JPH0676509B2 - Porous phenol resin cured product - Google Patents
Porous phenol resin cured productInfo
- Publication number
- JPH0676509B2 JPH0676509B2 JP60063705A JP6370585A JPH0676509B2 JP H0676509 B2 JPH0676509 B2 JP H0676509B2 JP 60063705 A JP60063705 A JP 60063705A JP 6370585 A JP6370585 A JP 6370585A JP H0676509 B2 JPH0676509 B2 JP H0676509B2
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- JP
- Japan
- Prior art keywords
- phenol resin
- porous
- cured product
- porous body
- cured
- 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 - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は多孔性フェノール樹脂硬化体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cured product of a porous phenolic resin.
さらに詳しくは極めて細い連通気孔を有する他孔性フェ
ノール樹脂硬化体に関する。More specifically, the present invention relates to a cured product of a multi-pore phenol resin having extremely thin continuous air holes.
連通気孔を有する高分子多孔体は、塩類溶出法、溶剤発
揮法あるいは焼結法等によって製造される。このような
方法で製造された高分子多孔体としては、例えば、ポリ
塩化ビニル多孔体、ポリビニルアルコール多孔体、セル
ロース多孔体、ポリプロピレン多孔体等が知られてい
る。これらの高分子多孔体はそのポリマー特性あるいは
孔径等に応じて、種々の分野で応用されている。例えば
セルロース多孔体では孔径が0.1〜５μｍと微細である
ため、微粒子、コロイド状物質あるいは細菌等の過に
適しており、医薬、食料品の製造を始め、多くの分野で
使用されている。また、塩類溶出法によって作られたポ
リ塩化ビニル多孔体は平均孔径が５μｍ程度であり、電
池のセパレーターを始めとして工業用炉材として用いら
れている。以上の従来技術は工業材料第25巻第２号10〜
17頁に纒められているので参照されたい。The polymer porous body having continuous ventilation holes is produced by a salt elution method, a solvent exertion method, a sintering method, or the like. As the polymer porous body produced by such a method, for example, polyvinyl chloride porous body, polyvinyl alcohol porous body, cellulose porous body, polypropylene porous body and the like are known. These polymeric porous materials are applied in various fields depending on the polymer characteristics, pore size, and the like. For example, since a porous cellulose body has a fine pore diameter of 0.1 to 5 μm, it is suitable for the passage of fine particles, colloidal substances, bacteria and the like, and is used in many fields including the production of medicines and food products. The polyvinyl chloride porous body produced by the salt elution method has an average pore diameter of about 5 μm and is used as an industrial furnace material including a battery separator. The above-mentioned conventional techniques are industrial materials Vol. 25, No. 2, 10-
See page 17 for reference.
上記高分子多孔体はいずれも熱可塑性高分子の多孔体で
ある。Each of the above polymer porous bodies is a porous body of a thermoplastic polymer.
一方、フェノール樹脂は耐熱性、耐薬品性等に優れた熱
硬化性樹脂であり、独立気泡構造を有するその多孔体は
断熱材等として使用されている。On the other hand, phenol resin is a thermosetting resin having excellent heat resistance and chemical resistance, and its porous body having a closed cell structure is used as a heat insulating material.
しかしながら、連続気泡を有するフェノール樹脂の多孔
体は市販品として入手することができない。特に、孔径
が10μｍ以上の細い連続気孔を有するフェノール樹脂多
孔体は材をはじめとして種々の利用分野があるにもか
かわらず、本発明者の知るかぎり従来知られていない。However, a phenol resin porous material having open cells cannot be obtained as a commercial product. In particular, as far as the present inventors know, a phenol resin porous body having fine continuous pores having a pore size of 10 μm or more has not been known so far, as far as the present inventors know.
本発明の目的は微細な連続気孔を有する多孔性フェノー
ル樹脂硬化体換言すれば微細な連続気孔を有する硬化さ
れたフェノール樹脂の多孔体を提供することにある。An object of the present invention is to provide a porous phenol resin cured product having fine continuous pores, in other words, a cured phenol resin porous body having fine continuous pores.
本発明の他の目的は耐熱性あるいは耐薬品性等に優れた
微細な連続気孔を持つ多孔体を提供することにある。Another object of the present invention is to provide a porous body having fine continuous pores excellent in heat resistance or chemical resistance.
本発明のさらに他の目的は軽量で機械的強度の大きい硬
化されたフェノール樹脂多孔体を提供することにある。Still another object of the present invention is to provide a cured phenolic resin porous body which is lightweight and has high mechanical strength.
