JPH0593054A - Thermoplastic synthetic resin molded product - Google Patents
Thermoplastic synthetic resin molded productInfo
- Publication number
- JPH0593054A JPH0593054A JP25529991A JP25529991A JPH0593054A JP H0593054 A JPH0593054 A JP H0593054A JP 25529991 A JP25529991 A JP 25529991A JP 25529991 A JP25529991 A JP 25529991A JP H0593054 A JPH0593054 A JP H0593054A
- Authority
- JP
- Japan
- Prior art keywords
- molded product
- condensate
- parts
- synthetic resin
- thermoplastic synthetic
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、物理的性能及び工程性
に優れた熱可塑性合成樹脂成形品に関する。更に詳しく
は、合成樹脂本来の特性を持ち、かつ吸湿性を有する熱
可塑性合成樹脂成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic synthetic resin molded article having excellent physical performance and processability. More specifically, the present invention relates to a thermoplastic synthetic resin molded product having the original characteristics of synthetic resin and having hygroscopicity.
【０００２】[0002]
【従来の技術】熱可塑性合成樹脂成形品は、その優れた
特性等により繊維及び、フィルム等をはじめ種々の形態
のものが、広く一般的に使用されている。しかしなが
ら、かかる熱可塑性合成樹脂成形品は、概ね疎水性であ
るため吸湿性が欠如していて展開が困難な分野がみられ
る。特に繊維、フィルムにおいてこの疎水性の性状は致
命的となって、著しく展開分野が限定されている。2. Description of the Related Art Thermoplastic synthetic resin molded articles are widely used in various forms such as fibers and films due to their excellent characteristics. However, since such thermoplastic synthetic resin molded articles are generally hydrophobic, they lack hygroscopicity and are difficult to develop in some fields. Especially in fibers and films, this hydrophobic property becomes fatal, and the field of development is remarkably limited.
【０００３】そこで、従来より熱可塑性合成樹脂成形品
に吸湿性を付与すべく、数々の提案がなされているが、
未だに実用化されたものは殆どない。例えば金属スルホ
ネート化合物及び、またはポリオキシアルキレングリコ
ール等の親水性第三成分を成形品を形成する熱可塑性合
成樹脂成分に共重合あるいはブレンドし、吸湿性あるい
は、制電性の改善を試みることが数多く提案されてい
る。Therefore, various proposals have heretofore been made to impart hygroscopicity to a thermoplastic synthetic resin molded article.
Few have been put to practical use yet. For example, it is often attempted to improve hygroscopicity or antistatic property by copolymerizing or blending a metal sulfonate compound and / or a hydrophilic third component such as polyoxyalkylene glycol with a thermoplastic synthetic resin component forming a molded article. Proposed.
【０００４】しかしながら、かかる方法によって得られ
る熱可塑性合成樹脂成形品の性能は、十分なものではな
い。このため性能を向上させるために添加量を増加する
と、得られる成形品の物理的な物性値は実用性の乏しい
ものとなり、本来の熱可塑性合成樹脂成形品の持つ優れ
た物理特性を犠牲にしなければならなかった。However, the performance of the thermoplastic synthetic resin molded product obtained by such a method is not sufficient. Therefore, if the addition amount is increased to improve the performance, the physical properties of the obtained molded product become poor in practicality, and the excellent physical properties of the original thermoplastic synthetic resin molded product must be sacrificed. I had to do it.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来公知の
熱可塑性合成樹脂成形品が有する前述の課題を解消し
て、実用上十分な吸湿性を有する熱可塑性合成樹脂成形
品を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of conventionally known thermoplastic synthetic resin molded articles and provides a thermoplastic synthetic resin molded article having practically sufficient hygroscopicity. With the goal.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前述の目
的を達成すべく鋭意検討した結果、ポリオキシアルキレ
ングリコールとスルホネート化合物を予め縮重合反応さ
せた縮合体は、２００℃以下の融点を有し、熱可塑性合
成樹脂に容易に混合または、反応させうることを発見し
た。また、この縮合体は、ポリオキシアルキレングリコ
ールあるいは、スルホネート化合物を各々単独及び、ま
たは、両者を単純に共重合する場合に比べ、著しく吸湿
性が向上することを発見し本発明に至ったものである。Means for Solving the Problems As a result of intensive investigations by the present inventors in order to achieve the above-mentioned object, the condensate obtained by subjecting a polyoxyalkylene glycol and a sulfonate compound to a condensation polymerization reaction in advance has a melting point of 200 ° C. or lower. It has been discovered that it can be easily mixed or reacted with a thermoplastic synthetic resin. Further, this condensate has led to the present invention by discovering that the polyoxyalkylene glycol or the sulfonate compound has remarkably improved hygroscopicity as compared with the case where the polyoxyalkylene glycol or the sulfonate compound is used alone and / or both are simply copolymerized. is there.
