JPH055045A - Production of polyvinyl acetal-based porous material - Google Patents
Production of polyvinyl acetal-based porous materialInfo
- Publication number
- JPH055045A JPH055045A JP18354091A JP18354091A JPH055045A JP H055045 A JPH055045 A JP H055045A JP 18354091 A JP18354091 A JP 18354091A JP 18354091 A JP18354091 A JP 18354091A JP H055045 A JPH055045 A JP H055045A
- Authority
- JP
- Japan
- Prior art keywords
- cross
- based porous
- water
- starch
- polyvinyl acetal
- 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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Links
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は化粧用パフ材，拭浄材
や、高精度濾材，体液の分離膜，バイオリアクターの担
体等に好適な、均質な連続気孔を有するポリビニールア
セタール系多孔体を、効率よく製造する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a polyvinyl acetal-based porous body having uniform continuous pores, which is suitable for cosmetic puff materials, wiping materials, high-precision filter media, body fluid separation membranes, bioreactor carriers and the like. The present invention relates to a method for efficiently manufacturing
【０００２】[0002]
【従来の技術】近年、多孔体の利用分野は拡大し、例え
ば高精度濾材，体液の分離膜，微生物や酵母の担体等、
従来の一般的な多孔体ではカバーし切れない程微細な気
孔を有する多孔体が要求されている。2. Description of the Related Art In recent years, the fields of use of porous materials have expanded, such as high-precision filter media, separation membranes for body fluids, carriers for microorganisms and yeasts, etc.
There is a demand for a porous body having fine pores that cannot be covered by a conventional general porous body.
【０００３】そう言った中でポリビニールアセタール系
（以下、ＰＶＡｔ系と略記する）多孔体は、極めて微細
かつ均質な気孔を持つ素材として注目を集めており、例
えば、気体中の微粒子や粉塵，液体中の夾雑物を効率よ
く除去する濾材や、バイオリアクター用の担体として用
いられている。またＰＶＡｔ系多孔体は、他の競合素材
たる不織布や濾紙等に見られる繊維屑やバインダーの細
片等の脱落による逆汚染という欠点のない、クリーンな
素材としても評価が高い。Among them, the polyvinyl acetal-based (hereinafter abbreviated as PVAt-based) porous material has been attracting attention as a material having extremely fine and uniform pores. For example, fine particles and dust in gas, It is used as a filter medium for efficiently removing contaminants in liquids and as a carrier for bioreactors. The PVAt-based porous material is also highly evaluated as a clean material that does not have the drawback of reverse contamination due to the loss of fiber scraps and binder particles found in other competitive materials such as nonwoven fabrics and filter papers.
【０００４】従来、ＰＶＡｔ系多孔体はおよそ次のよう
な方法で製造されていた。即ち、ポリビニールアルコー
ル水溶液に気孔形成材としての澱粉，架橋剤としてのア
ルデヒド類及び触媒としての酸類を加えて攪拌混合し、
これを所定の型枠に注型し、加熱してアセタール化反応
させ、得られた反応生成物を型枠より取り出し、水洗し
て気孔形成材及び未反応の架橋剤，触媒を除去して連続
気孔を有するＰＶＡｔ系多孔体とする方法である。Conventionally, PVAt type porous materials have been manufactured by the following method. That is, starch as a pore-forming material, aldehydes as a cross-linking agent, and acids as a catalyst are added to an aqueous polyvinyl alcohol solution, and the mixture is stirred and mixed.
This is cast in a predetermined mold, heated to cause an acetalization reaction, and the resulting reaction product is taken out from the mold and washed with water to remove the pore-forming material, unreacted cross-linking agent and catalyst, and continuously. This is a method of producing a PVAt-based porous body having pores.
【０００５】気孔形成材としては、反応後、水洗により
容易に除去できること等から、澱粉が一般に利用されて
いる。As the pore-forming material, starch is generally used because it can be easily removed by washing with water after the reaction.
【０００６】澱粉は、植物細胞中にデンプン粒として貯
えられており、その粒径は、母体となる植物によって異
なっている。このデンプン粒を乾燥すると、水分を放出
してその粒径は小さくなるが、水中に懸濁するとある程
度膨潤し、これを加熱すると更に膨潤して粒径は最大と
なり（もとの１０倍程度まで膨潤する）、その後破れて
糊化する。この時の温度（６０℃程度）をα化温度，あ
るいは糊化温度と言い、植物の種類によって異なる値を
示す。Starch is stored as starch granules in plant cells, and the particle size thereof varies depending on the mother plant. When the starch granules are dried, they release water to reduce their particle size, but when suspended in water they swell to a certain extent, and when heated, they further swell to the maximum particle size (up to about 10 times the original size). It swells) and then breaks and gelatinizes. The temperature at this time (about 60 ° C.) is referred to as α-gelatinization temperature or gelatinization temperature, and shows different values depending on the type of plant.
