JPH03290446A - Processing of porous film - Google Patents
Processing of porous filmInfo
- Publication number
- JPH03290446A JPH03290446A JP9295490A JP9295490A JPH03290446A JP H03290446 A JPH03290446 A JP H03290446A JP 9295490 A JP9295490 A JP 9295490A JP 9295490 A JP9295490 A JP 9295490A JP H03290446 A JPH03290446 A JP H03290446A
- Authority
- JP
- Japan
- Prior art keywords
- porous film
- porous
- film
- processing
- inorganic
- 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
- 238000012545 processing Methods 0.000 title claims description 27
- 239000011148 porous material Substances 0.000 claims abstract description 42
- 230000035699 permeability Effects 0.000 claims abstract description 31
- 238000009832 plasma treatment Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003672 processing method Methods 0.000 claims description 6
- 229920006254 polymer film Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 229920000098 polyolefin Polymers 0.000 abstract description 10
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 239000001913 cellulose Substances 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
上の
本発明は、この多孔性フィルムの空孔径を任意に制御す
ることができ、かつ溶媒の透過性の機能を自由に、選択
的に付与することができる有用な多孔性フィルムの加工
法に関するものであ る。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a useful method in which the pore diameter of this porous film can be arbitrarily controlled and the function of solvent permeability can be freely and selectively imparted. It concerns a method for processing porous films.
ｍ術
多孔性フィルムは、その選択性透過機能から包装材、衣
料材などとして広く利用されているが、近年さらに気体
分離能や分子分離能を持つような高性能多孔性フィルム
が要求され、その空孔の大きさを制御することができる
だけでなく、かつ溶媒の透過性の機能を自由に１選択的
に付与することができる加工法が必要とされている。Porous films are widely used as packaging materials, clothing materials, etc. due to their selective permeation function, but in recent years there has been a demand for high-performance porous films with even higher gas separation and molecular separation capabilities. There is a need for a processing method that not only allows the size of the pores to be controlled, but also allows for selectively imparting the function of solvent permeability.
無機系多孔質材含有高分子フィルムには、種々のものが
開発され、高分子フィルム中にゼオライト、活性炭、大
谷石等を練り込んだものがある、これらはフィルム自体
のガス透過性、透湿性に加えて、さらに無機系多孔質の
ガス吸着、脱臭、抗菌作用を持つものである。このフィ
ルムの従来の加工法には、これらの既存の無機系多孔質
材を第１〜数ｌＯμ■の粒径に微粉砕したものを高分子
材料に練り込みインフレーション法等で成型＠票する方
法であり、成型加工条件によってフィルム自体の空孔径
および溶媒の透過性、透湿性、気体分離機能などの高機
能性が決められている。Various types of polymer films containing inorganic porous materials have been developed, including those in which zeolite, activated carbon, Oya stone, etc. are kneaded into the polymer film. In addition, it has inorganic porous gas adsorption, deodorizing, and antibacterial properties. The conventional processing method for this film involves pulverizing these existing inorganic porous materials to a particle size of 1 to several 10 μm, kneading it into a polymeric material and molding it using an inflation method, etc. The pore diameter of the film itself and high functionality such as solvent permeability, moisture permeability, and gas separation function are determined by the molding conditions.
前記の如く、均一な粒径の無機系多孔質材を練り込むな
どの成型加工条件によって多孔性フィルムの空孔の径お
よびそれに伴う機能性を任意に変化させているのが従来
の方法である。As mentioned above, the conventional method is to arbitrarily change the diameter of the pores of the porous film and the associated functionality by changing the molding conditions such as kneading an inorganic porous material with a uniform particle size. .
これに対して、今日まで成型された多孔性フィルムを後
処理することによってフィルム自体の空孔径および溶媒
の透過性、透湿性、気体分離機能などの高機能性を自由
に、選択的に付与することは不可能であり、特に多孔性
フィルムは溶媒の透過性に劣っている。又既存の無機系
多孔質材自体の空孔径制御も困難であった。そこで本発
明は、従来の加工技術の問題点を解決した、簡便に空孔
径を任意制御でき、かつ多孔性フィルムの有用な加工法
を提供することを目的とするものである。On the other hand, by post-processing the porous films that have been molded to date, it is possible to freely and selectively impart the pore size of the film itself and high functionality such as solvent permeability, moisture permeability, and gas separation function. Porous films in particular have poor solvent permeability. Furthermore, it has been difficult to control the pore diameter of existing inorganic porous materials themselves. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for processing a porous film that solves the problems of conventional processing techniques, allows easy arbitrary control of the pore diameter, and is useful for processing porous films.