本発明のさらに他の目的は、コロイド状物質、細菌の如
き微小物体のろ過あるいは電池用セパレータの分野にま
で幅広い用途を有する多孔性フェノール樹脂硬化体を提
供することにある。Still another object of the present invention is to provide a cured porous phenol resin product which has a wide range of applications in the fields of filtration of microscopic substances such as colloidal substances and bacteria, and in the field of battery separators.
本発明のさらに他の目的および利点は以下の説明から明
らかとなろう。Further objects and advantages of the present invention will be apparent from the following description.
本発明によれば本発明の上記目的および利点は、樹枝状
フエノール樹脂硬化体よりなり、３次元網目状の連通気
孔を備え、0.03〜10μｍの平均孔径と0.3〜0.7g/cm3の
嵩密度を有することを特徴とする多孔性フエノール樹脂
硬化体によって達成される。According to the present invention, the above objects and advantages of the present invention include a cured dendritic phenol resin, three-dimensional mesh-like continuous ventilation holes, an average pore diameter of 0.03 to 10 μm and a bulk density of 0.3 to 0.7 g / cm 3 . It is achieved by a cured porous phenolic resin characterized by having
本発明において、フェノール樹脂とはフェノール性水酸
基を有する芳香族炭化水素化合物とアルデヒド類との縮
合物である。かかる芳香族炭化水素化合物としては、例
えばフェノール、クレゾール、キシレノールの如きいわ
ゆるフェノール類が好適であるが、これらに限られな
い。In the present invention, the phenol resin is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. As such an aromatic hydrocarbon compound, so-called phenols such as phenol, cresol, and xylenol are preferable, but not limited thereto.
例えば下記式 ここで、ｘおよびｙはそれぞれ独立に、０、１又は２で
ある、 で表されるメチレン−ビス・フェノール類であることが
でき、あるいはヒドロキシ−ビフェニル類、ヒドロキシ
ナフタレン類であることもできる。これらのうち、実用
的にはフェノール類特にフェノール類が好適である。For example, the following formula Here, x and y are each independently 0, 1 or 2 and may be a methylene-bisphenol represented by the following, or a hydroxy-biphenyl or a hydroxynaphthalene. Of these, phenols, especially phenols, are practically preferable.
本発明におけるフェノール樹脂としては、さらにフェノ
ール性水酸基を有する芳香族炭化水素化合物の１部をフ
ェノール性水酸基を有さない芳香族炭化水素化合物例え
ばキシレン、トルエン等で置換した変性芳香族系ポリマ
ー例えばフェノールとキシレンとホルムアルデヒドとの
縮合物である変性芳香族系ポリマーを用いることもでき
る。As the phenol resin in the present invention, a modified aromatic polymer such as phenol obtained by further substituting a part of an aromatic hydrocarbon compound having a phenolic hydroxyl group with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene or toluene. A modified aromatic polymer which is a condensate of xylene and formaldehyde can also be used.
また、アルデヒドとしてはホルムアルデヒドのみなら
ず、アセトアルデヒド、フルフラールの如きその他のア
ルデヒドも使用することができるが、ホルムアルデヒド
が好適である。フェノール・ホルムアルデヒド縮合物と
しては、ノボラック型又はレゾール型或はそれらの複合
物のいずれであってもよい。As the aldehyde, not only formaldehyde but also other aldehydes such as acetaldehyde and furfural can be used, but formaldehyde is preferable. The phenol-formaldehyde condensate may be a novolac type, a resol type, or a complex thereof.
本発明の多孔性フェノール樹脂硬化体は、上記の如きフ
ェノール樹脂から例えば次のようにして製造することが
できる。The porous phenol resin cured product of the present invention can be produced from the above-described phenol resin, for example, as follows.
フェノール性水酸基を有する芳香族炭化水素化合物又は
フェノール性水酸基を有する芳香族炭化水素化合物とフ
ェノール性水酸基を有さない芳香族炭化水素化合物およ
びアルデヒド類の初期縮合物を準備し、この初期縮合物
と無機塩とを含む水溶液を調整し、この水溶液を適当な
型に流し込み、ついで水分の蒸発を抑止しつつ該水溶液
を過熱して該型内でたとえば板状、フィルム状あるいは
円筒状等の形態に硬化し且つ変換し、その後この硬化体
を洗浄して該硬化体に含有される無機塩を除去する。Preparing an initial condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group or an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aromatic hydrocarbon compound not having a phenolic hydroxyl group and an aldehyde, and the initial condensation product An aqueous solution containing an inorganic salt is prepared, the aqueous solution is poured into an appropriate mold, and then the aqueous solution is heated while suppressing evaporation of water to form a plate-like, film-like or cylindrical form in the mold. After curing and conversion, the cured product is washed to remove the inorganic salt contained in the cured product.
