JPS62192431A - Production of porous membrane of ethylene-containing copolymer fluororesin - Google Patents
Production of porous membrane of ethylene-containing copolymer fluororesinInfo
- Publication number
- JPS62192431A JPS62192431A JP61033836A JP3383686A JPS62192431A JP S62192431 A JPS62192431 A JP S62192431A JP 61033836 A JP61033836 A JP 61033836A JP 3383686 A JP3383686 A JP 3383686A JP S62192431 A JPS62192431 A JP S62192431A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- porous membrane
- oligomer
- chlorotrifluoroethylene
- molding
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920001577 copolymer Polymers 0.000 title abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract 3
- 239000005977 Ethylene Substances 0.000 title abstract 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 13
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 claims description 12
- 229920001038 ethylene copolymer Polymers 0.000 claims description 10
- 229920001780 ECTFE Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000013638 trimer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000011148 porous material Substances 0.000 description 12
- 239000012510 hollow fiber Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エチレン共重合体フッ素樹脂からなる優れた
耐薬品性、優れた耐熱性、優れた濾過性能、優れた機械
的物性を備え、かつ微細な孔からなる均一多孔構造を有
する多孔膜の製造方法に関するものである。特に本発明
は優れた耐熱性と優れた濾過性能を備えたミクロフィル
ターＣ：適する多孔膜、さらには優れた耐薬品性を活か
して、強酸、強アルカリ等の薬品精製用ミクロフィルタ
ーに好適な多孔膜の製造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention comprises an ethylene copolymer fluororesin having excellent chemical resistance, excellent heat resistance, excellent filtration performance, and excellent mechanical properties. The present invention also relates to a method for producing a porous membrane having a uniform porous structure consisting of fine pores. In particular, the present invention is a microfilter C with excellent heat resistance and excellent filtration performance: a suitable porous membrane, and furthermore, by taking advantage of its excellent chemical resistance, a porous membrane suitable for microfilters for purifying chemicals such as strong acids and strong alkalis. The present invention relates to a method for manufacturing a membrane.
（従来技術とその問題点）
フッ素樹脂は耐薬品性、耐熱性に優れた樹脂であるが、
さらに優れた機械的物性をも兼ねそなえたフッ素樹脂と
して、エチレン−テトラフルオロエチレン共重合体、エ
チレン−クロロトリフルオロエチレン共重合体、が選ば
れる。これらのフッ素樹脂からなる多孔膜は、耐熱性、
耐薬品性、耐久性の優れた多孔膜として期待される。(Prior art and its problems) Fluororesin is a resin with excellent chemical resistance and heat resistance, but
Ethylene-tetrafluoroethylene copolymer and ethylene-chlorotrifluoroethylene copolymer are selected as fluororesins that also have excellent mechanical properties. Porous membranes made of these fluororesins have heat resistance,
It is expected to be a porous membrane with excellent chemical resistance and durability.
エチレン−テトラフルオロエチレン共重合体からなる多
孔膜及びその製造方法として、既に特開昭６０−／３６
３６グ号公報、特開昭５４ｔ−／ｊ♂４ｔ６！号公報、
特開昭ｊ？−／４ｔ７０３０号公報が知られている。特
開昭ｊＯ−／３乙３５グ号公報は、エチレン−テトラフ
ルオロエチレン共重合体微粉末をスチレンモノマーとス
ラリー混合液を作りスチレン重合後膜化してエチレン重
合体を溶出して多孔膜を作る方法であるが、この方法で
得られた多孔膜は孔径が７０μと大きい上、透過性が非
常に低くミクロフィルターに適さない。A porous membrane made of ethylene-tetrafluoroethylene copolymer and a method for producing the same have already been disclosed in JP-A-60-/36.
Publication No. 36, JP-A-54T-/j♂4t6! No. Publication,
Tokukai Shoj? -/4t7030 publication is known. JP-A No. 35-35 discloses that a slurry mixture of ethylene-tetrafluoroethylene copolymer fine powder and styrene monomer is prepared, and after styrene polymerization, it is formed into a film, and the ethylene polymer is eluted to form a porous film. However, the porous membrane obtained by this method has a large pore diameter of 70μ and has very low permeability, making it unsuitable for microfilters.
