JP3481880B2 - Method for producing layered silicate-containing polyvinyl alcohol molded article - Google Patents
Method for producing layered silicate-containing polyvinyl alcohol molded articleInfo
- Publication number
- JP3481880B2 JP3481880B2 JP06126499A JP6126499A JP3481880B2 JP 3481880 B2 JP3481880 B2 JP 3481880B2 JP 06126499 A JP06126499 A JP 06126499A JP 6126499 A JP6126499 A JP 6126499A JP 3481880 B2 JP3481880 B2 JP 3481880B2
- Authority
- JP
- Japan
- Prior art keywords
- layered silicate
- polyvinyl alcohol
- pva
- molded article
- containing polyvinyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、層状ケイ酸塩を
含有するポリビニルアルコールの成形体の製造方法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a molded product of polyvinyl alcohol containing a layered silicate.
【０００２】[0002]
【従来の技術】生分解性樹脂として知られるポリビニル
アルコールに層状ケイ酸塩を含有させることにより、機
械的特性に優れたポリビニルアルコール系繊維を得るこ
とが特開平１０−５３９１８号公報等に記載されてい
る。このポリビニルアルコール系繊維は、水やジメチル
スルホキシド等の有機溶媒等の溶媒にポリビニルアルコ
ールを溶解させ、かつ、層状ケイ酸塩を懸濁分散させて
紡糸原液を作製し、これを、紡糸口金を用いて、常温の
無機塩類飽和水溶液からなる凝固液中へ送り出し、ゲル
化させることにより紡糸される。2. Description of the Related Art It is described in JP-A-10-53918 that a polyvinyl alcohol fiber having excellent mechanical properties can be obtained by incorporating a layered silicate into polyvinyl alcohol known as a biodegradable resin. ing. This polyvinyl alcohol fiber is prepared by dissolving polyvinyl alcohol in a solvent such as water or an organic solvent such as dimethylsulfoxide, and suspending and dispersing the layered silicate to prepare a spinning dope, which is prepared using a spinneret. Then, it is sent into a coagulation liquid consisting of a saturated aqueous solution of an inorganic salt at room temperature and gelled, thereby spinning.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、紡糸原
液の溶媒として水を用いた場合、上記のように凝固液と
して無機塩類飽和水溶液を用いる必要がある。このた
め、得られた糸から無機塩類を除去するための洗浄工程
が必要となる。さらに、凝固液として無機塩類を含まな
いものを使用する場合は、凝固液の温度を−５〜−２０
℃程度まで冷却する必要がある。However, when water is used as the solvent of the spinning dope, it is necessary to use a saturated aqueous solution of inorganic salts as the coagulating liquid as described above. Therefore, a washing step for removing inorganic salts from the obtained yarn is necessary. Furthermore, when using a coagulation liquid that does not contain inorganic salts, the coagulation liquid temperature is -5 to -20.
It is necessary to cool to about ℃.
【０００４】また、紡糸原液の溶媒としてジメチルスル
ホキシドのみを用いた場合、ポリビニルアルコールは溶
解するものの、層状ケイ酸塩の分散性が悪くなり、得ら
れる糸やフィルム等の強度が低下することが考えられ
る。When only dimethylsulfoxide is used as the solvent for the spinning dope, the polyvinyl alcohol dissolves but the dispersibility of the layered silicate deteriorates, and the strength of the obtained yarn, film, etc. decreases. To be
【０００５】そこで、この発明の課題は、製造法が容易
で、かつ、層状ケイ酸塩が会合せずに、微粉砕された状
態で均質に分散されたポリビニルアルコール成形体を得
ることである。Therefore, an object of the present invention is to obtain a polyvinyl alcohol molded product which is easy to manufacture and in which the layered silicate is uniformly dispersed in a finely pulverized state without meeting.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
め、この発明は、ポリビニルアルコールをジメチルスル
ホキシドに溶解させてポリビニルアルコール溶液を作製
し、また、層状ケイ酸塩を水に分散させて層状ケイ酸塩
分散液を作製し、上記ポリビニルアルコール溶液と層状
ケイ酸塩分散液を混合した後、０〜２５℃の凝固浴中へ
押出成形する方法を採用したのである。In order to solve the above-mentioned problems, the present invention is to dissolve polyvinyl alcohol in dimethylsulfoxide to prepare a polyvinyl alcohol solution, and to disperse a layered silicate in water to form a layered layer. A method of preparing a silicate dispersion, mixing the polyvinyl alcohol solution and the layered silicate dispersion, and then extrusion molding into a coagulation bath at 0 to 25 ° C. was adopted.