【０００７】すなわち、本発明は、（１）式で示す平均
分子量が異なる２種以上のポリオキシアルキレングリコ
ールと（２）式で示すスルホネート化合物との縮合体を
成形品の重量１ｋｇ当たりスルホン酸基で０．１モル以
上０．７モル以下含有させることを特徴とする熱可塑性
合成樹脂成形品、である。That is, according to the present invention, a condensate of two or more polyoxyalkylene glycols having different average molecular weights represented by the formula (1) and a sulfonate compound represented by the formula (2) is used as a sulfonic acid group per 1 kg of the weight of a molded article. And 0.1 mol or more and 0.7 mol or less.
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】本発明でいう熱可塑性合成樹脂とは、熱可
塑性であれば、どのようなものでも使用できるが、ポリ
エチレン、ポリプロピレン等のポリオレフィン、また
は、ポリスチレン、ポリメタクリル酸メチル、または、
ナイロン６、ナイロン６６等のポリアミドである。な
お、これらを主成分とし、他の成分を共重合及び（また
は）混合した樹脂、さらにはこれらの樹脂を混合したも
のであっても一向に差し支えない。The thermoplastic synthetic resin referred to in the present invention may be any one as long as it is thermoplastic, but it may be a polyolefin such as polyethylene or polypropylene, or polystyrene, polymethylmethacrylate, or
Polyamides such as nylon 6 and nylon 66. It should be noted that a resin in which these are the main components, other components are copolymerized and / or mixed, or a mixture of these resins may be used.
【００１０】本発明でいうポリオキシアルキレングリコ
ールとは、繰り返し単位が、−ＣＨＲ1 −ＣＨＲ2 −Ｏ
−（但し、Ｒ1 、Ｒ2 は、水素または炭化水素であ
る。）なる構造であり、前記のスルホネート化合物と縮
合体を形成できれば、どの様なものでもよいが、ポリエ
チレングリコール及び、ポリプロピレングリコールが好
ましく、ポリエチレングリコールが特に好ましい。The polyoxyalkylene glycol referred to in the present invention has a repeating unit of --CHR 1 --CHR 2 --O.
-(Provided that R 1 and R 2 are hydrogen or hydrocarbon), and any structure may be used as long as it can form a condensate with the sulfonate compound, but polyethylene glycol and polypropylene glycol are Polyethylene glycol is particularly preferred.
【００１１】また、本発明でいうスルホネート化合物と
しては、例えば、３，５−ジカルボキシベンゼンスルホ
ン酸金属塩、３，５−ビス（カルボメトキシ）ベンゼン
スルホン酸金属塩、３，５−ビス（ヒドロキシエトキ
シ）ベンゼンスルホン酸金属塩、１，８−ビス（カルボ
キシメトキシ）ナフタレン−３−スルホン酸金属塩、
２，６−ビス（カルボキシメトキシ）ナフタレン−４−
スルホン酸金属塩、１，５−ビス（カルボメトキシ）ベ
ンゼンスルホン酸金属塩等があげられる。Examples of the sulfonate compound in the present invention include 3,5-dicarboxybenzenesulfonic acid metal salt, 3,5-bis (carbomethoxy) benzenesulfonic acid metal salt and 3,5-bis (hydroxy). Ethoxy) benzenesulfonic acid metal salt, 1,8-bis (carboxymethoxy) naphthalene-3-sulfonic acid metal salt,
2,6-bis (carboxymethoxy) naphthalene-4-
Examples thereof include sulfonic acid metal salts and 1,5-bis (carbomethoxy) benzenesulfonic acid metal salts.
【００１２】使用するポリオキシアルキレングリコール
の分子量は、前記の縮合体を形成可能で、以下に述べる
条件を満たしている方が本発明実施の上でより好適とな
る。すなわち、合成樹脂本来が有する優れた特性を損な
わないためには、配合する縮合体の吸湿性能は高い方が
好ましいことは自明のことである。本発明で使用される
縮合体は、含有されるスルホネート化合物の重量分率が
高い程、吸湿性能は高くなる。The molecular weight of the polyoxyalkylene glycol used is such that the above-mentioned condensate can be formed, and it is more preferable in the practice of the present invention that the following conditions are satisfied. That is, it is self-evident that the higher the moisture absorption performance of the condensate to be blended, the better in order not to impair the excellent properties inherent in the synthetic resin. In the condensate used in the present invention, the higher the weight fraction of the sulfonate compound contained, the higher the moisture absorption performance.