初期縮合物と共に用いる上記無機塩は後の工程で除去さ
れ硬化体に連通孔を付与するために用いられる孔形成剤
であり、たとえば塩化亜鉛、リン酸ナトリウム、水酸化
ナトリウムあるいは硫化カリウム等である。これらのう
ち塩化亜鉛が特に好ましくは用いられる。無機塩は、初
期縮合物のたとえば2.5〜10重量部の量で用いることが
できる。下限より少ない量では連通孔を有する多孔性硬
化体が得難くまた上限より多い量では多孔性硬化体の機
械的強度が低下する傾向が大きくなり望ましくない。初
期縮合物と無機塩の水溶液は、使用する無機塩の種類に
よっても異なるが例えば無機塩の0.1〜１重量倍の水を
用いて調整することができる。The above-mentioned inorganic salt used together with the initial condensate is a pore-forming agent which is removed in a later step and is used for imparting communicating pores to the cured product, and examples thereof include zinc chloride, sodium phosphate, sodium hydroxide or potassium sulfide. . Of these, zinc chloride is particularly preferably used. The inorganic salt can be used in an amount of, for example, 2.5 to 10 parts by weight of the initial condensate. If the amount is less than the lower limit, it is difficult to obtain a porous cured product having communicating pores, and if the amount is more than the upper limit, the mechanical strength of the porous cured product tends to decrease, which is not desirable. Although the aqueous solution of the initial condensate and the inorganic salt varies depending on the kind of the inorganic salt used, it can be prepared by using, for example, 0.1 to 1 times the weight of the inorganic salt water.
フェノール性樹脂の初期縮合物と無機塩の水溶液は、例
えば水溶性レゾールに塩化亜鉛塩水溶液を加えた後、攪
拌することにより、均一な溶液として調整することがで
き、またレゾールのメタノール溶液と塩化亜鉛水溶液を
混合することにより粘度の高いスラリー状に調整するこ
ともできる。その際、該水溶液に他の添加物、例えば硬
化フェノール樹脂の粉体あるいは繊維、あるいはセルロ
ースの微粒子等を混入しても良い。又、上記の如く、メ
タノール、エタノール、アセトンの如き有機溶媒を、均
一な混合のために加えても良い。かくして、例えば100,
000〜100センチポイズの粘度を有する水溶液は適当な型
に流し込まれ、例えば50〜200℃の温度に加熱される。
この加熱の際、水溶液中の水分の蒸発を抑止するのが肝
要で有る。すなわち、水溶液中において初期縮合物は過
熱を受けて徐々に硬化し、塩化亜鉛の如き無機塩、水と
分離しながら３次元網目構造に成長するものと考えられ
る。The aqueous solution of the initial condensate of the phenolic resin and the inorganic salt can be prepared as a uniform solution by, for example, adding a zinc chloride salt aqueous solution to the water-soluble resol and then stirring it. It is also possible to prepare a slurry having a high viscosity by mixing an aqueous zinc solution. At that time, other additives, for example, powders or fibers of cured phenol resin, or fine particles of cellulose may be mixed in the aqueous solution. Further, as mentioned above, an organic solvent such as methanol, ethanol or acetone may be added for uniform mixing. Thus, for example, 100,
An aqueous solution having a viscosity of 0000-100 centipoise is poured into a suitable mold and heated to a temperature of, for example, 50-200 ° C.
At the time of this heating, it is essential to suppress evaporation of water in the aqueous solution. That is, it is considered that in the aqueous solution, the initial condensate is gradually hardened by being overheated, and grows into a three-dimensional network structure while separating from inorganic salt such as zinc chloride and water.
得られた硬化体を水あるいは希塩酸等で十分に洗浄する
ことによって、硬化体中に含まれる無機塩を除去するこ
とができる。無機塩を除去したのち乾燥すると連通孔の
発達した多孔性硬化体を得ることができる。The inorganic salt contained in the cured product can be removed by thoroughly washing the obtained cured product with water, diluted hydrochloric acid or the like. When the inorganic salt is removed and then dried, a porous cured product having communication holes can be obtained.