【０００７】また、上記層状ケイ酸塩を、モンモリロナ
イトとすることができる。さらに、上記の押出成形を、
紡糸口金による紡糸とすることができる。The layered silicate may be montmorillonite. Furthermore, the above extrusion molding,
The spinning can be performed by a spinneret.
【０００８】ジメチルスルホキシドを溶媒とするポリビ
ニルアルコール溶液と水に分散させた層状ケイ酸塩分散
液との混合液を用いるので、室温近くの温度で水や有機
溶媒を凝固浴用の溶媒として使用してポリビニルアルコ
ールを凝固させることができ、また、層状ケイ酸塩の分
散性が向上するので、得られる成形体の強度をあげるこ
とができる。Since a mixed solution of a polyvinyl alcohol solution using dimethyl sulfoxide as a solvent and a layered silicate dispersion liquid dispersed in water is used, water or an organic solvent is used as a solvent for the coagulation bath at a temperature near room temperature. Since polyvinyl alcohol can be solidified and the dispersibility of the layered silicate is improved, the strength of the obtained molded product can be increased.
【０００９】[0009]
【発明の実施の形態】以下、この発明の実施形態を説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
【００１０】この発明は、層状ケイ酸塩を含有するポリ
ビニルアルコール（以下、「ＰＶＡ」と略する。）の成
形体を製造する方法についてである。The present invention relates to a method for producing a molded product of polyvinyl alcohol (hereinafter abbreviated as "PVA") containing a layered silicate.
【００１１】まず、上記ＰＶＡをジメチルスルホキシド
（以下、「ＤＭＳＯ」と称する。）に溶解させて、ポリ
ビニルアルコール溶液（ＰＶＡ溶液）を作製する。ＰＶ
Ａの平均重合度は、特に限定されないが、３００〜５０
００程度が好ましく、１０００〜３０００程度がより好
ましい。ＰＶＡのＤＭＳＯへの溶解量は、特に限定され
ないが、５〜５０重量％が好ましく、１０〜２０重量％
がより好ましい。First, the PVA is dissolved in dimethyl sulfoxide (hereinafter referred to as "DMSO") to prepare a polyvinyl alcohol solution (PVA solution). PV
The average degree of polymerization of A is not particularly limited, but is 300 to 50.
About 00 is preferable, and about 1000 to 3000 is more preferable. The amount of PVA dissolved in DMSO is not particularly limited, but is preferably 5 to 50% by weight, and 10 to 20% by weight.
Is more preferable.
【００１２】また、層状ケイ酸塩を水中で攪拌して層状
ケイ酸塩分散液を作製する。The layered silicate is stirred in water to prepare a layered silicate dispersion.
【００１３】上記層状ケイ酸塩とは、ケイ酸塩を含有す
る層状粘土鉱物をいう。この例としては、マイカ等の膨
潤性雲母、モンモリロナイト、ハイデライト、ヘクトラ
イト、サポナイト、スチブンサイト等のスメクタイト鉱
物、バーミキュライト、カオリナイト、ハロイサイト、
マーガライト、イモゴライト、クリントナイト等があげ
られる。これらは、各層毎に剥離しやすい鉱物である。The above-mentioned layered silicate means a layered clay mineral containing silicate. Examples of this include swelling mica such as mica, montmorillonite, hydelite, hectorite, saponite, smectite minerals such as stevensite, vermiculite, kaolinite, halloysite,
Examples include margarite, imogolite, and clint night. These are minerals that are easily separated from each other.
