JPH07228689A - Polyamide resin - Google Patents
Polyamide resinInfo
- Publication number
- JPH07228689A JPH07228689A JP6019584A JP1958494A JPH07228689A JP H07228689 A JPH07228689 A JP H07228689A JP 6019584 A JP6019584 A JP 6019584A JP 1958494 A JP1958494 A JP 1958494A JP H07228689 A JPH07228689 A JP H07228689A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyamide
- mol
- nonanediamine
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なポリアミドに関
する。詳しくは、極めて優れた成形加工性を有すると共
に、耐熱水性、表面美麗性、耐熱性、力学特性、低吸水
性、耐薬品性などに優れたポリアミドに関するものであ
る。本発明のポリアミドは、例えば、産業資材、工業材
料、家庭用品などの成形材料として好適に使用すること
ができる。FIELD OF THE INVENTION The present invention relates to a novel polyamide. More specifically, the present invention relates to a polyamide having extremely excellent moldability and excellent in hot water resistance, surface beauty, heat resistance, mechanical properties, low water absorption, chemical resistance and the like. The polyamide of the present invention can be suitably used as a molding material for industrial materials, industrial materials, household products, and the like.
【０００２】[0002]
【従来の技術】従来からナイロン６、ナイロン６６など
に代表される結晶性ポリアミドは、その優れた特性と溶
融成形の容易さから、衣料用、産業資材用繊維、あるい
は汎用のエンジニアリングプラスチックとして広く用い
られているが、一方では、耐熱性不足、吸水による寸法
安定性不良などの問題点も指摘されている。特に近年の
表面実装技術（ＳＭＴ）の発展に伴うリフローハンダ耐
熱性を必要とする電気・電子分野、あるいは年々耐熱性
への要求が高まる自動車のエンジンルーム部品などにお
いては、従来のポリアミドでの使用が困難となってきて
おり、より耐熱性、寸法安定性、機械特性、物理化学特
性に優れたポリアミドへの要求が高まっている。2. Description of the Related Art Conventionally, crystalline polyamides such as nylon 6 and nylon 66 have been widely used as fibers for clothes, industrial materials or general-purpose engineering plastics because of their excellent properties and ease of melt molding. However, on the other hand, problems such as insufficient heat resistance and poor dimensional stability due to water absorption have been pointed out. Especially in the electric and electronic fields that require heat resistance for reflow soldering due to the recent development of surface mount technology (SMT), or in the engine room parts of automobiles where the demand for heat resistance is increasing year by year, conventional polyamide is used. Is becoming difficult, and there is an increasing demand for polyamides that are more excellent in heat resistance, dimensional stability, mechanical properties, and physicochemical properties.
【０００３】このような世の中の要求に対し、アジピン
酸と１，４−ブタンジアミンからなる全脂肪族ポリアミ
ド、テレフタル酸と１，６−ヘキサンジアミンを主成分
とする半芳香族ポリアミドが種々提案され、一部は実用
化されている。しかしながら、アジピン酸と１，４−ブ
タンジアミンからなるポリアミド（以下ＰＡ４−６と略
称する）は、溶融粘度が低く、テレフタル酸と１，６−
ヘキサンジアミンを主成分とする半芳香族ポリアミドに
比べ、良好な成形性を有するものの、吸水率が高く、寸
法安定性などの実使用時の諸物性の変動が問題視されて
いる。In response to such demands in the world, various kinds of all-aliphatic polyamides composed of adipic acid and 1,4-butanediamine, and various semi-aromatic polyamides composed mainly of terephthalic acid and 1,6-hexanediamine have been proposed. , Some have been put to practical use. However, a polyamide composed of adipic acid and 1,4-butanediamine (hereinafter abbreviated as PA4-6) has a low melt viscosity, and terephthalic acid and 1,6-
Although it has better moldability than a semi-aromatic polyamide containing hexanediamine as a main component, it has a high water absorption rate, and variations in various physical properties during actual use such as dimensional stability are regarded as problems.
【０００４】一方、テレフタル酸と１，６−ヘキサンジ
アミンからなるポリアミド（以下、ＰＡ６−Ｔと略称す
る）は、ポリマーの分解温度を超える３７０℃付近に融
点があるため、溶融重合、溶融成形が困難であり、実用
に耐えるものではない。そのため実際には、アジピン
酸、イソフタル酸などのジカルボン酸成分、あるいはナ
イロン６などの脂肪族ポリアミドを３０〜４０モル％共
重合することにより、実使用可能温度領域、すなわち２
８０〜３２０℃程度にまで低融点化した組成で用いられ
ているのが現状である。このように多量の第３成分（場
合によっては第４成分）を共重合することは、確かにポ
リマーの低融点化には有効なものの、一方では結晶化速
度、到達結晶化度の低下を伴い、その結果、高温下での
剛性、耐薬品性、寸法安定性などの諸物性が低下するば
かりでなく、成形サイクルの延長に伴う生産性の低下を
も招く。また、吸水による寸法安定性などの諸物性の変
動に関しても、芳香族基の導入により、従来の脂肪族ポ
リアミドに比べれば多少改善されてはいるものの、実質
的な問題解決のレベルまでには達していない。On the other hand, a polyamide composed of terephthalic acid and 1,6-hexanediamine (hereinafter abbreviated as PA6-T) has a melting point near 370 ° C., which is higher than the decomposition temperature of the polymer, so that it is melt-polymerized and melt-molded. It is difficult and not practical. Therefore, in practice, a dicarboxylic acid component such as adipic acid or isophthalic acid, or an aliphatic polyamide such as nylon 6 is copolymerized in an amount of 30 to 40 mol% so that the temperature can be practically used, that is, 2
At present, it is used in a composition having a low melting point of about 80 to 320 ° C. Copolymerization of such a large amount of the third component (in some cases, the fourth component) is effective for lowering the melting point of the polymer, but on the other hand, it is accompanied by a decrease in crystallization rate and ultimate crystallinity. As a result, not only the physical properties such as rigidity at high temperature, chemical resistance, and dimensional stability are deteriorated, but also the productivity is deteriorated as the molding cycle is extended. In addition, with regard to changes in various physical properties such as dimensional stability due to water absorption, although it is somewhat improved by introducing an aromatic group as compared with conventional aliphatic polyamides, it has reached a level of practical problem solving. Not not.
【０００５】特公昭６４−１１０７３号公報、特開昭６
２−３６４５９号公報、特公平１−１９８０９号公報な
どには、半芳香族ポリアミドのジアミン成分として、
１，６−ヘキサンジアミンの他に、より長鎖の直鎖脂肪
族ジアミンが使用可能であることが言及されている。英
国特許第１０７０４１６号明細書には、テレフタル酸と
１，９−ノナンジアミンからなるナイロン塩を、ジアミ
ンに対して３．１〜４．０モル％のテレフタル酸存在下
に重縮合することにより、固有粘度（ηinh）が０．６
７〜１．０３ｄｌ／ｇのポリアミド（以下、ＰＡ９−Ｔ
と略称する）を製造したことが開示されている。また、
特開昭５９−１５５４２７号公報、米国特許第４６１７
３４２号明細書には、テレフタル酸と直鎖脂肪族ジアミ
ンである１，６−ヘキサメチレンジアミンおよび分岐鎖
脂肪族ジアミンである２，２，４−（２，４，４−）ト
リメチルヘキサメチレンからなるポリアミドが記載され
ている。しかしながら、これらの先行文献には、直鎖脂
肪族ジアミンである１，９−ノナンジアミンおよび分岐
鎖脂肪族ジアミンである２−メチル−１，８−オクタン
ジアミンを特定の比率で用いたポリアミドの具体的な開
示はない。Japanese Patent Publication No. 64-11073, JP-A-6-6
As a diamine component of semi-aromatic polyamide, Japanese Patent Publication No. 2-36459, Japanese Patent Publication No. 1-19809, etc.
