JPH0116253B2 - - Google Patents
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- Publication number
- JPH0116253B2 JPH0116253B2 JP56102047A JP10204781A JPH0116253B2 JP H0116253 B2 JPH0116253 B2 JP H0116253B2 JP 56102047 A JP56102047 A JP 56102047A JP 10204781 A JP10204781 A JP 10204781A JP H0116253 B2 JPH0116253 B2 JP H0116253B2
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- polyamide
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- constituent
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- Polyamides (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
【発明の詳細な説明】
本発明は新規な低吸水率共重合ポリエステルア
ミド樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel low water absorption copolymerized polyesteramide resin.
周知の如くポリアミド樹脂は繊維はじめ広範な
用途に用いられているが、アミド結合を有する構
造により本質的に吸水率が高く、成型品の寸法安
定性が劣つたり、電気的特性などの物性が湿度に
より大きく変化するなどの欠点がある。たとえば
ポリアミド樹脂はそのインピーダンスの温度依存
性と結晶性高分子であるために明確な融点を有
し、温度ヒユーズとして用い得る特性を利用し
て、電気毛布、電気カーペツトなど発熱体におい
て感熱素子として用いられるが、かかる用途にお
いてはポリアミド樹脂のインピーダンスが湿度に
よつて影響されないことが必要である。したがつ
てポリアミド樹脂のうち、比較的吸湿性の小さい
ナイロン11、ナイロン12がかかる用途に用いられ
るが、それでもなお、湿度の影響を受けるという
点において充分満足できる性能は得られていな
い。 As is well known, polyamide resin is used in a wide range of applications including fibers, but due to its structure with amide bonds, it inherently has a high water absorption rate, resulting in poor dimensional stability of molded products and poor physical properties such as electrical properties. It has the disadvantage that it varies greatly depending on humidity. For example, polyamide resin has temperature dependence of its impedance and has a clear melting point because it is a crystalline polymer. Utilizing its characteristics that it can be used as a temperature fuse, it is used as a heat-sensitive element in heating elements such as electric blankets and electric carpets. However, in such applications it is necessary that the impedance of the polyamide resin is not affected by humidity. Therefore, among polyamide resins, nylon 11 and nylon 12, which have relatively low hygroscopicity, are used for such applications, but even so, sufficiently satisfactory performance cannot be obtained in terms of being affected by humidity.
本発明の目的は、ポリアミド樹脂の固有の欠点
である吸水性を改善し、なおポリアミド樹脂に特
有の機械的性質、成型加工性、柔軟性を有する改
良された新規共重合ポリエステルアミド樹脂を提
供することにある。 The purpose of the present invention is to improve water absorption, which is an inherent drawback of polyamide resins, and to provide a new and improved copolymerized polyesteramide resin that has mechanical properties, moldability, and flexibility specific to polyamide resins. There is a particular thing.
発明者等は鋭意検討の結果、両末端に水酸基が
結合している水素化ポリブタジエンをポリアミド
とエステル結合により共縮合して得られるポリエ
ステルアミド樹脂が本発明の目的に適合するもの
であることを見出した。 As a result of extensive studies, the inventors found that a polyesteramide resin obtained by co-condensing hydrogenated polybutadiene with hydroxyl groups bonded to both ends with polyamide through ester bonds is suitable for the purpose of the present invention. Ta.
