JPH1129684A - PVA / PU blend and method for producing the same - Google Patents
PVA / PU blend and method for producing the sameInfo
- Publication number
- JPH1129684A JPH1129684A JP21693397A JP21693397A JPH1129684A JP H1129684 A JPH1129684 A JP H1129684A JP 21693397 A JP21693397 A JP 21693397A JP 21693397 A JP21693397 A JP 21693397A JP H1129684 A JPH1129684 A JP H1129684A
- Authority
- JP
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- Prior art keywords
- pva
- blend
- producing
- mixture
- same
- 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.)
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- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
(57)【要約】
【目的】 ポリビニルアルコール（ＰＶＡ）とポリウレ
タン（ＰＵ）を両者の共通溶媒に溶解させた後、貧溶媒
に注入して得たＰＶＡとＰＵのブレンドを熱成形して得
られるＰＶＡ／ＰＵのブレンド物の製造法。
【構成】 ＰＶＡとＰＵの混合物をジメチルスルホキシ
ドのような共通溶媒に溶解した溶液をメタノールのよう
な貧溶媒中に注入し得られるブレンド物の１００〜１８
０℃の熱成形法。(57) [Abstract] [Purpose] A blend of PVA and PU obtained by dissolving polyvinyl alcohol (PVA) and polyurethane (PU) in a common solvent for both and then pouring the mixture into a poor solvent is obtained. A method for producing a PVA / PU blend. A mixture obtained by dissolving a mixture of PVA and PU in a common solvent such as dimethyl sulfoxide is poured into a poor solvent such as methanol, and the resulting blend is 100 to 18%.
Thermoforming method at 0 ° C.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、親水性高分子であるポ
リビニルアルコール（ＰＶＡ）と疎水性高分子であるポ
リウレタン（ＰＵ）が分子オーダーで均一に相溶したブ
レンド物とその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blend in which polyvinyl alcohol (PVA), which is a hydrophilic polymer, and polyurethane (PU), which is a hydrophobic polymer, are uniformly compatible in molecular order, and a method for producing the same.
【０００２】近年、合成高分子材料が繊維、プラスチッ
クス、フィルム、あるいはゴム等の形状でさまざまな構
造部材として工業用や医療用として使用されるにつれ、
高機能性材料に関する関心が高まっている。この高機能
性材料を開発する方法として、互いに相反する特性を有
する高分子同士のポリマーブレンド法が古くから用いら
れている。[0002] In recent years, as synthetic polymer materials have been used in various forms such as fibers, plastics, films, and rubbers as various structural members for industrial and medical uses,
There is increasing interest in high-performance materials. As a method for developing this highly functional material, a polymer blend method of polymers having mutually contradictory characteristics has been used for a long time.
【０００３】ＰＶＡは代表的な水溶性高分子であり機械
的性質に優れ、タンパタ質や細胞の付着性が低く生体内
で分解も劣化も起こらない安全性に優れる等の特徴を有
するが、反面、結晶融点が高く、また、その融点以上で
は炭化と分解が起こるので熱可塑性がなく、成形性に劣
ることが知られている。[0003] PVA is a typical water-soluble polymer, has excellent mechanical properties, has low adhesion to proteins and cells, and has excellent features such as excellent safety without decomposition or deterioration in vivo. It is known that the crystalline melting point is high, and if the melting point is higher than the melting point, carbonization and decomposition occur, resulting in no thermoplasticity and poor moldability.
【０００４】一方、ＰＵは機械的性質に優れる熱可塑性
の疎水性高分子であるがタンパク質や細胞の付着性が高
く、また、生体内で分解や劣化が起こる等、安全性に問
題があるとされている。[0004] On the other hand, PU is a thermoplastic hydrophobic polymer having excellent mechanical properties, but has a high degree of adhesion to proteins and cells, and has problems in safety such as degradation and degradation in vivo. Have been.
【０００５】そこで本発明では、ＰＶＡとＰＵの両者の
欠点と問題点を改良すると同時に、両者の優れた性質を
有する新しい機能性材料を開発することを目的とした。Accordingly, an object of the present invention is to improve the disadvantages and problems of both PVA and PU, and at the same time, to develop a new functional material having excellent properties of both.
【０００６】[0006]
【従来の技術】米国特許第４４６４４３８号（１９８４
年）は、酸素バリアーと耐グリース特性に優れた溶融押
し出しフィルムの製造のため、ＰＶＡとエチレン−ビニ
ルアルコール共重合体やポリアミドまたはＰＵとのブレ
ンドに関して開示している。2. Description of the Related Art U.S. Pat. No. 4,446,438 (1984).
Discloses a blend of PVA with an ethylene-vinyl alcohol copolymer or polyamide or PU for the production of a melt-extruded film having excellent oxygen barrier and grease resistance properties.
【０００７】また、米国特許第４６１１０１９号（１９
８６年）は、酸素バリアー特性の改善のため、溶融押し
出し可能なＰＶＡを可塑化するポリアミドまたはポリエ
ステルのブレンドに関して開示している。Further, US Pat. No. 4,611,019 (19)
1986) discloses polyamide or polyester blends that plasticize melt extrudable PVA for improved oxygen barrier properties.
