JPS59117546A - Manufacture of porous polymeric film - Google Patents
Manufacture of porous polymeric filmInfo
- Publication number
- JPS59117546A JPS59117546A JP23070082A JP23070082A JPS59117546A JP S59117546 A JPS59117546 A JP S59117546A JP 23070082 A JP23070082 A JP 23070082A JP 23070082 A JP23070082 A JP 23070082A JP S59117546 A JPS59117546 A JP S59117546A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polymer film
- radiation
- irradiation
- etching
- 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
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】 この発明は、多孔性高分子フィルムの製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing porous polymer films.
さらに詳しくは、高エネルギー粒子の照射と化学的エツ
チング処理とを組合せた多孔性高分子フィルムの製造法
の改良に関する。More specifically, the present invention relates to an improved method for producing porous polymer films that combines irradiation with high-energy particles and chemical etching treatment.
多孔性高分子フィルムの製造法の一つとして従来から高
エネルギー粒子の照射と化学的エツチング処理とを組合
せた方法が知られている。この方法は、高分子フィルム
に加速イオン等の高エネルギー粒子を照射した場合にこ
れら粒子の通過した経路の近傍に照射損傷（例えば、高
分子フィルムの高分子鎮の開裂やイオン化等を意味する
）が生じそれによシ高エネルギー粒子の通過した部分と
通過しない部分とで化学的エツチング処理（例えば、水
酸化す） ＩＪウム等のアルカリ溶液への浸漬処理）に
よるエツチング速度に変化が生じることを利用したもの
であシ、損傷部分に対応して微小な孔が多数形成される
ものである。すなわち、図面で模式的に説明すれば第１
図において、高分子フィルム（１）における高エネルギ
ー粒子（２）の通過経路（３）近傍に形成された照射損
傷部分Ｂと通過の影響を受けない未損傷部分Ａにおける
エラ形成されるものであシ、この比が充分に太きけれに
第２図に示すような孔径の均一な孔（４）が形成され多
孔性高分子フィルムが得られる。しかし、従来の単なる
高エネルギー粒子の照射では、Ｂ部／Ａ部のエツチング
比が充分に大きくならずその結果、孔を形成するのに長
時間のエツチング時間を必要とし、第３図に示すように
、孔（４りが形成されても長時間のエツチングによって
損傷を受けていない高分子フィルム自体の表面部分Ａ′
がエツチングされてＰｇ ＜ ’ｌ り易く、さらに孔
（４つ自体もフィルムの厚み方向においてその孔径の変
化が大きいものであった。As one of the methods for producing porous polymer films, a method that combines irradiation with high-energy particles and chemical etching treatment has been known. In this method, when a polymer film is irradiated with high-energy particles such as accelerated ions, irradiation damage (e.g., cleavage or ionization of the polymer chain of the polymer film) occurs near the path of these particles. This process takes advantage of the fact that the etching rate changes due to chemical etching treatment (e.g., hydroxide treatment, immersion treatment in an alkaline solution such as IJum) between the areas where high-energy particles have passed and the areas where they have not. In this case, many tiny holes are formed corresponding to the damaged area. In other words, the first
In the figure, elas are formed in the irradiation-damaged part B, which is formed near the passage path (3) of the high-energy particles (2) in the polymer film (1), and in the undamaged part A, which is not affected by the passage. If this ratio is sufficiently large, pores (4) with uniform pore diameters as shown in FIG. 2 are formed and a porous polymer film is obtained. However, with conventional irradiation with high-energy particles, the etching ratio of part B/part A is not sufficiently large, and as a result, a long etching time is required to form holes, as shown in Figure 3. In addition, the surface area A' of the polymer film itself that has not been damaged by long-term etching even if holes are formed.
The pores (Pg <'l) were easily etched and the diameter of the 4 pores themselves varied greatly in the thickness direction of the film.