本発明のポリエステルアミド樹脂においては、
ポリアミドブロツクとポリブタジエンブロツクと
がエステル結合しているので、アミド結合に消費
さるべきカルボン酸末端が不足するため、高分子
量化するためには両末端に水酸基が結合している
水素化ポリブタジエンの水酸基濃度にほぼ等モル
の酸濃度の二塩基カルボン酸を加える必要があ
る。かくして本発明のポリエステルアミド樹脂の
構成は次のようになる。すなわち下記(A)、(B)、(C)
により規定される構成単位を有し、(A)の構成単位
と(B)の構成単位はアミド結合により結合し、(A)の
構成単位と(C)の構成単位及び(B)の構成単位(C)の構
成単位とはエステル結合により結合し、(C)の構成
単位が１〜80重量％をしめ、(B)の構成単位と(C)の
構成単位のモル比が１：1.2ないし１：0.8の新規
共重合ポリエステルアミド樹脂である。 In the polyesteramide resin of the present invention,
Since the polyamide block and polybutadiene block have ester bonds, there is a shortage of carboxylic acid terminals that should be consumed by amide bonds, so in order to increase the molecular weight, the hydroxyl group concentration of hydrogenated polybutadiene, which has hydroxyl groups bonded to both terminals, is required. It is necessary to add dibasic carboxylic acid at approximately equimolar acid concentration to Thus, the composition of the polyesteramide resin of the present invention is as follows. That is, the following (A), (B), (C)
The structural unit of (A) and the structural unit of (B) are bonded by an amide bond, and the structural unit of (A), the structural unit of (C), and the structural unit of (B) The constituent units of (C) are bonded to each other through an ester bond, the constituent units of (C) account for 1 to 80% by weight, and the molar ratio of the constituent units of (B) to the constituent units of (C) is 1:1.2 to 1.2. This is a new copolymerized polyesteramide resin with a ratio of 1:0.8.
(A)：一般式(1)、又は(2)で表わされる繰返し単位一
種以上を有するポリアミド高分子成分、
−NH−（CH2）−CO−（ｎは５〜12の整数） (1)
−NH−Ｘ−NH−CO−Ｙ−CO− (2)
（式中ＸはCnH2n〔ｍは６〜12の整数〕、イソホ
ロン基、フエニレン基又はシクロヘキシレン基
を表わし、ＹはClH2l〔ｌは４〜10の整数〕、フ
エニレン基又はシクロヘキシレン基を表わす。）
(B)：次式で表わされる構成単位、
−CO−CnH2n−CO−（ｍは１〜36の整数）
(C)：次式で表わされる構成単位、
−Ｏ−Ｚ−Ｏ−
（式中Ｚは平均分子量500〜10000の二重結合に
水素添加されたポリブタジエン成分であつて、
末端において酸素と結合している。）
ポリアミド高分子成分はラクタムの開環重合あ
るいはアミノ酸の縮合重合、ジアミンとダイカル
ボン酸との縮合重合等によつて形成され得る。ポ
リエステルアミド樹脂の末端基濃度を合わせて高
分子量化するために加える二官能性カルボン酸は
特に限定された構造を有する必要はないが、ポリ
アミド高分子部分に共縮合成分として入つてポリ
アミドの規則性を乱して結晶性を低下させること
がないよう、できるだけポリアミドのメチレン鎖
の数に近い数のメチレン鎖を有するものが好適で
ある。たとえばナイロン12がポリアミド成分であ
る場合はα，ωドデカンダイカルボン酸が最も適
している。その添加量はポリエステルアミドの無
限大の分子量を得るためには、ジオールとダイカ
ルボン酸が等モルであることが理論的に必要であ
るが、目的に応じてその比率の上下20％までが許
容される。水素化ポリブタジエン成分は共縮合体
とした時にブロツクを形成することによつてポリ
アミド樹脂としての好ましい性能を保持すること
ができる。したがつて水素化ポリブタジエンの数
平均分子量が500以下となるとポリアミド部分の
分子鎖が必然的に短かくなり、ポリアミド部分が
独自の結晶相とならず、ポリエステルアミド樹脂
全体が非晶質となるので好ましくない。又、数平
均分子量10000以上の水素化ポリブタジエン成分
を用いるとマクロな相分離が起こり、良好な成型
品、フイルム等が成型できず不適である。したが
つてポリブタジエン成分の分子量の好ましい範囲
は数平均分子量で500〜10000であり、最も好まし
い範囲は1000〜2000である。(A): Polyamide polymer component having one or more repeating units represented by general formula (1) or (2), -NH-( CH2 )-CO- (n is an integer from 5 to 12) (1) -NH-X-NH-CO-Y-CO- ( 2 ) (wherein, l H 2l [l is an integer of 4 to 10], represents a phenylene group or a cyclohexylene group.) (B): Constituent unit represented by the following formula, -CO-C n H 2n -CO- (m is 1 to (an integer of 36) (C): a structural unit represented by the following formula, -O-Z-O- (wherein Z is a polybutadiene component hydrogenated to a double bond with an average molecular weight of 500 to 10,000,
It is bonded to oxygen at the end. ) The polyamide polymer component can be formed by ring-opening polymerization of lactam, condensation polymerization of amino acids, condensation polymerization of diamine and dicarboxylic acid, etc. The bifunctional carboxylic acid added to adjust the end group concentration of the polyesteramide resin and increase its molecular weight does not need to have a particularly limited structure, but it is necessary to enter the polyamide polymer part as a co-condensation component and improve the regularity of the polyamide. It is preferable that the polyamide has a number of methylene chains as close as