JPH0784538B2 - Method for producing porous body - Google Patents
Method for producing porous bodyInfo
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- JPH0784538B2 JPH0784538B2 JP62112449A JP11244987A JPH0784538B2 JP H0784538 B2 JPH0784538 B2 JP H0784538B2 JP 62112449 A JP62112449 A JP 62112449A JP 11244987 A JP11244987 A JP 11244987A JP H0784538 B2 JPH0784538 B2 JP H0784538B2
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- porous body
- polymer
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- preform
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、多孔質体の製造方法に関する、更に詳しく
は、耐熱性ポリマーを多孔質基材とする多孔質体の製造
方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a porous body, and more particularly to a method for producing a porous body using a heat resistant polymer as a porous substrate.
多孔質体の一般的な製造方法としては、１）ミクロ分散
による方法（例えば特開昭61−89237号公報）、２）延
伸法、３）荷電粒子によるエッチング、４）モールディ
ングパウダーに水溶性の無機塩類を混合したものを圧縮
成形した後で成形品から塩類を抽出する方法などを挙げ
ることができる。As a general method for producing a porous body, 1) a method by microdispersion (for example, JP-A-61-89237), 2) a stretching method, 3) etching by charged particles, and 4) a water-soluble molding powder. Examples thereof include a method in which a mixture of inorganic salts is compression-molded, and then the salts are extracted from the molded product.
しかしながら、上記１）の方法では有機溶媒や再沈剤の
調製、回収が面倒であり、３）の方法では設備が高価で
あり、また４）の方法では抽出する無機塩等が混合時に
ポリマー中に包含されて貫通孔が得られ難く、使用時に
析出する等の欠点があった。However, in the method 1), preparation and recovery of the organic solvent and the reprecipitating agent are troublesome, in the method 3), the equipment is expensive, and in the method 4), the inorganic salt or the like to be extracted is mixed in the polymer at the time of mixing. However, there are drawbacks such that it is difficult to obtain a through-hole because of being included in the above, and precipitation occurs during use.
耐薬品性が要求される用途においては、通常フッ素樹脂
系の多孔質体が利用されるが、フッ素樹脂については、
上記１）、４）の方法はその性質上利用され難く、２）
の延伸法による方法では、微小孔径の多孔質体が得られ
難く、また孔付近の引裂抵抗が弱い等の問題があった。In applications that require chemical resistance, fluororesin-based porous materials are usually used.
The above methods 1) and 4) are difficult to use due to their nature. 2)
In the method by the stretching method (1), it is difficult to obtain a porous body having a small pore size, and tear resistance in the vicinity of pores is weak.
更に、耐熱性樹脂の多孔質体の製造方法として、四フッ
化エチレン樹脂粉末とアクリル樹脂粉末を混合してプレ
フォームを作り、焼成の工程でアクリル樹脂のみを熱分
解により揮散させ、ポーラス化する技術も知られてい
る。しかしながら、この技術では、原料の一次粒子は細
かくても、混合時に凝集して大きい二次粒子を形成し、
二次粒子は一次粒子に解きほぐすことが困難なため、得
られた多孔質体の細孔径は大きく、かつ不均一であると
いう欠点を有する。Further, as a method for producing a porous body of a heat-resistant resin, a tetrafluoroethylene resin powder and an acrylic resin powder are mixed to form a preform, and only the acrylic resin is volatilized by thermal decomposition in the firing step to make it porous. The technology is also known. However, in this technique, even if the primary particles of the raw material are fine, they aggregate during mixing to form large secondary particles,
Since it is difficult for secondary particles to be disentangled into primary particles, the resulting porous material has the disadvantages of large pore size and non-uniformity.
本発明は、耐熱性のポリマーの多孔質体の製造におい
て、細孔径の微細化および均一化を達成することを目的
とする。本発明の他の目的は、簡便な方法で、かつ焼成
工程で残存物質が残らない多孔質体を製造する方法を提
供することにある。It is an object of the present invention to achieve finer and more uniform pore size in the production of a heat-resistant polymer porous body. Another object of the present invention is to provide a method for producing a porous body which is a simple method and does not leave a residual substance in the firing step.