本発明の硬化されたフェノール樹脂多孔体は、樹脂部又
は連通孔３次元網目構造を採っているため、流体が細部
まで自由に出入りし易い連通孔を有している。平均孔径
は10μｍ以下と例えば10〜0.03μｍと微細であり、孔径
の揃った、即ち孔径分布のシャープな多孔体である。塩
化亜鉛の如き無機塩を含む未硬化フェノール樹脂水溶液
の組成あるいは熱硬化条件を適当に選定することによっ
て上記の如く平均孔径が、0.03〜0.1μｍと極めて微細
な多孔体から、平均孔径が10μｍ程度の多孔体まで得る
ことが可能である。そのため比較的大きな粒子等を別
するフィルター、あるいは電池用のセパレーター等から
細菌あるいはコロイド状の微粒子の分別まで種々の分野
において使用される。The cured phenol resin porous body of the present invention has a resin portion or a communication hole having a three-dimensional network structure, and therefore has a communication hole through which a fluid can easily flow in and out in detail. The average pore size is 10 μm or less and is as fine as, for example, 10 to 0.03 μm, and the pore size is uniform, that is, the pore size distribution is sharp. By appropriately selecting the composition of the uncured phenol resin aqueous solution containing an inorganic salt such as zinc chloride or the thermosetting conditions, the average pore diameter is 0.03 to 0.1 μm as described above, and the average pore diameter is about 10 μm. It is possible to obtain even a porous body of. Therefore, it is used in various fields such as filters for separating relatively large particles or the like, separators for batteries, etc. to separation of bacteria or colloidal particles.
本発明の硬化されたフェノール樹脂多孔体の見掛け密度
は0.3〜0.7g/cm3である。換言すれば本発明の多孔体に
は気孔率の高い多孔体から比較的気孔率の低い多孔体ま
で包含される。多孔体の機械的強度はその見掛け密度に
関係しているが、例えば0.3g/cm3の見掛け密度の本発明
の多孔体でも実用上充分な強度を有しており、しかも可
撓性があるため、取り扱いが簡便である。The apparent density of the cured phenolic resin porous material of the present invention is 0.3 to 0.7 g / cm 3 . In other words, the porous body of the present invention includes a porous body having a high porosity to a porous body having a relatively low porosity. Although the mechanical strength of the porous body is related to its apparent density, for example, even the porous body of the present invention having an apparent density of 0.3 g / cm 3 has practically sufficient strength and is flexible. Therefore, it is easy to handle.
本発明の、硬化されたフェノール樹脂多孔体は、フィル
ム状、板状、円筒状あるいはパイプ状等、任意の形状を
採ることができるため、その用途に応じて使い分けるこ
とが可能である。The cured phenol resin porous body of the present invention can have any shape such as a film shape, a plate shape, a cylindrical shape, or a pipe shape, and thus can be used properly according to its application.
また本発明の多孔体は熱硬化性のフェノール樹脂から成
っているため、耐熱性、耐薬品性に優れており、従来の
ポリ塩化ビニルあるいはポリビニルアルコール等の多孔
体が使用出来なかった過酷な条件下にも応用できる多孔
体である。以下実施例によって本発明をさらに詳述す
る。Further, since the porous body of the present invention is made of a thermosetting phenolic resin, it is excellent in heat resistance and chemical resistance, and the harsh conditions that conventional porous bodies such as polyvinyl chloride or polyvinyl alcohol cannot be used. It is a porous material that can be applied underneath. The present invention will be described in more detail below with reference to examples.
なお、本発明書において、連通孔の平均孔径は次のよう
にして測定されまた定義される。In addition, in the present invention, the average pore diameter of the communicating holes is measured and defined as follows.
資料について、例えば1,000〜10,000倍で電子顕微鏡写
真を撮影する。この写真に任意の直線を引き、その直線
と交叉する孔の数をｎとすると、平均孔径（）は下記
式により算出される。An electron micrograph of the material is taken at a magnification of 1,000 to 10,000, for example. If an arbitrary straight line is drawn on this photograph and the number of holes intersecting the straight line is n, the average pore diameter () is calculated by the following formula.
ここで、liは直線が交叉する孔で切断される長さであ
り、 はｎ個の孔についての該切断される長さの和であり、ｎ
は該直線と交叉する交叉する孔の数である、但しｎは10
以上の値をとるものとする。 Where li is the length cut at the hole where the straight lines intersect, Is the sum of the cut lengths for n holes, and n
Is the number of intersecting holes intersecting the straight line, where n is 10
The above value shall be taken.
