JPH0710914B2 - Amorphous high Tg polyamide - Google Patents
Amorphous high Tg polyamideInfo
- Publication number
- JPH0710914B2 JPH0710914B2 JP270786A JP270786A JPH0710914B2 JP H0710914 B2 JPH0710914 B2 JP H0710914B2 JP 270786 A JP270786 A JP 270786A JP 270786 A JP270786 A JP 270786A JP H0710914 B2 JPH0710914 B2 JP H0710914B2
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- Japan
- Prior art keywords
- polyamide
- mol
- mixture
- acid
- diamine
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Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は高いガラス転移点（Tg）を有し、寸法安定性の
すぐれた非晶性ポリアミドに関し、更に詳しくは高温の
焼付け塗装に耐え、成形収縮、線膨脹係数が小さく、寸
法安定性が良好な自動車等の外装部品用に適した非晶性
高Tgポリアミドに関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to an amorphous polyamide having a high glass transition point (Tg) and excellent dimensional stability, and more specifically, it can withstand high temperature baking coating, The present invention relates to an amorphous high Tg polyamide suitable for exterior parts such as automobiles, which has a small molding shrinkage and a linear expansion coefficient and has good dimensional stability.
＜従来の技術＞ ポリアミド樹脂は強度、剛性、強靭性などの機械特性、
耐熱性、耐摩耗性、耐薬品性などがすぐれているため、
一般機械部品、自動車部品、電気、電子材料部品とし
て、幅広く使用されているエンジニアリングプラスチッ
クである。特に自動車製造分野においては従来から車体
重量の軽量化や、デザインの自由度向上などの要求か
ら、金属材料からプラスチック材料への代替が積極的に
なされており、ナイロン６や66に代表されるポリアミド
樹脂はそのすぐれた耐熱性、耐薬品性、耐摩耗性が認め
られてラジエタータンク、シリンダヘッドカバー、ホィ
ールキャップなどのアンダーフード部品に極めて好適に
用いられている。最近になって本自動車分野における金
属材料からプラスチック材料への転換は更に急速な進展
を見せ、これまでの内装部品、アンダーフード部品ばか
りでなく、フェンダー、ドアパネル、スポイラーなどの
大型外装部品をもプラスチック化するべく多くの検討が
なされている。これらの大型外装部品用プラスチック材
料として要求される特性の主たるものは、１）自動車の
オンライン塗装の焼付け塗装温度に耐えられる耐熱性を
有すること、２）成形収縮が小さいこと、３）加熱、吸
水などによる成形片の寸法変化が小さいこと、４）剛
性、耐衝撃性が高いこと、等であり、ナイロン６やナイ
ロン66などの結晶性汎用ポリアミド樹脂は成形収縮、加
熱や吸水による寸法変化が大きいために上記大型外装用
部品用途には適した材料とはいえない。<Prior art> Polyamide resin has mechanical properties such as strength, rigidity and toughness.
As it has excellent heat resistance, abrasion resistance, chemical resistance, etc.,
It is an engineering plastic that is widely used as general mechanical parts, automobile parts, electric and electronic material parts. Particularly in the field of automobile manufacturing, replacement of metal materials with plastic materials has been aggressively made in response to demands for weight reduction of vehicle bodies and improvement of design freedom, and polyamides represented by nylon 6 and 66 Resin has been recognized for its excellent heat resistance, chemical resistance, and wear resistance, and is therefore very suitably used for underhood parts such as radiator tanks, cylinder head covers, and wheel caps. In recent years, the shift from metal materials to plastic materials in this automobile field has made rapid progress, and not only conventional interior parts and underhood parts but also large exterior parts such as fenders, door panels and spoilers are made of plastic. Many studies have been made to realize this. The main characteristics required of these plastic materials for large exterior parts are: 1) Heat resistance that can withstand the baking temperature of online painting of automobiles, 2) Small mold shrinkage, 3) Heating and water absorption. For example, the dimensional change of the molded piece due to, etc. is small, 4) the rigidity and impact resistance are high, etc., and the crystalline general-purpose polyamide resins such as nylon 6 and nylon 66 have large dimensional changes due to molding shrinkage, heating and water absorption. Therefore, it cannot be said that the material is suitable for the large-scale exterior parts.