本発明者らは、かかる課題を解決すべく鋭意研究の結
果、耐熱性ポリマーと分解性ポリマーを混合するに当
り、それらのポリマーを分散液または溶液の形態で用い
ることによって、微細孔かつ均一な多孔質体が得られる
ことを見出した。As a result of earnest research to solve the above problems, the present inventors have found that when mixing a heat-resistant polymer and a decomposable polymer, by using these polymers in the form of a dispersion or solution, it is possible to obtain fine pores and uniform It was found that a porous body can be obtained.
従って、本発明は多孔質体の製造方法に係り、多孔質体
の製造は、耐熱性ポリマーの分散液と分解性ポリマーの
分散液または溶液とを混合し、得られたポリマー混合液
からプレフォームを形成し、プレフォームを分解性ポリ
マーの天井温度以上の温度で加熱焼成することにより分
解性ポリマーを分解除去し、平均孔径約0.01〜10μｍの
多孔質体を形成することにより行われる。Therefore, the present invention relates to a method for producing a porous body, in which the production of a porous body is performed by mixing a dispersion liquid of a heat resistant polymer and a dispersion liquid or solution of a degradable polymer and preforming from the obtained polymer mixed liquid. And the preform is heated and baked at a temperature not lower than the ceiling temperature of the degradable polymer to decompose and remove the degradable polymer to form a porous body having an average pore diameter of about 0.01 to 10 μm.
本発明において用いられる多孔質基材は耐熱性ポリマー
であり、300℃付近の温度に加熱しても、一時的にでも
形状保持が可能な粘度を有するフッ素樹脂が利用され
る。フッ素樹脂の例としては、ポリテトラフルオロエチ
レン、テトラフルオロエチレン−ヘキサフルオロプロペ
ン共重合体、ポリクロルトリフルオロエチレン、テトラ
フルオロエチレン−エチレン共重合体、テトラフルオロ
エチレン−パーフルオロアルキルビニルエーテル共重合
体などが挙げられる。The porous substrate used in the present invention is a heat-resistant polymer, and a fluororesin having a viscosity capable of retaining its shape even when heated to a temperature of around 300 ° C. is used. Examples of the fluororesin include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and the like. Is mentioned.
分解性ポリマーは、約250〜400℃、好ましくは約280〜3
50℃の温度において解重合または熱分解するホモポリマ
ーまたはコポリマーであり、解重合性ポリマーにはコポ
リマーを含まない。これらの分解性ポリマーは、固型分
として耐熱性ポリマーとの合計量に対し、約５〜50体積
％の割合で用いられる。これより少ない割合で用いられ
ると、多孔質化に必要な分解量が少なくなり、一方これ
以上の割合で用いられると、粒子面の融着が小さくな
り、不均一性や強度低下の原因となる。The degradable polymer is about 250-400 ° C, preferably about 280-3.
A homopolymer or copolymer that depolymerizes or thermally decomposes at a temperature of 50 ° C., and the depolymerizable polymer does not include a copolymer. These degradable polymers are used as solid components in a proportion of about 5 to 50% by volume based on the total amount of the heat-resistant polymer. When it is used in a smaller proportion, the amount of decomposition required for porosity is reduced, while when it is used in a higher proportion, the fusion of particle surfaces becomes small, which causes non-uniformity and strength reduction. .