占 るための手
本発明者らはこれらの欠点を解決するために、多孔性フ
ィルムおよび気体分離能、分子分離能を持つ高性能多孔
性フィルムなどの将来性に着目し、多孔性フィルムに高
機能性を自由に、選択的に付与させることについて鋭意
広範囲な系統的研究を行った結果、多孔性フィルム表面
に低温プラズマ処理を行うことによってフィルム自体の
空孔径および溶媒の透過性などの高機能性を自由に１選
択的に付与することができ、所期の効果が得られること
を見い出し１本発明に到達したものである。In order to solve these drawbacks, the present inventors focused on the future potential of porous films and high-performance porous films with gas separation ability and molecular separation ability. As a result of intensive and extensive systematic research into freely and selectively imparting functionality, we found that high-performance properties such as the pore size and solvent permeability of the film itself can be achieved by performing low-temperature plasma treatment on the surface of the porous film. The present invention was achieved based on the discovery that the desired effect can be obtained by freely and selectively imparting the desired effect.
低温プラズマによって素材表面領域数オンクーストロー
ム−数千オンクーストトムの範囲内でエツチング、分解
され、 また低温プラズマ処理の際に用いられるガス種
により素材表面の活性化が決定されることは既知の如く
である。この現象に注目し、シリカ系多孔質材の一種で
あるクリストバライトの微粉末を含む多孔性フィルム表
面に低温プラズマ処理することにより、フィルムのエツ
チングおよび活性化によってフィルム自体の空孔径を広
げることができ、かつ溶媒の透過性などの高機能性を自
由に、選択的に付与させることができた。It is well known that low-temperature plasma etches and decomposes the surface area of a material within a range of a few to several thousand koostomes, and that the activation of the material surface is determined by the type of gas used during low-temperature plasma treatment. be. Focusing on this phenomenon, by applying low-temperature plasma treatment to the surface of a porous film containing fine powder of cristobalite, a type of silica-based porous material, it is possible to expand the pore diameter of the film itself by etching and activating the film. , and it was possible to freely and selectively impart high functionality such as solvent permeability.
このような低温プラズマ処理を用いる本発明の多孔性フ
ィルムの加工工程は従来のそれと非常に異なるものであ
る。すなわち従来法では、多孔性フィルムの空孔径の大
きさはフィルム生成前の成型条件によって決められてい
た。これに対して本発明法では、多孔性フィルム生成後
のプラズマ処理条件によって決められることができた。The processing process of the porous film of the present invention using such low temperature plasma treatment is very different from conventional ones. That is, in the conventional method, the size of the pore diameter of the porous film was determined by the molding conditions before film production. On the other hand, in the method of the present invention, it was possible to determine the plasma treatment conditions after forming the porous film.
単なるフィルムをプラズマ処理することによって多孔性
フィルムが得られないことは良く知られている。 また
、時開Ｖｉ５６−９０８３８では、 「ポリプロピレン
多孔性フィルムをプラズマ処理した結果素材表面が親水
化し、孔径を大きくできても透水性をうるまでには至ら
なかった。」と記載されている。シリカ系多孔質材の一
種であるクリストバライトの微粉末を１０重量％以上含
む多孔性フィルム表面に低温プラズマ処理し、エツチン
グすることによってフィルム自体の空孔径が更に広げら
れ、かつ溶媒の透過性を高める現象を見いだし、本発明
に到達した。It is well known that porous films cannot be obtained by simply plasma treating a film. In addition, Jikai Vi56-90838 states, ``As a result of plasma treatment of a polypropylene porous film, the surface of the material became hydrophilic, and even though the pore size could be increased, water permeability could not be achieved.'' By subjecting the surface of a porous film containing 10% by weight or more of fine powder of cristobalite, a type of silica-based porous material, to low-temperature plasma treatment and etching, the pore diameter of the film itself is further expanded and the permeability of solvents is increased. We discovered this phenomenon and arrived at the present invention.