In addition to 1,6-hexanediamine, it is mentioned that longer chain linear aliphatic diamines can be used. British Patent No. 1070416 has a unique property by polycondensing a nylon salt consisting of terephthalic acid and 1,9-nonanediamine in the presence of 3.1 to 4.0 mol% of terephthalic acid with respect to the diamine. Viscosity (ηinh) is 0.6
7 to 1.03 dl / g polyamide (hereinafter referred to as PA9-T
Abbreviated) is disclosed. Also,
JP-A-59-155427, US Pat. No. 4,617.
No. 342 describes terephthalic acid, 1,6-hexamethylenediamine which is a linear aliphatic diamine, and 2,2,4- (2,4,4-) trimethylhexamethylene which is a branched aliphatic diamine. Polyamides are described. However, in these prior art documents, a specific example of a polyamide in which 1,9-nonanediamine, which is a linear aliphatic diamine, and 2-methyl-1,8-octanediamine, which is a branched aliphatic diamine, are used in a specific ratio is disclosed. There is no disclosure.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らの研究によ
れば、英国特許第１０７０４１６号明細書に記載の方法
を追試して得られる、テレフタル酸と１，９−ノナンジ
アミンからなり、末端にテレフタル酸残基を有するポリ
アミドは、溶融成形時に着色または発泡する傾向が認め
られ、また成形物の表面美麗性が不十分であり、耐熱水
性にも劣るという問題点がある。さらに、特開昭５９−
１５５４２７号公報、米国特許第４６１７３４２号明細
書に記載されている、ＰＡ６−Ｔポリアミドに分岐鎖脂
肪族ジアミンである２，２，４−（２，４，４−）トリ
メチルヘキサメチレンを共重合させたポリアミドでは、
高温下での剛性、耐薬品性、吸水時の寸法安定性などが
劣っているという問題点がある。DISCLOSURE OF THE INVENTION According to the research conducted by the present inventors, terephthalic acid and 1,9-nonanediamine, which are obtained by supplementing the method described in British Patent No. 1070416, are added to the terminal. A polyamide having a terephthalic acid residue has a problem that it tends to be colored or foamed during melt molding, the surface beauty of the molded article is insufficient, and the hot water resistance is poor. Furthermore, JP-A-59-
No. 155427 and US Pat. No. 4,617,342, PA6-T polyamide is copolymerized with a branched chain aliphatic diamine, 2,2,4- (2,4,4-) trimethylhexamethylene. With polyamide,
There are problems that rigidity at high temperature, chemical resistance, dimensional stability when absorbing water, etc. are poor.
【０００７】本発明の目的は、従来の半芳香族ポリアミ
ドに比較して、顕著に改善された成型加工性を有すると
共に、耐熱性、低吸水性、耐薬品性、軽量性などに優
れ、かつ寸法安定性、耐熱水性、表面美麗性、耐衝撃性
に優れたポリアミドを提供することにある。The object of the present invention is to have molding properties that are remarkably improved as compared with conventional semi-aromatic polyamides, and to have excellent heat resistance, low water absorption, chemical resistance, light weight, and the like, and It is to provide a polyamide having excellent dimensional stability, hot water resistance, surface beauty and impact resistance.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するために鋭意研究した結果、ＰＡ９−Ｔ系ポ
リアミドに２−メチル−１，８−オクタンジアミンをを
特定量共重合することにより、ＰＡ９−Ｔ系ポリアミド
の特性を損なうことなく、溶融成形性、表面美麗性、耐
衝撃性などがより優れたポリアミドが得られることを見
出して本発明を完成した。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a specific amount of 2-methyl-1,8-octanediamine is copolymerized with PA9-T polyamide. By doing so, they have found that a polyamide having more excellent melt moldability, surface beauty, impact resistance and the like can be obtained without impairing the properties of PA9-T polyamide, and completed the present invention.
【０００９】本発明によれば、上記の目的は、ジカルボ
ン酸成分の６０〜１００モル％がテレフタル酸であるジ
カルボン酸成分（ａ）と、ジアミン成分の６０〜１００
モル％が１，９−ノナンジアミンおよび２−メチル−
１，８−オクタンジアミンからなり、かつ１，９−ノナ
ンジアミンと２−メチル−１，８−オクタンジアミンの
モル比が６０：４０〜９９：１であるジアミン成分
（ｂ）とからなるポリアミドであって、濃硫酸中３０℃
で測定した極限粘度［η］が０．４〜３．０ｄｌ／ｇで
あるポリアミドを提供することにより達成される。According to the present invention, the above object is to provide a dicarboxylic acid component (a) in which 60 to 100 mol% of the dicarboxylic acid component is terephthalic acid, and 60 to 100 of the diamine component.
Mol% is 1,9-nonanediamine and 2-methyl-
A polyamide comprising 1,8-octanediamine and a diamine component (b) in which the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 60:40 to 99: 1. 30 ° C in concentrated sulfuric acid
It is achieved by providing a polyamide having an intrinsic viscosity [η] of 0.4 to 3.0 dl / g measured in.
【００１０】本発明のポリアミドでは、極限粘度［η］
が０．４〜３．０ｄｌ／ｇの範囲内で、極限粘度［η］
と剪断速度１０００ｓ-1で測定した溶融粘度（ＭＶ）と
の間に、下記の式（１）で示される関係が成立する。 ｌｏｇＭＶ＝１．９［η］＋Ａ ………（１） （ここでＡは温度により変化する数である。）In the polyamide of the present invention, the intrinsic viscosity [η]
Is in the range of 0.4 to 3.0 dl / g, the intrinsic viscosity [η]
And the melt viscosity (MV) measured at a shear rate of 1000 s −1 , the relationship represented by the following formula (1) is established. logMV = 1.9 [η] + A (1) (where A is a number that changes with temperature)
【００１１】本発明の好ましいポリアミドの場合、３４
０℃でのＡ値は０．６〜１．０であり、３３０℃でのＡ
値と３５０℃でのＡ値との差は０．１〜０．６である。
一方、従来のＰＡ６−Ｔ系ポリアミドの場合、極限粘度
［η］の係数は本発明のポリアミドとほぼ同じである
が、３４０℃でのＡ値は１．３〜１．７であり、３３０
℃でのＡ値と３５０℃でのＡ値との差は０．７〜１．１
である。このように、成形温度として好ましい３３０〜
３５０℃において、本発明のポリアミドは従来のＰＡ６
−Ｔ系ポリアミドに比較して、同じ極限粘度［η］であ
っても溶融粘度が小さく、成形温度の変化にともなう溶
融粘度の変化も小さい。さらに、本発明のポリアミド
は、成形時の滞留時間中での溶融粘度の変化が小さいと
いう特性をも有しており、従来のＰＡ６−Ｔ系ポリアミ
ドに比較して成形性が顕著に向上している。In the case of the preferred polyamides according to the invention, 34
The A value at 0 ° C is 0.6 to 1.0, and the A value at 330 ° C is
The difference between the value and the A value at 350 ° C. is 0.1 to 0.6.