特開昭ｔｇ−／！♂ダ６！号公報は、エチレン−テトラ
フルオロエチレン共重合体フィルムを荷電粒子照射した
後苛性ソーダ水溶液でエツチングして多孔膜を作る方法
であるが、得られた多孔膜は三次元網状構造を有しない
ので濾過性能が不良な上機械的物性にも劣り、均一な中
空糸状多孔膜から得られず、さらに原子炉を用いるので
大量生産に向かない問題がある。特開昭！ター／４ｔ７
θ３０号公報は、エチレン−テトラフルオロエチレン共
重合体フィルムにレジストを塗布して膏孔レジストパタ
ーンを形成した後スパッタエツチング処理してレジスト
パターンに対応する貫通孔を形成して多孔膜を作る方法
であるが、この多孔膜も三次元網状構造を有しないので
濾過性能が不良な上、機械的物性にも劣り、均一な中空
糸状多孔膜を得ることが困難で、さらに長時間のスパッ
タエツチング処理を必要とするので生産性（＝も問題が
ある。Tokukai Sho tg-/! ♂ Da 6! The publication discloses a method of making a porous membrane by irradiating an ethylene-tetrafluoroethylene copolymer film with charged particles and then etching it with an aqueous solution of caustic soda. However, the resulting porous membrane does not have a three-dimensional network structure, so its filtration performance is poor. In addition, it has poor mechanical properties, cannot be obtained from a uniform hollow fiber-like porous membrane, and furthermore, because it uses a nuclear reactor, it is not suitable for mass production. Tokukai Akira! Tar/4t7
θ30 discloses a method of forming a porous film by applying a resist to an ethylene-tetrafluoroethylene copolymer film to form a hole resist pattern, and then performing sputter etching treatment to form through holes corresponding to the resist pattern. However, since this porous membrane does not have a three-dimensional network structure, it has poor filtration performance and poor mechanical properties, making it difficult to obtain a uniform hollow fiber porous membrane and requiring a long sputter etching process. There is also a problem with productivity (=) because it requires
以上の問題点を改善する方法として、特開昭６３−７９
０／／号公報、特開昭！乙−／！り／２♂号公報、特開
昭タフ−２♂／３９号公報、特Ｂｈ昭ｊ♂−タ３７り♂
号公報、特開昭ｊ♂−／７９２９７号公報等、エチレン
ーテトラフルオロエチレン共重合体、微粉珪酸、ジオク
チルフタレートを混合後溶融成形し、ついで該成形物よ
り微粉珪酸、ジオクチルフタレートを抽出して多孔膜を
作る方法が知られている。As a method to improve the above problems, JP-A-63-79
Publication No. 0//, Tokukaisho! Otsu-/! RI/2♂ Publication, JP-A-2011-2013-2/39 Publication, Special Bh Shoj♂-TA 37RI♂
No. 79297, JP-A No. 79297, etc., ethylene-tetrafluoroethylene copolymer, finely powdered silicic acid, and dioctyl phthalate are mixed and then melt-molded, and then finely powdered silicic acid and dioctyl phthalate are extracted from the molded product. Methods for making porous membranes are known.
しかしこの方法で得られる多孔膜は、多孔構造の均一性
が十分なものでない上、微粉珪酸を第０口したのち抽出
して除去するという複雑な方法のため生産性が悪く、製
造コスト面でも問題があった。However, the porous membrane obtained by this method does not have sufficient uniformity of the porous structure, and the complicated method of extracting and removing finely divided silicic acid after injecting it results in poor productivity and production costs. There was a problem.
以上のように、エチレン−テトラフルオロエチレン共重
合体からなる多孔膜及びその製法として満足できるもの
が従来なかった。As described above, there has not been a satisfactory porous membrane made of an ethylene-tetrafluoroethylene copolymer and a method for producing the same.