分解性ポリマーとしては、より微小にして均一な多孔質
体を与え得る解重合性ポリマーが好んで用いられ、例え
ばポリ（メタ）アクリル酸エステル、ポリエチレンカー
ボネート、ポリプロピレンカーボネートなどのポリ炭酸
エステル、ポリα−メチルスチレン、ポリトリフルオロ
スチレン、ポリイソブチレンなどが用いられる。また、
熱分解性ポリマーとしては、ポリアクリル樹脂、ポリビ
ニルアルコールポリアセタール、ナイロン６、ナイロン
6,6などのポリアミド、ポリエチレンテレフタレートな
どのポリエステル、ポリプロピレン、ポリスチレンなど
が用いられる。As the degradable polymer, a depolymerizable polymer capable of giving a finer and more uniform porous body is preferably used, and examples thereof include poly (meth) acrylic acid ester, polyethylene carbonate, polypropylene carbonate and other polycarbonate esters, and poly α. -Methylstyrene, polytrifluorostyrene, polyisobutylene, etc. are used. Also,
As the heat decomposable polymer, polyacrylic resin, polyvinyl alcohol polyacetal, nylon 6, nylon
Polyamides such as 6,6, polyesters such as polyethylene terephthalate, polypropylene, polystyrene and the like are used.
これらの熱分解性ポリマーは、ほぼ300℃付近でモノマ
ーまたは低分子物質に分解するため、焼成により残存物
はほとんど残らない。These thermally decomposable polymers decompose into monomers or low-molecular substances at around 300 ° C., so that almost no residue remains after firing.
耐熱性ポリマーは、水または有機溶媒を分散媒とする分
散液として用いられ、また分解性ポリマーは同様の分散
液または有機溶媒中の溶液としてそれぞれ用いられ、混
合される。分散液は、水性エマルジョンまたはラテック
スが好ましい。The heat-resistant polymer is used as a dispersion liquid in which water or an organic solvent is used as a dispersion medium, and the degradable polymer is used as a similar dispersion liquid or a solution in an organic solvent, and mixed. The dispersion is preferably an aqueous emulsion or latex.
耐熱性ポリマーと分解性ポリマーを混合し、プレフォー
ムを形成し、焼成して分解性成分を揮散させ、多孔質体
を得る方法においては、両ポリマー成分の混合状態が多
孔質体の特性を決めることになる。両成分を粉体として
混合した場合には、分解性成分を細かく、かつ均一に分
散させた混合体は得られない。In a method of mixing a heat-resistant polymer and a decomposable polymer, forming a preform, and firing to vaporize the decomposable components to obtain a porous body, the mixed state of both polymer components determines the characteristics of the porous body. It will be. When both components are mixed as a powder, a mixture in which degradable components are finely and uniformly dispersed cannot be obtained.
本発明におけるように、両成分を分散液として用いる場
合、粒径は約0.01〜１μｍレベルであり、従って両成分
の混合状態では粒径レベルで隣り合い、かかるプレフォ
ームを焼成することにより、平均孔径約0.01〜10μｍの
多孔質体を得ることができる。また、分解性ポリマーの
溶液の例としては、ポリエチレンカーボネートの塩化メ
チレン溶液、ポリα−メチルスチレンの1,4−ジオキサ
ン溶液などを挙げることができる。When both components are used as dispersions, as in the present invention, the particle size is about 0.01-1 μm level, so in the mixed state of both components they are next to each other at the particle size level and by firing such preforms, the average It is possible to obtain a porous body having a pore size of about 0.01 to 10 μm. Further, examples of the solution of the degradable polymer include a methylene chloride solution of polyethylene carbonate and a 1,4-dioxane solution of poly α-methylstyrene.
本発明において、プレフォームは、ポリマー混合液か
ら、例えば次のようにして形成される。In the present invention, the preform is formed from the polymer mixed solution, for example, as follows.
（１）ポリマー混合液をガラス板等の支持体上に注難成
膜し、乾燥後支持体から剥離する。(1) A polymer mixed solution is hardly poured onto a support such as a glass plate to form a film, which is dried and then peeled off from the support.
（２）ポリマー混合液にガラスクロス等の支持体を浸漬
し、支持体にポリマー混合液を含浸させ、乾燥後支持体
により補強されたシートを得る。(2) A support such as glass cloth is immersed in the polymer mixed solution to impregnate the support with the polymer mixed solution, and after drying, a sheet reinforced by the support is obtained.