On the other hand, in the case of the conventional PA6-T type polyamide, the coefficient of intrinsic viscosity [η] is almost the same as that of the polyamide of the present invention, but the A value at 340 ° C is 1.3 to 1.7, and 330
The difference between the A value at 0 ° C and the A value at 350 ° C is 0.7 to 1.1.
Is. Thus, the preferable molding temperature is 330 to
At 350 ° C., the polyamide of the present invention is
Compared with -T polyamide, the melt viscosity is small even with the same intrinsic viscosity [η], and the change in melt viscosity with the change in molding temperature is also small. Further, the polyamide of the present invention also has a characteristic that the change in melt viscosity during the residence time during molding is small, and the moldability is significantly improved as compared with the conventional PA6-T based polyamide. There is.
【００１２】以下、本発明を具体的に説明する。本発明
のポリアミドに用いられるジカルボン酸成分（ａ）とし
ては、テレフタル酸成分が６０モル％以上であり、好ま
しくは７５モル％以上、より好ましくは９０モル％以上
である。テレフタル酸成分が６０モル％未満の場合に
は、得られるポリアミドの耐熱性、耐薬品性などの諸物
性が低下するため好ましくない。テレフタル酸成分以外
の他のジカルボン酸成分としては、マロン酸、ジメチル
マロン酸、コハク酸、グルタル酸、アジピン酸、２−メ
チルアジピン酸、トリメチルアジピン酸、ピメリン酸、
２，２−ジメチルグルタル酸、３，３−ジエチルコハク
酸、アゼライン酸、セバシン酸、スベリン酸などの脂肪
族ジカルボン酸；１，３−シクロペンタンジカルボン
酸、１，４−シクロヘキサンジカルボン酸などの脂環式
ジカルボン酸；イソフタル酸、２，６−ナフタレンジカ
ルボン酸、２，７−ナフタレンジカルボン酸、１，４−
ナフタレンジカルボン酸、１，４−フェニレンジオキシ
ジ酢酸、１，３−フェニレンジオキシジ酢酸、ジフェン
酸、ジ安息香酸、４，４’−オキシジ安息香酸、ジフェ
ニルメタン−４，４’−ジカルボン酸、ジフェニルスル
ホン−４，４’−ジカルボン酸、４，４’−ビフェニル
ジカルボン酸などの芳香族ジカルボン酸、あるいはこれ
らの任意の混合物を挙げることができる。これらのうち
芳香族ジカルボン酸が好ましく使用される。さらに、ト
リメリット酸、トリメシン酸、ピロメリット酸などの多
価カルボン酸を溶融成形が可能な範囲内で用いることも
できる。The present invention will be specifically described below. As the dicarboxylic acid component (a) used in the polyamide of the present invention, the terephthalic acid component is 60 mol% or more, preferably 75 mol% or more, more preferably 90 mol% or more. When the content of the terephthalic acid component is less than 60 mol%, various properties such as heat resistance and chemical resistance of the obtained polyamide are deteriorated, which is not preferable. Other dicarboxylic acid components other than the terephthalic acid component include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid,
Aliphatic dicarboxylic acids such as 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; fats such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Cyclic dicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-
Naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, Aromatic dicarboxylic acids such as diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid, or any mixture thereof can be mentioned. Of these, aromatic dicarboxylic acids are preferably used. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within the range where melt molding is possible.
【００１３】本発明のポリアミドに用いられるジアミン
成分（ｂ）としては、１，９−ノナンジアミン成分およ
び２−メチル−１，８−オクタンジアミン成分の合計量
が６０モル％以上であり、好ましくは７５モル％以上、
より好ましくは９０モル％以上である。さらに、１，９
−ノナンジアミン成分と２−メチル−１，８−オクタン
ジアミン成分のモル比は、６０：４０〜９９：１モル％
であり、好ましくは７０：３０〜９５：５モル％、より
好ましくは８０：２０〜９５：５モル％である。１，９
−ノナンジアミン成分に加え、２−メチル−１，８−オ
クタンジアミン成分を上記の特定量共重合することによ
り、成形可能温度範囲が広く、成形加工性が極めて優れ
ているのみならず、結晶性および力学特性、特に耐衝撃
性に優れたポリアミドが得られる。As the diamine component (b) used in the polyamide of the present invention, the total amount of the 1,9-nonanediamine component and the 2-methyl-1,8-octanediamine component is 60 mol% or more, preferably 75. Mol% or more,
More preferably, it is 90 mol% or more. Furthermore, 1,9
-The molar ratio of the nonanediamine component and the 2-methyl-1,8-octanediamine component is 60:40 to 99: 1 mol%.
And is preferably 70:30 to 95: 5 mol%, more preferably 80:20 to 95: 5 mol%. 1,9
-In addition to the nonanediamine component, by copolymerizing the above-mentioned specific amount of 2-methyl-1,8-octanediamine component, the moldable temperature range is wide, and not only the moldability is extremely excellent but also the crystallinity and A polyamide having excellent mechanical properties, especially impact resistance can be obtained.
【００１４】１，９−ノナンジアミン成分および２−メ
チル−１，８−オクタンジアミン成分以外の他のジアミ
ン成分としては、エチレンジアミン、プロピレンジアミ
ン、１，４−ブタンジアミン、１，６−ヘキサンジアミ
ン、１，８−オクタンジアミン、１，１０−デカンジア
ミン、１，１２−ドデカンジアミン、３−メチル−１，
５−ペンタンジアミン、２，２，４−トリメチル−１，
６−ヘキサンジアミン、２，４，４−トリメチル−１，
６−ヘキサンジアミン、５−メチル−１，９−ノナンジ
アミンなどの脂肪族ジアミン；シクロヘキサンジアミ
ン、メチルシクロヘキサンジアミン、イソホロンジアミ
ンなどの脂環式ジアミン；ｐ−フェニレンジアミン、ｍ
−フェニレンジアミン、キシレンジアミン、４，４’−
ジアミノジフェニルメタン、４，４’−ジアミノジフェ
ニルスルホン、４，４’−ジアミノジフェニルエーテル
などの芳香族ジアミン、あるいはこれらの任意の混合物
を挙げることができる。As diamine components other than the 1,9-nonanediamine component and the 2-methyl-1,8-octanediamine component, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1 , 8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,
5-pentanediamine, 2,2,4-trimethyl-1,
6-hexanediamine, 2,4,4-trimethyl-1,
Aliphatic diamines such as 6-hexanediamine and 5-methyl-1,9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m
-Phenylenediamine, xylenediamine, 4,4'-
Aromatic diamines such as diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether and the like, or any mixture thereof can be mentioned.