又、エチンンークロロトリフルオロエチレン共重合体か
らなる多孔膜及びその製法Ｃ二ついては従来全く検討さ
れていなかった。Furthermore, porous membranes made of ethyne-chlorotrifluoroethylene copolymers and method C for producing the same have not been studied at all.
（問題点を解決するための手段）
本発明者は、エチレン共重合体フッ素樹脂からなる優れ
た耐薬品性、優れた耐熱性、優れた濾過特性、優れた機
械的物性を備え、かつ微細な孔からなる均一多孔構造を
存する多孔膜を生産性よく製造できる方法について鋭意
検討した結果、本発明を完成するに至った。(Means for Solving the Problems) The present inventor has discovered that an ethylene copolymer fluororesin has excellent chemical resistance, excellent heat resistance, excellent filtration characteristics, and excellent mechanical properties, and that The present invention has been completed as a result of extensive research into a method for manufacturing a porous membrane having a uniform porous structure consisting of pores with good productivity.
即ち本発明は、特許請求の範囲に記載の多孔膜の製法を
提供する。That is, the present invention provides a method for producing a porous membrane according to the claims.
本発明において、エチレン−テトラフルオロエチレン共
重合体又はエチレン−クロロトリフルオロエチレン共重
合体からなるエチレン共重合体フッ素樹脂１０〜７０容
ｔチと、クロロトリフルオロエチレンオリゴマー３０〜
りθ容量係が使用される。In the present invention, 10 to 70 volumes of ethylene copolymer fluororesin consisting of ethylene-tetrafluoroethylene copolymer or ethylene-chlorotrifluoroethylene copolymer and 30 to 70 volumes of chlorotrifluoroethylene oligomer are used.
The θ capacity factor is used.
本発明において、多孔膜素材として、耐薬品性、耐熱性
、機械的物性（＝すぐれることからエチレン−テトラフ
ルオロエチレン共重合体又はエチレン−クロロトリフル
オロエチレン共重合体が選ばれる。又、これら樹脂の混
合物も可能である。In the present invention, as the porous membrane material, ethylene-tetrafluoroethylene copolymer or ethylene-chlorotrifluoroethylene copolymer is selected because of its excellent chemical resistance, heat resistance, and mechanical properties. Mixtures of resins are also possible.
本発明において、クロロトリフルオロエチレンオリゴマ
ーの使用が必須であり、これを用いることにより均一孔
構造を有する微粒子除去性にすぐれた多孔膜を、安定し
た膜品質で、生産性よく製造することが始めて可能とな
った。クロロトリフルオロエチレンオリゴマーは、クロ
ロトリフルオロエチレンオリゴマーは、クロロトリフル
オロエチレンのグ〜λθ量体が好ましく、♂〜／！は体
がさらに好ましく、９〜／２址体が最も好ましい。In the present invention, the use of chlorotrifluoroethylene oligomer is essential, and by using this, for the first time, a porous membrane with a uniform pore structure and excellent particle removability can be manufactured with stable membrane quality and high productivity. It has become possible. The chlorotrifluoroethylene oligomer is preferably a g~λθmer of chlorotrifluoroethylene, and ♂~/! A body of 9 to 2 is more preferable, and a body of 9 to 2 is most preferable.
３慣体以下では耐熱性が低くて溶融成形時の蒸散が大き
く、かつ多孔膜の透過性が小さくて好ましくなく、２７
量体以上では混合作業性が悪く、かつ抽出性も悪くて好
ましくない。なお、本発明にお（するクロロトリフルオ
ロエチレンオリゴ１−の量体数は、各種量体数のクロロ
トリフルオロエチレンオリゴマーの混合物からなるクロ
ロトリフルオロエチレンオリゴマーにおいては平均の量
体数である。If it is less than 3 inertia, the heat resistance is low, evaporation during melt molding is large, and the permeability of the porous membrane is low, which is undesirable.
If the amount exceeds 50%, the mixing workability is poor and the extractability is also poor, which is not preferable. In addition, the number of mer of chlorotrifluoroethylene oligo 1- according to the present invention is the average number of mer of chlorotrifluoroethylene oligomer which is composed of a mixture of chlorotrifluoroethylene oligomers having various number of mer.