この発明は、このような従来の問題点に鑑みなされたも
のであり、照射損傷部分と未損傷部分とのエツチング速
度比を向上させて、エツチング処理時間の短縮、膜厚の
減少の抑制及び孔径の均一化を意図すべくなされたもの
である。The present invention was made in view of these conventional problems, and improves the etching rate ratio between radiation-damaged areas and undamaged areas, shortens etching processing time, suppresses reduction in film thickness, and improves pore diameter. This was done with the intention of making it more uniform.
かくしてこの発明によれば、高分子フィルムに加速イオ
ン等の高エネルギー粒子を照射して微小な照射損傷を形
成し、次いで化学的エツチング処理に付すことからなる
多孔性高分子フィルムの製造法において、照射損傷を受
けた高分子フィルムに、電離性放射線もしくは紫外線を
照射した後又は照射を行ないつつ化学的エツチング処理
に付すことを特徴とする多孔性高分子フィルムの製造法
が提供される。Thus, according to the present invention, in the method for producing a porous polymer film, the method comprises irradiating the polymer film with high-energy particles such as accelerated ions to form minute irradiation damage, and then subjecting the film to a chemical etching treatment. A method for producing a porous polymer film is provided, which comprises subjecting a polymer film damaged by radiation to a chemical etching treatment after or while irradiating with ionizing radiation or ultraviolet rays.
この発明において最も特徴とする点は、照射損傷を受け
た高分子フィルムをアルカリ等の化学的エツチング処理
に付すに当り、予め電離性放射線もしくは紫外線による
照射処理を行なうか又はエツチング時の高分子フィルム
に照射することである。The most distinctive feature of this invention is that when subjecting a polymer film that has been damaged by radiation to chemical etching treatment such as alkali, it is necessary to perform irradiation treatment with ionizing radiation or ultraviolet rays in advance, or to remove the polymer film during etching. irradiation.
上記電離性放射線や紫外線の照射によって、フィルム中
に形成されている高エネルギー粒子による照射損傷部分
における損傷度合、すなわち高分子鎖の開裂やイオン化
度合が増加され、結果的にエツチング速度の比Ｂ部／Ａ
部が増加されるものと考えられる。すなわち、電離性放
射線や紫外線は、照射損傷部分の増感作用を発現し、そ
れにより、意図する多孔性高分子フィルムが得られるも
のと信じられる。By irradiating the ionizing radiation or ultraviolet rays, the degree of damage, that is, the degree of cleavage and ionization of the polymer chain, in the portion damaged by the high-energy particles formed in the film is increased, and as a result, the etching rate ratio B is increased. /A
It is thought that the number of people will be increased. That is, it is believed that ionizing radiation and ultraviolet rays exert a sensitizing effect on areas damaged by radiation, and thereby the intended porous polymer film can be obtained.
この発明における高エネルギー粒子とは、高分子フィル
ムを貫通しかつ所望の照射損傷を形成し３−
うる公知の種々の荷電、非荷電粒子を意味し、具体的に
は核***性物質の核***によって得られる核***片、放
射性同位元素の崩壊によって得られるα粒子及び加速器
によって得られる加速イオン等が挙げられ、そのエネル
ギー域としては１〜１゜ＭｅＶが適当である。これらの
うち、通常、加速器による加速イオンを用いるのが工業
上簡便で好ましい。In this invention, high-energy particles refer to various charged and uncharged particles known to be capable of penetrating polymeric films and creating desired radiation damage, and specifically, particles that can be obtained by nuclear fission of fissile materials. These include nuclear fission fragments obtained by the decay of radioactive isotopes, α particles obtained by the decay of radioactive isotopes, and accelerated ions obtained by an accelerator.The appropriate energy range is 1 to 1° MeV. Among these, it is usually preferable to use accelerated ions using an accelerator because it is industrially convenient.
この発明に用いる高分子フィルムとしては、照射損傷と
化学的エツチング処理が適用される種々の高分子フィル
ムが挙げられ、具体的にはポリカーボネート、ポリエチ
レンテレフタレート、硝酸セｙｏ−ｘ、酢酸セルロース
、ポリフッ化ビニリデン、ポリテトラフルオロエチレン
、ポリアクリロニトリル等のフィルムが挙げられる。Examples of the polymer film used in this invention include various polymer films to which radiation damage and chemical etching treatments are applied. Examples include films of vinylidene, polytetrafluoroethylene, polyacrylonitrile, and the like.