possible to the number of methylene chains of the polyamide so as not to disturb the crystallinity and reduce the crystallinity. For example, when nylon 12 is a polyamide component, α,ω dodecane dicarboxylic acid is most suitable. In order to obtain the infinite molecular weight of polyesteramide, it is theoretically necessary for the diol and dicarboxylic acid to be equimolar, but depending on the purpose, it is permissible to add up to 20% above or below that ratio. be done. The hydrogenated polybutadiene component can maintain desirable performance as a polyamide resin by forming blocks when it is made into a co-condensate. Therefore, when the number average molecular weight of hydrogenated polybutadiene is less than 500, the molecular chain of the polyamide part will inevitably become shorter, the polyamide part will not form its own crystalline phase, and the entire polyesteramide resin will become amorphous. Undesirable. Furthermore, if a hydrogenated polybutadiene component having a number average molecular weight of 10,000 or more is used, macro phase separation occurs, making it impossible to form good molded products, films, etc., and is therefore unsuitable. Therefore, the preferred range of the molecular weight of the polybutadiene component is 500 to 10,000 in terms of number average molecular weight, and the most preferred range is 1,000 to 2,000.
かかる構成成分を有する本発明の共重合ポリエ
ステルアミド樹脂の分子量はカルボン酸末端基濃
度をアミノ末端基濃度と末端水酸基濃度の和に対
し調整することにより、又、縮合反応率を調整す
ることによつてある程度調節し得るが、その範囲
は数平均分子量として約5000ないし500000であ
る。 The molecular weight of the copolymerized polyesteramide resin of the present invention having such constituent components can be determined by adjusting the carboxylic acid terminal group concentration relative to the sum of the amino terminal group concentration and the terminal hydroxyl group concentration, and by adjusting the condensation reaction rate. Although the number average molecular weight can be adjusted to some extent, the number average molecular weight is approximately 5,000 to 500,000.
かかる本発明に係る共重合ポリエステルアミド
樹脂を合成するには、二官能性カルボン酸とアミ
ノ酸又はダイカルボン酸とジアミンの縮合反応に
より、あるいは二官能性カルボン酸の存在下のラ
クタムの開環重合により、末端にカルボン酸基を
有するポリアミドオリゴマーを形成させ、このオ
リゴマーの末端カルボン酸基と、両末端に水酸基
を有する水素化ポリブタジエンジオールとのエス
テル形成反応によりブロツク共重合体を形成させ
る。水素化ポリブタジエンジオールはポリアミド
オリゴマーの合成の後添加してもよく、又ポリア
ミド合成の当初から共存させておき、アミド結合
形成反応とエステル結合形成反応が並行して起こ
るようにすることも可能である。いずれにしても
アミド結合の形成反応とエステル結合の形成反応
ではこれら可逆反応の平衡定数に差があるため、
アミド結合形成が先行して起こり、エステル結合
形成反応によりブロツク共重合体を完成させるた
めには、高温減圧下の脱離水除去工程が必須であ
る。又、水素化ポリブタジエンジオールと二官能
性カルボン酸との縮合反応を先ず行なつて、末端
にカルボン酸基を有するポリエステルオリゴマー
を合成し、このオリゴマーの存在下にアミド酸又
はダイカルボン酸とジアミンの重縮合反応、ある
いはラクタムの開環重合を行なつて、エステル変
換反応を伴なう縮合反応によりブロツク共重合体
とする方法、あるいは上述のポリエステルオリゴ
マーとポリアミドオリゴマーの反応によりエステ
ル変換反応をともなつた縮合反応によりブロツク
共重合体とする方法も可能である。 The copolymerized polyesteramide resin according to the present invention can be synthesized by a condensation reaction of a difunctional carboxylic acid and an amino acid or a dicarboxylic acid and a diamine, or by ring-opening polymerization of a lactam in the presence of a difunctional carboxylic acid. A polyamide oligomer having a terminal carboxylic acid group is formed, and a block copolymer is formed by an ester formation reaction between the terminal carboxylic acid group of this oligomer and a hydrogenated polybutadiene diol having a hydroxyl group at both ends. The hydrogenated polybutadiene diol may be added after the synthesis of the polyamide oligomer, or it may be allowed to coexist from the beginning of the polyamide synthesis so that the amide bond-forming reaction and the ester bond-forming reaction occur in parallel. . In any case, there is a difference in the equilibrium constants of the reversible reactions between the amide bond formation reaction and the ester bond formation reaction.
