十—酸之量變更爲6.03kg以 外，投入1.46kg己二酸（對苯二甲酸以外的二羧酸）以外， 與實施例1同樣地合成共聚合聚醯胺。表1中顯示原料單 體的投入比率及所得之共聚合聚醯胺的特性。 <實施例5 > 除了將7_04kg 11-胺基十一酸變更爲6.41kg十一內醯 胺以外，與實施例1同樣地合成共聚合聚醯胺。表1中顯 示原料單體的投入比率及所得之共聚合聚醯胺的特性。 <比較例1 > -25- 201122019 除了將己二胺之量變更爲9.28kg，將對苯一甲酸 變更爲13.28kg，將11-胺基十一酸之量變更爲4.02kg —軸擠壓機的樹脂溫度變更爲350 °C以外，與實施例 樣地合成共聚合聚醯胺。表1中顯示原料單體的投入 及所得之共聚合聚醯胺的特性。 <比較例2 > 除了將己二胺之量變更爲5.22kg，將對苯一甲酸 變更爲7.47kg，將1 1-胺基_(——酸之量變更爲11.06kg 實施例1同樣地合成共聚合聚醯胺。表1中顯7K原料 的投入比率及所得之共聚合聚醯胺的特性。 <比較例3 > 除了將7.44kg 11-胺基]--酸變更爲7.53kg 12- 十二酸以外，與實施例1同樣地合成共聚合聚醯胺。 中顯示原料單體的投入比率及所得之共聚合聚醯胺 性。 <比較例4 > 除了不使用11-胺基十一酸，而使用10.18kg己 及14.5 6kg對苯二甲酸以外，與實施例1同樣地合成 合聚醯胺。所合成的聚醯胺係在聚合階段中流動性降 無法得到聚合物。 之量 ，將 1同 比率 之量 ,與 單體 胺基 表1 的特 二胺 共聚 低，S -24- 201122019 Ratio and characteristics of the resulting copolymerized polyamine. <Example 2 > In addition to changing the amount of hexamethylenediamine to 8.12 kg, the amount of terephthalic acid was changed to 11.62 kg', and the amount of 1 丨-aminoundecanoic acid was changed to 6'03 kg, The resin temperature of the shaft extruder was changed to 335 〇c. In the same manner as in Example 1, except that the copolymerized polyamine was synthesized. Table 1 shows the input ratio of the raw material monomers and the characteristics of the obtained copolymerized polyamine. <Example 3 > In addition to changing the amount of hexamethylenediamine to 6.96 kg, the amount of benzoic acid was changed to 9.96 kg', and the amount of 11-aminoundecanoic acid was changed to 8. 4 kg. The copolymerized polyamine was synthesized in the same manner as in Example 1. Table 1 shows the input ratio of the raw monomer and the characteristics of the obtained copolymerized polyamine. <Example 4 > In addition to changing the amount of hexamethylenediamine to 8_1 2 kg, the amount of terephthalic acid was changed to 9.9 6 kg, and the amount of 11-aminododeic acid was changed to 6.03 kg, and 1.46 kg was charged. A copolymerized polyamine was synthesized in the same manner as in Example 1 except for adipic acid (dicarboxylic acid other than terephthalic acid). Table 1 shows the input ratio of the raw material monomers and the characteristics of the obtained copolymerized polyamine. <Example 5> The copolymerized polyamine was synthesized in the same manner as in Example 1 except that 7 to 10 kg of 11-aminoundecanoic acid was changed to 6.41 kg of indoleamine. Table 1 shows the input ratio of the raw material monomers and the characteristics of the obtained copolymerized polyamine. <Comparative Example 1 > -25- 201122019 In addition to changing the amount of hexamethylenediamine to 9.28 kg, the amount of p-phenylenecarboxylic acid was changed to 13.28 kg, and the amount of 11-aminoundecanoic acid was changed to 4.02 kg. The copolymerized polyamine was synthesized in the same manner as in the example except that the resin temperature of the press was changed to 350 °C. Table 1 shows the input of the raw material monomers and the characteristics of the obtained copolymerized polyamine. <Comparative Example 2 > In addition to changing the amount of hexamethylenediamine to 5.22 kg, the amount of phenylenecarboxylic acid was changed to 7.47 kg, and the amount of 1 1-amino group was changed to 11.06 kg in the same manner as in Example 1. The copolymerized polyamine was synthesized. The input ratio of the 7K raw material in Table 1 and the characteristics of the obtained copolymerized polyamine. <Comparative Example 3 > In addition to changing 7.44 kg of 11-amino]-acid to 7.53 The copolymerized polyamine was synthesized in the same manner as in Example 1 except for kg 12-dodecanoic acid. The input ratio of the raw material monomers and the obtained copolymerized polyamidamine were shown. <Comparative Example 4 > In the same manner as in Example 1, except that 10.18 kg of hexanic acid and 11.58 kg of terephthalic acid were used, the polyamine was synthesized in the same manner as in Example 1. The fluidity of the synthesized polyamine was not polymerized during the polymerization stage. The amount of the same ratio, the amount of the same ratio, and the monomeric amine group 1 of the special diamine copolymerization,
S -26- 201122019S -26- 201122019