【００１３】つまり、スルホネート化合物とポリオキシ
アルキレングリコールとは等モル反応しているため、ス
ルホネート化合物と共に縮合体を構成するポリオキシア
ルキレングリコールの分子量は低い方がスルホネート化
合物の重量分率が高くなるため、好ましく、その結果、
吸湿性は高くなる。しかしながら、分子量の低い方にも
限界があり、（１）式のＲ1 、Ｒ2 が共に水素で、ｍが
１のエチレングリコールの重量分率が２０％以上になる
と、熱溶融性が不良となるので好ましくない。このた
め、使用するポリオキシアルキレングリコールの分子量
としては、１００以上が好ましい。That is, since the sulfonate compound and the polyoxyalkylene glycol react with each other in an equimolar amount, the lower the molecular weight of the polyoxyalkylene glycol forming the condensate together with the sulfonate compound, the higher the weight fraction of the sulfonate compound. , And, as a result,
Higher hygroscopicity. However, there is a limit to the lower molecular weight, and when both R 1 and R 2 of the formula (1) are hydrogen and the weight fraction of ethylene glycol having m of 1 is 20% or more, the heat melting property is poor. Therefore, it is not preferable. Therefore, the molecular weight of the polyoxyalkylene glycol used is preferably 100 or more.
【００１４】一方、理由は明らかではないが、分子量１
０００未満のポリオキシアルキレングリコールのみで縮
合体を構成すると、同量のスルホネート化合物を含有し
ていても吸湿性が低下してくるため分子量は、高い方が
好ましく、具体的には、１０００以上が好ましい。従っ
て、これらの相反する条件を満足させるために、鋭意検
討した結果、本発明者らは、スルホネート化合物と反応
させるポリオキシアルキレングリコールとして、縮合体
の吸湿性の低下を防ぐために、分子量が１０００から４
０００のものを一部使用し、また、スルホネート化合物
の重量分率を上げ、縮合体の吸湿性を高くするために、
低分子量の１００以上１０００以下のものを、更に好ま
しくは、１５０以上６００以下のもの使い、スルホネー
ト化合物とのモル比率を合わせ縮合体を構成することに
より、優れた吸湿性を有する熱溶融性の縮合体を合成で
きることを発見した。On the other hand, although the reason is not clear, the molecular weight is 1
If the condensate is composed of only polyoxyalkylene glycol of less than 000, the hygroscopicity will decrease even if the sulfonate compound is contained in the same amount, so that the molecular weight is preferably high, specifically, 1000 or more. preferable. Therefore, as a result of diligent studies to satisfy these contradictory conditions, the present inventors have determined that the polyoxyalkylene glycol to be reacted with a sulfonate compound has a molecular weight of 1,000 or less in order to prevent a decrease in hygroscopicity of the condensate. Four
000 in part, in order to increase the weight fraction of the sulfonate compound and increase the hygroscopicity of the condensate,
A low-molecular weight 100 or more and 1000 or less, more preferably 150 or more and 600 or less, is used to form a condensate by combining a molar ratio with a sulfonate compound to form a condensate. It was discovered that the body can be synthesized.
【００１５】例えば、分子量１５０のトリエチレングリ
コール１０８ｇ（０．７２モル）、平均分子量１０００
のポリエチレングリコール６８ｇ（０．０６８モル）、
３，５−ビス（ヒドロキシルエトキシ）スルホイソフタ
レートナトリウム塩の３５％エチレングリコール溶液
（但し、ヒドロキシエトキシ基７０％、カルボキシメト
キシ基３０％の反応混合物）７５６ｇ（０．７８８モ
ル）及び、触媒等を縮合機に仕込み、重縮合反応を行う
ことによりエチレングリコールの含有量が８重量％、融
点１２０℃、粘性のある淡黄色の縮合体が得られる。For example, 108 g (0.72 mol) of triethylene glycol having a molecular weight of 150 and an average molecular weight of 1000
68 g (0.068 mol) of polyethylene glycol,
A 35% ethylene glycol solution of 3,5-bis (hydroxylethoxy) sulfoisophthalate sodium salt (however, 756 g (0.788 mol) of a reaction mixture of 70% hydroxyethoxy group and 30% carboxymethoxy group) and a catalyst and the like were added. A viscous pale yellow condensate having a content of ethylene glycol of 8% by weight, a melting point of 120 ° C. and a polycondensation reaction is prepared by charging in a condensation machine.