【００１５】本発明のポリアミドは、その分子鎖の末端
基の１０％以上が末端封止剤により封止されているのが
好ましく、末端基の４０％以上が封止されているのがよ
り好ましく、末端基の６０％以上が封止されているのが
より好ましく、末端基の７０％以上が封止されているの
がさらに好ましい。末端の封止率を求めるにあたって
は、ポリアミドに存在しているカルボキシル基末端、ア
ミノ基末端および末端封止剤によって封止された末端の
数をそれぞれ測定し、下記の式（２）により末端の封止
率を求めることができる。各末端基の数は、1Ｈ−ＮＭ
Ｒにより、各末端基に対応する特性シグナルの積分値よ
り求めるのが精度、簡便さの点で好ましい。末端封止剤
によって封止された末端の特性シグナルが同定できない
場合には、ポリアミドの極限粘度［η］を測定し、 Ｍｎ＝２１９００［η］−７９００ （Ｍｎは数平均
分子量を表す） 分子鎖末端基総数（ｅｑ／ｇ）＝２／Ｍｎ の関係を用いて分子鎖末端基総数を算出する。さらに、
滴定によりポリアミドのカルボキシル基末端の数（ｅｑ
／ｇ）〔ポリアミドのベンジルアルコール溶液を０．１
Ｎ水酸化ナトリウムで滴定する〕およびアミノ基末端の
数（ｅｑ／ｇ）〔ポリアミドのフェノール溶液を０．１
Ｎ塩酸で滴定する〕を測定し、下記の式（２）により末
端の封止率を求めることができる。In the polyamide of the present invention, 10% or more of the terminal groups of its molecular chain are preferably capped with an end cap, and more preferably 40% or more of the terminal groups are capped. More preferably, 60% or more of the terminal groups are blocked, and more preferably 70% or more of the terminal groups are blocked. In determining the terminal blocking rate, the number of carboxyl group terminals, amino group terminals and terminals blocked by the terminal blocking agent present in the polyamide were measured, and the terminal of the terminals was calculated by the following formula (2). The sealing rate can be obtained. The number of each terminal group is 1 H-NM
From the viewpoint of accuracy and simplicity, it is preferable to obtain the integrated value of the characteristic signal corresponding to each terminal group by R. When the characteristic signal of the terminal blocked by the terminal blocking agent cannot be identified, the intrinsic viscosity [η] of the polyamide is measured, and Mn = 21900 [η] -7900 (Mn represents a number average molecular weight) molecular chain The total number of end groups of the molecular chain is calculated using the relationship of the total number of end groups (eq / g) = 2 / Mn. further,
The number of carboxyl group terminals of the polyamide by titration (eq
/ G) [0.1% benzyl alcohol solution of polyamide
Titration with N sodium hydroxide] and the number of amino group terminals (eq / g) [0.1% polyamide solution in phenol]
Titration with N hydrochloric acid] can be measured, and the terminal sealing rate can be determined by the following formula (2).
【００１６】 封止率（％）＝［（Ａ−Ｂ）÷Ａ］×１００ ………（２） 〔式中、Ａは分子鎖末端基総数（これは通常、ポリアミ
ド分子の数の２倍に等しい）を表し、Ｂはカルボキシル
基末端およびアミノ基末端の合計数を表す〕Sealing rate (%) = [(A−B) ÷ A] × 100 (2) [In the formula, A is the total number of end groups of the molecular chain (this is usually twice the number of polyamide molecules). And B represents the total number of carboxyl group terminals and amino group terminals.)
【００１７】末端封止剤としては、ポリアミド末端のア
ミノ基またはカルボキシル基と反応性を有する単官能性
の化合物であれば特に制限はないが、反応性および封止
末端の安定性などの点から、モノカルボン酸またはモノ
アミンが好ましく、取扱いの容易さなどの点から、モノ
カルボン酸がより好ましい。その他、無水フタル酸など
の酸無水物、モノイソシアネート、モノ酸ハロゲン化
物、モノエステル類、モノアルコール類なども使用でき
る。The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the polyamide terminal, but from the viewpoint of reactivity and stability of the terminal block. , Monocarboxylic acid or monoamine is preferable, and monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters and monoalcohols can be used.
【００１８】末端封止剤として使用されるモノカルボン
酸としては、アミノ基との反応性を有するものであれば
特に制限はないが、例えば、酢酸、プロピオン酸、酪
酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、ト
リデシル酸、ミリスチン酸、パルチミン酸、ステアリン
酸、ピバリン酸、イソブチル酸などの脂肪族モノカルボ
ン酸；シクロヘキサンカルボン酸などの脂環式モノカル
ボン酸；安息香酸、トルイル酸、α−ナフタレンカルボ
ン酸、β−ナフタレンカルボン酸、メチルナフタレンカ
ルボン酸、フェニル酢酸などの芳香族モノカルボン酸、
あるいはこれらの任意の混合物を挙げることができる。
これらの内、反応性、封止末端の安定性、価格などの点
から、酢酸、プロピオン酸、酪酸、吉草酸、カプロン
酸、カプリル酸、ラウリン酸、トリデシル酸、ミリスチ
ン酸、パルチミン酸、ステアリン酸、安息香酸が特に好
ましい。The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid and caproic acid. Aliphatic monocarboxylic acids such as caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid,
Alternatively, mention may be made of any mixture thereof.
Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, from the viewpoints of reactivity, stability of the capped terminal, price Benzoic acid is particularly preferred.
【００１９】本発明のポリアミドのアミノ基末端は、こ
れらのモノカルボン酸で封止されることにより、下記の
一般式（Ｉ）で示される封止末端を形成する。The amino group terminal of the polyamide of the present invention is blocked with these monocarboxylic acids to form a blocked terminal represented by the following general formula (I).
【００２０】[0020]
【化１】 （式中、Ｒは上記のモノカルボン酸からカルボキシル基
を除いた残基であり、好ましくはアルキル基、シクロア
ルキル基、アリール基、アラルキル基である。）[Chemical 1] (In the formula, R is a residue obtained by removing a carboxyl group from the above monocarboxylic acid, and is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.)
【００２１】末端封止剤として使用されるモノアミンと
しては、カルボキシル基との反応性を有するものであれ
ば特に制限はないが、例えば、メチルアミン、エチルア
ミン、プロピルアミン、ブチルアミン、ヘキシルアミ
ン、オクチルアミン、デシルアミン、ステアリルアミ
ン、ジメチルアミン、ジエチルアミン、ジプロピルアミ
ン、ジブチルアミンなどの脂肪族モノアミン；シクロヘ
キシルアミン、ジシクロヘキシルアミンなどの脂環式モ
ノアミン；アニリン、トルイジン、ジフェニルアミン、
ナフチルアミンなどの芳香族モノアミン、あるいはこれ
らの任意の混合物を挙げることができる。これらの内、
反応性、沸点、封止末端の安定性および価格などの点か
ら、ブチルアミン、ヘキシルアミン、オクチルアミン、
デシルアミン、ステアリルアミン、シクロヘキシルアミ
ン、アニリンが特に好ましい。The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine and octylamine. , Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine,
Mention may be made of aromatic monoamines such as naphthylamine or any mixtures thereof. Of these,
Butylamine, hexylamine, octylamine, in terms of reactivity, boiling point, stability of the capped end and price.
Decylamine, stearylamine, cyclohexylamine, aniline are particularly preferred.
【００２２】本発明のポリアミドのカルボキシル基末端
は、これらのモノアミンで封止されることにより、下記
の一般式（II）で示される封止末端を形成する。The carboxyl group terminal of the polyamide of the present invention is capped with these monoamines to form a capped terminal represented by the following general formula (II).
【００２３】[0023]
【化２】 （式中、Ｒ1は上記のモノアミンからアミノ基を除いた
残基であり、好ましくはアルキル基、シクロアルキル
基、アリール基、アラルキル基である。Ｒ2は水素原子
または上記のモノアミンからアミノ基を除いた残基であ
り、好ましくは水素原子、アルキル基、シクロアルキル
基、アリール基、アラルキル基である。）[Chemical 2] (In the formula, R 1 is a residue obtained by removing an amino group from the above monoamine, and is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R 2 is a hydrogen atom or an amino group from the above monoamine. Is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.)