201122019 由表1可明知，實施例1〜5的共聚合聚醯胺係高度 滿足成形性、耐熱老化性及阻汽油性的三個特性全部。其 中’若考慮高熔點、成形性（6T成分多且Tel爲140°C以 下之良好）、低吸水率（11成分多者爲佳）之平衡，則可說 實施例1最好。另一方面，11尼龍的共聚合量過少的比較 例1之共聚合聚醯胺係Tm及Tc 1高，脫模困難。11尼龍 的共聚合量過多的比較例2之共聚合聚醯胺係Tm低，且 由於胺基十一烷成分而阻礙6T成分的結晶化，結晶性係 不足’故脫模不完全，成形性差。又，代替11尼龍，使 12尼龍共聚合的比較例3之共聚合聚醯胺，與共聚合有 11尼龍的共聚合聚醯胺比較下，係耐熱老化性及阻汽油 性差。僅由6T尼龍所成的比較例4之聚醯胺，由於Tm 及Tel極高，故在聚合階段中流動性降低，無法得到聚合 物。 產業上的利用可能性 本發明的共聚合聚醯胺，由於1 1尼龍以特定的比例 對主成分的6T尼龍進行共聚合，而可一邊活用3〇〇t：以 上的高熔點、機械特性、滑動性等之6T尼龍的特性，一 邊亦高度滿足低吸水性、成形性、耐熱老化性及阻汽油 性’故可適用作爲汽車或電子零件用的成形材料或滑動用 材料。 【圖式簡單說明】 钿〇 【主要元件符號說明】 鈿。 /\\\201122019 It is understood from Table 1 that the copolymerized polyamines of Examples 1 to 5 are highly satisfactory in all three properties of formability, heat aging resistance, and gas barrier properties. In the above, it is preferable to consider that the high melting point and the formability (the 6T component is large and the Tel is good below 140 °C) and the low water absorption ratio (the 11 components are preferable) are preferable. On the other hand, the copolymerized polyamines Tm and Tc 1 of Comparative Example 1 having a too small amount of copolymerization of 11 nylon were high, and demolding was difficult. When the copolymerization amount of 11 nylon is too large, the copolymerized polyamine-based Tm of Comparative Example 2 is low, and the crystallization of the 6T component is inhibited by the aminoundecane component, and the crystallinity is insufficient. Therefore, the mold release is incomplete and the formability is poor. . Further, in place of the 11 nylon, the copolymerized polyamine of Comparative Example 3 in which 12 nylon was copolymerized was inferior in heat aging resistance and gasoline resistance as compared with the copolymerized polyamine copolymerized with 11 nylon. Since the polyamine of Comparative Example 4, which was formed only of 6T nylon, had extremely high Tm and Tel, the fluidity was lowered during the polymerization stage, and the polymer could not be obtained. INDUSTRIAL APPLICABILITY The copolymerized polyamine of the present invention can copolymerize 6T nylon having a main component in a specific ratio, and can utilize a high melting point and mechanical properties of 3〇〇t or more. The properties of 6T nylon, such as slidability, are highly suitable for low water absorption, formability, heat aging resistance, and gasoline resistance. Therefore, it can be used as a molding material or a sliding material for automobiles or electronic parts. [Simple description of the diagram] 钿〇 [Description of main component symbols] 钿. /\\\
S -28-S -28-
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| US10851206B2 (en) | 2017-12-18 | 2020-12-01 | Taiwan Textile Research Institute | Modified nylon 66 fiber |
| CN112204075A (en) * | 2018-03-29 | 2021-01-08 | 东洋纺株式会社 | Semi-aromatic polyamide resin and method for producing same |
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| JP5804313B2 (en) * | 2011-05-30 | 2015-11-04 | 東洋紡株式会社 | Polyamide resin composition for sliding members |
| JP5769013B2 (en) * | 2011-08-31 | 2015-08-26 | 株式会社ジェイテクト | Roller and roller device |
| JP6210217B2 (en) * | 2013-12-26 | 2017-10-11 | 東洋紡株式会社 | Carbon fiber reinforced polyamide resin composition |
| JP6269044B2 (en) * | 2013-12-26 | 2018-01-31 | 東洋紡株式会社 | High melting point polyamide resin composition with excellent vibration characteristics and hot rigidity during water absorption |
| WO2017077901A1 (en) * | 2015-11-02 | 2017-05-11 | 東洋紡株式会社 | Semi-aromatic polyamide resin and method for producing same |
| CN106336508B (en) * | 2016-09-14 | 2018-05-18 | 金发科技股份有限公司 | A kind of semi-aromatic copolyamide resin and the polyamide moulding composition being made from it |
| CN111133038B (en) * | 2017-09-25 | 2022-10-14 | 东洋纺株式会社 | Molded article comprising semi-aromatic polyamide resin composition as component |
| WO2020122170A1 (en) | 2018-12-14 | 2020-06-18 | 東洋紡株式会社 | Semi-aromatic polyamide resin and method for manufacturing same |
| CN111635520A (en) * | 2020-06-19 | 2020-09-08 | 山东东辰瑞森新材料科技有限公司 | High-temperature-resistant polyamide material and preparation method thereof |
| CN115975181B (en) * | 2023-01-09 | 2024-02-13 | 华润化学材料科技股份有限公司 | Ternary polymerization transparent nylon and preparation method thereof |
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| FR2685700B1 (en) * | 1991-12-31 | 1995-02-24 | Atochem | NEW POLYAMIDES AND OBJECTS OBTAINED THEREFROM. |
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