（３）ポリマー混合液にエタノールなどの溶媒を滴親し
て沈殿物を生成させ、沈殿物をチューブ状に押出成形す
る。(3) A solvent such as ethanol is added dropwise to the polymer mixture to form a precipitate, and the precipitate is extruded into a tube.
（４）ポリマー混合液を、ノズルを通して中空糸状に押
し出し、エタノールなどの凝固浴溶媒中でゲル化させ
る。(4) The polymer mixed solution is extruded into a hollow fiber shape through a nozzle and gelled in a coagulation bath solvent such as ethanol.
このようにして形成されたプレフォームを、分解性ポリ
マーの分解温度以上の温度で加熱焼成することにより、
微細孔かつ均一な多孔質体が得られる。分解性ポリマー
は焼成により揮散し、多孔質体中にほとんど残存しない
が、ポリマー混合液中に界面活性剤等の添加物が含まれ
る場合において、焼成によりそれが残留物となるとき、
または分解性ポリマーの分解除去が十分でない場合は、
得られた多孔質体を洗浄し、残存物質を除去する。The preform thus formed is heated and baked at a temperature equal to or higher than the decomposition temperature of the decomposable polymer,
A porous body having fine pores and a uniform size can be obtained. The decomposable polymer is volatilized by firing and hardly remains in the porous body, but when the polymer mixture contains an additive such as a surfactant, when it becomes a residue by firing,
Or if the decomposable polymer is not removed sufficiently,
The obtained porous body is washed to remove residual substances.
本発明によれば、簡便な方法により、残存物質のない、
微細孔かつ均一な多孔質体を得ることができる。According to the present invention, there is no residual substance by a simple method,
It is possible to obtain a porous body having fine pores and uniform.
以下、実施例を参照し、本発明を更に説明する。 Hereinafter, the present invention will be further described with reference to Examples.
実施例１ ポリテトラフルオロエチレンの水性ディスパージョン
（三井デュポンフロロケミカル製品テフロン30−Ｊ）
を、乳化重合によって得られた平均分子量40万、平均粒
径0.1μｍ、固形分濃度25％のポリメチルメタクリレー
トラテックスと体積化で10:3.6の割合で、ゆるやかに撹
拌混合した。この混合液を平滑なガラス板上にキャスト
して、150℃で水分を揮散させた後取り出し、200メッシ
ュのステンレス金網上に寸法変化がないように固定し
た。これを、窒素置換した炉内で、昇温速度10℃/minで
350℃まで昇温し、そのまま10分間定温加熱した後、室
温下で冷却した。Example 1 Aqueous dispersion of polytetrafluoroethylene (Mitsui DuPont Fluorochemicals Teflon 30-J)
Was gently stirred and mixed with polymethyl methacrylate latex obtained by emulsion polymerization having an average molecular weight of 400,000, an average particle size of 0.1 μm, and a solid content concentration of 25% at a volume ratio of 10: 3.6. This mixed solution was cast on a smooth glass plate, vaporized at 150 ° C. to remove water, and then taken out and fixed on a 200-mesh stainless wire mesh so that there was no dimensional change. In a furnace purged with nitrogen, this was heated at a heating rate of 10 ° C / min.
The temperature was raised to 350 ° C., and the temperature was kept constant for 10 minutes and then cooled at room temperature.
この試料を、走査難電子顕微鏡で観察したところ、平均
孔径で0.1μｍの連続孔をもつ多孔質体になっているこ
とが分かった。Observation of this sample with a scanning electron microscope revealed that it was a porous body having continuous pores with an average pore diameter of 0.1 μm.
比較例１ 実施例１の方法において、ポリメチルメタクリレートラ
テックスの代わりに、酢酸ｎ−ブチルを混入した混合液
を用い、焼成フィルムを得た。Comparative Example 1 A fired film was obtained by using a mixed solution containing n-butyl acetate instead of the polymethylmethacrylate latex in the method of Example 1.