この発明における化学的エツチング処理とは、化学処理
エツチング剤に高分子フィルムラ所定時間浸漬させて行
なう所謂湿式エツチング処理を示し、具体的な化学処理
エツチング剤としては、水酸化ナトリウム、重クロム酸
カリウム等のアル４−
カリ溶液や硝酸、硫酸等の酸性溶液が挙げられ高分子フ
ィルムの損傷を受けた部分を主として溶出しうる溶剤も
使用可能である。The chemical etching treatment in this invention refers to a so-called wet etching treatment in which a polymer film is immersed in a chemical etching agent for a predetermined period of time.Specific examples of the chemical etching agent include sodium hydroxide and potassium dichromate. Solvents that can mainly elute damaged portions of the polymer film can also be used, such as alkaline solutions such as Al-4-potassium solutions and acidic solutions such as nitric acid and sulfuric acid.
この発明における電離性放射線としては、前記高分子フ
ィルムの未損傷部分にはほとんど影響を与えないが、損
傷部分に対して増感作用を与える各種放射線が挙げられ
、具体的にはγ線、β線、χ線、加速電子線及びこれら
の反射、散乱によって得られる放射線等が挙げられる。Ionizing radiation in the present invention includes various types of radiation that have little effect on undamaged parts of the polymer film but have a sensitizing effect on damaged parts, specifically γ-rays, β-rays, etc. rays, x-rays, accelerated electron beams, and radiation obtained by reflection and scattering of these.
一方、この発明における紫外線としては２００〜４００
ｎｍ程度の比較的長波長な紫外線が挙げられ、中高圧
水銀灯超高圧水銀灯、メタルハライドランプ等からの紫
外線が利用できる。なお、上記電離性放射線や紫外線を
未損傷の高分子フィルムに照射しても高エネルギー粒子
を照射した際のごとき照射損傷は得られない。これらの
放射線や紫外線は、高エネルギー粒子による照射損傷部
分を効率良く増感することにのみ寄与しているものと考
えられる。従って、他の観点によればこの発明は高分子
フィルムに、意図する孔に対応する照射損傷を形成させ
、次いでかような照射損傷を形成し得ない電離性放射線
や紫外線を全体に照射した後、化学的エソテムの製造法
を提供するものである。On the other hand, the ultraviolet rays in this invention are 200 to 400
Examples include ultraviolet rays with a relatively long wavelength of about nm, and ultraviolet rays from medium-high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, etc. can be used. Incidentally, even if an undamaged polymer film is irradiated with the above-mentioned ionizing radiation or ultraviolet rays, the damage caused by the irradiation cannot be obtained as in the case of irradiation with high-energy particles. It is thought that these radiations and ultraviolet rays only contribute to efficiently sensitizing the areas damaged by irradiation with high-energy particles. Accordingly, another aspect of the present invention provides that the polymeric film is subjected to radiation damage that corresponds to the intended pores, and then after being irradiated with ionizing radiation or ultraviolet radiation that cannot form such radiation damage. , provides a method for producing chemical esothems.
なお、化学的エツチング処理と、同時にその照射を行な
っても同様な結果が得られる。Note that similar results can be obtained even if the chemical etching treatment and the irradiation are performed at the same time.
このようにして照射処理された又はされつつある高分子
フーｆルムを化学的エツチング処理に付すことにより、
所望の多孔性高分子フィルムが得られる。この際、得ら
れるフィルムは従来の照射法によるフィルムに比して膜
厚の減少も抑制されたものであり、形成された孔径の厚
み方向のばらつき、変動も小さい。従って各種フィルタ
ーとして好都合なものである。さらに同様な孔径の孔を
形成させる場合にもこの発明の方法によればその化学的
エツチング処理に要する時間を短縮させることができ、
逆に同じ化学的工）チング処理時間でも大きな孔径を有
する多孔佐高分子フィルムを得ることができる。By subjecting the polymer film that has been or is being irradiated in this way to a chemical etching treatment,
A desired porous polymer film is obtained. At this time, the film obtained has a reduced thickness that is suppressed compared to a film obtained by conventional irradiation methods, and variations and fluctuations in the diameter of the formed pores in the thickness direction are also small. Therefore, it is convenient for various filters. Furthermore, even when forming pores with similar pore diameters, the method of the present invention can shorten the time required for chemical etching treatment.