【０００７】従来は、このα化直前の、最も膨潤かつ形
態的に最も安定した状態の澱粉粒を気孔形成材として用
いていたため、粒径の最も小さい米澱粉を用いても、Ｐ
ＶＡｔ系多孔体の平均気孔径が４５μｍを下回ることは
なかった。Conventionally, since the starch particles in the most swollen and morphologically most stable state immediately before the gelatinization were used as the pore-forming material, even if the rice starch having the smallest particle size was used, P
The average pore diameter of the VAt-based porous body did not fall below 45 μm.
【０００８】本発明者等はすでにこの問題を解決するた
めに、ポリビニールアルコールと澱粉粒とを混合した混
合液を、澱粉粒をα化させない温度で１時間以上熟成
し、多孔体を得るという方法を提案した（特願平３−１
２８６６３号）。In order to solve this problem, the present inventors have already said that a mixed solution of polyvinyl alcohol and starch granules is aged for 1 hour or more at a temperature at which the starch granules are not gelatinized to obtain a porous body. Proposed a method (Japanese Patent Application No. 3-1
28663).
【０００９】しかしながら、この方法においても次に述
べるが如き問題点があり、完全なものとは言い難かっ
た。However, this method also has the following problems, and it is difficult to say that the method is perfect.
【００１０】即ち、例え同じ植物から抽出された澱粉で
あっても、その産地，生産年度，作柄，経時変化等によ
って、その径が微妙に異なり、また水，温度に対する挙
動もかなり変動するため、製品の気孔率，平均気孔径等
の様な、孔径を重視する濾材や担体の用途において極め
て重要な物性に、多大な影響を与えてしまうのである。That is, even if the starch is extracted from the same plant, its diameter is slightly different depending on its place of origin, production year, crop, change over time, etc., and its behavior with respect to water and temperature varies considerably. This has a great influence on the extremely important physical properties such as the porosity of the product and the average pore size, which are extremely important in the use of the filter medium and the carrier in which the pore size is important.
【００１１】それを解決するためには、澱粉のロットが
変わる度に製造試験を行ない、温度，熟成時間等の製造
条件を都度変更せねばならなかった。In order to solve this, a production test had to be carried out every time the lot of starch changed, and the production conditions such as temperature and aging time had to be changed each time.
【００１２】[0012]
【発明が解決しようとする課題】本発明者等は、上述の
問題点に鑑み、鋭意研究を行ない本発明になるＰＶＡｔ
系多孔体の製造方法を完成するに至ったものであり、そ
の目的とする所は、微細かつ均質な連続気孔を有するポ
リビニールアセタール系多孔体を安定にかつ効率よく製
造する方法を提供するにある。DISCLOSURE OF THE INVENTION In view of the above-mentioned problems, the inventors of the present invention have conducted earnest research, and become PVAt of the present invention.
The present invention is to complete a method for producing a porous body, and an object thereof is to provide a method for stably and efficiently producing a polyvinyl acetal porous body having fine and uniform continuous pores. is there.
【００１３】[0013]
【課題を解決するための手段】上述の目的は、ポリビニ
ールアルコールの水溶液に、架橋剤，触媒，及び気孔形
成材を加えて加温し、架橋反応を行なった後、余剰の架
橋剤，触媒，及び気孔形成材を水洗してポリビニールア
セタール系多孔体を製造する方法において、気孔形成材
として、水酸基に官能基を結合させるか或いは、水酸基
間を多官能基で架橋した変性澱粉を用いることを特徴と
する、ポリビニールアセタール系多孔体の製造方法によ
って達成される。[Means for Solving the Problems] The above-mentioned object is to add a crosslinking agent, a catalyst, and a pore-forming material to an aqueous solution of polyvinyl alcohol, to heat the mixture, and to carry out a crosslinking reaction. , And a method for producing a polyvinyl acetal-based porous body by washing the pore-forming material with water, using a modified starch in which a functional group is bound to a hydroxyl group or a cross-linking group between the hydroxyl groups is a polyfunctional group, as the pore-forming material. And a method for producing a polyvinyl acetal-based porous body.