実施例 １ 水溶性レゾール（約60％濃度）／塩化亜鉛／水を重量比
で10/25/4の割合で混合した水溶液をフィルムアプリケ
ータでガラス板状に成膜した。次に成膜した水溶液の上
にポリエステルフィルムを被せ、水分が蒸発しない様に
した後、約100℃の温度で１時間硬化させた。得られた
硬化フィルムを希塩酸で洗浄した後、水洗し次に乾燥さ
せることによって約200μｍ厚のフィルム状の硬化した
フェノール樹脂多孔体を得た。該多孔体の見掛け密度は
0.60g/cm3であり、しかも可撓性に富んだ機械的強度に
優れたフィルムであった。該フィルムの断面の電子顕微
鏡写真を第１図に示す。第１図に見られるように、樹脂
部は樹枝状で３次元網目構造を採っており10μｍ以下の
平均孔径を有していた。Example 1 An aqueous solution prepared by mixing water-soluble resol (about 60% concentration) / zinc chloride / water in a weight ratio of 10/25/4 was formed into a glass plate with a film applicator. Next, a polyester film was covered on the formed aqueous solution to prevent water from evaporating, and then cured at a temperature of about 100 ° C. for 1 hour. The obtained cured film was washed with diluted hydrochloric acid, washed with water and then dried to obtain a film-shaped cured phenol resin porous body having a thickness of about 200 μm. The apparent density of the porous body is
It was 0.60 g / cm 3 and was a film that was rich in flexibility and excellent in mechanical strength. An electron micrograph of the cross section of the film is shown in FIG. As seen in FIG. 1, the resin portion was dendritic and had a three-dimensional network structure, and had an average pore diameter of 10 μm or less.
第１図は、本発明の硬化されたフェノール樹脂多孔体
（フイルム状）の断面の電子顕微鏡写真である。写真
中、右下に示す棒線の長さは５μｍである。FIG. 1 is an electron micrograph of a cross section of a cured phenol resin porous body (film-like) of the present invention. In the photograph, the length of the bar line shown in the lower right is 5 μm.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 桜井 和朗 大阪府大阪市都島区友淵町１丁目６番10― 401号 (56)参考文献 特開 昭60−1238（ＪＰ，Ａ) 特公 昭56−35435（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuro Sakurai 1-6-10-401, Tomobuchicho, Miyakojima-ku, Osaka-shi, Osaka (56) References JP 60-1238 (JP, A) JP 56-35435 (JP, B2)
Claims (2)
次元網目状の連通気孔を備え、0.03〜10μｍの平均孔径
と0.3〜0.7g/cm3の嵩密度を有することを特徴とする多
孔性フエノール樹脂硬化体。1. A dendritic phenol resin cured product, 3
A cured porous phenolic resin, which is provided with three- dimensional mesh-like continuous air holes and has an average pore diameter of 0.03 to 10 μm and a bulk density of 0.3 to 0.7 g / cm 3 .
請求の範囲第１項記載の多孔性フエノール樹脂硬化体。2. A cured product of a porous phenol resin according to claim 1, wherein the cured product is a film or a plate.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60063705A JPH0676509B2 (en) | 1985-03-29 | 1985-03-29 | Porous phenol resin cured product |
| US06/842,335 US4753717A (en) | 1985-03-25 | 1986-03-21 | Porous article having open pores prepared from aromatic condensation polymer and use thereof |
| EP92100194A EP0480909B1 (en) | 1985-03-25 | 1986-03-25 | Porous active carbon prepared from aromatic condensation polymer and use thereof in electrodes for electrochemical cells |
| EP86104063A EP0196055B1 (en) | 1985-03-25 | 1986-03-25 | Porous article having open pores prepared from aromatic condensation polymer and use thereof |
| DE86104063T DE3689239T2 (en) | 1985-03-25 | 1986-03-25 | Porous article made of aromatic condensation polymers with open pores and its application. |
| DE3650725T DE3650725T2 (en) | 1985-03-25 | 1986-03-25 | Porous activated carbon made from aromatic condensation polymers and their application in electrodes for electrochemical cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60063705A JPH0676509B2 (en) | 1985-03-29 | 1985-03-29 | Porous phenol resin cured product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61223037A JPS61223037A (en) | 1986-10-03 |
| JPH0676509B2 true JPH0676509B2 (en) | 1994-09-28 |
Family
ID=13237055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60063705A Expired - Lifetime JPH0676509B2 (en) | 1985-03-25 | 1985-03-29 | Porous phenol resin cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676509B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01165427A (en) * | 1987-12-21 | 1989-06-29 | Unitika Ltd | Porous composite sheet and manufacture thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635435A (en) * | 1979-08-31 | 1981-04-08 | Fujitsu Ltd | Manufacturing of semiconductor device |
| JPS601238A (en) * | 1983-06-20 | 1985-01-07 | Kanebo Ltd | Production of porous phenolic resin |
-
1985
- 1985-03-29 JP JP60063705A patent/JPH0676509B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61223037A (en) | 1986-10-03 |
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