一方ポリアミド樹脂の内で成形収縮が小さく、寸法安定
性が良好なものとして、一般に透明ナイロンと呼ばれる
非晶性ポリアミドがある。これらは、通常、主鎖中に側
鎖、環構造を含んでおり、その代表的なものとして2,2,
4−および／または2,4,4−トリメチルヘキサメチレンテ
レフタルアミド（例えば、特公昭49−21115号公報）、
ヘキサメチレンイソフタルアミドに50モル％以下（64.5
重量％以下）の脂環族ジアミンを導入した共重合体（特
開昭53−18697号公報）などの例が開示されている。On the other hand, among polyamide resins, an amorphous polyamide, which is generally called transparent nylon, is one having a small molding shrinkage and good dimensional stability. These usually include a side chain and a ring structure in the main chain, and as a typical one, 2,2,
4- and / or 2,4,4-trimethylhexamethylene terephthalamide (for example, JP-B-49-21115),
50 mol% or less in hexamethylene isophthalamide (64.5
Examples of copolymers (Japanese Unexamined Patent Publication No. Sho 53-18697) into which alicyclic diamine of (wt% or less) is introduced are disclosed.
＜発明が解決しようとする問題点＞ しかしながら、上記の如き従来の透明ナイロンはその熱
変形温度が高々160℃程度であり、自動車のオンライン
塗装の際の160〜180℃/30分という焼付け塗装条件に耐
えることができず、自動車大型外装部品材料としては耐
熱性が不足している。<Problems to be Solved by the Invention> However, the conventional transparent nylon as described above has a heat distortion temperature of at most about 160 ° C., and a baking coating condition of 160 to 180 ° C./30 minutes for online coating of automobiles. Therefore, the heat resistance is insufficient as a material for large automobile exterior parts.
そこで本発明者らは、自動車のオンライン塗装プロセス
に耐える耐熱性を有し、成形収縮、線膨脹係数が小さ
く、寸法安定性が良好で更に剛性、耐衝撃性も良好な溶
融成形可能な自動車大型外装部品材料に適したポリアミ
ド樹脂を得るべく検討を重ねた結果、極めて厳密に組成
を選択して得られる特定の非晶高Tgポリアミドが上記の
要求を全て満足し、好適な自動車大型外装用部品材料と
なることを見出し、本発明に到達した。Therefore, the present inventors have proposed a large-sized automobile capable of being melt-molded, which has heat resistance to withstand the online coating process of automobiles, has a small molding shrinkage and linear expansion coefficient, has good dimensional stability, and has good rigidity and impact resistance. As a result of repeated studies to obtain a polyamide resin suitable for exterior part materials, a specific amorphous high Tg polyamide obtained by selecting the composition extremely strictly satisfies all the above requirements, and is suitable for large automobile exterior parts. The inventors have found that it can be used as a material and arrived at the present invention.
＜問題点を解決するための手段＞ すなわち本発明は（１）（ａ）下記一般式で示される脂
環族ジアミンの少なくとも一種95〜65重量％および
（ｂ）炭素数６〜12の直鎖脂肪族ジアミンの少なくとも
一種５〜35重量％の混合物と （２）該ジアミン混合物と実質的に等モル量のイソフタ
ル酸との混合物或いはナイロン塩を縮重合することによ
り得られる非晶高Tgポリアミドを提供するものである。<Means for Solving Problems> That is, the present invention relates to (1) (a) 95 to 65% by weight of at least one alicyclic diamine represented by the following general formula and (b) a straight chain having 6 to 12 carbon atoms. A mixture of at least 5 to 35% by weight of an aliphatic diamine, and (2) a mixture of the diamine mixture and a substantially equimolar amount of isophthalic acid, or an amorphous high Tg polyamide obtained by polycondensation of a nylon salt. It is provided.