【００１４】使用される上記層状ケイ酸塩の大きさは、
特に限定されないが、一辺０．１〜１０μｍ、厚み０．
０１〜０．５μｍが好ましく、一辺０．５〜３μｍ、厚
み０．０５〜０．１μｍがより好ましい。The size of the layered silicate used is
Although not particularly limited, one side is 0.1 to 10 μm, and the thickness is 0.
The thickness is preferably 01 to 0.5 μm, more preferably 0.5 to 3 μm on a side, and more preferably 0.05 to 0.1 μm.
【００１５】上記層状ケイ酸塩分散液中の層状ケイ酸塩
の量は、特に限定されないが、水１００重量部に対し５
〜１５０重量部が好ましい。The amount of the layered silicate in the layered silicate dispersion is not particularly limited, but is 5 per 100 parts by weight of water.
˜150 parts by weight is preferred.
【００１６】次に、上記ＰＶＡ溶液と層状ケイ酸塩分散
液を混合して混合液を作製する。この混合割合は、特に
限定されないが、ＰＶＡ溶液／層状ケイ酸塩分散液が３
／７〜７／３が好ましい。Next, the PVA solution and the layered silicate dispersion liquid are mixed to prepare a mixed liquid. The mixing ratio is not particularly limited, but the PVA solution / layered silicate dispersion is 3%.
/ 7 to 7/3 is preferable.
【００１７】上記混合液は、室温以下、すなわち、２５
℃以下でゲル化するのが好ましい。従って、冷却装置を
使用しない０〜２５℃の範囲でゲル化が可能となる。The above-mentioned mixed solution is at room temperature or below, that is, 25
It is preferably gelled at a temperature of not more than ° C. Therefore, gelation is possible in the range of 0 to 25 ° C. without using a cooling device.
【００１８】そして、上記混合液を通常の押出成形装置
で押出成形し、ＰＶＡ成形体が得られる。口金としてＴ
ダイ等を使用すれば、フィルム状物やシート状物が得ら
れ、また、口金として紡糸口金を使用すると、紡糸され
て糸状物（フィラメント）が得られる。Then, the above-mentioned mixed liquid is extrusion-molded by a usual extrusion-molding apparatus to obtain a PVA molded body. T as a base
If a die or the like is used, a film-like material or a sheet-like material is obtained, and if a spinneret is used as the spinneret, it is spun into a filamentous material.
【００１９】このとき、上記口金は、上記温度条件を満
たす凝固液を入れた凝固浴中に設置される。上記凝固液
としては、水、ＤＭＳＯ、メタノール又はこれらの混合
物等のＰＶＡ易溶性溶媒、エチレングリコールやヘキサ
ン等のＰＶＡ難溶性溶媒、硫酸ナトリウム飽和水溶液、
炭酸ナトリウム飽和水溶液等の無機塩類飽和水溶液等も
使用することができる。これらの中でも、口金より押し
出された上記ＰＶＡ成形体の前駆体に浸透してこの前駆
体をすばやく冷却することにより、早期にゲル化を生じ
させることのできるＰＶＡ易溶性溶媒を用いるのが好ま
しい。At this time, the die is placed in a coagulation bath containing a coagulation liquid satisfying the temperature conditions. Examples of the coagulation liquid include water, DMSO, methanol or a mixture of PVA such as a mixture thereof, a PVA hardly soluble solvent such as ethylene glycol or hexane, a saturated aqueous solution of sodium sulfate,
A saturated aqueous solution of inorganic salts such as a saturated aqueous solution of sodium carbonate can also be used. Among these, it is preferable to use a PVA easily soluble solvent capable of causing gelation at an early stage by penetrating into the precursor of the PVA molded body extruded from the die and rapidly cooling the precursor.