本発明（：おいて、クロロトリフルオロエチレンオリゴ
マーとクロロトリフルオロエチレンオリゴマーを除＜ｓ
ｐ値５〜／／の耐熱性有機物質との混合物を用いること
もできる。これにより多孔膜の孔径調節が容易となる。The present invention (: except for chlorotrifluoroethylene oligomers and chlorotrifluoroethylene oligomers)
It is also possible to use mixtures with heat-resistant organic substances having a p value of 5 to //. This facilitates adjustment of the pore diameter of the porous membrane.
即ち、耐熱性有機物質の選定及び／又はクロロトリフル
オロエチレンオリゴマーと耐熱性有機物質との混合比を
調節すること（二より望みの孔径（＝容易（二孔径のコ
ントロールが可能となる。That is, by selecting the heat-resistant organic material and/or adjusting the mixing ratio of the chlorotrifluoroethylene oligomer and the heat-resistant organic material, the pore diameter can be easily controlled.
本発明における耐熱性有機物質とは、７気圧における沸
点が少なくとも２０θ℃以上好ましくは２夕０℃以上な
る耐熱性を備え、本発明多孔膜の溶融成形時１；液体で
ある有機物質である。ＳＰ値が！〜／／の耐熱性有機物
質としてシリコンオイル、パーフルオロポリエーテルオ
リゴマー、フタル酸エステル、トリメリット酸エステル
、セ１＜チン酸エステル、アジピン酸エステル、アゼラ
イン酸エステル、リン酸エステル等が挙げられる。The heat-resistant organic substance in the present invention is an organic substance that has heat resistance such that the boiling point at 7 atmospheres is at least 20θ°C or higher, preferably 0°C or higher for 2 days, and is a liquid during melt molding of the porous membrane of the present invention. SP value! Examples of the heat-resistant organic substance ~// include silicone oil, perfluoropolyether oligomer, phthalic acid ester, trimellitic acid ester, se1<tinic acid ester, adipic acid ester, azelaic acid ester, phosphoric acid ester, and the like.
これらの内、特にシリコンオイル、パーフルオロポリエ
ーテルオリゴマー、トリメリット酸エステルが好ましい
。Among these, silicone oil, perfluoropolyether oligomer, and trimellitic acid ester are particularly preferred.
特に、シリコンオイルが、溶融成形時の熱安定性、価格
等の点からより好ましい。シリコンオイルとはシロキチ
ン構造をもった耐熱性有機物質で、ンメチルシリコン、
メチルフェニルシリコン、ジフェニルシリコン等である
。Particularly, silicone oil is more preferable from the viewpoint of thermal stability during melt molding, cost, etc. Silicone oil is a heat-resistant organic substance with a xylochitin structure.
Examples include methylphenyl silicone and diphenyl silicone.
本発明の多孔膜を製造するに当って、まずエチレン−テ
トラフルオロエチレン共重合体又はエチレン−クロロト
リフルオロエチレン共重合体からなるエチレン共重合体
フッ素樹脂と、クロロトリフルオロエチレンオリゴマー
を混合する。その混合割合は、エチレン共重合体フッ素
樹脂７０〜７Ｑ容量係、好ましくはコθ〜ｊθ容量係、
クロロトリフルオロエチレンオリゴマー（又は耐熱性有
機物質との混合物）３０〜９０容ｔ％、好ましくはｊθ
〜♂Ｏ容歓チである。In producing the porous membrane of the present invention, first, an ethylene copolymer fluororesin consisting of an ethylene-tetrafluoroethylene copolymer or an ethylene-chlorotrifluoroethylene copolymer and a chlorotrifluoroethylene oligomer are mixed. The mixing ratio is ethylene copolymer fluororesin 70 to 7Q capacity ratio, preferably koθ to jθ capacity ratio,
Chlorotrifluoroethylene oligomer (or mixture with heat-resistant organic substance) 30 to 90 volume t%, preferably jθ
~♂O Yong Huanchi.