（式中R1、R2は水素原子又はメチル基を表し、R1とR2は
互いに同じでも異なっていてもよい。二つのシクロヘキ
サン環の1,4−位を占めるアミノ基と炭素原子の幾何異
性に関してはトランス−トランス体が30モル％以上、シ
ス−シス体が20モル％以下。） 本発明の非晶高Tgポリアミドの原料となる（ａ）成分の
脂環族ジアミンは各々相当する芳香族ジアミンの核水添
によって、得ることが出来、これら脂環族ジアミンの代
表的な例としては、ビス−ｐ−アミノシクロヘキシルメ
タン（以下PACMと略す）、ビス−ｐ−アミノシクロヘキ
シルプロパン（以下PACPと略す）および2,2′−又は3,
3′−ジメチル−ビス−ｐ−アミノシクロヘキシルメタ
ン（以下diMe−PACMと略す）などを挙げることができ
る。これら脂環族ジアミンは、通常、その核水添過程で
生成するシクロヘキサン環の1,4−位を占めるアミノ基
と炭素原子に関する三種の幾何異性体すなわちトランス
−トランス（ｔ−ｔ）体、トランス−シス（ｔ−ｃ）体
およびシス−シス（ｃ−ｃ）体の混合物であり、異性体
の含有量によって生成するポリアミドの耐熱性が変化す
るので本発明においては異性体の含有量も特定化されな
ければならない。 (In the formula, R 1 and R 2 represent a hydrogen atom or a methyl group, and R 1 and R 2 may be the same or different from each other. An amino group occupying the 1,4-position of two cyclohexane rings and a carbon atom Regarding the geometrical isomerism, the trans-trans isomer is 30 mol% or more and the cis-cis isomer is 20 mol% or less.) The alicyclic diamine of the component (a) which is a raw material of the amorphous high Tg polyamide of the present invention corresponds to each. It can be obtained by nuclear hydrogenation of an aromatic diamine, and typical examples of these alicyclic diamines include bis-p-aminocyclohexylmethane (hereinafter abbreviated as PACM) and bis-p-aminocyclohexylpropane (hereinafter (Abbreviated as PACP) and 2, 2'- or 3,
3'-Dimethyl-bis-p-aminocyclohexylmethane (hereinafter abbreviated as diMe-PACM) and the like can be mentioned. These alicyclic diamines are usually three types of geometrical isomers regarding the amino group occupying the 1,4-position of the cyclohexane ring formed in the nuclear hydrogenation process and a carbon atom, that is, a trans-trans (t-t) form, a trans-form. -A mixture of cis (t-c) and cis-cis (c-c) isomers, and since the heat resistance of the polyamide produced changes depending on the content of the isomer, the content of the isomer is also specified in the present invention. Must be embodied.
本発明の非晶高Tgポリアミドの原料として用いられる
（ａ）成分の脂環族ジアミンはそのｔ−ｔ体含有量が30
モル％以上、ｃ−ｃ体含有量が20モル％以下であること
が必要であり、特にｔ−ｔ体含有量が40モル％以上、ｃ
−ｃ体含有量が15モル％以下であることが好ましい。異
性体含有量が上記の範囲をはずれると、得られるポリア
ミドのTgが低下し、耐熱性が不足するので好ましくな
い。The alicyclic diamine as the component (a) used as a raw material for the amorphous high Tg polyamide of the present invention has a t-t content of 30.
It is necessary that the content of the cc-form is 20 mol% or less and the content of the tt-form is 40 mol% or more.
It is preferable that the content of the -c-form is 15 mol% or less. If the isomer content is out of the above range, the Tg of the obtained polyamide is lowered and the heat resistance is insufficient, which is not preferable.
本発明で用いられる（ｂ）成分の直鎖脂肪族ジアミンの
例としてはヘキサメチレンジアミン、ヘプタメチレンジ
アミン、オクタメチレンジアミン、ノナメチレンジアミ
ン、デカメチレンジアミン、ウンデカメチレンジアミン
およびドデカメチレンジアミンを挙げることができるが
中でもヘキサメチレンジアミンが好適に用いられる。Examples of the (b) component linear aliphatic diamine used in the present invention include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine and dodecamethylenediamine. Among them, hexamethylenediamine is preferably used.
上記（ａ）成分と（ｂ）成分の混合割合は（ａ）の脂環
族ジアミン95〜65重量％および（ｂ）の直鎖脂肪族ジア
ミン５〜35重量％の範囲内にあることが必要である。
（ａ）の脂環族ジアミンの量が６（ａ）の脂環族ジアミ
ンの量が65重量％に満たない場合には、得られるポリア
ミドの耐熱性が不足するので好ましくない。また（ａ）
の脂環族ジアミン量が95重量％を越えると生成するポリ
アミドの溶融粘性が高くなり過ぎ溶融成形が困難になり
好ましくない。The mixing ratio of the component (a) and the component (b) must be within the range of 95 to 65% by weight of the alicyclic diamine of (a) and 5 to 35% by weight of the linear aliphatic diamine of (b). Is.