Conversely, a porous polymer film having a large pore size can be obtained even with the same chemical processing time.
以下、この発明全実施例により詳説する。Hereinafter, this invention will be explained in detail with reference to all embodiments.
実施例１
厚さ１２μｍのポリカーボネートフィルムに、加速器に
より加速されたＨｅイオンを照射後、さらに加速電子線
’ｉ ５ Ｍ ｒａｄ照射した。このフィルムラ６０℃
、６Ｎの水酸化ナトリウム溶液に６０分間浸漬してエツ
チングを行ない多孔性ポリカーボネートフィルムを得た
。エツチング終了後、水洗しす。Example 1 A polycarbonate film having a thickness of 12 μm was irradiated with He ions accelerated by an accelerator, and then further irradiated with an accelerated electron beam of 'i 5 M rad. This film la 60℃
A porous polycarbonate film was obtained by etching the film by immersing it in a 6N sodium hydroxide solution for 60 minutes. After etching, rinse with water.
比較例として、電子線の照射を行なわない以外第５図に
示す。A comparative example is shown in FIG. 5 except that no electron beam irradiation was performed.
その結果、この発明の多孔性ポリカーボネートフィルム
における孔径＃−１：２μｍであるのに対し比較例のも
のは１μｍであった。さらＫその孔の形状も比較例に比
し厚み方向に対して均一なものであった。As a result, the pore diameter #-1 in the porous polycarbonate film of the present invention was 2 μm, while that of the comparative example was 1 μm. Furthermore, the shape of the pores in K was also more uniform in the thickness direction than in the comparative example.
実施例２
７−
厚さ１２μｔｎのポリカーボネートフィルムに、加速器
によシ加速され７２Ｈｅイオンを照射後、さらに紫外線
（４００Ｗの高圧水銀灯を使用）を２時間照射した。こ
のフィルムラ６０℃、６Ｎの水酸化ナトリウム溶液に６
０分間浸漬してエツチングを行ない多孔性ポリカーボネ
ートフィルムを得た。エツチング終了後、水洗したのち
空気中で乾燥させ、実施例と同様にＳＫＭにてその孔径
全観察した。Example 2 7- A polycarbonate film with a thickness of 12 μtn was irradiated with 72He ions accelerated by an accelerator, and then further irradiated with ultraviolet rays (using a 400 W high-pressure mercury lamp) for 2 hours. This film was heated to 60℃ and 6N sodium hydroxide solution.
Etching was performed by dipping for 0 minutes to obtain a porous polycarbonate film. After etching, it was washed with water and then dried in the air, and the entire pore size was observed using SKM in the same manner as in Examples.
その結果、多孔性フィルムの孔径は３μｍであり、紫外
線未照射のものはｌ ｐＢであった。さらにその孔の形
状も紫外線未照射のものに比して、厚み方向の均一性も
優れたものであった。As a result, the pore diameter of the porous film was 3 μm, and the pore diameter of the porous film that had not been irradiated with ultraviolet rays was 1 pB. Furthermore, the shape of the pores was also superior in uniformity in the thickness direction compared to those not irradiated with ultraviolet rays.