これを走査型電子顕微鏡で観察したところ、きわめてボ
イドの少ないフィルムであり、多孔質体になっていない
ことが分かった。Observation with a scanning electron microscope revealed that the film had very few voids and was not a porous body.
比較例２ 実施例１の方法において、ポリメチルメタクリレートラ
テックスの代わりに市販のポリ塩化ビニルラテックス
（日本ゼオン製品のGeron 150×15;固形分濃度48％）
を、体積比で5:4の割合で添加したものでフィルムを作
成した。Comparative Example 2 In the method of Example 1, a commercially available polyvinyl chloride latex was used instead of the polymethylmethacrylate latex (Geron 150 × 15 manufactured by Nippon Zeon Products; solid content concentration 48%).
Was added at a volume ratio of 5: 4 to form a film.
このフィルムを走査型電子顕微鏡で観察したところ、と
ころどころに孔がみられるが貫通しておらず、またポリ
塩化ビニルの加熱分解残存物と思われる物質が全体に付
着、包埋していた。When this film was observed with a scanning electron microscope, holes were found in some places but were not penetrated, and a substance thought to be a thermal decomposition residue of polyvinyl chloride was adhered and embedded in the whole.
実施例２ テトラフルオロエチレン−ヘキサフルオロプロペン共重
合体の水性ディスパージョン（三井デュポンフロロケミ
カル製品Ｔ−120;固形分濃度50％）に、特公昭55−2909
3号公報に記載の方法で得られたポリエチレンカーボネ
ート（エチレンオキサイド−二酸化炭素共重合体）の10
重量％塩化メチレン溶液を、体積比で2:3の割合で撹拌
混合した後、この混合物中に撹拌しながらエタノールを
滴下し、不溶性沈澱物を得た。これを、温度180℃、押
出圧5ton/cm2で、外径5mm、肉厚1mmのチューブ状に押出
成形し、これを窒素置換した炉中で、昇温速度５℃/min
で350℃まで昇温し、その温度で30分定温加熱した後、
室温で急冷した。Example 2 Aqueous dispersion of tetrafluoroethylene-hexafluoropropene copolymer (Mitsui DuPont Fluorochemicals product T-120; solid content concentration 50%) was added to Japanese Patent Publication No. 55-2909.
10 of polyethylene carbonate (ethylene oxide-carbon dioxide copolymer) obtained by the method described in JP-A-3
A weight% methylene chloride solution was stirred and mixed at a volume ratio of 2: 3, and then ethanol was added dropwise to this mixture while stirring to obtain an insoluble precipitate. This was extruded into a tube with an outer diameter of 5 mm and a wall thickness of 1 mm at a temperature of 180 ° C. and an extrusion pressure of 5 ton / cm 2 , and this was heated in a furnace with nitrogen substitution at a heating rate of 5 ° C./min.
After heating up to 350 ° C with 30 minutes of constant temperature heating,
Quenched at room temperature.
この試料の走査型電子顕微鏡で観察したところ、平均孔
径0.5μｍ、多孔度35％の多孔質体になっていることが
分った。また、このチューブに塩化メチレンを流したと
ころ、流量は４×103/m2・hr・atmであり、流出物を
調べたが、不純物の混入はみられなかった。Observation of this sample with a scanning electron microscope revealed that it was a porous body having an average pore diameter of 0.5 μm and a porosity of 35%. When methylene chloride was passed through this tube, the flow rate was 4 × 10 3 / m 2 · hr · atm, and the effluent was examined, but impurities were not mixed.
比較例３ 実施例２と同様にチューブ状に押出成形したものを、加
熱除去せずに塩化メチレン中に浸漬、洗浄する操作を48
時間行ない、成形チューブを得た。これを走査型電子顕
微鏡で観察したところ、多孔質状をしていたが、成形品
内部にポリエチレンカーボネートと思われる物質が残存
していた。Comparative Example 3 The same procedure as in Example 2 except that a tubular extrudate was immersed in methylene chloride and washed without being removed by heating.