When the amount of the alicyclic diamine of (a) is less than 65% by weight, the amount of the alicyclic diamine of 6 (a) is not preferable because the heat resistance of the obtained polyamide is insufficient. Also (a)
If the amount of the alicyclic diamine is more than 95% by weight, the melt viscosity of the produced polyamide becomes too high, and the melt molding becomes difficult, which is not preferable.
本発明で用いられるジカルボン酸は、上記ジアミン混合
物と実質的に等モル量のイソフタル酸であるが、生成す
るポリアミドの重合性、耐熱性等の特性を損わない限り
において、少量の他のジカルボン酸を添加導入すること
ができる。これらジカルボン酸の例としてはアジピン
酸、アゼライン酸、セバシン酸、ドデカン二酸、シクロ
ヘキサンジカルボン酸、テレフタル酸などを挙げること
ができる。The dicarboxylic acid used in the present invention is isophthalic acid in a substantially equimolar amount to the above diamine mixture, but as long as it does not impair the properties such as the polymerizability and heat resistance of the resulting polyamide, a small amount of other dicarboxylic acid is used. An acid can be added and introduced. Examples of these dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid and terephthalic acid.
本発明のポリアミドを重縮合させる方法については特に
制限はなく、通常公知の溶融重合、溶液重合、界面重合
などの方法を用いることができる。なかでも好適なの
は、溶融重合であり、その代表的な例としては、原料を
５〜50％の水と共に加℃で反応せしめた後、徐々に水分
を除去しながら250〜330℃で重合せしめる加圧重合法を
挙げることができる。The method for polycondensing the polyamide of the present invention is not particularly limited, and generally known methods such as melt polymerization, solution polymerization and interfacial polymerization can be used. Of these, melt polymerization is preferable, and a typical example thereof is that the raw material is reacted with 5 to 50% of water at a temperature of 250 ° C and then gradually polymerized at a temperature of 250 to 330 ° C while gradually removing water. A pressure polymerization method can be mentioned.
本発明のポリアミドの重合度についても特に制限はな
く、通常、98％濃硫酸中１重量％濃度で25℃で測定した
溶液相対粘度が1.3以上のものを用いることができる。The degree of polymerization of the polyamide of the present invention is also not particularly limited, and it is usually possible to use one having a solution relative viscosity of 1.3 or more measured at 25 ° C. at a concentration of 1% by weight in 98% concentrated sulfuric acid.
このようにして得られた本発明のポリアミドは、実質的
に次の一般式（Ｉ）および（II）で示される構造単位か
らなるランダム共重合体であり、 高いTgおよび熱変形温度を有しているため、高温の焼付
け塗装に耐え、また、成形収縮、寸法変化も小さいの
で、自動車の外装部品用材料として好適である。The polyamide of the present invention thus obtained is a random copolymer substantially composed of structural units represented by the following general formulas (I) and (II), Since it has a high Tg and heat distortion temperature, it can withstand high temperature baking coating, and has little molding shrinkage and dimensional change, so it is suitable as a material for exterior parts of automobiles.
本発明のポリアミドにはその成形性、物性を損わない限
りにおいて他の成分、例えば顔料、染料、補強材、充填
材、耐熱剤、耐光剤、酸化劣化防止剤、滑剤、可塑剤、
帯電防止剤、難燃剤、離型剤、他の重合体などを添加導
入することができる。Moldability of the polyamide of the present invention, other components as long as it does not impair the physical properties, such as pigments, dyes, reinforcing materials, fillers, heat-resistant agents, light-resistant agents, oxidative deterioration inhibitors, lubricants, plasticizers,
An antistatic agent, a flame retardant, a release agent, another polymer, etc. can be added and introduced.
とりわけ、酸無水物基、カルボン酸基、イミド基、エポ
キシ基、水酸基などの官能基で変性されたポリエチレ
ン、ポリプロピレン、エチレン／プロピレン共重合体、
エチレン／ブテン共重合体やエチレン（メタ）アクリル
酸エステル共重合体などの変性ポリオレフィンを添加導
入することはポリアミドの耐衝撃性向上に効果があるた
め、本発明でも好適に用いられる態様の一つである。In particular, polyethylene, polypropylene, ethylene / propylene copolymers modified with functional groups such as acid anhydride groups, carboxylic acid groups, imide groups, epoxy groups and hydroxyl groups,
One of the modes preferably used in the present invention is that adding and introducing a modified polyolefin such as an ethylene / butene copolymer or an ethylene (meth) acrylic acid ester copolymer is effective in improving impact resistance of polyamide. Is.