【０００８】更に、日本特開平４−２２６５５７号に
は、熱可塑性ＰＵ含有押し出し成形可能なＰＶＡ組成物
について開示している。Further, JP-A-4-226557 discloses an extrudable PVA composition containing thermoplastic PU.
【０００９】以上の公知の方法では、いずれもＰＶＡを
押し出し成形可能にするため、グリセリンやエチレング
リコール等の可塑剤とポリアミド、ポリエステル、エチ
レン−ビニルアルコール共重合体、あるいはＰＵ等の熱
可塑性ポリマーをブレンドしている。In any of the above known methods, in order to make PVA extrudable, a plasticizer such as glycerin or ethylene glycol and a thermoplastic polymer such as polyamide, polyester, ethylene-vinyl alcohol copolymer or PU are used. Blend.
【００１０】しかし、これらの方法ではＰＶＡが高温下
でも完全に溶解しておらず、半溶融状態にあるため、ブ
レンド物は完全に相溶状態でなく、混和不十分でゲル部
分が残存する欠点のあることが指摘されている。However, in these methods, the PVA is not completely dissolved even at a high temperature and is in a semi-molten state. Therefore, the blend is not completely compatible, and the mixture is insufficiently mixed. It is pointed out that there is.
【００１１】ここで、部分ゲルを減少させるには機械的
エネルギーと熱エネルギーを同時に加えて撹拌混合する
ことと、また一方では、熱分解をさけるために両エネル
ギーを速やかに除去することが必要となり、困難の一因
をなしている。Here, in order to reduce the partial gel, it is necessary to add mechanical energy and thermal energy at the same time and to carry out stirring and mixing. On the other hand, it is necessary to remove both energies promptly in order to avoid thermal decomposition. Play a part in the difficulties.
【００１２】[0012]
【発明が解決しようとする問題点】本発明者らは、水と
有機溶媒混合系からＰＶＡの低温結晶化（日本特許第１
９７０３６０）に関する一連の研究において、高分子量
ＰＶＡの延伸性の改善における共晶成分の一つとして、
ＰＵとＰＶＡのブレンドを検討する過程でＰＶＡとＰＵ
の共通溶媒、例えばジメチルスルホキシド（ＤＭＳＯ）
等の有機溶媒に種々の割合で溶解したところ、その割合
に関係なくブレンド溶液は極めて安定で、長時間経過後
でも溶液状態でも相分離が起こらず、また、それら均一
ブレンド乾燥物が良好な熱成形加工性を示すことを見い
だした。DISCLOSURE OF THE INVENTION The present inventors have studied the low temperature crystallization of PVA from a mixture of water and an organic solvent (Japanese Patent No.
970360), as one of the eutectic components in improving the stretchability of high molecular weight PVA,
In the process of studying the blend of PU and PVA, PVA and PU
Common solvents such as dimethyl sulfoxide (DMSO)
When dissolved in organic solvents at various ratios, the blend solution is extremely stable irrespective of the ratio, phase separation does not occur even after a long period of time or even in a solution state, and the uniform blend dried product has good heat It has been found that it exhibits moldability.
【００１３】本発明は、有機溶媒を使用するという不利
はあるが、形成される材料の均質性において優れてお
り、物性の安定化の効果は極めて甚大である。Although the present invention has the disadvantage of using an organic solvent, it is excellent in the homogeneity of the formed material, and the effect of stabilizing the physical properties is extremely large.
【００１４】[0014]
【発明の効果】本発明により得られるブレンド物の応用
上の特徴は、ＰＶＡの親水性を保持すると同時に、ＰＵ
の柔軟性と耐水性を兼ね備えた独特な物性を持ち、しか
も、押し出しや射出成形等の熱成形可能なことから、医
療用のチューブやカテーテル、ＡＶシャント、人工血管
基材、更に、スポーツ用のマウスガード、伸縮性の衣料
用材料、繊維、フィルム、および屈曲性チューブ等に適
している。The application of the blend obtained according to the present invention is characterized in that while maintaining the hydrophilicity of PVA,
It has unique physical properties that combine flexibility and water resistance, and is capable of thermoforming such as extrusion and injection molding, so it can be used for medical tubing, catheters, AV shunts, artificial vascular bases, and sports. Suitable for mouth guards, stretchable clothing materials, fibers, films, flexible tubes and the like.
【実施例】以下に実施例を挙げて本発明を詳細に説明す
る。The present invention will be described in detail below with reference to examples.