【００１４】本発明に用いられるポリビニールアルコー
ル（以下ＰＶＡと略記する。）は、完全ケン化または部
分ケン化したもの，あるいはそれらを混合したものであ
って、平均重合度が３００〜３０００のものである。The polyvinyl alcohol (hereinafter abbreviated as PVA) used in the present invention is completely saponified or partially saponified, or a mixture thereof, and has an average degree of polymerization of 300 to 3000. Is.
【００１５】本発明に用いられる架橋剤とはアルデヒド
類のことであって、例えばホルムアルデヒド，アセトア
ルデヒド，ブチルアルデヒド，ノニルアルデヒド，ベン
ゾアルデヒド，アクロレインあるいはグリオキサザール
等を挙げることができる。また、この他に、多価のアル
デヒド類を用いる事もできる。The cross-linking agent used in the present invention is an aldehyde, and examples thereof include formaldehyde, acetaldehyde, butyraldehyde, nonyl aldehyde, benzaldehyde, acrolein and glyoxazal. In addition to this, polyvalent aldehydes can also be used.
【００１６】本発明に用いられる触媒としては、硫酸，
塩酸，リン酸等の無機酸類、しゅう酸，ギ酸，酢酸等の
有機酸類等の他、強酸と弱塩基からなる塩類で、水溶液
中で酸性を呈するもの等を用いることができる。The catalyst used in the present invention is sulfuric acid,
Inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as oxalic acid, formic acid, acetic acid, and the like, as well as salts consisting of a strong acid and a weak base, which are acidic in an aqueous solution can be used.
【００１７】本発明に用いる変性澱粉の原料である澱粉
粒とは、各種植物から抽出精製された粒状構造をした澱
粉であって、例えば米，小麦，トウモロコシ，サツマイ
モ，馬鈴薯，タロイモ，タピオカあるいはバナナ等から
抽出されたものを挙げることができ、必要に応じ粉砕分
級されたものが用いられる。より小さな孔径の多孔体を
得たい場合には、好ましくは小麦又は米から抽出された
澱粉粒が用いられる。Starch granules, which is a raw material of the modified starch used in the present invention, are starches having a granular structure extracted and purified from various plants, and include, for example, rice, wheat, corn, sweet potato, potato, taro, tapioca or banana. And the like, and those pulverized and classified may be used as necessary. When it is desired to obtain a porous body having a smaller pore size, starch granules extracted from wheat or rice are preferably used.
【００１８】本発明に用いられる変性澱粒とは、上述し
たような澱粉粒のグルコースの水酸基に、官能基を結合
させる工程と、該水酸基間を多官能基で架橋する工程
を、適宜組み合わせることによって、反応後の水洗除去
を容易にする適度な膨潤性と、所望の粒径で膨潤を抑え
る為の耐水性を必要に応じて付与した澱粉である。The modified starch used in the present invention is obtained by appropriately combining the step of binding a functional group to the hydroxyl group of glucose of the starch particle as described above and the step of crosslinking the hydroxyl groups with a polyfunctional group. According to the above, the starch has a suitable swelling property that facilitates washing and removal after the reaction, and water resistance for suppressing swelling at a desired particle size, if necessary.
【００１９】官能基としては、ヒドロキシアルキル基，
アルキル基，ベンジル基，等があり、これらはエーテル
結合によって澱粉に結合している。As the functional group, a hydroxyalkyl group,
There are alkyl groups, benzyl groups, etc., which are linked to starch by an ether bond.
【００２０】多官能基としては、グリセリン等の多価ア
ルコール類等が挙げられ、わずかな架橋により、加熱時
の澱粉粒の膨潤を著しく抑えることができる。Examples of the polyfunctional group include polyhydric alcohols such as glycerin and the like, and swelling of starch granules during heating can be significantly suppressed by slight crosslinking.
【００２１】中でも、ヒドロキシルプロピル基による処
理又はグリセリンによる処理を施したもの，あるいはヒ
ドロキシルプロピル基とグリセリンの両方で処理した変
性澱粉が、適度な耐水性及び膨潤性を持つという点で特
に好ましい。Among them, those treated with a hydroxyl propyl group or glycerin, or modified starch treated with both a hydroxyl propyl group and glycerin are particularly preferable in that they have appropriate water resistance and swelling properties.