【００２４】本発明のポリアミドを製造する際に用いら
れる末端封止剤の使用量は、用いる末端封止剤の反応
性、沸点、反応装置、反応条件などによって変化する
が、通常、ジカルボン酸とジアミンの総モル数に対して
０．１〜１５モル％の範囲内で使用される。The amount of the end-capping agent used in the production of the polyamide of the present invention varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent used. It is used within the range of 0.1 to 15 mol% with respect to the total number of moles of diamine.
【００２５】本発明のポリアミドは、結晶性ポリアミド
を製造する方法として知られている任意の方法を用いて
製造することができる。本発明者らの研究によれば、触
媒および必要に応じて末端封止剤を、最初にジアミンお
よびジカルボン酸に一括して添加し、ナイロン塩を製造
した後、いったん２８０℃以下の温度において濃硫酸中
３０℃における極限粘度［η］が０．１０〜０．６０ｄ
ｌ／ｇのプレポリマーとし、さらに固相重合するか、あ
るいは溶融押出機を用いて重合を行うことにより、容易
に本発明のポリアミドを得ることができる。プレポリマ
ーの極限粘度［η］が０．１０〜０．６０ｄｌ／ｇの範
囲内であると、後重合の段階においてカルボキシル基と
アミノ基のモルバランスのずれや重合速度の低下が少な
く、さらに分子量分布の小さな、各種性能や成形性に優
れたポリアミドが得られる。重合の最終段階を固相重合
により行う場合、減圧下または不活性ガス流通下に行う
のが好ましく、重合温度が１８０〜２８０℃の範囲内で
あれば、重合速度が大きく、生産性に優れ、着色やゲル
化を有効に押さえることができるので好ましい。重合の
最終段階を溶融押出機により行う場合、重合温度が３７
０℃以下であるとポリアミドの分解がほとんどなく、劣
化の無いポリアミドが得られるので好ましい。The polyamide of the present invention can be produced by any method known as a method for producing a crystalline polyamide. According to the research conducted by the present inventors, a catalyst and, if necessary, an end-capping agent were first added all at once to a diamine and a dicarboxylic acid to prepare a nylon salt, which was once concentrated at a temperature of 280 ° C. or lower. Intrinsic viscosity [η] at 30 ° C in sulfuric acid is 0.10 to 0.60d
The polyamide of the present invention can be easily obtained by using 1 / g of a prepolymer and further performing solid-phase polymerization or polymerization using a melt extruder. When the intrinsic viscosity [η] of the prepolymer is within the range of 0.10 to 0.60 dl / g, the deviation of the molar balance between the carboxyl group and the amino group and the decrease in the polymerization rate are small in the post-polymerization stage, and the molecular weight is further reduced. A polyamide with a small distribution and excellent performance and moldability can be obtained. When the final step of the polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under the flow of an inert gas, and if the polymerization temperature is in the range of 180 to 280 ° C., the polymerization rate is high and the productivity is excellent. It is preferable because coloring and gelation can be effectively suppressed. When the final stage of the polymerization is carried out by a melt extruder, the polymerization temperature is 37
When the temperature is 0 ° C. or lower, the polyamide is hardly decomposed and a polyamide having no deterioration is obtained, which is preferable.
【００２６】本発明のポリアミドは、濃硫酸中３０℃で
測定した極限粘度［η］が０．４〜３．０ｄｌ／ｇの範
囲内であり、０．６〜２．０ｄｌ／ｇの範囲内のものが
好ましく、０．８〜１．６ｄｌ／ｇの範囲内のものがよ
り好ましい。The polyamide of the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.4 to 3.0 dl / g and 0.6 to 2.0 dl / g. Those of 0.8 to 1.6 dl / g are more preferable.
【００２７】上記の触媒としては、リン酸、亜リン酸、
次亜リン酸、またはそれらの塩、さらにはそれらのエス
テル、具体的にはカリウム、ナトリウム、マグネシウ
ム、バナジウム、カルシウム、亜鉛、コバルト、マンガ
ン、錫、タングステン、ゲルマニウム、チタン、アンチ
モンなどの金属塩やアンモニウム塩、エチルエステル、
イソプロピルエステル、ブチルエステル、ヘキシルエス
テル、イソデシルエステル、オクタデシルエステル、デ
シルエステル、ステアリルエステル、フェニルエステル
などを挙げることができる。その他必要に応じて、銅化
合物などの安定剤、着色剤、紫外線吸収剤、光安定化
剤、酸化防止剤、帯電防止剤、難燃剤、結晶化促進剤、
ガラス繊維、可塑剤、潤滑剤などを重縮合反応時、また
はその後に添加することもできる。As the above catalyst, phosphoric acid, phosphorous acid,
Hypophosphorous acid or a salt thereof, or an ester thereof, specifically, a metal salt such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, or antimony, Ammonium salt, ethyl ester,
Examples thereof include isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester and phenyl ester. Others, if necessary, stabilizers such as copper compounds, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators,
Glass fibers, a plasticizer, a lubricant, etc. can be added during or after the polycondensation reaction.
【００２８】本発明のポリアミドには射出成形、ブロー
成形、押し出し成形、圧縮成形、延伸、真空成形などの
成形法が適用できる。エンジニアリングプラスチックと
して通常の成形体のみならず、フィルムや繊維の形態に
も成形可能であり、産業資材、工業材料、家庭用品など
に好適に使用することができる。Molding methods such as injection molding, blow molding, extrusion molding, compression molding, stretching and vacuum molding can be applied to the polyamide of the present invention. As an engineering plastic, it can be molded into not only ordinary molded products but also films and fibers, and can be suitably used for industrial materials, industrial materials, household products and the like.
【００２９】[0029]
【実施例】以下、実施例を挙げて本発明を具体的に説明
するが、本発明はこれらにより何ら制限されるものでは
ない。なお、実施例中の末端封止率、極限粘度、引張強
度、引張伸び、曲げ強度、曲げ弾性率、熱水処理後の極
限粘度［η］の保持率、熱水処理後の引張強度の保持
率、熱変形温度、耐衝撃強度、高温弾性率、平衡吸水
率、溶融粘度、結晶化速度、比重、耐薬品性、および成
形可能温度幅は以下の方法により測定した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The terminal sealing rate, the intrinsic viscosity, the tensile strength, the tensile elongation, the bending strength, the flexural modulus, the retention rate of the intrinsic viscosity [η] after the hot water treatment, and the retention of the tensile strength after the hot water treatment in Examples. The rate, heat distortion temperature, impact strength, high temperature elastic modulus, equilibrium water absorption rate, melt viscosity, crystallization rate, specific gravity, chemical resistance, and moldable temperature range were measured by the following methods.
【００３０】末端封止率：1Ｈ−ＮＭＲ（５００ＭＨ
ｚ，重水素化トリフルオロ酢酸中、５０℃で測定）を用
い、各末端基ごとの特性シグナルの積分値よりカルボキ
シル基末端、アミノ基末端および封止末端の数をそれぞ
れ測定し、前記の式（２）から末端封止率を求めた。測
定に用いた代表的なシグナルの化学シフト値を以下に示
す。 End capping ratio : 1 H-NMR (500 MH
z, measured in deuterated trifluoroacetic acid at 50 ° C.) to measure the number of carboxyl group end, amino group end and capping end respectively from the integrated value of the characteristic signal for each end group, The terminal sealing rate was calculated from (2). The chemical shift values of typical signals used for measurement are shown below.