【００１５】[0015]
【実施例 １】 ポリビニルアルコール（ＰＶＡ）重合度５０００：７００ｇ ポリウレタン（ＰＵ）Ｐｅｌｌｅｔｈａｎｅ：３００ｇ ジメチルスルホキシド（ＤＭＳＯ）：９０００ｇ これらを撹拌下に加熱溶解する。次いで沈殿剤のメタメ
ール中に室温で注入して再沈殿して、なるべく小塊とな
るように切断をして、脱ＤＭＳＯをする。メタノールを
乾燥除去して粗粒、ＰＶＡ−ＰＵブレンド物を得る。得
られたＰＶＡ−ＰＵは、 熱加圧、圧縮成形１４０℃、２００ｋｇ／ｃｍ２する
とき、透明なシートが得られた。このシートは、引張り
強度２０ＭＰａ／ｃｍ２であった。 注射筒型で射出成形すると透明な注射筒が得られた。 ノズル径５ｍｍより押し出し成形すると、内径４．５
ｍｍ外径６．２ｍｍの屈曲性チューブを得た。Example 1 Polyvinyl alcohol (PVA) polymerization degree 5000: 700 g Polyurethane (PU) Pelletane: 300 g Dimethyl sulfoxide (DMSO): 9000 g These are heated and dissolved under stirring. Next, the solution is poured into metamer as a precipitant at room temperature to reprecipitate, cut into small lumps as much as possible, and subjected to DMSO removal. The methanol is dried off to give a coarse, PVA-PU blend. When the obtained PVA-PU was subjected to hot pressing, compression molding at 140 ° C., and 200 kg / cm 2 , a transparent sheet was obtained. This sheet had a tensile strength of 20 MPa / cm 2 . Injection molding with a syringe barrel gave a clear syringe. When extruded from a nozzle diameter of 5 mm, the inner diameter is 4.5.
A flexible tube having an outer diameter of 6.2 mm was obtained.
【００１６】[0016]
【実施例 ２】 ポリビニルアルコール（ＰＶＡ）重合度１２００：７００ｇ ポリウレタン（ＰＵ）Ｐｅｌｌｅｔｈａｎｅ：３００ｇ ジメチルホルムアマイド（ＤＭＦ）：９０００ｇ これらを撹拌下に加熱溶解する。実験１と同様に粗粒Ｐ
ＶＡ−ＰＵを得る。 １４０℃、２００ｋｇ／ｃｍ２熱加圧、圧縮すると、
透明なシートが得られた。このシートは、引張り強度１
７ＭＰａ／ｃｍ２であった。 注射筒型で射出成形すると透明な注射筒が得られた。Example 2 Polyvinyl alcohol (PVA) polymerization degree 1200: 700 g Polyurethane (PU) Pelletane: 300 g Dimethylformamide (DMF): 9000 g These are heated and dissolved under stirring. Coarse grain P as in Experiment 1
Obtain VA-PU. 140 ℃, 200kg / cm 2 NetsuKa圧, compressing,
A transparent sheet was obtained. This sheet has a tensile strength of 1
It was 7 MPa / cm 2 . Injection molding with a syringe barrel gave a clear syringe.
【００１７】本法の実施において活用される溶解、再沈
の技術は従来より行われている方法が使用でき、例えば
湿式方法による紡糸とそれのペレット化を用いることが
できる。The technique of dissolution and reprecipitation utilized in the practice of the present method may be a conventionally used method, for example, spinning by a wet method and pelletization thereof.
Claims (2)
ウレタン（ＰＵ）が分子オーダーで均一に混合されたブ
レンド物1. A blend in which polyvinyl alcohol (PVA) and polyurethane (PU) are uniformly mixed in a molecular order.
せた後、その貧溶媒に注入してＰＶＡとＰＵのブレンド
物を得た後、次いで乾燥し高温（１００〜１８０℃）に
て熱成形（押し出し成形、射出成形等）することにより
得られるＰＶＡ／ＰＵブレンド物の製造法2. PVA and PU are dissolved in a common solvent of both, and then poured into the poor solvent to obtain a blend of PVA and PU, then dried and heated at a high temperature (100 to 180 ° C.). Method for producing PVA / PU blend obtained by molding (extrusion molding, injection molding, etc.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21693397A JP3814769B2 (en) | 1997-07-07 | 1997-07-07 | PVA / PU blend and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21693397A JP3814769B2 (en) | 1997-07-07 | 1997-07-07 | PVA / PU blend and production method thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH1129684A true JPH1129684A (en) | 1999-02-02 |
| JPH1129684A5 JPH1129684A5 (en) | 2005-05-12 |
| JP3814769B2 JP3814769B2 (en) | 2006-08-30 |
Family
ID=16696209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21693397A Expired - Fee Related JP3814769B2 (en) | 1997-07-07 | 1997-07-07 | PVA / PU blend and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3814769B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937136A (en) * | 2014-04-22 | 2014-07-23 | 苏州羽帆新材料科技有限公司 | Environment-friendly plastic for athletic tracks and preparation method thereof |
-
1997
- 1997-07-07 JP JP21693397A patent/JP3814769B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937136A (en) * | 2014-04-22 | 2014-07-23 | 苏州羽帆新材料科技有限公司 | Environment-friendly plastic for athletic tracks and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3814769B2 (en) | 2006-08-30 |
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