【００２２】これらの変性デンプンは、水とのなじみは
良いが、その分子鎖中の水酸基がある程度封鎖されてい
る為、膨潤が抑制されている。従って、これを用いるこ
とによって、微小な粒径の気孔を持ったＰＶＡｔ系多孔
体を製造することができる。These modified starches have good compatibility with water, but swelling is suppressed because the hydroxyl groups in their molecular chains are blocked to some extent. Therefore, by using this, it is possible to manufacture a PVAt-based porous body having pores having a minute particle size.
【００２３】また、変性の条件によって、自由に澱粉粒
径を設定できる為、植物の種類，産地，生産年度，作
柄，経時変化に左右されず、気孔率，平均気孔径の一定
したＰＶＡｔ系多孔体を、容易かつ確実に製造すること
ができる。Since the starch particle size can be freely set depending on the denaturing conditions, the PVAt-based porosity having a constant porosity and average pore diameter is not affected by the type of plant, production area, production year, cropping, and change over time. The body can be manufactured easily and reliably.
【００２４】本発明においては、上記変性澱粉のうち、
該変性澱粉の５重量％水溶液を一旦１．５℃／ｍｉｎの
昇温速度で９０℃まで加熱した後放冷し、３０℃になっ
た時点での粘度が１５ｃｐ以上のものが好ましく用いら
れる。粘度が１５ｃｐに満たないもの，即ち架橋度が大
きすぎるものは膨潤し難く、ＰＶＡの架橋反応終了後の
水洗の際、除去が困難である。In the present invention, among the modified starches mentioned above,
A 5 wt% aqueous solution of the modified starch is once heated to 90 ° C. at a temperature rising rate of 1.5 ° C./min and then allowed to cool, and a viscosity of 15 cp or more at 30 ° C. is preferably used. If the viscosity is less than 15 cp, that is, if the degree of crosslinking is too large, it is difficult to swell, and it is difficult to remove it when washing the PVA with water after the completion of the crosslinking reaction.
【００２５】本発明のＰＶＡｔ系多孔体の製造方法は以
下の様にして実施する。The method for producing the PVAt porous material of the present invention is carried out as follows.
【００２６】まず、ＰＶＡを温水に溶解して１０〜２５
重量％程度の水溶液と為し、これに変性澱粉の微粉末を
所定量投入してから十分に攪拌混合し、分散斑のない均
一混合液を調製する。変性澱粉の投入量は、目的とする
多孔体の気孔率、平均気孔径に応じて適宜選定する。First, PVA is dissolved in warm water to obtain 10-25
An aqueous solution of about% by weight is prepared, and a predetermined amount of modified starch fine powder is added thereto, and the mixture is sufficiently stirred and mixed to prepare a uniform mixed solution without dispersion spots. The amount of modified starch added is appropriately selected according to the porosity and average pore diameter of the target porous body.
【００２７】変性澱粉微粉は、あらかじめ別の容器にて
水または温水に分散し水と十分になじませた分散液を調
製しておくのが好ましい。こうする事によって、澱粉粒
子同士の凝集や団粒，あるいは一般的に“ままこ”と称
せられる塊状物の形成を回避する事が出来る。The modified starch fine powder is preferably dispersed in water or warm water in another container in advance to prepare a dispersion liquid sufficiently mixed with water. By doing so, it is possible to avoid agglomeration of starch particles, aggregation of starch particles, or formation of agglomerates generally referred to as "mamako".
【００２８】変性澱粉は水又は温水に投ずる事によって
も、ほとんど体積・形状の変化を起さないものではある
が、前述の通り完全に疎水性としたものではないので、
若干の変化はあり、又水とのなじみ更には、同伴した気
泡を脱離させるといった点からも、混合後多少の時間的
経過を与えてから次の反応に用いる方が好ましい。The modified starch hardly changes in volume and shape even when it is poured into water or warm water, but it is not completely hydrophobic as described above.
It is preferable to use it for the next reaction after some time has passed after mixing, since there are some changes, and also from the viewpoint of compatibility with water and elimination of entrained bubbles.
【００２９】次に上述の混合液に、架橋剤，触媒を加
え、充分攪拌し反応原液とした後、これを型枠に流し込
み、加熱して架橋反応を行う。Next, a cross-linking agent and a catalyst are added to the above-mentioned mixed solution and sufficiently stirred to prepare a reaction stock solution, which is poured into a mold and heated to carry out a cross-linking reaction.