After a while, a molded tube was obtained. When it was observed with a scanning electron microscope, it was found to be porous, but a substance thought to be polyethylene carbonate remained inside the molded product.
これを、実施例２と同様に塩化メチレを流したところ、
流量は１×103/m2・hr・atmであり、流出物を調べた
ところ、カーボネート結合をもつ物質が溶出しているこ
とが分った。When methyl chloride was poured in the same manner as in Example 2,
The flow rate was 1 × 10 3 / m 2 · hr · atm, and when the effluent was examined, it was found that a substance having a carbonate bond was eluted.
比較例４ 実施例２の方法において、ポリエチレンカーボネートの
塩化メチレン溶液を添加せずに、チューブを押出成形し
た。Comparative Example 4 In the method of Example 2, a tube was extruded without adding a methylene chloride solution of polyethylene carbonate.
このチューブを走査型電子顕微鏡で観察したところ、と
ころどころに空隙があるが、貫通孔はみられなかった。When this tube was observed with a scanning electron microscope, there were voids here and there, but no through holes were observed.
実施例３ ポリテトラフルオロエチレンの水性ディスパージョン
（三井デュポンフロロケミカル製品テフロン30−Ｊ）21
gとアクリル樹脂エマルジョン（東亜合成化学製品アロ
ンNS−1050）12gを撹拌機により混合する。アスピレー
ター吸引により脱泡し、ステンレス板上に塗布する。厚
く塗布すると焼成品に割れが発生するため、板を斜めに
し余分な液をたらしながら薄く塗布する。風乾後、100
℃前後の恒温槽に入れ乾燥する。次に焼成炉に入れ、常
温から380℃まで1.5時間かけ昇温し、380℃で１時間保
持、焼成する。冷却後、ステンレス板より剥離してフィ
ルムを得る。フィルム厚は0.01〜0.03mmである。フィル
ムの表面を走査型電子顕微鏡写真で調べた結果、網の目
状平均孔径0.5〜１μｍで連通孔を有する多孔物質であ
ることが確認された。Example 3 Polytetrafluoroethylene aqueous dispersion (Mitsui DuPont Fluorochemicals Teflon 30-J) 21
g and 12 g of acrylic resin emulsion (Toa Gosei Chemical product Aron NS-1050) are mixed with a stirrer. Degas by aspirator suction and apply on a stainless steel plate. If it is applied thickly, cracks will occur in the fired product, so apply it thinly while tilting the plate and spreading excess liquid. 100 after air drying
Put in a constant temperature bath at around ℃ and dry. Next, it is put in a firing furnace, heated from room temperature to 380 ° C. over 1.5 hours, held at 380 ° C. for 1 hour, and fired. After cooling, it is peeled from the stainless plate to obtain a film. The film thickness is 0.01-0.03 mm. As a result of examining the surface of the film with a scanning electron micrograph, it was confirmed that the film was a porous substance having a network-like average pore diameter of 0.5 to 1 μm and having communicating pores.
実施例４ 実施例３と同様の方法で混合した液にガラスクロスを浸
漬し、ロールで絞りながら引き上げる。乾燥後、実施例
３と同様条件で焼成する。焼成の結果、ガラスクロスを
支持体とするポリテトラフルオロエチレンよりなる多孔
質体が得られた。形成された孔の状況は、実施例３と同
様であった。Example 4 A glass cloth is immersed in a liquid mixed in the same manner as in Example 3 and pulled up while squeezing with a roll. After drying, firing is performed under the same conditions as in Example 3. As a result of the firing, a porous body made of polytetrafluoroethylene having glass cloth as a support was obtained. The condition of the holes formed was the same as in Example 3.
Claims (7)
と解重合性ポリマーまたは熱分解性ポリマーである分解
性ポリマーの分散液または溶液とを混合し、得られたポ
リマー混合液からプレフォームを形成し、プレフォーム
を分解性ポリマーの天井温度以上の温度で加熱焼成する
ことにより分解性ポリマーを分解除去し、平均孔径約0.