エチレン共重合体フッ素樹脂が／θｇ量係未満では樹脂
が少なすぎて強度が小さく成形性も悪く、７θ容蝋憾を
超えると気孔率の大きい多孔膜が得られず好ましくない
。クロロトリフルオロエチレンオリゴマーが３０容ＷＬ
係未満では、得られる多孔膜の気孔率は低くて透過性の
すぐれた多孔膜が得られず、９θ容量幅を超えると成形
が困難となり、機械的強度の高い多孔膜が得られない。When the ethylene copolymer fluororesin content is less than /θg, the resin is too small, resulting in low strength and poor moldability, and when it exceeds 7θ, a porous film with high porosity cannot be obtained, which is not preferred. 30 volumes WL of chlorotrifluoroethylene oligomer
If the 9θ capacity width is less than 9θ, the resulting porous membrane will have a low porosity and a porous membrane with excellent permeability cannot be obtained.If the 9θ capacity width is exceeded, molding becomes difficult and a porous membrane with high mechanical strength cannot be obtained.
本発明における混合、溶融成形法は以下の方法が適用さ
れる。The following methods are applied to the mixing and melt molding methods in the present invention.
エチレン共重合体フッ素樹脂とクロロトリフルオロエチ
レンオリゴマーをパッチ式ニー！−（コニーダー等）で
溶融混合したのち、粉砕又はベレット化する。そして、
この原料を用いて、Ｔダイ、中空紡口等のダイスをとり
つけた押出装置により、平膜状、中空糸状等（二溶融成
形される。Patch type knee using ethylene copolymer fluororesin and chlorotrifluoroethylene oligomer! - After melting and mixing in a co-kneader or the like, the mixture is crushed or pelletized. and,
Using this raw material, it is melt-molded into the shape of a flat film, hollow fiber, etc., using an extrusion device equipped with a die such as a T-die or a hollow spinneret.
生産性のすぐれださら（＝好ましい方法として、Ｔダイ
、中空紡口等のダイスをとりつけたミキンングヘッド付
押出装置を使用して、エチレン共重合体フッ素樹脂とク
ロロトリフルオロエチレンオリゴマーの混合と溶融成形
を、一工程で実施する方法が採用できる。Excellent productivity (= As a preferred method, mixing and melt molding of ethylene copolymer fluororesin and chlorotrifluoroethylene oligomer is performed using an extrusion device with a mixing head equipped with a die such as a T-die or hollow spinneret. A method can be adopted in which the steps are performed in one step.
次いで、成形された膜状物から溶剤を用いてクロロトリ
フルオロエチレンオリゴマー又はこれと耐熱性有機物質
との混合物の抽出を行なう。抽出は回分法や向流多段法
等の膜状物の一般的な抽出方法により行なわれる。抽出
に用いられる溶剤としては／、／、／−トリクロロエタ
ン、テトラクロルエチレン等のハロゲン系炭化水素が好
ましい。Next, the chlorotrifluoroethylene oligomer or a mixture of the chlorotrifluoroethylene oligomer and the heat-resistant organic substance is extracted from the formed film using a solvent. Extraction is carried out by a general method for extracting membrane-like substances, such as a batch method or a countercurrent multistage method. As the solvent used for extraction, halogen hydrocarbons such as /, /, /-trichloroethane and tetrachloroethylene are preferred.
得られた多孔膜は、耐熱性を向上させるために熱風オー
ブン中でアニール処理することができる。The resulting porous membrane can be annealed in a hot air oven to improve heat resistance.
父、多孔膜の孔径を大きくしたり、気孔率を高めたり、
機械的物性を向上させたりするために、公知の条件で一
軸または二軸（−延伸をすることもできる。Father, increasing the pore size of porous membranes, increasing the porosity,
In order to improve mechanical properties, uniaxial or biaxial (-) stretching can be carried out under known conditions.
本発明の方法（二より、平均孔径θ、０／〜夕μ、気孔
率３０〜７０％で均一多孔構造を有する多孔膜を得るこ
とが可能である。According to the method of the present invention (secondary method), it is possible to obtain a porous membrane having a uniform porous structure with an average pore diameter θ of 0/~μ and a porosity of 30 to 70%.