【００３０】加熱は、気孔が形成されるまで攪乱が起き
ないように一定温度で行なう事が肝要であり、また、そ
の温度も、架橋反応が急速にすすみすぎないように４０
〜６０℃程度の温度を選定する事が好適である。架橋反
応が完結するには大略１０時間以上を要し、均一な反応
生成物を得るには２０時間程度おく事が好ましい。It is essential that the heating is carried out at a constant temperature so as not to cause disturbance until pores are formed, and the temperature should be 40 so that the crosslinking reaction does not proceed too rapidly.
It is preferable to select a temperature of about -60 ° C. It takes about 10 hours or more to complete the crosslinking reaction, and about 20 hours is preferable to obtain a uniform reaction product.
【００３１】続いて、架橋反応によって得られた反応生
成物を型枠より取り出し、これを水洗して未反応の架橋
剤，触媒及び澱粉を除去することで、微細且つ均質な連
続気孔構造をしたＰＶＡｔ系多孔体を得ることができ
る。Subsequently, the reaction product obtained by the cross-linking reaction was taken out from the mold and washed with water to remove the unreacted cross-linking agent, catalyst and starch to form a fine and homogeneous continuous pore structure. A PVAt-based porous body can be obtained.
【００３２】以上の様にして得られたＰＶＡｔ系多孔体
は、アセタール化度が通常６０モル％程度で、乾燥状態
では硬化物であるが、湿潤状態では柔軟なゴム弾性を発
現するスポンジ状のものであり、化粧用パフ材，拭浄材
等に用いることができる。The PVAt type porous body obtained as described above has a degree of acetalization of usually about 60 mol% and is a cured product in a dry state, but in a wet state, it is a sponge-like substance which exhibits soft rubber elasticity. It can be used as a cosmetic puff material, a cleaning material, and the like.
【００３３】本発明の方法によって得られた上記ＰＶＡ
ｔ系多孔体は、更に次の様な後加工を施すことによっ
て、他の色々な用途にも利用できるようになる。The above PVA obtained by the method of the present invention
The t-based porous body can be used for various other purposes by further performing the following post-processing.
【００３４】後加工には、架橋剤（アルデヒド），触媒
（酸）の濃厚混合液中に投入して架橋反応を更に一段進
め、アセタール化度を８０モル％程度まで進める方法
や、熱硬化性樹脂を施与して熱処理し、素材を硬化する
方法等がある。For the post-processing, a method of advancing the cross-linking reaction one step further by introducing it into a concentrated mixed solution of a cross-linking agent (aldehyde) and a catalyst (acid) to accelerate the degree of acetalization to about 80 mol%, and thermosetting There is a method of applying a resin and heat-treating it to cure the material.
【００３５】これらのうち、前者は、ＰＶＡｔ系樹脂そ
のものの持つ化学構造を生かす用途，即ち、酵母等の微
生物を保持する為の担体用途等，後者は、より寸法安定
性・耐水性が要求される用途，即ち、液体用高精度濾材
用途等に好適である。Of these, the former uses the chemical structure of the PVAt resin itself, that is, the carrier for holding microorganisms such as yeast, and the latter requires more dimensional stability and water resistance. It is suitable for applications such as high precision filter media for liquids.
【００３６】硬化に用いられる熱硬化性樹脂としては、
例えばメラミン樹脂，フェノール樹脂，エポキシ樹脂等
を挙げることができるが、中でもメラミン樹脂が好適で
ある。As the thermosetting resin used for curing,
For example, melamine resin, phenol resin, epoxy resin and the like can be mentioned, and among them, melamine resin is preferable.
【００３７】上記熱硬化性樹脂を施与する方法として
は、浸漬，吹き付け，塗布等適宜な方法によればよい
が、好ましくはＰＶＡｔ系多孔体を熱硬化性樹脂の溶液
又はエマルジョン中に浸漬し、ＰＶＡｔ系多孔体に樹脂
液を含浸した後、余剰の液を除去する方法が挙げられ
る。The above-mentioned thermosetting resin may be applied by any suitable method such as dipping, spraying or coating, but preferably the PVAt porous material is dipped in a solution or emulsion of the thermosetting resin. After impregnating the PVAt-based porous body with the resin liquid, the excess liquid is removed.
【００３８】熱処理の温度，時間等の条件は施与する熱
硬化性樹脂の種類に応じ適宜選定すればよい。Conditions such as temperature and time of heat treatment may be appropriately selected according to the type of thermosetting resin to be applied.