In order to complete the block copolymer by the ester bond formation reaction, in which amide bond formation occurs first, a step of removing desorbed water at high temperature and under reduced pressure is essential. In addition, a polyester oligomer having a carboxylic acid group at the end is synthesized by first carrying out a condensation reaction between hydrogenated polybutadiene diol and a difunctional carboxylic acid, and in the presence of this oligomer, an amic acid or a dicarboxylic acid is mixed with a diamine. A method of polycondensation reaction or ring-opening polymerization of lactam to produce a block copolymer through a condensation reaction accompanied by an ester conversion reaction, or a method involving an ester conversion reaction by the reaction of the above-mentioned polyester oligomer and polyamide oligomer. It is also possible to form a block copolymer by a condensation reaction.
本発明のポリエステルアミドは水素化ポリブタ
ジエンの導入によつて、極性のあるアミド結合及
びエステル結合の濃度が炭化水素鎖によつて希釈
されるため、低吸水率であり、吸水による寸法、
物性の変化が少なく、又熱安定性にもすぐれてい
るため、射出、押出等による成型品に好適に用い
られる。又この共重合体は吸水率の低い熱接着剤
としても用いられ得る。更に水素化ポリブタジエ
ンの含量が30％以上となると柔軟性が増し、かつ
耐衝撃性も増すので、柔軟性、耐衝撃性を要求さ
れる用途に有利に用いられる。又吸水性が小さい
ために、電気特性、特にインピーダンスの湿度依
存性が小さく、又ポリアミドブロツク部分の明瞭
な融点による熱ヒユーズとしての特性もあるため
に、インピーダンスの温度依存性及び熱ヒユーズ
性を利用する電気毛布、電気カーペツト等の感熱
素子としての用途は特に有利である。 The polyester amide of the present invention has a low water absorption rate due to the introduction of hydrogenated polybutadiene, and the concentration of polar amide bonds and ester bonds is diluted by hydrocarbon chains.
Since there is little change in physical properties and excellent thermal stability, it is suitably used for molded products by injection, extrusion, etc. This copolymer can also be used as a thermal adhesive with low water absorption. Furthermore, when the content of hydrogenated polybutadiene is 30% or more, flexibility and impact resistance also increase, so that it is advantageously used in applications requiring flexibility and impact resistance. In addition, due to its low water absorption, the humidity dependence of electrical properties, especially impedance, is small, and the polyamide block has properties as a thermal fuse due to its clear melting point, so the temperature dependence of impedance and thermal fuse properties can be utilized. The use as a heat-sensitive element in electric blankets, electric carpets, etc. is particularly advantageous.
以下に本発明を実施例によつて説明するが、勿
論これによつて本発明を限定するものではない。 The present invention will be explained below with reference to Examples, but of course the present invention is not limited thereto.
実施例 １
ω−アミノドデカン酸39.6ｇ、α，ω−ドデカ
ンダイカルボン酸4.54ｇを撹拌器つきセパラブル
フラスコ中で窒素気流下に190℃、４時間縮合反
応させ、この反応混合物へ数平均分子量（o）
1490の末端に水酸基を有する水素化ポリブタジエ
ン29.4ｇとジブチルすずオキサイド0.05ｇを添加
し、更に190℃で窒素気流下７時間反応せしめた。
得られた低縮合度反応物のうち14ｇをステンレス
スチール製マイクロボンベへ移し、１mmHgの減
圧下に210℃で１時間、230℃で２時間、270℃で
８時間反応せしめた。得られたポリマーは末端基
分析による数平均分子量が9100であり、強靫なシ
ートに成型することができた。Example 1 39.6 g of ω-aminododecanoic acid and 4.54 g of α,ω-dodecanedicarboxylic acid were subjected to a condensation reaction at 190°C for 4 hours under a nitrogen stream in a separable flask equipped with a stirrer, and the number average molecular weight of the reaction mixture was ( o )
29.4 g of hydrogenated polybutadiene having a hydroxyl group at the terminal of 1490 and 0.05 g of dibutyltin oxide were added, and the mixture was further reacted at 190° C. for 7 hours under a nitrogen stream.