【００３１】[0031]
【表１】 [Table 1]
【００３２】極限粘度［η］：濃硫酸中、３０℃にて、
０．０５，０．１，０．２，０．４ｇ／ｄｌの濃度の試
料の固有粘度（ηinh ）を測定し、これを濃度０に外挿
した値を極限粘度［η］とした。 ηinh ＝［ｌｎ（ｔ1／ｔ0）］／ｃ 〔式中、ηinh は固有粘度（ｄｌ／ｇ）を表し、ｔ0は
溶媒の流下時間（秒）を表し、ｔ1は試料溶液の流下時
間（秒）を表し、ｃは溶液中の試料の濃度（ｇ／ｄｌ）
を表す。〕 Intrinsic viscosity [η] : in concentrated sulfuric acid at 30 ° C.
The intrinsic viscosity (ηinh) of the samples having the concentrations of 0.05, 0.1, 0.2 and 0.4 g / dl was measured, and the value obtained by extrapolating this to the concentration of 0 was defined as the intrinsic viscosity [η]. ηinh = [ln (t 1 / t 0 )] / c [wherein, ηinh represents an intrinsic viscosity (dl / g), t 0 represents a solvent flowing time (second), and t 1 represents a sample solution flowing down. Time (second), c is the concentration of the sample in the solution (g / dl)
Represents ]
【００３３】引張強度、引張伸び、曲げ強度、曲げ弾性
率、熱変形温度、耐衝撃強度：融点より約２０℃高い温
度で射出成形した絶乾状態の試験片を、以下の方法で測
定した。 Tensile strength, tensile elongation, bending strength, bending elasticity
Rate, heat distortion temperature, impact strength : A test piece in an absolutely dry state injection-molded at a temperature about 20 ° C. higher than the melting point was measured by the following method.
【００３４】[0034]
【表２】 [Table 2]
【００３５】熱水処理後の極限粘度［η］および引張強
度の保持率：ＪＩＳ１号ダンベル型射出成形片を、耐圧
オートクレーブ中でスチーム処理し（１２０℃／２気圧
／１２０時間）、さらにその試料を１２０℃で１２０時
間真空乾燥した。処理後のサンプルの極限粘度［η］お
よび引張強度を測定し、処理前の値に対する保持率
（％）を求めた。 Intrinsic viscosity [η] and tensile strength after hot water treatment
Retention rate : JIS No. 1 dumbbell type injection molded piece was steam-treated in a pressure-resistant autoclave (120 ° C / 2 atm / 120 hours), and the sample was vacuum dried at 120 ° C for 120 hours. The intrinsic viscosity [η] and the tensile strength of the sample after the treatment were measured, and the retention rate (%) with respect to the value before the treatment was determined.
【００３６】高温弾性率：上記の曲げ弾性率を２００℃
で測定し、その値を高温弾性率とした。 High temperature elastic modulus : The above bending elastic modulus is 200 ° C.
And the value was defined as the high temperature elastic modulus.
【００３７】平衡吸水率：融点より２０℃高い温度で熱
プレスし、１５０℃で５分間の冷却を行った、厚さ約２
００μｍのフィルム（５ｃｍ×５ｃｍ）を、減圧下にて
１２０℃で５日間乾燥し、秤量した後、２３℃の水中に
１０日間浸漬し、秤量して、増量分の浸漬前の重量に対
する割合（％）として求めた。 Equilibrium water absorption : hot pressed at a temperature 20 ° C. higher than the melting point and cooled at 150 ° C. for 5 minutes, thickness about 2
A 00 μm film (5 cm × 5 cm) was dried under reduced pressure at 120 ° C. for 5 days, weighed, immersed in water at 23 ° C. for 10 days, weighed, and the proportion of the increased amount to the weight before immersion ( %).
【００３８】溶融粘度およびＡ値：減圧下にて１２０℃
で２日間乾燥した試料について、フローテスター（島津
製作所製）を用い、３３０℃〜３５０℃の温度範囲で、
剪断速度１０００ｓ-1での溶融粘度（ＭＶ）を測定し
た。ＭＶと極限粘度［η］との関係式： ｌｏｇＭＶ＝１．９［η］＋Ａ からＡ値を求めた。 Melt viscosity and A value : 120 ° C. under reduced pressure
The sample dried for 2 days in a flow tester (manufactured by Shimadzu Corporation) was used in a temperature range of 330 ° C to 350 ° C.
The melt viscosity (MV) at a shear rate of 1000 s -1 was measured. Relational expression between MV and intrinsic viscosity [η]: A value was obtained from logMV = 1.9 [η] + A.
【００３９】結晶化速度：示差走査熱量計（メトラー社
製、ＤＳＣ−３０）を用いて測定した。絶乾状態の試料
を、窒素気流下３５０℃で溶融させた後、１０℃／分の
冷却速度で５０℃まで冷却し、その際に出現する結晶化
ピークを結晶化点（Ｔcc）とした。次いで、１０℃／分
で昇温して、融点（Ｔｍ）を測定した。融点と結晶化点
の差（Ｔｍ−Ｔcc）を結晶化速度とした。 Crystallization rate : Measured using a differential scanning calorimeter (DSC-30, manufactured by Mettler). The absolutely dried sample was melted at 350 ° C. under a nitrogen stream and then cooled to 50 ° C. at a cooling rate of 10 ° C./min. The crystallization peak that appeared at that time was taken as the crystallization point (Tcc). Then, the temperature was raised at 10 ° C./min and the melting point (Tm) was measured. The difference between the melting point and the crystallization point (Tm-Tcc) was defined as the crystallization rate.
【００４０】比重：密度勾配管を用いて測定した。 Specific gravity : Measured using a density gradient tube.
【００４１】耐薬品性：融点より約２０℃高い温度で熱
プレスした、厚さ２００μｍのフィルムをＪＩＳ３号ダ
ンベルで打ち抜いた試料片を、２３℃の各種薬品（メチ
ルアルコール、１０％硫酸、５０％水酸化ナトリウム水
溶液、５０％塩化カルシウム水溶液）中に７日間浸漬
し、引張強度の処理前の試料に対する保持率（％）を測
定した。 Chemical resistance : A 200 μm-thick film hot-pressed at a temperature about 20 ° C. higher than the melting point was punched out with a JIS No. 3 dumbbell, and a sample piece was cut with various chemicals at 23 ° C. (methyl alcohol, 10% sulfuric acid, 50%). The sample was dipped in a sodium hydroxide aqueous solution, a 50% calcium chloride aqueous solution) for 7 days, and the retention rate (%) of the tensile strength of the sample before treatment was measured.
【００４２】成形可能温度幅：溶融滞留時間を５分間、
金型温度を１５０℃として、温度条件を変えて射出成形
を行い、成形可能な下限温度と、分解による気泡が発生
し始める、成形可能な上限温度を測定した。 Moldable temperature range : Melt residence time of 5 minutes,
The mold temperature was set to 150 ° C., injection molding was performed under different temperature conditions, and the lower limit temperature at which the mold was formed and the upper limit temperature at which the mold started generating bubbles due to decomposition were measured.