【００１６】また、ここでいう縮合体とは、縮重合反応
で得られる重合度の低いものから重合度の高いものまで
包括した縮重合反応物をいう。縮合体の重合度は低いも
のから高いものまで使用できるが、反応性と得られる組
成の観点から好適な範囲があるので必要に応じて選択す
るのが好ましい。本発明に用いる縮合体は、熱可塑性合
成樹脂中にブロック状で存在することが肝要であり、ス
ルホネート化合物成分とポリオキシアルキレングリコー
ル成分とがランダム共重合化するような熱履歴は極力避
けるべきである。ランダム共重合に比べ、縮合体をブロ
ック共重合させることにより高い吸湿性が発現する理由
は明らかではないが、ブロック共重合状で存在するとア
ルキレングリコール基とスルホネート化合物中のスルホ
ン酸金属基とがより近接して存在するために、ランダム
共重合体のものから予測されるより高い吸湿性を生じる
ものと推測している。従って、本発明に用いる縮合体の
熱可塑性合成樹脂への添加時期は、成形時あるいは樹脂
の合成反応終了直前が好ましい。The term "condensate" as used herein means a polycondensation reaction product obtained from a polycondensation reaction and having a low polymerization degree to a high polymerization degree. Although the degree of polymerization of the condensate can be from low to high, it can be used in a suitable range from the viewpoint of reactivity and the composition to be obtained, and therefore it is preferable to select as necessary. It is essential that the condensate used in the present invention exists in a block form in the thermoplastic synthetic resin, and thermal history such that the sulfonate compound component and the polyoxyalkylene glycol component are randomly copolymerized should be avoided as much as possible. is there. Compared with random copolymerization, the reason why high hygroscopicity is exhibited by block copolymerizing the condensate is not clear, but when it exists in a block copolymerized state, the alkylene glycol group and the sulfonate metal group in the sulfonate compound are more It is speculated that due to their close proximity, they give rise to a higher hygroscopicity than expected from that of random copolymers. Therefore, it is preferable that the condensate used in the present invention is added to the thermoplastic synthetic resin at the time of molding or immediately before the completion of the synthetic reaction of the resin.
【００１７】また、本発明の熱可塑性樹脂成形品に用い
る縮合体の含有量は、実用的な吸湿性を付与するために
スルホン酸基で０．１モル以上０．７モル以下成形品１
ｋｇ含有されていることが必要である。更には、０．２
５モル以上０．５モル以下が、特に好ましい。本発明の
合成樹脂成形品は、必要に応じて、各種添加剤、例えば
染料、顔料、充填剤、滑剤、補強剤、難燃剤、安定剤及
び紫外線吸収剤等を配合されていてもよい。The content of the condensate used in the thermoplastic resin molded product of the present invention is 0.1 mol or more and 0.7 mol or less based on the sulfonic acid group in order to impart practical hygroscopicity to the molded product 1.
It is necessary to contain kg. Furthermore, 0.2
It is particularly preferably 5 mol or more and 0.5 mol or less. The synthetic resin molded article of the present invention may be mixed with various additives such as dyes, pigments, fillers, lubricants, reinforcing agents, flame retardants, stabilizers, and ultraviolet absorbers, if necessary.
【００１８】本発明の熱可塑性合成樹脂成形品には、各
種繊維、その編織物、不織布、フィルム、シート（板）
及び管等任意の形態のものが含まれる。本発明の熱可塑
性樹脂成形品は、合成樹脂原料と縮合体等から任意の成
形、賦形手段で、例えば紡糸、延伸成形、押出成形、射
出成形、圧縮成形等により容易に製造できる。The thermoplastic synthetic resin molded article of the present invention includes various fibers, knitted and woven fabrics, non-woven fabrics, films and sheets (plates) thereof.
And pipes and other arbitrary shapes are included. The thermoplastic resin molded product of the present invention can be easily manufactured from a synthetic resin raw material and a condensate by any molding and shaping means, for example, spinning, stretch molding, extrusion molding, injection molding, compression molding and the like.
【００１９】[0019]
【実施例】以下、実施例により本発明を具体的に説明す
るが、これらは本発明の範囲を制限するものでない。実
施例中の％は重量％、部は重量部の省略である。なお吸
湿率（以下ＭＲと略す）の測定は、２０℃、相対湿度６
５％の恒温恒湿器（タバイエスペック（株）製、ＰＲ−
２Ｇ）中に、恒量になるまで放置して得られた値であ
り、次式により算出した。EXAMPLES The present invention will be described in detail below with reference to examples, but these do not limit the scope of the present invention. In the examples,% means% by weight, and parts means parts by weight. The moisture absorption rate (hereinafter abbreviated as MR) was measured at 20 ° C. and a relative humidity of 6
5% constant temperature and humidity chamber (Tabay Espec Co., Ltd., PR-
2G) is a value obtained by leaving it in a constant weight until calculated by the following equation.