又、本発明（二より得られた多孔膜は三次元網状構造を
有している。この三次元網状構造とは、多孔膜の表面及
び各方向の断面において、樹脂から成る網状構造が観測
される多孔構造のことであって、連通孔を有する、いわ
ゆるスポンジ構造を指す。このような三次元網状構造は
、多孔膜として強度的に優れ、かつこの多孔膜をフィル
ター用（二使用する場合は、スクリーンを多数枚積層し
たのと同じ効果（二より微粒子除去性に優れている。In addition, the porous membrane obtained in accordance with the present invention (2) has a three-dimensional network structure. It refers to a so-called sponge structure with communicating pores.Such a three-dimensional network structure has excellent strength as a porous membrane. , the same effect as laminating multiple screens (better ability to remove particulates).
本発明（二より、機械的物性にすぐれる膜厚の大きな多
孔膜が容易に製造できるが、多孔膜の膜厚は、０．０２
！；−認、！鴫が好ましい。０．Ｏｕ ｊ咽未満では機
械的物性（二劣り、又、”２．ｊｍを超えると透過性が
劣る傾向でいずれも好ましくないことがある。According to the present invention (2), a porous membrane with excellent mechanical properties and a large thickness can be easily produced, but the thickness of the porous membrane is 0.02
! ;-Acknowledgement! Shizu is preferred. 0. If it is less than 2.jm, the mechanical properties are inferior, and if it exceeds 2.jm, the permeability tends to be poor, which may be unfavorable.
膜の形状としては中空糸状、チューブ状、平膜状等が可
能であるが、ミクロフィルター用途（＝おいて、モジュ
ール化した際の装置のコンパクト性等の理由で中空糸状
が好ましい。The shape of the membrane can be a hollow fiber, a tube, a flat membrane, etc., but for microfilter applications (=), a hollow fiber shape is preferred for reasons such as compactness of the device when modularized.
なお本願明細書中に示されている諸物性は、次の測定方
法（＝よる。The various physical properties shown in this specification are determined by the following measurement method.
・平均孔径（μ） 電子顕微鏡により測定した。・Average pore diameter (μ) Measured using an electron microscope.
Ｏ気孔率（チ） 次の式により求めた。O porosity (chi) It was calculated using the following formula.
ただし、空孔容積は、多孔体孔中に水を満たした多孔体
の重置より多孔体のみの重量を差し引くことによって求
めた。However, the pore volume was determined by subtracting the weight of only the porous body from the superposition of the porous body whose pores were filled with water.
Ｏ透水ｆｉ （ｔｌ、ｒｒ”、ｈ「、ａｒｍ 、 ２
ｊ ’Ｃ）、！！℃、差圧／ρ個にて測定。O water permeability fi (tl, rr", h", arm, 2
j 'C),! ! Measured at °C, differential pressure/ρ units.
０三次元網状構造 電子顕微鏡観察（二より判定 ｏｓｐ値（溶解パラメーター） 次式（Ｓｍａｌｌの式）により算出する。0 three-dimensional network structure Electron microscopy observation (judgment from two points) osp value (solubility parameter) Calculated using the following formula (Small formula).
ｄ：比重、Ｇ：モル牽引定数、Ｍ：分子量ただし、詳細
は、［ジェー・ブランドラップ、ポリマーハンドブック
、セクショング、第３４ｔ４を頁、／り６≦年、インタ
ーサイエンスバブリイツシャーズ、ア デイヴイジョン
オブ ジョンウイリイ・アンドサンズ（Ｊ −８ＲＡ
ＮＤＲＵＰ ｅｔａｌ、 Ｐｏｌｙｍｅｒ Ｈａｎｄｂ
ｏｏｋ、 ＩＹ−３’１４１． ／ ９６６ 。d: Specific gravity, G: Molar traction constant, M: Molecular weight. However, for details, see [J. Brandrup, Polymer Handbook, Sectional, page 34t4, / 6≦, Interscience Publications, A.D. John of John Willy & Sons (J-8RA
NDRUP etal, Polymer Handb
ook, IY-3'141. / 966.