クリストバライトの微粉末を１０１量％未満含有する多
孔性フィルムおよびクリストバライト以外の無機化合物
（例えばゼオライト、ＣａＣ○、など）を含有する多孔
性フィルムでは、上記の現象に到らなかった。The above phenomenon did not occur with porous films containing less than 101% by weight of fine cristobalite powder and porous films containing inorganic compounds other than cristobalite (for example, zeolite, CaC◯, etc.).
本発明の目的は、低温プラズマ処理法により多孔性フィ
ルムの空孔径を任意に制御することができ、かつ溶媒の
透過性の機能を自由に、選択的に付与することができる
有用な多孔性フィルムの加工法を提供することにある。An object of the present invention is to provide a useful porous film in which the pore diameter of the porous film can be arbitrarily controlled by a low-temperature plasma treatment method, and in which a solvent permeability function can be freely and selectively imparted. The objective is to provide a processing method for
豊」Ｌ曵」Ｌ曵
本発明に用いる多孔性フィルムは、高分子材料であるが
、例えばポリオレフィン系としてポリプロピレン、ポリ
エチレン、ポリブタジェン等や、ポリスチレン、 ポリ
エステル、セルロース、多糖類が挙げられ、また、これ
らの材質のブレンド系でもかま♂ない。上記の高分子材
料中に分散するクリストバライトは、 シリカ系天然多
孔質鉱物で、粒径が１μｍから１００μｍの範囲のもの
が最も好ましい。その含有率は１０％以上であるが、２
０％〜４０％が好ましい、フィルムの膜厚は０．１μｍ
から１００μｍが好ましい。The porous film used in the present invention is made of a polymeric material, such as polyolefins such as polypropylene, polyethylene, polybutadiene, polystyrene, polyester, cellulose, and polysaccharides. A blend of materials is also acceptable. The cristobalite dispersed in the above polymeric material is a silica-based natural porous mineral, and most preferably has a particle size in the range of 1 μm to 100 μm. Its content is 10% or more, but 2
The film thickness is preferably 0% to 40%, 0.1 μm
to 100 μm is preferable.
また、その形状はフィルム状のみならず不織布、紙、ｌ
ｌｌ１維等とのラミネート状でもかまゎない。In addition, the shape is not only film-like, but also non-woven fabric, paper, l
A laminate with ll1 fiber etc. may also be used.
本発明の多孔性フィルム素材を低温プラズマ処理するこ
とにより、素材表面領域がエツチングされると同時に活
性化されて、フィルム自体の空孔径を広げることができ
、かつ溶媒の透過性などの高機能性を自由に、選択的に
付与させることかできる。By subjecting the porous film material of the present invention to low-temperature plasma treatment, the surface region of the material is etched and activated at the same time, making it possible to expand the pore size of the film itself and to improve functionality such as solvent permeability. can be given freely and selectively.
溶媒とは、水、溶質（無機、有機化合物）の水溶液、ア
ルコールおよびベンゼンなどの有機溶媒、それらの混合
溶媒を扉開する。Solvents include water, aqueous solutions of solutes (inorganic and organic compounds), organic solvents such as alcohol and benzene, and mixed solvents thereof.
この素材表面領域のエツチングおよび活性化を行う低温
プラズマ処理条件の決定要素はガスの成分、圧力、流量
であり、さらに出力、処理時間であり、 これらにより
多孔性フィルムの透水性などの可能性が決定される。The determining factors of the low-temperature plasma processing conditions for etching and activating the surface area of the material are the gas composition, pressure, and flow rate, as well as the output power and processing time, which determine the water permeability of the porous film. It is determined.
本発明のプラズマガスは窒素、歎素、水素。The plasma gas of the present invention is nitrogen, nitrogen, or hydrogen.
アルゴン、ネオン、ヘリウム、空気、水！！糺塩素、ア
ンモニア、−酸化炭素、二酸化炭素、亜酸化窒素、二酸
化窒素、二酸化イオウ、フロン等が有り、さらに重合性
プラズマガスがあり。Argon, neon, helium, air, water! ! These include chlorine, ammonia, carbon oxide, carbon dioxide, nitrous oxide, nitrogen dioxide, sulfur dioxide, and chlorofluorocarbons, as well as polymerizable plasma gases.