【００３９】熱硬化性樹脂の付着量はＰＶＡｔ系多孔体
に対し好ましくは２０〜４０重量％であり、多過ぎると
気孔の目づまりを起し易く、少な過ぎると耐水性，寸法
安定性が悪くなる。The amount of the thermosetting resin adhered is preferably 20 to 40% by weight based on the PVAt type porous material. If it is too large, the pores are likely to be clogged, and if it is too small, water resistance and dimensional stability are deteriorated. ..
【００４０】以下、実施例を挙げて本発明を更に詳細に
説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
【００４１】実施例１ 重合度１７００の完全ケン化ＰＶＡ，重合度５００の完
全ケン化ＰＶＡを８：２の割合で混合したＰＶＡを温水
に溶解し、温度５３℃、濃度１１重量％の水溶液６０ l
を準備した。次に、エーテル化（ヒドロキシルプロピ
ル）と架橋（グリセリン・エーテル結合）の処理を二重
に施し、糊化温度が低く、膨潤及び粒子の崩壊を抑制す
る特性を付与したタピオカ澱粉（松谷化学工業（株）ユ
ニークガム Ｍ−７０１０）で平均１４μの変性澱粉
（粘度２０ｃｐ）１６ｋｇを、５３℃，３７ lの温水に
加えて十分に攪拌混合を行なった後、先に準備したＰＶ
Ａ水溶液中にゆっくりと投入し、攪拌混合を行ない、均
一混合液を得た。この混合液に、３７％ホルマリン１
５．２ lと５０％硫酸１２ lを加えて攪拌混合し、これ
を型枠に流し込み、６０℃にて２０時間加温反応し、反
応生成物を得た。得られた反応生成物を型枠から取り出
し、水洗して澱粉，硫酸，及び未反応のホルマリンを除
去、更に遠心脱水機にてこれらを除き、ＰＶＡｔ系多孔
体を得た。Example 1 PVA in which fully saponified PVA having a degree of polymerization of 1700 and fully saponified PVA having a degree of polymerization of 500 were mixed at a ratio of 8: 2 was dissolved in warm water to prepare an aqueous solution 60 having a temperature of 53 ° C. and a concentration of 11% by weight. l
Prepared. Next, tapioca starch (Matsutani Chemical Industry (Matsuya Chemical Industry (Matsutani Chemical Industry Co., Ltd. 16 kg of modified starch (viscosity 20 cp) having an average of 14 μ with Unique Gum M-7010) was added to warm water at 53 ° C. and 37 l and sufficiently stirred and mixed, and then the PV prepared in advance was used.
The mixture was slowly added to the aqueous solution A and mixed by stirring to obtain a uniform mixed solution. Add 37% formalin 1 to this mixture.
5.2 l and 12 l of 50% sulfuric acid were added and mixed with stirring, and this was poured into a mold and reacted by heating at 60 ° C. for 20 hours to obtain a reaction product. The obtained reaction product was taken out of the mold, washed with water to remove starch, sulfuric acid, and unreacted formalin, and further removed by a centrifugal dehydrator to obtain a PVAt-based porous body.
【００４２】このものは、湿潤時柔軟で若干のゴム弾性
を持った均一多孔体であり、平均気孔径３５〜４０μ，
気孔率９１％の連続気孔を有するものであった。This is a uniform porous body which is soft when wet and has some rubber elasticity, and has an average pore diameter of 35 to 40 μm.
It had continuous pores with a porosity of 91%.