【００４３】実施例１ テレフタル酸３２７２．９ｇ（１９．７０モル）、１，
９−ノナンジアミン２８４９．２ｇ（１８．０モル）、
２−メチル−１，８−オクタンジアミン３１６．５８ｇ
（２．０モル）、安息香酸７３．２７ｇ（０．６０モ
ル）、次亜リン酸ナトリウム一水和物６．５ｇ（原料に
対して０．１重量％）および蒸留水６リットルを内容積
２０リットルのオートクレーブに入れ、窒素置換した。
１００℃で３０分間撹拌し、２時間かけて内部温度を２
１０℃に昇温した。この時、オートクレーブは２２ｋｇ
／ｃｍ2まで昇圧した。そのまま１時間反応を続けた後
２３０℃に昇温し、その後２時間、２３０℃に温度を保
ち、水蒸気を徐々に抜いて圧力を２２ｋｇ／ｃｍ2に保
ちながら反応させた。次に、３０分かけて圧力を１０ｋ
ｇ／ｃｍ2まで下げ、更に１時間反応させて、極限粘度
［η］が０．２５ｄｌ／ｇのプレポリマーを得た。これ
を、１００℃、減圧下で１２時間乾燥し、２ｍｍ以下の
大きさまで粉砕した。これを２３０℃、０．１ｍｍＨｇ
下にて、１０時間固相重合し、融点が３１０℃、極限粘
度［η］が１．３３ｄｌ／ｇ、末端の封止率が９０％で
ある白色のポリアミドを得た。次に、このポリアミド
を、シリンダ温度３４０℃、金型温度１００℃で射出成
形し、得られた成形品の各種物性値を測定した。得られ
た結果を下記の表３に示す。Example 1 3272.9 g (19.70 mol) of terephthalic acid, 1,
2849.2 g (18.0 mol) of 9-nonanediamine,
2-methyl-1,8-octanediamine 316.58 g
(2.0 mol), benzoic acid 73.27 g (0.60 mol), sodium hypophosphite monohydrate 6.5 g (0.1% by weight based on the raw material) and 6 liters of distilled water as an internal volume. It was placed in a 20 liter autoclave and purged with nitrogen.
Stir for 30 minutes at 100 ° C, and increase the internal temperature to 2 over 2 hours.
The temperature was raised to 10 ° C. At this time, the autoclave is 22 kg
The pressure was increased to / cm 2 . After continuing the reaction for 1 hour, the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was performed while gradually removing steam to maintain the pressure at 22 kg / cm 2 . Next, pressure is 10k over 30 minutes.
It was lowered to g / cm 2 and further reacted for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.25 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. 230 ℃, 0.1mmHg
Solid-state polymerization was performed under the conditions for 10 hours to obtain a white polyamide having a melting point of 310 ° C., an intrinsic viscosity [η] of 1.33 dl / g, and a terminal sealing rate of 90%. Next, this polyamide was injection-molded at a cylinder temperature of 340 ° C. and a mold temperature of 100 ° C., and various physical properties of the obtained molded product were measured. The results obtained are shown in Table 3 below.
【００４４】実施例２ 実施例１において、１，９−ノナンジアミン２５３２．
４ｇ（１６．０モル）、２−メチル−１，８−オクタン
ジアミン６３３．１６ｇ（４．０モル）とした以外は、
実施例１に記載した方法でポリアミドおよびその成形品
を製造し、各種物性値を測定した。得られた結果を下記
の表３に示す。Example 2 In Example 1, 1,9-nonanediamine 2532.
4 g (16.0 mol) and 2-methyl-1,8-octanediamine 633.16 g (4.0 mol), except that
Polyamide and its molded article were manufactured by the method described in Example 1, and various physical properties were measured. The results obtained are shown in Table 3 below.
【００４５】実施例３ 実施例１において、１，９−ノナンジアミン２２１６．
１ｇ（１４．０モル）、２−メチル−１，８−オクタン
ジアミン９４９．７４ｇ（６．０モル）とした以外は、
実施例１に記載した方法でポリアミドおよびその成形品
を製造し、各種物性値を測定した。得られた結果を下記
の表３に示す。Example 3 In Example 1, 1,9-nonanediamine 2216.
1 g (14.0 mol) and 2-methyl-1,8-octanediamine 949.74 g (6.0 mol) except that
Polyamide and its molded article were manufactured by the method described in Example 1, and various physical properties were measured. The results obtained are shown in Table 3 below.
【００４６】比較例１ 実施例１において、安息香酸および次亜リン酸ナトリウ
ムを使用せず、テレフタル酸の量を３３８９．２ｇ（２
０．４モル）とし、１，９−ノナンジアミン３１６５．
８ｇ（２０．０モル）として、２−メチル−１，８−オ
クタンジアミンをまったく使用しなかった以外は、実施
例１に記載した方法でポリアミドおよびその成形品を製
造し、各種物性値を測定した。得られた結果を下記の表
３に示す。Comparative Example 1 In Example 1, benzoic acid and sodium hypophosphite were not used, and the amount of terephthalic acid was 3389.2 g (2
0.4 mol) and 1,9-nonanediamine 3165.
8 g (20.0 mol), except that no 2-methyl-1,8-octanediamine was used, polyamide and its molded product were produced by the method described in Example 1, and various physical properties were measured. did. The results obtained are shown in Table 3 below.
【００４７】[0047]
【表３】 [Table 3]
【００４８】実施例４ 実施例１において、テレフタル酸および安息香酸の量を
それぞれ、テレフタル酸３２２３．０ｇ（１９．４０モ
ル）、安息香酸１４６．６ｇ（１．２モル）とした以外
は、実施例１に記載した方法でポリアミドおよびその成
形品を製造し、各種物性値を測定した。得られた結果を
下記の表４に示す。Example 4 Example 4 was repeated except that the amounts of terephthalic acid and benzoic acid were changed to 3223.0 g (19.40 mol) of terephthalic acid and 146.6 g (1.2 mol) of benzoic acid, respectively. Polyamide and molded articles thereof were produced by the method described in Example 1 and various physical properties were measured. The results obtained are shown in Table 4 below.
【００４９】実施例５ 実施例１において、安息香酸に替えてオクチルアミンを
用い、テレフタル酸、１，９−ノナンジアミン、２−メ
チル−１，８−オクタンジアミン、オクチルアミン、次
亜リン酸ナトリウムの量をそれぞれ、テレフタル酸３３
２２．７ｇ（２０．０モル）、１，９−ノナンジアミン
２８１３．６ｇ（１７．７７５モル）、２−メチル−
１，８−オクタンジアミン３１２．６ｇ（１．９７５モ
ル）、オクチルアミン６４．６３ｇ（０．５０モル）、
次亜リン酸ナトリウム１３．０ｇ（原料に対して０．２
重量％）とした以外は、実施例１に記載した方法でポリ
アミドおよびその成形品を製造し、各種物性値を測定し
た。得られた結果を下記の表４に示す。Example 5 In Example 1, octylamine was used in place of benzoic acid, and terephthalic acid, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, octylamine and sodium hypophosphite were used. Terephthalic acid 33
22.7 g (20.0 mol), 1,9-nonanediamine 2813.6 g (17.775 mol), 2-methyl-
31.26 g (1.975 mol) of 1,8-octanediamine, 64.63 g (0.50 mol) of octylamine,
Sodium hypophosphite 13.0g (0.2 against raw material)
(Wt%) except that the polyamide and molded articles thereof were manufactured by the method described in Example 1 and various physical properties were measured. The results obtained are shown in Table 4 below.