【００２０】ＭＲ＝（吸湿成形品重量−絶乾成形品重
量）／絶乾成形品重量×１００MR = (weight of hygroscopic molded product−weight of absolutely dry molded product) / weight of absolutely dry molded product × 100
【００２１】[0021]
【実施例１】分子量１５０のトリエチレングリコール１
０８部、平均分子量１０００のポリエチレングリコール
６８部、３，５−ビス（ヒドロキシルエトキシ）スルホ
イソフタレートナトリウム塩の３５％エチレングリコー
ル溶液（但し、ヒドロキシエトキシ基７０％、カルボキ
シメトキシ基３０％の反応混合物）７５６部、酢酸リチ
ウム２水塩０．８部、テトライソプロピルチタネート
１．２部を重合機に仕込み、２２０℃にて窒素フローの
もとで２時間加熱攪拌した後、温度を２４０℃に上げ、
４５分間かけて減圧し、最終的には０．２ｍｍＨｇまで
減圧した。Example 1 Triethylene glycol 1 having a molecular weight of 150
08 parts, 68 parts of polyethylene glycol having an average molecular weight of 1000, 35% ethylene glycol solution of 3,5-bis (hydroxylethoxy) sulfoisophthalate sodium salt (however, a reaction mixture of 70% hydroxyethoxy group and 30% carboxymethoxy group) 756 parts, lithium acetate dihydrate 0.8 parts, and tetraisopropyl titanate 1.2 parts were charged into a polymerization machine, and the mixture was heated and stirred at 220 ° C. under a nitrogen flow for 2 hours, and then the temperature was raised to 240 ° C.
The pressure was reduced over 45 minutes and finally to 0.2 mmHg.
【００２２】この状態で、１５分間保った後、重合機よ
り払い出し、淡黄色で粘性のある縮合体（以下ＳＰｌと
略す）を得た。得られたＳＰ１は、１２０℃で溶融し
た。また、ＳＰ１のＭＲは１３％であった。得られたＳ
Ｐ１の２０部をηｒが２．４５（１ｇポリマー／９５．
５％硫酸１００ｍｌ、２５℃）のナイロン６チップ８０
部にチップブレンドし通常の手法にて紡糸、延伸し１０
０デニール２４フィラメントの長繊維を得た。得られた
長繊維のＭＲは、６．９％であった。After being kept for 15 minutes in this state, it was discharged from the polymerization machine to obtain a light yellow viscous condensate (hereinafter abbreviated as SPl). The obtained SP1 was melted at 120 ° C. The MR of SP1 was 13%. The obtained S
20 parts of P1 had an ηr of 2.45 (1 g polymer / 95.
Nylon 6 tip 80 of 5% sulfuric acid 100 ml, 25 ° C)
10 parts are blended with a chip, spun and stretched by the usual method 10
Long filaments of 0 denier 24 filaments were obtained. The MR of the obtained long fiber was 6.9%.
【００２３】[0023]
【実施例２】実施例１で用いたＳＰ１の２０部をηｒが
２．５０（１ｇポリマー／９５．５％硫酸１００ｍｌ、
２５℃）８０部のナイロン６６に溶融成形時に配合し、
実施例１と同様に１００デニール２４フィラメントの長
繊維を得た。得られた長繊維のＭＲは、６．７％であっ
た。Example 2 20 parts of SP1 used in Example 1 had an ηr of 2.50 (1 g polymer / 95.5% sulfuric acid 100 ml,
(25 ° C) 80 parts of nylon 66 was blended during melt molding,
Long fibers having 100 denier 24 filaments were obtained in the same manner as in Example 1. The MR of the obtained long fiber was 6.7%.
【００２４】[0024]
【実施例３】実施例１で用いたＳＰ１の１５部を溶融流
れ指数（Ｍｅｌｔ Ｆｌｏｗ Ｒａｔｅ（以下ＭＦＲと
略す）が４．５ｇ／１０分（ＪＩＳＫ−６７５８法に準
拠）８５部のポリプロピレンに溶融成形時に配合し、厚
さ１００μｍのフィルムを得た。得られたフィルムのＭ
Ｒは、２．１％であった。Example 3 Melting 15 parts of SP1 used in Example 1 into polypropylene having a melt flow index (Melt Flow Rate (hereinafter abbreviated as MFR) of 4.5 g / 10 min (according to JIS K-6758 method)). It was compounded at the time of molding to obtain a film having a thickness of 100 μm.
R was 2.1%.
【００２５】[0025]
【実施例４】実施例１で用いたＳＰ１の１５部をＭＦＲ
が７．５ｇ／１０分（荷重５ｋｇ、２００℃）８５部の
ポリスチレンに溶融成形時に配合し、厚さ１ｍｍのプレ
ートを得た。得られたプレートのＭＲは、２．５％であ
った。Example 4 15 parts of SP1 used in Example 1 was MFR
Of 7.5 g / 10 min (load: 5 kg, 200 ° C.) was mixed with 85 parts of polystyrene at the time of melt molding to obtain a plate having a thickness of 1 mm. The MR of the obtained plate was 2.5%.