第１図は、高分子フィルムに高エネルギー粒子全照射し
た状態を模式的に説明する部分断面図であり、第２図及
び第３図は、多孔性高分子フィルムの孔の形成状台ヲそ
れぞれ模式的に例示する部分断面図である。また第４図
はこの発明の方法によシ得られた多孔性高分子フィルム
の多孔構造を ８−
示す拡大平面写真であり、第５図は従来の方法により得
られた多孔性高分子フィルムの多孔構造を示す拡大平面
写真である。
（１）・・・高分子フィルム、
（２）・・・高エネルギー粒子、
（３）・・・通過経路、
（４）（４’）・・・ 了し。
第 Ｉ Ｍ
Ａ′４′
第４図
第８図FIG. 1 is a partial cross-sectional view schematically illustrating a state in which a polymer film is fully irradiated with high-energy particles, and FIGS. 2 and 3 show the formation of pores in a porous polymer film, respectively. FIG. 2 is a schematic partial cross-sectional view. Furthermore, FIG. 4 is an enlarged planar photograph showing the porous structure of the porous polymer film obtained by the method of the present invention, and FIG. 5 is an enlarged planar photograph showing the porous structure of the porous polymer film obtained by the conventional method. It is an enlarged planar photograph showing a porous structure. (1)...polymer film, (2)...high energy particles, (3)...passage path, (4)(4')...Complete. Figure 4 Figure 8
Claims (1)
子を照射して微小な照射損傷を形成し、次いで化学的エ
ツチング処理に付すことからなる多孔性高分子フィルム
の製造法において、照射損傷を受けた高分子フィルムに
、電離性放射線もしくは紫外線を照射した後又は照射を
行ないつつ化学的エツチング処理に付すことを特徴とす
る多孔性高分子フィルムの製造法。(1) In the manufacturing method of porous polymer film, which involves irradiating the polymer film with high-energy particles such as accelerated ions to form minute radiation damage, and then subjecting it to chemical etching treatment, A method for producing a porous polymer film, which comprises subjecting the porous polymer film to chemical etching treatment after or while irradiating it with ionizing radiation or ultraviolet rays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23070082A JPS59117546A (en) | 1982-12-25 | 1982-12-25 | Manufacture of porous polymeric film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23070082A JPS59117546A (en) | 1982-12-25 | 1982-12-25 | Manufacture of porous polymeric film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59117546A true JPS59117546A (en) | 1984-07-06 |
Family
ID=16911944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23070082A Pending JPS59117546A (en) | 1982-12-25 | 1982-12-25 | Manufacture of porous polymeric film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59117546A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02180624A (en) * | 1989-01-06 | 1990-07-13 | Sumitomo Electric Ind Ltd | Manufacture of porous polymer membrane |
| JP2008525180A (en) * | 2004-12-22 | 2008-07-17 | ドレセル プライヴェイト リミテッド | Membrane card and method for producing and using the same |
| WO2013145742A1 (en) | 2012-03-30 | 2013-10-03 | 日東電工株式会社 | Method for producing porous polymer film and porous polymer film |
| WO2014156154A1 (en) | 2013-03-27 | 2014-10-02 | 日東電工株式会社 | Manufacturing method for porous polymer film |
| WO2014156155A1 (en) | 2013-03-27 | 2014-10-02 | 日東電工株式会社 | Manufacturing method for porous polymer film, and porous polymer film |
-
1982
- 1982-12-25 JP JP23070082A patent/JPS59117546A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02180624A (en) * | 1989-01-06 | 1990-07-13 | Sumitomo Electric Ind Ltd | Manufacture of porous polymer membrane |
| JP2008525180A (en) * | 2004-12-22 | 2008-07-17 | ドレセル プライヴェイト リミテッド | Membrane card and method for producing and using the same |
| WO2013145742A1 (en) | 2012-03-30 | 2013-10-03 | 日東電工株式会社 | Method for producing porous polymer film and porous polymer film |
| WO2014156154A1 (en) | 2013-03-27 | 2014-10-02 | 日東電工株式会社 | Manufacturing method for porous polymer film |
| WO2014156155A1 (en) | 2013-03-27 | 2014-10-02 | 日東電工株式会社 | Manufacturing method for porous polymer film, and porous polymer film |
| US9708453B2 (en) | 2013-03-27 | 2017-07-18 | Nitto Denko Corporation | Method for producing porous polymer film and porous polymer film |
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