14 g of the obtained low degree of condensation reaction product was transferred to a stainless steel micro cylinder and reacted under a reduced pressure of 1 mmHg at 210°C for 1 hour, 230°C for 2 hours, and 270°C for 8 hours. The obtained polymer had a number average molecular weight of 9100 according to end group analysis, and could be molded into a strong sheet.
参考例 １
実施例１の成型シートを40℃の水中に一週間保
持した後の水分は0.502重量％であつた。Reference Example 1 After the molded sheet of Example 1 was kept in water at 40° C. for one week, the moisture content was 0.502% by weight.
このシートのインピーダンスを70℃真空乾燥５
日間後のドライな状態及び40℃水中保持一週間後
の状態に於て測定したところ、それぞれ100Hz、
50℃において3.0×109Ωcm及び2.4×109Ωcmであ
り、その差はわずか0.6×109Ωcmであつた。昇温
速度10℃／minでDSCを測定したところ、融解範
囲153〜176℃、ピーク温度170℃、融解熱
7.1cal／ｇの明瞭な結晶性高分子の融解挙動を示
した。この様にインピーダンスが湿度の影響を受
けにくく、又明瞭な融点によつて熱ヒユーズとし
ても用い得るので、この共重合ポリエステルアミ
ド樹脂は電気毛布や電気カーペツトの感熱素子と
して好適に用い得る。 Dry the impedance of this sheet under vacuum at 70℃5
Measurements were made in a dry state after several days and in a state after being held in water at 40℃ for one week.
They were 3.0×10 9 Ωcm and 2.4×10 9 Ωcm at 50° C., and the difference between them was only 0.6×10 9 Ωcm. When DSC was measured at a heating rate of 10°C/min, the melting range was 153 to 176°C, the peak temperature was 170°C, and the heat of fusion was
It showed clear crystalline polymer melting behavior of 7.1 cal/g. In this way, the impedance is not easily affected by humidity, and the clear melting point allows it to be used as a thermal fuse, so this copolymerized polyesteramide resin can be suitably used as a heat-sensitive element for electric blankets and electric carpets.
参考例 ２
数平均分子量24000のナイロン12のシートを40
℃の水中に一週間保持した後の水分は1.6重量％
であつた。このシートのインピーダンスを70℃５
日間の真空乾燥後と水中40℃１週間保持後に測定
したところ100Hz、50℃において、3.0×109Ωcm
及び1.1×109Ωcmであり、その差は1.9×109Ωcm
にも達した。このシートについてもDSCを測定
したところ、融解範囲164〜184℃、ピーク温度
179℃、融解熱は9.2cal／ｇであつた。Reference example 2 40 sheets of nylon 12 with a number average molecular weight of 24,000
Moisture content after one week in water at ℃ is 1.6% by weight
It was hot. The impedance of this sheet is 70℃5
Measured after vacuum drying for 1 day and after being kept in water at 40℃ for 1 week, it was 3.0×10 9 Ωcm at 100Hz and 50℃.
and 1.1×10 9 Ωcm, and the difference is 1.9×10 9 Ωcm
It also reached When this sheet was also measured by DSC, the melting range was 164-184℃, and the peak temperature was
The temperature was 179°C and the heat of fusion was 9.2 cal/g.