【００２６】[0026]
【実施例５】実施例１で用いたＳＰ１の１５部をＭＦＲ
が５．１ｇ／１０分（荷重１０ｋｇ、２００℃）８５部
のポリメタクリル酸メチルに溶融成形時に配合し、厚さ
１ｍｍのプレートを得た。得られたプレートのＭＲは、
３．８％であった。Example 5 15 parts of SP1 used in Example 1 was MFR
Of 5.1 g / 10 min (load 10 kg, 200 ° C.) was mixed with 85 parts of polymethylmethacrylate during melt molding to obtain a plate having a thickness of 1 mm. The MR of the obtained plate is
It was 3.8%.
【００２７】[0027]
【比較例１〜５】実施例１〜５で用いたナイロン６、ナ
イロン６６、ポリプロピレン、ポリスチレン及びポリメ
タクリル酸メチルのみを成形し、ＭＲを測定した。得ら
れた成形品のＭＲを表１に示す。Comparative Examples 1 to 5 Only the nylon 6, nylon 66, polypropylene, polystyrene and polymethylmethacrylate used in Examples 1 to 5 were molded and the MR was measured. Table 1 shows the MR of the obtained molded product.
【００２８】[0028]
【比較例６】ヘキサメチレンジアミン４１部、アジピン
酸５２部、ポリエチレングリコール１０００を３．６
部、トリエチレングリコール５．８部、５−ナトリウム
スルホイソフタル酸１１．３部を重合機に仕込み、２９
０℃のソルトバスに入れ、内圧が１７．５ｋｇ／ｃｍ2
に達してから２時間保った。その後、徐々に圧力を下げ
て、常圧で３０分保ってから払いだし、ηｒが２．２０
の共重合ナイロン６６得た。このポリマーを実施例１と
同様に紡糸した。得られた繊維のＭＲは５．９％であ
り、ブロック共重合であり、添加量が同一である実施例
３に比較し、０．８％ＭＲが低下していた。COMPARATIVE EXAMPLE 6 41 parts of hexamethylenediamine, 52 parts of adipic acid and 3.6 parts of polyethylene glycol 1000 were used.
Part, 5.8 parts of triethylene glycol, 11.3 parts of 5-sodium sulfoisophthalic acid were charged to a polymerization machine, and 29
Put it in a salt bath at 0 ℃ and the internal pressure is 17.5kg / cm 2.
I kept it for 2 hours. After that, the pressure was gradually reduced and kept at normal pressure for 30 minutes before being discharged, and ηr was 2.20.
A copolymer of nylon 66 was obtained. This polymer was spun as in Example 1. The MR of the obtained fiber was 5.9%, which was block copolymerization, and was 0.8% lower than that of Example 3 in which the addition amount was the same.
【００２９】[0029]
【比較例７】平均分子量１０００のポリエチレングリコ
ール７８８部、３，５−ビス（ヒドロキシルエトキシ）
スルホイソフタレートナトリウム塩の３５％エチレング
リコール溶液（但し、ヒドロキシエトキシ基７０％、カ
ルボキシメトキシ基３０％の反応混合物）７５６部、酢
酸リチウム２水塩０．８部、テトライソプロピルチタネ
ート１．２部を重合機に仕込み、実施例１と同様に反応
させ淡黄色で粘性のある縮合体（以下ＳＰ２と略す）を
得た。得られたＳＰ２は、１２０℃で溶融した。また、
ＳＰ２のＭＲは５％であり、ＳＰ１の約４０％であっ
た。Comparative Example 7 Polyethylene glycol 788 parts having an average molecular weight of 1000, 3,5-bis (hydroxylethoxy)
35% ethylene glycol solution of sulfoisophthalate sodium salt (however, reaction mixture of 70% hydroxyethoxy group and 30% carboxymethoxy group) 756 parts, 0.8 part lithium acetate dihydrate, 1.2 parts tetraisopropyl titanate The mixture was charged into a polymerization machine and reacted in the same manner as in Example 1 to obtain a light yellow viscous condensate (hereinafter abbreviated as SP2). The obtained SP2 was melted at 120 ° C. Also,
The MR of SP2 was 5% and about 40% of SP1.