ＩＮＴＦＲ８ＣＩＥＮＣＩ３ ＰＵＢＬＩ８ＨＦ３Ｒ８
−ａ ｄｉｖｉｓｉｏｎ ｏｆＪｏｈｎ Ｗｉｌｅｙ
＆ ５ｏｎｓ ） Ｊ ｉ二記載されている。INTFR8CIENCI3 PUBLI8HF3R8
-a division of John Wiley
& 5ons) J i 2 is described.
（実施例）
次（二本発明を明らかにするため実施例を示すが本発明
はこれらの実施例（二よって限定されるものではない。(Examples) The following Examples are shown to clarify the present invention, but the present invention is not limited by these Examples.
実施例／〜グ
エチレン−テトラフルオロエチレン共重合体〔ネオフα
ンＥＴＦＢｇＰ−１グθ（商品名）〕を、ミミキシング
ヘッド付抽出機３０■２）に中空状紡口を取付けた中空
糸製造装置にて、表／に示す各種条件（二てりａロトリ
フルオロエチレンオリゴマーと混合させながら中空糸状
Ｃ，２＋ｇ（７℃にて成形した。クロロトリフルオロエ
チレンオリゴマーはミキシングヘッド部（＝インジエタ
ンヨンポンプにて圧入されており、溶融したエチレン−
テトラフルオロエチレン共重合体とミキシングヘッド部
にて均一に混合されたのち中空状紡口より吐出したのち
冷却される。Examples/~Ethylene-tetrafluoroethylene copolymer [Neof α
ETFBgP-1gθ (trade name)] was processed under the various conditions shown in the table (Futari a rotori The hollow fiber C,2+g (molded at 7°C) was mixed with fluoroethylene oligomer.
After being uniformly mixed with the tetrafluoroethylene copolymer in a mixing head, it is discharged from a hollow spinneret and then cooled.
成形された中空糸を５０℃の／、／、／−） ９クロル
工タン中Ｃ二／時間浸漬して、クロロトリフルオロエチ
レンオリゴマーを抽出したのち乾燥させた。The formed hollow fibers were immersed in 50° C. /, /, /−)9 chlorothane for C2 hours to extract the chlorotrifluoroethylene oligomer, and then dried.
得られたエチレン−テトラフルオロエチレン共重合体多
孔膜は内径／ｎａ、膜淳約、２夕θμの中空糸で、三次
元網状構造からなる均一多孔構造を仔していた。その性
能を表／に記す。The obtained ethylene-tetrafluoroethylene copolymer porous membrane had a uniform porous structure consisting of a three-dimensional network structure with hollow fibers having an inner diameter/na, a membrane thickness of 2 θμ. Its performance is shown in Table/.
実施例５〜７
エチレンークロロトリフルオロエチレン共重合体〔ヘイ
ラータコθ（商品名）〕を、実施例／と同様にして表２
に示す各種条件にてクロロトリフルオロエチレンオリゴ
マーと混合させながら中空糸状に２６０℃にて成形した
のちりσロトリフルオロエチレンオリゴマーを抽出し乾
燥させた。Examples 5 to 7 Ethylene-chlorotrifluoroethylene copolymer [Hailertaco θ (trade name)] was prepared in the same manner as in Example/Table 2
The σ-rotrifluoroethylene oligomer was molded into a hollow fiber shape at 260° C. while being mixed with the chlorotrifluoroethylene oligomer under various conditions shown below, and then dried.
得うレタエチレンークロロトリフルオロエチレン共重合
体多孔膜は内径／１、膜厚約、２５θμの中空糸で、三
次元網状構造からなる均一多孔構造を有していた。その
性能を表２に記す。The resulting retaethylene-chlorotrifluoroethylene copolymer porous membrane was a hollow fiber with an inner diameter of 1/1 and a membrane thickness of approximately 25θμ, and had a uniform porous structure consisting of a three-dimensional network structure. Its performance is shown in Table 2.