＜実施例＞ 以下に実施例を挙げて本発明を更に詳しく説明する。<Examples> The present invention will be described in more detail with reference to the following examples.
なお、実施例および比較例の中で述べる諸特性は下記の
方法で測定したものである。The properties described in the examples and comparative examples are measured by the following methods.
（１）相対粘度：ポリマ1gを100mlの濃硫酸に溶解した
溶液の25℃における相対粘度。(1) Relative viscosity: Relative viscosity at 25 ° C. of a solution prepared by dissolving 1 g of polymer in 100 ml of concentrated sulfuric acid.
（２）元素分析：柳本（株）製微量元素定量分析装置Mu
-2型を用いて測定した。(2) Elemental analysis: Trace element quantitative analyzer Mu by Yanagimoto Co., Ltd.
It was measured using a -2 model.
（３）脂環族ジアミンの異性体比定量：ジアミンを20倍
量のジメチルフォルムアミドジメチルアセタールで処理
してメチル化し、反応生成分を島津製作所製GC-7A型ガ
スクロマトグラフを用い、カラム長1m充填材シリコーン
OV−17のカラムで分離し、レコーダーの面積比から異性
体比を定量した。(3) Determination of isomer ratio of alicyclic diamine: Diamine was treated with 20 times amount of dimethylformamide dimethyl acetal to methylate, and the reaction product was analyzed using Shimadzu GC-7A type gas chromatograph with a column length of 1 m. Filler silicone
Separation was carried out using an OV-17 column, and the isomer ratio was quantified from the recorder area ratio.
（４）ガラス転移点（Tg）：パーキンエルマー（株）製
DSC-1B型示差差動熱量計を用い20℃／分の昇温速度で昇
温した際に観測される変曲点。(4) Glass transition point (Tg): Perkin Elmer Co., Ltd.
Inflection point observed when the temperature was raised at a heating rate of 20 ° C / min using the DSC-1B differential differential calorimeter.
（５）成形収縮率:JIS1号ダンベル片を射出成形した際
の流れ方向の収縮率。(5) Molding shrinkage: Shrinkage in the flow direction when a JIS No. 1 dumbbell piece is injection molded.
（６）引張特性:ASTM D638 （７）曲げ特性:ASTM D790 （８）熱変形温度:ASTM D648 （９）アイゾット衝撃強度:ASTM D256 実施例１ 異性体含有量がｔ−ｔ体52％、ｃ−ｃ体５％であるPACM
7.02Kg（33.3モル）、ヘキサメチレンジアミン3.0Kg（2
5.9モル）、イソフタル酸9.8Kg（59.2モル）および水5.
0Kgの混合物を重合缶に仕込み、窒素置換した後、加熱
し、内圧15Kg/cm2Gにもたらした。この加圧下で約２時
間保持した後、徐々に放圧し、常圧に戻してから更に窒
素気流下280〜290℃で１時間反応せしめ、重合を完了し
た。ここで得られたポリアミドは元素分析の結果ヘキサ
メチレンジアミン・イソフタル酸/PACM・イソフタル酸
（６・I/PACM・Ｉ）＝44/56（モル／モル）の組成を有
していた。(6) Tensile property: ASTM D638 (7) Bending property: ASTM D790 (8) Heat distortion temperature: ASTM D648 (9) Izod impact strength: ASTM D256 Example 1 isomer content is t-t body 52%, c -PACM with 5% c body
7.02Kg (33.3mol), Hexamethylenediamine 3.0Kg (2
5.9 mol), 9.8 kg of isophthalic acid (59.2 mol) and water 5.
A 0 Kg mixture was charged into a polymerization vessel, and after nitrogen substitution, it was heated and brought to an internal pressure of 15 Kg / cm 2 G. After the pressure was maintained for about 2 hours, the pressure was gradually released, the pressure was returned to normal pressure, and the reaction was further continued under a nitrogen stream at 280 to 290 ° C. for 1 hour to complete the polymerization. As a result of elemental analysis, the polyamide obtained here had a composition of hexamethylenediamine · isophthalic acid / PACM · isophthalic acid (6 · I / PACM · I) = 44/56 (mol / mol).