【００４３】実施例２ 重合度１７００の完全ケン化ＰＶＡ，重合度５００の完
全ケン化ＰＶＡを８：２の割合で混合したＰＶＡを温水
に溶解し、温度５３℃濃度１１重量％の水溶液６０ lを
準備した。次に、エーテル化（ヒドロキシルプロピル）
と架橋（グリセリン・エーテル結合）の処理を施し、未
処理の物より膨潤し易く且つ粒子の崩壊が抑制される処
理を行なったコーンスターチ（松谷化学工業（株）ユニ
ークガム Ｋ−３０１）で平均１３μの変性澱粉（粘度
８００ｃｐ）１６ｋｇを、５３℃，３７ lの温水に加え
て十分に攪拌混合を行なった後、先に準備したＰＶＡ水
溶液中にゆっくりと投入し、攪拌混合を行ない均一混合
液を得た。この混合液に、３７％ホルマリン１５．２ l
と５０％硫酸１２ lを加えて攪拌混合し、これを型枠に
流し込み、６０℃にて２０時間加温反応し、反応生成物
を得た。得られた反応生成物を型枠から取り出し、水洗
して澱粉，硫酸，及び未反応のホルマリンを除去、更に
遠心脱水機にてこれらを除き、ＰＶＡｔ系多孔体を得
た。Example 2 PVA in which fully saponified PVA having a degree of polymerization of 1700 and fully saponified PVA having a degree of polymerization of 500 were mixed in a ratio of 8: 2 was dissolved in warm water, and 60 l of an aqueous solution having a concentration of 11% by weight at a temperature of 53 ° C. Prepared. Next, etherification (hydroxylpropyl)
Corn starch (Unique gum K-301, Matsutani Chemical Industry Co., Ltd.), which has been subjected to a treatment of cross-linking (glycerin / ether bond) and swelling more easily than untreated ones and suppressing the disintegration of particles, has an average of 13μ 16 kg of modified starch (viscosity 800 cp) was added to warm water at 53 ° C. and 37 l, and sufficiently stirred and mixed. Then, the mixture was slowly charged into the PVA aqueous solution prepared above, and stirred and mixed to obtain a uniform mixed solution. Obtained. To this mixed solution, 37% formalin 15.2 l
And 50% sulfuric acid (12 l) were added and mixed with stirring, and this was poured into a mold and reacted by heating at 60 ° C. for 20 hours to obtain a reaction product. The obtained reaction product was taken out of the mold, washed with water to remove starch, sulfuric acid, and unreacted formalin, and further removed by a centrifugal dehydrator to obtain a PVAt-based porous body.
【００４４】このものは、湿潤時柔軟で若干のゴム弾性
を持った均一多孔体であり、平均気孔径３５〜４０μ，
気孔率９１％の連続気孔を有するものであった。This is a uniform porous body which is soft when wet and has some rubber elasticity, and has an average pore diameter of 35 to 40 μm.
It had continuous pores with a porosity of 91%.
【００４５】実施例３ 重合度１７００の完全ケン化ＰＶＡ、重合度５００の完
全ケン化ＰＶＡを８：２の割合で混合したＰＶＡを温水
に溶解し、温度５３℃，濃度１１重量％の水溶液６０ l
を準備した。次にエーテル化（ヒドロキシルプロピル）
の処理を行ない、コーンスターチより粒子が小さく、本
来膨潤し難い粒子であるが、加工によりある程度膨潤す
る処理を行なったハイアミロース・コーンスターチ（松
谷化学工業（株）試作品 Ｇ−２２）で平均１０μの変
性澱粉１６ｋｇを、５３℃、３７ lの温水に加えて十分
に攪拌混合を行なった後、先に準備したＰＶＡ水溶液中
にゆっくりと投入し、攪拌混合を行ない均一混合液を得
た。この混合液に、３７％ホルマリン１５．２ lと５０
％硫酸１２ lを加えて攪拌混合し、これを型枠に流し込
み、６０℃にて２０時間加温反応し、反応生成物を得
た。得られた反応生成物を型枠から取り出し、水洗して
澱粉，硫酸，及び未反応のホルマリンを除去、更に遠心
脱水機にてこれらを除き、ＰＶＡｔ系多孔体を得た。Example 3 PVA in which fully saponified PVA having a degree of polymerization of 1700 and fully saponified PVA having a degree of polymerization of 500 were mixed in a ratio of 8: 2 was dissolved in warm water to prepare an aqueous solution 60 having a temperature of 53 ° C. and a concentration of 11% by weight. l
Prepared. Then etherification (hydroxylpropyl)
The particles are smaller than cornstarch and are particles that are difficult to swell by nature. 16 kg of modified starch was added to 37 liters of warm water at 53 ° C. and sufficiently stirred and mixed, and then slowly poured into the previously prepared PVA aqueous solution to carry out stirring and mixing to obtain a uniform mixed solution. Add 37% formalin 15.2 l and 50% to this mixture.
% Sulfuric acid (12 l) was added, and the mixture was stirred and mixed, poured into a mold, and reacted by heating at 60 ° C. for 20 hours to obtain a reaction product. The obtained reaction product was taken out of the mold, washed with water to remove starch, sulfuric acid, and unreacted formalin, and further removed by a centrifugal dehydrator to obtain a PVAt-based porous body.
【００４６】このものは、湿潤時柔軟で若干のゴム弾性
を持った均一多孔体であり、平均気孔径３５〜４０μ，
気孔率９１％の連続気孔を有するものであった。This is a uniform porous body which is soft when wet and has some rubber elasticity, and has an average pore diameter of 35 to 40 μm.