【００２０】得られたＰＶＡ成形体は、続いて、ローラ
延伸、湿熱延伸、乾燥等の各種工程を行うことができ
る。The obtained PVA molded product can be subsequently subjected to various processes such as roller stretching, wet heat stretching and drying.
【００２１】得られたフィルム状物、シート状物、糸状
物等のＰＶＡ成形体は、そのままで、又は、アセタール
化等を行って、農業用資材、包装用資材、各種繊維等、
任意の用途に使用できる。The obtained PVA molded product such as a film-shaped material, a sheet-shaped material, a thread-shaped material or the like is used as it is or subjected to acetalization or the like to produce agricultural materials, packaging materials, various fibers, etc.
It can be used for any purpose.
【００２２】また、上記のＰＶＡ成形体は、層状ケイ酸
塩が分散されているので、機械的強度が向上する。さら
に、アセタール化を行わないＰＶＡ成形体を環境中で放
置すると、環境中の水分や微生物等により加水分解や生
分解が生じる。このとき、層状ケイ酸塩が層状構造を有
していることから、この層状ケイ酸塩の部分で成形体の
剥離が生じやすい。このため、ＰＶＡ成形体の表面で分
解が始まると、層状ケイ酸塩の部分で剥離が生じ、さら
にその内部のＰＶＡ成形体が分解されるので、分解速度
を著しく速めることができる。Further, in the above PVA molded product, since the layered silicate is dispersed, the mechanical strength is improved. Furthermore, if the PVA molded product that is not acetalized is left in the environment, hydrolysis or biodegradation occurs due to water and microorganisms in the environment. At this time, since the layered silicate has a layered structure, peeling of the molded body is likely to occur at the layered silicate portion. For this reason, when decomposition starts on the surface of the PVA molded product, peeling occurs at the portion of the layered silicate and the PVA molded product inside is decomposed, so that the decomposition rate can be remarkably increased.
【００２３】[0023]
【実施例】（実施例１）ＤＭＳＯ１００重量部を８０℃
に加温し、これにＰＶＡ（（株）クラレ社製）１５重量
部を加えて攪拌し、溶解させた。また、水１００重量部
に、微粉砕したモンモリロナイト（Ｋｕｎｉｍｉｎｅ
Ｉｎｄ． Ｃｏ．社製：ＫｕｎｉｐｉａＦ）１５重量部
を加えて攪拌し、ほぼ均一に分散させた。そして、上記
のＰＶＡ溶液及びモンモリロナイト分散液を別のビーカ
ーに一緒に入れて攪拌し、混合した。Example 1 Example 1 100 parts by weight of DMSO at 80 ° C.
The mixture was heated to, and 15 parts by weight of PVA (manufactured by Kuraray Co., Ltd.) was added and stirred to dissolve. Further, 100 parts by weight of water was added to finely pulverized montmorillonite (Kunimine).
Ind. Co. 15 parts by weight (Kunipia F) (manufactured by the company) was added and stirred to disperse almost uniformly. Then, the above PVA solution and montmorillonite dispersion were put together in another beaker, stirred and mixed.
【００２４】得られた混合液を、口金としてＴダイを用
いた押出成形機に入れて押出成形した。上記Ｔダイは、
温度２０℃に調整したＤＭＳＯを凝固液とする凝固浴中
に入れられ、凝固浴中に直接、押出成形してシート状物
を得た。The obtained mixed liquid was put into an extrusion molding machine using a T die as a die and extrusion molded. The T die is
It was placed in a coagulation bath having DMSO adjusted to a temperature of 20 ° C. as a coagulation liquid, and extrusion-molded directly in the coagulation bath to obtain a sheet-like material.
【００２５】（比較例１）実施例１のＰＶＡ溶液のみを
用いて実施例１に記載の方法で押出成形してシート状物
を得た。(Comparative Example 1) A sheet-like material was obtained by extrusion molding using the PVA solution of Example 1 by the method described in Example 1.