その特性は下記に示す通りであり、耐熱性にすぐれ、成
形収縮も小さく寸法安定性にすぐれた外装部品材料とし
て極めて好適なものであることが判明した。The characteristics are as shown below, and it has been found that it is extremely suitable as a material for exterior parts which has excellent heat resistance, small molding shrinkage and excellent dimensional stability.
比較例１ 実施例１で用いたPACM4.0Kg（19.0モル）、ヘキサメチ
レンジアミン6.0Kg（51.7モル）、イソフタル酸11.7Kg
（70.7モル）および水5.3Kgの混合物を重合缶に仕込
み、以下実施例１と全く同様に重合を実施した。 Comparative Example 1 4.0 kg of PACM (19.0 mol) used in Example 1, 6.0 kg of hexamethylenediamine (51.7 mol), 11.7 kg of isophthalic acid
A mixture of (70.7 mol) and 5.3 kg of water was charged into a polymerization vessel, and the polymerization was carried out in the same manner as in Example 1 below.
ここで得られたポリアミドは６・I/PACM・Ｉ＝73/27
（モル／モル）の組成を有し、相対粘度1.70、ガラス転
移点160℃、熱変形温度（18.6Kg/cm2荷重）131℃であ
り、耐熱性が不足であった。The polyamide obtained here is 6 · I / PACM · I = 73/27.
It had a composition of (mol / mol), a relative viscosity of 1.70, a glass transition point of 160 ° C., and a heat distortion temperature (18.6 Kg / cm 2 load) of 131 ° C., and the heat resistance was insufficient.
比較例２ 異性体含有量がｔ−ｔ体10％、ｃ−ｃ体50％のPACMを用
いた以外は実施例１と全く同様に重合を実施し、実施例
１で得たポリアミドと同組成の６・I/PACM・Ｉ＝44/56
（モル／モル）のポリマを得た。しかしこのポリアミド
のガラス転移点、熱変形温度（18.6Kg/cm2荷重）は各々
171℃、139℃であり、これも耐熱性が不足であった。Comparative Example 2 Polymerization was carried out in exactly the same manner as in Example 1 except that PACM having an isomer content of 10% in tt form and 50% in cc form was used, and had the same composition as the polyamide obtained in Example 1. 6. I / PACM I = 44/56
(Mol / mol) polymer was obtained. However, the glass transition point and heat distortion temperature (18.6 Kg / cm 2 load) of this polyamide are
It was 171 ° C. and 139 ° C., which also lacked heat resistance.
実施例２ 異性体含有量がｔ−ｔ体45％、ｃ−ｃ体15％のPACP8.0K
g（33.6モル）、ヘキサメチレンジアミン2.0Kg（17.2モ
ル）、イソフタル酸8.4Kg（50.8モル）および水7.9Kgの
混合物を実施例１に記したのと同様の方法で重縮合せし
め、ヘキサメチレンジアミン・イソフタル酸/PACP・イ
ソフタル酸（６・I/PACP・Ｉ）＝34/66（モル／モル）
の組成を有する相対粘度1.72のポリアミドを得た。Example 2 PACP8.0K having an isomer content of 45% tt form and 15% cc form
A mixture of g (33.6 mol), hexamethylenediamine 2.0 Kg (17.2 mol), isophthalic acid 8.4 Kg (50.8 mol) and water 7.9 Kg was polycondensed in the same manner as described in Example 1 to give hexamethylenediamine.・ Isophthalic acid / PACP ・ Isophthalic acid (6 ・ I / PACP ・ I) = 34/66 (mol / mol)
A polyamide having a relative viscosity of 1.72 having the composition
このものの元素分析結果および物性は下記に示す通りで
あり、耐熱性、寸法安定性が極めて良好な材料であるこ
とが判明した。The results of elemental analysis and physical properties of this product are as shown below, and it was found that the material has extremely good heat resistance and dimensional stability.