【００５０】実施例６ 実施例１において、テレフタル酸および安息香酸の量を
それぞれ、テレフタル酸３３２２．７ｇ（２０．０モ
ル）、安息香酸３４．１９ｇ（０．２８モル）とした以
外は、実施例１に記載した方法でポリアミドおよびその
成形品を製造し、各種物性値を測定した。得られた結果
を下記の表４に示す。Example 6 Example 6 was carried out except that the amounts of terephthalic acid and benzoic acid were changed to 3322.7 g (20.0 mol) of terephthalic acid and 34.19 g (0.28 mol) of benzoic acid, respectively. Polyamide and molded articles thereof were produced by the method described in Example 1 and various physical properties were measured. The results obtained are shown in Table 4 below.
【００５１】実施例７ 実施例１において、テレフタル酸および安息香酸の量を
それぞれ、テレフタル酸３３５５．９ｇ（２０．２モ
ル）、安息香酸１２．２１ｇ（０．１０モル）とした以
外は、実施例１に記載した方法でポリアミドおよびその
成形品を製造し、各種物性値を測定した。得られた結果
を下記の表４に示す。Example 7 Example 7 was carried out except that the amounts of terephthalic acid and benzoic acid were changed to 3355.9 g (20.2 mol) of terephthalic acid and 12.21 g (0.10 mol) of benzoic acid, respectively. Polyamide and molded articles thereof were produced by the method described in Example 1 and various physical properties were measured. The results obtained are shown in Table 4 below.
【００５２】比較例２ 実施例１において、テレフタル酸および安息香酸の量を
それぞれ、テレフタル酸３７３８．０ｇ（２２．５モ
ル）とし、安息香酸を使用しなかった以外は、実施例１
に記載した方法でポリアミドおよびその成形品を製造
し、各種物性値を測定した。得られた結果を下記の表４
に示す。Comparative Example 2 Example 1 was repeated except that the amounts of terephthalic acid and benzoic acid were respectively 3738.0 g (22.5 mol) of terephthalic acid and no benzoic acid was used.
Polyamide and molded articles thereof were produced by the method described in Section 1 above, and various physical properties were measured. The results obtained are shown in Table 4 below.
Shown in.
【００５３】[0053]
【表４】 [Table 4]
【００５４】比較例３ 実施例１において、テレフタル酸２３２５．９ｇ（１
４．０モル）、イソフタル酸９９６．８ｇ（６．０モ
ル）、１，６−ヘキサンジアミン２３２４．２ｇ（２
０．０モル）、安息香酸２４．４３ｇ（０．２０モル）
とした以外は、実施例１に記載した方法でポリアミドお
よびその成形品を製造し、各種物性値を測定した。得ら
れた結果を、実施例１の結果と併せて下記の表５に示
す。Comparative Example 3 In Example 1, 2325.9 g of terephthalic acid (1
4.0 mol), isophthalic acid 996.8 g (6.0 mol), 1,6-hexanediamine 2324.2 g (2
0.0 mol), benzoic acid 24.43 g (0.20 mol)
Except for the above, polyamide and molded articles thereof were manufactured by the method described in Example 1 and various physical properties were measured. The obtained results are shown in Table 5 below together with the results of Example 1.
【００５５】[0055]
【表５】 [Table 5]
【００５６】[0056]
【発明の効果】本発明のポリアミドは、極めて優れた成
形加工性を有すると共に、耐熱水性、表面美麗性、耐熱
性、力学特性、低吸水性、耐薬品性などに優れており、
産業資材、工業材料、家庭用品などの成形材料として好
適に使用することができる。EFFECTS OF THE INVENTION The polyamide of the present invention has extremely excellent moldability and is excellent in hot water resistance, surface beauty, heat resistance, mechanical properties, low water absorption, chemical resistance and the like.
It can be suitably used as a molding material for industrial materials, industrial materials, household products and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林原 広 岡山県倉敷市酒津2045番地の１ 株式会社 クラレ内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Harabara 1) 2045 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.
Claims (2)
がテレフタル酸であるジカルボン酸成分（ａ）と、ジア
ミン成分の６０〜１００モル％が１，９−ノナンジアミ
ンおよび２−メチル−１，８−オクタンジアミンからな
り、かつ１，９−ノナンジアミンと２−メチル−１，８
−オクタンジアミンのモル比が６０：４０〜９９：１で
あるジアミン成分（ｂ）とからなるポリアミドであっ
て、濃硫酸中３０℃で測定した極限粘度［η］が０．４
〜３．０ｄｌ／ｇであるポリアミド。1. 60 to 100 mol% of the dicarboxylic acid component
Is a terephthalic acid component (a), and 60 to 100 mol% of the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2- Methyl-1,8
A polyamide comprising a diamine component (b) in which the molar ratio of octanediamine is 60:40 to 99: 1, and the intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid is 0.4.
A polyamide that is ˜3.0 dl / g.
求項１記載のポリアミド。2. The polyamide according to claim 1, wherein 10% or more of the terminal groups are capped.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01958494A JP3242781B2 (en) | 1994-02-16 | 1994-02-16 | Polyamide resin |
| CA002137477A CA2137477C (en) | 1993-12-24 | 1994-12-07 | Polyamide and polyamide composition |
| TW083111536A TW299338B (en) | 1993-12-24 | 1994-12-12 | |
| US08/361,371 US5670608A (en) | 1993-12-24 | 1994-12-22 | Polyamide and polyamide composition |
| CN94119297A CN1048743C (en) | 1993-12-24 | 1994-12-23 | Polyamide and polyamide composition |
| EP94120607A EP0659799B1 (en) | 1993-12-24 | 1994-12-23 | Polyamide and polyamide composition |
| DE69419119T DE69419119T2 (en) | 1993-12-24 | 1994-12-23 | Polyamide and polyamide composition |
| SG1996003360A SG55041A1 (en) | 1993-12-24 | 1994-12-23 | Polyamide and polyamide composition |
| KR1019940037012A KR0168468B1 (en) | 1993-12-24 | 1994-12-24 | Polyamide and polyimide compositions |
| CN98114849A CN1110521C (en) | 1993-12-24 | 1998-06-13 | Polyamide composition |
| HK98113284A HK1012019A1 (en) | 1993-12-24 | 1998-12-14 | Polyamide and polyamide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01958494A JP3242781B2 (en) | 1994-02-16 | 1994-02-16 | Polyamide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07228689A true JPH07228689A (en) | 1995-08-29 |
| JP3242781B2 JP3242781B2 (en) | 2001-12-25 |
Family
ID=12003317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01958494A Expired - Lifetime JP3242781B2 (en) | 1993-12-24 | 1994-02-16 | Polyamide resin |
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| Country | Link |
|---|---|
| JP (1) | JP3242781B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002220461A (en) * | 2001-01-29 | 2002-08-09 | Mitsui Chemicals Inc | Polyamide resin, polyamide resin composition and its molded article |
| JP2006200059A (en) * | 2005-01-19 | 2006-08-03 | Kuraray Co Ltd | Textile product to be reused after undergoing steam sterilization treatment |
| JP2006274061A (en) * | 2005-03-29 | 2006-10-12 | Kuraray Co Ltd | Continuous fiber reinforced semi-aromatic polyamide resin composition |
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