01〜10μｍの多孔質体を形成させることを特徴とする多
孔質体の製造方法。1. A preform is prepared from a polymer mixture obtained by mixing a dispersion of a heat resistant polymer which is a fluororesin with a dispersion or a solution of a depolymerizable polymer or a decomposable polymer which is a thermally decomposable polymer. Forming and decomposing and removing the degradable polymer by heating and firing the preform at a temperature above the ceiling temperature of the degradable polymer, an average pore size of about 0.
A method for producing a porous body, which comprises forming a porous body having a diameter of 01 to 10 μm.
ある特許請求の範囲第１項記載の多孔質体の製造方法。2. The method for producing a porous body according to claim 1, wherein the dispersion liquid is an emulsion or a latex.
たはフィルムである特許請求の範囲第１項記載の多孔質
体の製造方法。3. The method for producing a porous body according to claim 1, wherein the preform is a cast-formed sheet or film.
に浸漬することによって得られた支持体補強物である特
許請求の範囲第１項記載の多孔質体の製造方法。4. The method for producing a porous body according to claim 1, wherein the preform is a support reinforcing material obtained by immersing the support in a polymer mixed solution.
囲第４項記載の多孔質体の製造方法。5. The method for producing a porous body according to claim 4, wherein the support is glass cloth.
添加することにより生成する沈澱物をチューブ状に押出
成形したものである特許請求の範囲第１項記載の多孔質
体の製造方法。6. The method for producing a porous body according to claim 1, wherein the preform is a tube formed by extrusion-molding a precipitate formed by adding a solvent to the polymer mixture.
を通して中空糸状に押出し、凝固浴溶媒中でゲル化させ
たものである特許請求の範囲第１項記載の多孔質体の製
造方法。7. The method for producing a porous body according to claim 1, wherein the preform is one in which a polymer mixed solution is extruded through a nozzle into a hollow fiber shape and gelled in a coagulation bath solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62112449A JPH0784538B2 (en) | 1987-05-11 | 1987-05-11 | Method for producing porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62112449A JPH0784538B2 (en) | 1987-05-11 | 1987-05-11 | Method for producing porous body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63278943A JPS63278943A (en) | 1988-11-16 |
| JPH0784538B2 true JPH0784538B2 (en) | 1995-09-13 |
Family
ID=14586908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62112449A Expired - Lifetime JPH0784538B2 (en) | 1987-05-11 | 1987-05-11 | Method for producing porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784538B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895263A (en) * | 1996-12-19 | 1999-04-20 | International Business Machines Corporation | Process for manufacture of integrated circuit device |
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| US5700844A (en) * | 1996-04-09 | 1997-12-23 | International Business Machines Corporation | Process for making a foamed polymer |
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| US6420441B1 (en) | 1999-10-01 | 2002-07-16 | Shipley Company, L.L.C. | Porous materials |
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| JP6355972B2 (en) * | 2014-05-27 | 2018-07-11 | 株式会社ジェイエスピー | Method for producing polyimide resin porous body and composite |
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| JP6701834B2 (en) * | 2015-03-26 | 2020-05-27 | 富士ゼロックス株式会社 | Method for producing resin particle-dispersed polyimide precursor solution, resin particle-dispersed polyimide precursor solution, resin particle-containing polyimide film, method for producing porous polyimide film, and porous polyimide film |
| JPWO2019021963A1 (en) * | 2017-07-25 | 2020-05-28 | 東レ株式会社 | Fluid separation membrane |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4957069A (en) * | 1972-10-04 | 1974-06-03 | ||
| JPS5832170B2 (en) * | 1976-09-03 | 1983-07-11 | 東ソー株式会社 | Manufacturing method of porous synthetic resin membrane |
-
1987
- 1987-05-11 JP JP62112449A patent/JPH0784538B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895263A (en) * | 1996-12-19 | 1999-04-20 | International Business Machines Corporation | Process for manufacture of integrated circuit device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63278943A (en) | 1988-11-16 |
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