（以下余白）
（発明の効果）
本発明により、優れた耐薬品性、優れた耐熱性、優れた
濾過性能、優れた耐久性を備えた均一多孔構造を有する
エチレン共重合体フッ素樹脂多孔膜が生産性よく得られ
るようになった。(Left below) (Effects of the invention) The present invention provides an ethylene copolymer fluororesin porous membrane having a uniform porous structure with excellent chemical resistance, excellent heat resistance, excellent filtration performance, and excellent durability. Productivity has improved.
Claims (1)
ン−クロロトリフルオロエチレン共重合体１０〜７０容
量％、クロロトリフルオロエチレンオリゴマー３０〜９
０容量％を混合して溶融成形し、該成形物よりクロロト
リフルオロエチレンオリゴマーを抽出除去するエチレン
共重合体フッ素樹脂多孔膜の製造方法Ethylene-tetrafluoroethylene copolymer or ethylene-chlorotrifluoroethylene copolymer 10-70% by volume, chlorotrifluoroethylene oligomer 30-9%
A method for producing an ethylene copolymer fluororesin porous membrane, comprising mixing 0% by volume, melt-molding, and extracting and removing chlorotrifluoroethylene oligomer from the molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61033836A JPS62192431A (en) | 1986-02-20 | 1986-02-20 | Production of porous membrane of ethylene-containing copolymer fluororesin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61033836A JPS62192431A (en) | 1986-02-20 | 1986-02-20 | Production of porous membrane of ethylene-containing copolymer fluororesin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62192431A true JPS62192431A (en) | 1987-08-24 |
Family
ID=12397571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61033836A Pending JPS62192431A (en) | 1986-02-20 | 1986-02-20 | Production of porous membrane of ethylene-containing copolymer fluororesin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62192431A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340732A2 (en) * | 1988-05-04 | 1989-11-08 | Millipore Corporation | Fluorocarbon membranes and process for making fluorocarbon membranes |
| JP2004307864A (en) * | 2003-04-01 | 2004-11-04 | Solvay Solexis Spa | Ctfe-based thermally processable composition |
| JP2012512947A (en) * | 2008-12-19 | 2012-06-07 | スリーエム イノベイティブ プロパティズ カンパニー | Microporous material from ethylene-chlorotrifluoroethylene copolymer and process for producing the same |
| JP2018144005A (en) * | 2017-03-08 | 2018-09-20 | 旭化成株式会社 | Porous hollow fiber membrane and manufacturing method of the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617340A (en) * | 1984-06-20 | 1986-01-14 | Asahi Chem Ind Co Ltd | Fluorine-containing electrically conductive microporous membrane and production thereof |
-
1986
- 1986-02-20 JP JP61033836A patent/JPS62192431A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617340A (en) * | 1984-06-20 | 1986-01-14 | Asahi Chem Ind Co Ltd | Fluorine-containing electrically conductive microporous membrane and production thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340732A2 (en) * | 1988-05-04 | 1989-11-08 | Millipore Corporation | Fluorocarbon membranes and process for making fluorocarbon membranes |
| JPH02208329A (en) * | 1988-05-04 | 1990-08-17 | Millipore Corp | Fluorocarbon film and manufacture thereof |
| JP2004307864A (en) * | 2003-04-01 | 2004-11-04 | Solvay Solexis Spa | Ctfe-based thermally processable composition |
| JP4620376B2 (en) * | 2003-04-01 | 2011-01-26 | ソルヴェイ ソレクシス エス．ピー．エー． | CTFE-based thermoprocessable composition |
| JP2012512947A (en) * | 2008-12-19 | 2012-06-07 | スリーエム イノベイティブ プロパティズ カンパニー | Microporous material from ethylene-chlorotrifluoroethylene copolymer and process for producing the same |
| US10240013B2 (en) | 2008-12-19 | 2019-03-26 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
| JP2018144005A (en) * | 2017-03-08 | 2018-09-20 | 旭化成株式会社 | Porous hollow fiber membrane and manufacturing method of the same |
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