Claims (1)
有し、(A)の構成単位と(B)の構成単位はアミド結合
により結合し、(A)の構成単位と(C)の構成単位及び
(B)の構成単位と(C)の構成単位とはエステル結合に
より結合し、(C)の構成単位が１〜80重量％を占
め、(B)の構成単位と(C)の構成単位のモル比が１：
1.2ないし１：0.8であり、数平均分子量が5000〜
500000である、新規共重合ポリエステルアミド樹
脂。 (A)：一般式(1)又は(2)で表わされる繰返し単位一種
以上を有するポリアミド高分子成分、 −NH−（CH2）o−CO−（ｎは５〜11の整数）
(1) −NHXNHCOYCO− (2) （式中、ＸはCnH2n（ｍは６〜12の整数）、イソ
ホロン基、フエニレン基又はシクロヘキシレン
基を表わし、ＹはClH2l（ｌは４〜10の整数）、
フエニレン基又はシクロヘキシレン基を表わ
す。） (B)：次式で表わされる構成単位、 −CO−CnH2n−CO−（ｍは１〜36の整数） (C)：次式で表わされる構成単位、 −Ｏ−Ｚ−Ｏ− （Ｚは平均分子量500〜10000の二重結合に水素
添加されたポリブタジエン成分であつて、末端
において酸素と結合している）[Scope of Claims] 1 It has structural units defined by the following (A), (B), and (C), and the structural unit (A) and the structural unit (B) are bonded by an amide bond, and ( The constituent units of A) and the constituent units of (C) and
The structural units of (B) and (C) are bonded by an ester bond, and the structural units of (C) account for 1 to 80% by weight, and the structural units of (B) and (C) are bonded together by an ester bond. Molar ratio is 1:
1.2 to 1:0.8, and the number average molecular weight is 5000 to 1:0.8.
500,000, a new copolymerized polyesteramide resin. (A): Polyamide polymer component having one or more repeating units represented by general formula (1) or (2), -NH-(CH 2 ) o -CO- (n is an integer from 5 to 11)
(1) -NHXNHCOYCO- ( 2 ) (wherein , integer from 4 to 10),
Represents a phenylene group or a cyclohexylene group. ) (B): Constituent unit represented by the following formula, -CO-C n H 2n -CO- (m is an integer from 1 to 36) (C): Constituent unit represented by the following formula, -O-Z-O - (Z is a polybutadiene component with an average molecular weight of 500 to 10,000 and hydrogenated double bonds, and is bonded to oxygen at the terminal)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10204781A JPS582330A (en) | 1981-06-30 | 1981-06-30 | Copolymerized polyester amide resin |
| US06/651,633 US4555566A (en) | 1981-03-16 | 1982-03-16 | Copolymer polyamide resin containing polyolefin moiety |
| DE8282900827T DE3278735D1 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
| PCT/JP1982/000068 WO1982003219A1 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
| EP82900827A EP0073838B2 (en) | 1981-03-16 | 1982-03-16 | Copolymerized polyamide resin |
| US06/888,095 US5025070A (en) | 1981-03-16 | 1986-07-17 | Copolymer polyamide resin from hydrogenated polyolefin condensate |
| US07/475,184 US5093421A (en) | 1981-03-16 | 1990-02-02 | Copolymer polyamide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10204781A JPS582330A (en) | 1981-06-30 | 1981-06-30 | Copolymerized polyester amide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS582330A JPS582330A (en) | 1983-01-07 |
| JPH0116253B2 true JPH0116253B2 (en) | 1989-03-23 |
Family
ID=14316849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10204781A Granted JPS582330A (en) | 1981-03-16 | 1981-06-30 | Copolymerized polyester amide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS582330A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0633754B2 (en) * | 1984-09-26 | 1994-05-02 | いすゞ自動車株式会社 | Engine warm-up device |
| JPS6269009A (en) * | 1985-09-19 | 1987-03-30 | Isuzu Motors Ltd | combustor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5033119A (en) * | 1973-07-26 | 1975-03-31 | ||
| JPS5337919A (en) * | 1976-09-20 | 1978-04-07 | Asahi Seiki Kk | Valve and it*s finishing method |
| DE2712987C2 (en) * | 1977-03-24 | 1981-09-24 | Chemische Werke Hüls AG, 4370 Marl | Process for the production of thermoplastic polyetheresteramides with units of the starting components randomly distributed in the polymer chain |
| CH631189A5 (en) * | 1977-10-28 | 1982-07-30 | Ciba Geigy Ag | METHOD FOR PRODUCING NEW TRANSPARENT ALIPHATIC POLYAMIDES. |
-
1981
- 1981-06-30 JP JP10204781A patent/JPS582330A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS582330A (en) | 1983-01-07 |
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