【００２６】〔引張試験〕実施例１及び比較例１のシー
ト状物の引っ張り試験を、テンシロン型引張試験機（東
洋ボールドウィン社製；ＵＴＭ−II−２０）を用い、２
０℃の雰囲気下で測定した。その結果、比較例１のシー
ト状物に対して、実施例１のシート状物の引張強度は、
１．３倍向上していた。[Tensile Test] A tensile test of the sheet-like materials of Example 1 and Comparative Example 1 was carried out using a tensilon tensile tester (Toyo Baldwin Co .; UTM-II-20).
The measurement was performed in an atmosphere of 0 ° C. As a result, the tensile strength of the sheet-shaped article of Example 1 was higher than that of the sheet-shaped article of Comparative Example 1.
It was 1.3 times better.
【００２７】[0027]
【発明の効果】この発明によれば、層状ケイ酸塩を分散
させたＰＶＡ成形体を室温近くで容易に製造することが
できる。According to the present invention, a PVA molded body in which a layered silicate is dispersed can be easily manufactured near room temperature.
【００２８】また、このＰＶＡ成形体は、層状ケイ酸塩
が均質に分散されるので、機械的強度が向上し、また、
環境下での加水分解時や生分解時、分解速度が早められ
る。Further, in this PVA molded product, since the layered silicate is uniformly dispersed, the mechanical strength is improved, and
The rate of decomposition is accelerated during hydrolysis and biodegradation in the environment.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 5/00 C08J 5/18 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C08J 5/00 C08J 5/18
Claims (3)
キシドに溶解させてポリビニルアルコール溶液を作製
し、また、層状ケイ酸塩を水に分散させて層状ケイ酸塩
分散液を作製し、上記ポリビニルアルコール溶液と層状
ケイ酸塩分散液を混合した後、凝固浴中で成形する層状
ケイ酸塩含有ポリビニルアルコール成形体の製造方法。1. A polyvinyl alcohol solution is prepared by dissolving polyvinyl alcohol in dimethylsulfoxide, and a layered silicate dispersion is prepared by dispersing a layered silicate in water to prepare a layered silicate dispersion. A method for producing a layered silicate-containing polyvinyl alcohol molding, which comprises molding an acid salt dispersion and molding the mixture in a coagulation bath.
である請求項１に記載の層状ケイ酸塩含有ポリビニルア
ルコール成形体の製造方法。2. The method for producing a layered silicate-containing polyvinyl alcohol molded article according to claim 1, wherein the layered silicate is montmorillonite.
である請求項１又は２に記載の層状ケイ酸塩含有ポリビ
ニルアルコール成形体の製造方法。3. The method for producing a layered silicate-containing polyvinyl alcohol molded article according to claim 1, wherein the molding method is spinning with a spinneret.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06126499A JP3481880B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing layered silicate-containing polyvinyl alcohol molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06126499A JP3481880B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing layered silicate-containing polyvinyl alcohol molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000256474A JP2000256474A (en) | 2000-09-19 |
| JP3481880B2 true JP3481880B2 (en) | 2003-12-22 |
Family
ID=13166210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06126499A Expired - Fee Related JP3481880B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing layered silicate-containing polyvinyl alcohol molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3481880B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111051584A (en) * | 2017-09-08 | 2020-04-21 | 株式会社可乐丽 | Polyvinyl alcohol fiber |
| WO2020090649A1 (en) * | 2018-11-01 | 2020-05-07 | 株式会社クラレ | Polyvinyl alcohol fiber |
| CN109853070B (en) * | 2019-02-28 | 2021-06-15 | 陕西师范大学 | Montmorillonite/polyvinyl alcohol composite flame-retardant fiber |
-
1999
- 1999-03-09 JP JP06126499A patent/JP3481880B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000256474A (en) | 2000-09-19 |
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