実施例３ 実施例１で得たポリアミド75重量部と、Ｎ−フェニルマ
レイミドで変性したエチレン／プロピレン共重合体25重
量部をドライブレンドした後、40mmφ単軸押出機に供給
し、混練温度290℃で溶融混練を行った。得られたブレ
ンド体を乾燥後、シリンダー温度280℃、金型温度80℃
で射出成形し、テストピースを得た。これらの特性は次
の通りであり、本ブレンド体は耐熱性、寸法安定性、更
に耐衝撃性にすぐれた極めて実用価値の高いものであっ
た。 Example 3 After 75 parts by weight of the polyamide obtained in Example 1 and 25 parts by weight of an ethylene / propylene copolymer modified with N-phenylmaleimide were dry blended, the mixture was fed to a 40 mmφ single screw extruder and kneading temperature was 290 ° C. Was melt-kneaded. After drying the obtained blend, cylinder temperature 280 ℃, mold temperature 80 ℃
Injection molding was carried out to obtain a test piece. These properties are as follows, and the blend was excellent in heat resistance, dimensional stability, and impact resistance, and had extremely high practical value.
成形収縮率 0.62％ 熱変形温度（18.6Kg/cm2） 158℃ （ 4.6Kg/cm2） 173℃ 引張強度 580Kg/cm2 曲げ弾性率 15,200Kg/cm2 アイゾット衝撃強度 13Kg/cm2ノッチ ＜発明の効果＞ 本発明の如く、原料成分、ポリマ組成を極めて厳密に選
択／最適化することにより、自動車外装部品用材料とし
て要求される耐熱性、寸法安定性などの諸特性を全て満
足できるすぐれたポリアミドを得ることが可能になっ
た。Mold shrinkage 0.62% Heat distortion temperature (18.6Kg / cm 2 ) 158 ℃ (4.6Kg / cm 2 ) 173 ℃ Tensile strength 580Kg / cm 2 Flexural modulus 15,200Kg / cm 2 Izod impact strength 13Kg / cm 2 Notch <Invention Effect> By rigorously selecting / optimizing the raw material components and the polymer composition as in the present invention, it is possible to satisfy all the various characteristics such as heat resistance and dimensional stability required as materials for automobile exterior parts. It became possible to obtain polyamide.
Claims (2)
ンの少なくとも一種95〜65重量％および（ｂ）炭素数６
〜12の直鎖脂肪族ジアミンの少なくとも一種５〜35重量
％の混合物と(A) 95 to 65% by weight of at least one alicyclic diamine represented by the following general formula and (b) 6 carbon atoms.
A mixture of at least one of the linear aliphatic diamines of
ソフタル酸との混合物或いはナイロン塩を縮重合するこ
とにより得られる非晶高Tgポリアミド。 （式中R1、R2は水素原子又はメチル基を表し、R1とR2は
互いに同じでも異なっていてもよい。二つのシクロヘキ
サン環の1,4−位を占めるアミノ基と炭素原子の幾何異
性に関してはトランス−トランス体が30モル％以上、シ
ス−シス体が20モル％以下。）2. An amorphous high Tg polyamide obtained by polycondensation of a mixture of the diamine mixture and isophthalic acid in a substantially equimolar amount or a nylon salt. (In the formula, R 1 and R 2 represent a hydrogen atom or a methyl group, and R 1 and R 2 may be the same or different from each other. An amino group occupying the 1,4-position of two cyclohexane rings and a carbon atom Regarding geometrical isomerism, trans-trans isomers are 30 mol% or more and cis-cis isomers are 20 mol% or less.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP270786A JPH0710914B2 (en) | 1986-01-09 | 1986-01-09 | Amorphous high Tg polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP270786A JPH0710914B2 (en) | 1986-01-09 | 1986-01-09 | Amorphous high Tg polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62161829A JPS62161829A (en) | 1987-07-17 |
| JPH0710914B2 true JPH0710914B2 (en) | 1995-02-08 |
Family
ID=11536763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP270786A Expired - Lifetime JPH0710914B2 (en) | 1986-01-09 | 1986-01-09 | Amorphous high Tg polyamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710914B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0725878B2 (en) * | 1986-03-11 | 1995-03-22 | 三井石油化学工業株式会社 | polyamide |
| DE3934926A1 (en) * | 1989-10-20 | 1991-04-25 | Huels Chemische Werke Ag | SHAPE-RESISTANT DIMENSIONS TO ALCOHOLS AND BOILING WATER |
| JP4898282B2 (en) * | 2006-05-10 | 2012-03-14 | 株式会社ビービーリッチ | Air brush |
| DE102006041138A1 (en) * | 2006-09-01 | 2008-03-06 | Evonik Degussa Gmbh | Composite of a film and a substrate based on an amorphous polyamide |
-
1986
- 1986-01-09 JP JP270786A patent/JPH0710914B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62161829A (en) | 1987-07-17 |
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