【００３０】[0030]
【比較例８】分子量１５０のトリエチレングリコール９
７部、平均分子量１０００のポリエチレングリコール６
１部、３，５−ビス（ヒドロキシルエトキシ）スルホイ
ソフタレートナトリウム塩の３５％エチレングリコール
溶液（但し、ヒドロキシエトキシ基７０％、カルボキシ
メトキシ基３０％の反応混合物）７５６部、酢酸リチウ
ム２水塩０．８部、テトライソプロピルチタネート１．
２部を重合機に仕込み、実施例１と同様に反応させ、濁
りのある淡黄色で粘性のある縮合体（以下ＳＰ３と略
す）を得た。得られたＳＰ３は、エチレングリコールの
含有量が２５％であり、溶融試験を行ったところ不融物
が見られた。Comparative Example 8 Triethylene glycol 9 having a molecular weight of 150
7 parts, polyethylene glycol 6 with an average molecular weight of 1000
1 part, 35% ethylene glycol solution of 3,5-bis (hydroxylethoxy) sulfoisophthalate sodium salt (however, reaction mixture of 70% hydroxyethoxy group and 30% carboxymethoxy group) 756 parts, lithium acetate dihydrate 0 .8 parts, tetraisopropyl titanate 1.
Two parts were charged into a polymerization machine and reacted in the same manner as in Example 1 to obtain a cloudy pale yellow viscous condensate (hereinafter abbreviated as SP3). The SP3 thus obtained had an ethylene glycol content of 25%, and an infusible material was found in the melting test.
【００３１】[0031]
【比較例９】分子量１５０のトリエチレングリコール１
０８部、平均分子量４００のポリエチレングリコール２
７部、３，５−ビス（ヒドロキシルエトキシ）スルホイ
ソフタレートナトリウム塩の３５％エチレングリコール
溶液（但し、ヒドロキシエトキシ基７０％、カルボキシ
メトキシ基３０％の反応混合物）７５６部、酢酸リチウ
ム２水塩０．８部、テトライソプロピルチタネート１．
２部を重合機に仕込み、実施例１と同様に反応させ、淡
黄色で粘性のある縮合体（以下ＳＰ４と略す）を得た。
得られたＳＰ４は、１１０℃で溶融した。また、ＳＰ４
のＭＲは１０％であり、ＳＰ１に比較し３％低かった。Comparative Example 9 Triethylene glycol 1 having a molecular weight of 150
08 parts, polyethylene glycol 2 with an average molecular weight of 400
7 parts, 35% ethylene glycol solution of 3,5-bis (hydroxylethoxy) sulfoisophthalate sodium salt (however, reaction mixture of 70% hydroxyethoxy group and 30% carboxymethoxy group) 756 parts, lithium acetate dihydrate 0 .8 parts, tetraisopropyl titanate 1.
Two parts were charged into a polymerization machine and reacted in the same manner as in Example 1 to obtain a light yellow viscous condensate (hereinafter abbreviated as SP4).
The obtained SP4 was melted at 110 ° C. Also, SP4
Had an MR of 10%, which was 3% lower than that of SP1.
【００３２】[0032]
【比較例１０】実施例１で用いたＳＰ１の２部を実施例
２で用いた９８部のナイロン６に溶融成形時に配合し、
１００デニール２４フィラメントの長繊維を得た。得ら
れた長繊維のＭＲは、４．６％であった。Comparative Example 10 2 parts of SP1 used in Example 1 was blended with 98 parts of nylon 6 used in Example 2 during melt molding,
Long fibers of 100 denier 24 filaments were obtained. The MR of the obtained long fiber was 4.6%.
【００３３】[0033]
【比較例１１】実施例１でＳＰ１の配合量を４０％（ス
ルホン酸基で０．８５モル／ｋｇ）にして、溶融紡糸し
たところ、紡糸性が非常に悪く、繊維が採取できなかっ
た。[Comparative Example 11] Melt spinning was carried out using SP1 in Example 1 at a blending amount of 40% (0.85 mol / kg of sulfonic acid group), and the spinnability was very poor, and fibers could not be collected.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】本発明の熱可塑性合成樹脂成形品は、熱
可塑性樹脂の本来の物理特性を損なうことなく、従来の
ものに比較して優れた吸湿性をもつものである。INDUSTRIAL APPLICABILITY The thermoplastic synthetic resin molded article of the present invention has excellent hygroscopicity as compared with the conventional ones without impairing the original physical characteristics of the thermoplastic resin.
Claims (1)
以上のポリオキシアルキレングリコールと（２）式で示
すスルホネート化合物との縮合体を成形品の重量１ｋｇ
当たりスルホン酸基で０．１モル以上０．７モル以下含
有させることを特徴とする熱可塑性合成樹脂成形品。 【化１】 1. A molded product comprising a condensate of two or more kinds of polyoxyalkylene glycols having different average molecular weights represented by the formula (1) and a sulfonate compound represented by the formula (2) having a weight of 1 kg.