It had continuous pores with a porosity of 91%.
【００４７】[0047]
【発明の効果】上述の如く、本発明の方法によれば、均
質かつ微小な連続気孔を有するポリビニールアセタール
系多孔体を、安定にかつ効率よく製造することができ
る。As described above, according to the method of the present invention, it is possible to stably and efficiently produce a polyvinyl acetal-based porous body having homogeneous and minute continuous pores.
Claims (1)
橋剤，触媒，及び気孔形成材を加えて加温し、架橋反応
を行なった後、余剰の架橋剤，触媒，及び気孔形成材を
水洗してポリビニールアセタール系多孔体を製造する方
法において、気孔形成材として、水酸基に官能基を結合
させるか或いは、水酸基間を多官能基で架橋した変性澱
粉を用いることを特徴とする、ポリビニールアセタール
系多孔体の製造方法。 【請求項２】 変性澱粉が、３０℃に於いて１５ｃｐ以
上の粘度を有するものである、請求項１記載のポリビニ
ールアセタール系多孔体の製造方法。Claims: 1. A crosslinking agent, a catalyst, and a pore-forming material are added to an aqueous solution of polyvinyl alcohol, and the mixture is heated to carry out a crosslinking reaction. In the method for producing a polyvinyl acetal-based porous body by washing a forming material with water, as a pore forming material, a functional group is bound to a hydroxyl group, or a modified starch in which hydroxyl groups are cross-linked with a polyfunctional group is used. A method for producing a polyvinyl acetal-based porous body. 2. The method for producing a polyvinyl acetal-based porous body according to claim 1, wherein the modified starch has a viscosity of 15 cp or more at 30 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18354091A JPH055045A (en) | 1991-06-27 | 1991-06-27 | Production of polyvinyl acetal-based porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18354091A JPH055045A (en) | 1991-06-27 | 1991-06-27 | Production of polyvinyl acetal-based porous material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH055045A true JPH055045A (en) | 1993-01-14 |
Family
ID=16137609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18354091A Pending JPH055045A (en) | 1991-06-27 | 1991-06-27 | Production of polyvinyl acetal-based porous material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH055045A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211918A (en) * | 1993-01-19 | 1994-08-02 | Kanebo Ltd | Production of porous body of polyvinyl alcohol |
| WO1999036464A1 (en) * | 1998-01-19 | 1999-07-22 | Aion Co., Ltd. | Spongy porous spherical particles and process for producing the same |
| JP2000084348A (en) * | 1998-09-09 | 2000-03-28 | Kanebo Ltd | Deodorizing agent and deodorizing device |
| EP0897000A4 (en) * | 1996-05-01 | 2002-04-10 | Aion Co Ltd | Microorganism carrier and process for production thereof |
| KR20230037294A (en) * | 2021-09-09 | 2023-03-16 | 김나연 | Manufacturing method of eco-friendly micro filter and eco-friendly micro filter manufactured by the same that |
| CN115894073A (en) * | 2022-09-26 | 2023-04-04 | 琼海鑫海混凝土有限公司 | Light foamed concrete and preparation method thereof |
-
1991
- 1991-06-27 JP JP18354091A patent/JPH055045A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211918A (en) * | 1993-01-19 | 1994-08-02 | Kanebo Ltd | Production of porous body of polyvinyl alcohol |
| EP0897000A4 (en) * | 1996-05-01 | 2002-04-10 | Aion Co Ltd | Microorganism carrier and process for production thereof |
| WO1999036464A1 (en) * | 1998-01-19 | 1999-07-22 | Aion Co., Ltd. | Spongy porous spherical particles and process for producing the same |
| JP2000084348A (en) * | 1998-09-09 | 2000-03-28 | Kanebo Ltd | Deodorizing agent and deodorizing device |
| KR20230037294A (en) * | 2021-09-09 | 2023-03-16 | 김나연 | Manufacturing method of eco-friendly micro filter and eco-friendly micro filter manufactured by the same that |
| CN115894073A (en) * | 2022-09-26 | 2023-04-04 | 琼海鑫海混凝土有限公司 | Light foamed concrete and preparation method thereof |
| CN115894073B (en) * | 2022-09-26 | 2023-09-22 | 琼海鑫海混凝土有限公司 | Lightweight foamed concrete and preparation method thereof |
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