A thermoplastic synthetic resin molded article, characterized in that it is contained in an amount of 0.1 mol or more and 0.7 mol or less per sulfonic acid group. [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03255299A JP3086507B2 (en) | 1991-10-02 | 1991-10-02 | Thermoplastic synthetic resin molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03255299A JP3086507B2 (en) | 1991-10-02 | 1991-10-02 | Thermoplastic synthetic resin molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0593054A true JPH0593054A (en) | 1993-04-16 |
| JP3086507B2 JP3086507B2 (en) | 2000-09-11 |
Family
ID=17276848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03255299A Expired - Fee Related JP3086507B2 (en) | 1991-10-02 | 1991-10-02 | Thermoplastic synthetic resin molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3086507B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004095A1 (en) * | 1998-07-17 | 2000-01-27 | Alliedsignal Inc. | Stain-resistant shaped polymer blends made with polyester additives and process for making same |
| WO2012176473A1 (en) | 2011-06-22 | 2012-12-27 | パナソニック株式会社 | Semiconductor substrate having dot markings, and method for producing same |
| US8661231B2 (en) | 2003-05-12 | 2014-02-25 | International Business Machines Corporation | Multi-function instruction that determines whether functions are installed on a system |
| US20190259884A1 (en) * | 2016-10-26 | 2019-08-22 | Kaneka Corporation | Photoelectric conversion element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2587903A1 (en) | 2004-11-17 | 2006-05-26 | Amgen Fremont Inc. | Fully human monoclonal antibodies to il-13 |
-
1991
- 1991-10-02 JP JP03255299A patent/JP3086507B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004095A1 (en) * | 1998-07-17 | 2000-01-27 | Alliedsignal Inc. | Stain-resistant shaped polymer blends made with polyester additives and process for making same |
| US8661231B2 (en) | 2003-05-12 | 2014-02-25 | International Business Machines Corporation | Multi-function instruction that determines whether functions are installed on a system |
| WO2012176473A1 (en) | 2011-06-22 | 2012-12-27 | パナソニック株式会社 | Semiconductor substrate having dot markings, and method for producing same |
| US20190259884A1 (en) * | 2016-10-26 | 2019-08-22 | Kaneka Corporation | Photoelectric conversion element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3086507B2 (en) | 2000-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103025934B (en) | Amorphous heat fusion fiber, fiber structure body, and heat-resistant molded article | |
| US3632666A (en) | Polyether-polyamide block copolymers containing polyamide polyester or polyamide-polyester or polyamidepolyester block copolymeric synthetic resins and ionic compounds | |
| US4150674A (en) | Three-component blends of a polyamide, and a polyester and a lactam terpolymer | |
| US7786215B2 (en) | Thermoplastic polymer, use thereof in polyamide compositions with improved hydrophily and anti-staticity | |
| JP3086507B2 (en) | Thermoplastic synthetic resin molded product | |
| US3040003A (en) | Synthetic polymers | |
| CA2107386A1 (en) | Poly(etheramide) segmented block copolymers | |
| EP0451952A2 (en) | Nylon-6 modified with low molecular weight polyethylene glycol diamines | |
| US5274071A (en) | Wholly aromatic polyamide | |
| TWI222476B (en) | Process for manufacturing yarns, fibres and filaments | |
| CH636079A5 (en) | PROCEDURE FOR OBTAINING DIHESTERED THERMAL AND THEIR USE. | |
| US4168602A (en) | Block copolymer of poly (dioxaarylamide) and polyamide and fibers and fibrous material produced therefrom | |
| JPH0593077A (en) | Polyamide molding having moisture absorption | |
| KR102564978B1 (en) | Novel Polyester fiber for binder | |
| US4148960A (en) | Polyester having improved antistatic properties | |
| JPH02238052A (en) | Meltable (co)polymer composition, its manufacture,and molding compound and fiber obtained from said composition | |
| JPS60163920A (en) | Copolyester for binder fiber | |
| KR100208953B1 (en) | The manufacture method of the polyamide fiber to superior hygroscopicity | |
| US4007250A (en) | Method for producing infusible and insoluble styrene copolymeric fibers | |
| KR930011339B1 (en) | Process for preparation of absorbent polyamide fiber | |
| KR970010722B1 (en) | Process for preparing antistatic polyester fiber | |
| US2628219A (en) | Process for preparing polyamides from dinitrile and ditertiary diolefin | |
| US3438947A (en) | Copoly-beta-amides and process for their manufacture | |
| KR20200023891A (en) | Method of manufacturing copolymerized polyamide having good hygroscopic property and durability | |
| JPH0446926A (en) | Polyesteramide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20000627 |
|
| LAPS | Cancellation because of no payment of annual fees |