これらは単独または混合して使用可能であるが。These can be used alone or in combination.
特に多孔性フィルムの透水性などの可能性には無機ガス
が有効であり、非極性溶媒の透過性にはフロン系の有機
ガスが有効である。In particular, inorganic gases are effective for increasing the water permeability of porous films, and fluorocarbon-based organic gases are effective for increasing the permeability of nonpolar solvents.
本発明の目的を速攻するには、低温プラズマ処理ガスの
分圧５０）ル以下、より好ましくは５×１０−ｚトル以
下の雰囲気とすることが望ましい。２０トルを越える分
圧をもつプラズマ雰囲気中では、プラズマ処理の効果が
急激に低下する。プラズマガスの流量は反応器の容積お
よびプラズマガスの分圧により決定される。To quickly achieve the object of the present invention, it is desirable to create an atmosphere in which the partial pressure of the low-temperature plasma processing gas is 50) torr or less, more preferably 5 x 10 -z torr or less. In a plasma atmosphere with a partial pressure greater than 20 Torr, the effectiveness of plasma processing decreases rapidly. The flow rate of the plasma gas is determined by the volume of the reactor and the partial pressure of the plasma gas.
出力は一般に５００ワツト以下で使用される場合が多い
が、処理時間との組合せにより目的の性能をうることが
可能である。Although the output is generally 500 watts or less, it is possible to obtain the desired performance by combining it with the processing time.
プラズマ処理時間は素材の種類や形状および処理装置な
どによって異なるが、通常数秒から数十分間であり、好
ましくは５分〜１５分間程度である。The plasma processing time varies depending on the type and shape of the material, the processing equipment, etc., but is usually from several seconds to several tens of minutes, preferably from about 5 minutes to 15 minutes.
プラズマガスを、プラスチック素材およびガラス素材の
表面に作用させる場合、多くの組合せが考えられる。す
なわち、反応器の構造、電源の種類、周波数、放電形式
および電極の位置などさまざまの選択が可能である。When applying plasma gas to the surfaces of plastic materials and glass materials, many combinations are possible. That is, various choices can be made, such as the structure of the reactor, the type of power source, frequency, discharge format, and electrode position.
プラズマ処理にあたり、電源としては高周波（１３，５
６ＭＨ２）、マイクロ波（２，４５ＧＨｚ）−低周波（
数ＫＨｚ）などがある、放電方式としてはグロー放電が
有効である。！ｌ！た、電極の位置については内部式お
よび外部式等があるが、効果の均一性を考えれば内部式
の方が操作が容品である。For plasma processing, high frequency (13,5
6MH2), microwave (2,45GHz) - low frequency (
As a discharge method, glow discharge is effective. ! l! Regarding the position of the electrodes, there are internal and external types, but the internal type is easier to operate in terms of uniformity of effect.
上記のガス種、ガス流量、 出力および処理時間などの
プラズマ処理条件の組合せにより、任意の孔径サイズに
処理を行うことが可能である。By combining the above plasma treatment conditions such as gas type, gas flow rate, output, and treatment time, it is possible to perform treatment to any pore size.
なるべく出力数は２００ＷＪＸ下で処理時間を伸ばすこ
とで処理を行う方が、フィルムの形状を損なわずに孔径
を広げることができ有効である。It is more effective to extend the treatment time under an output of 200 WJX as much as possible, as this allows the pore diameter to be expanded without impairing the shape of the film.
プラズマ処理時間は、 １〜３６００秒、 好ましくは
１〜１８００秒である。The plasma treatment time is 1 to 3600 seconds, preferably 1 to 1800 seconds.
プラズマガスをフィルム表面に作用させる場合、反応器
の構造、電源の種類、周波数、放電方式および電極の位
置等様々の選択が可能であり、 とくに限定されるもの
ではない。When plasma gas is applied to the film surface, various choices can be made such as the structure of the reactor, the type of power source, the frequency, the discharge method, the position of the electrodes, etc., and there are no particular limitations.
なお、本発明において制御できるフィルムの孔径の晩囲
は、０．０１μｍから１０００μｍであり、少す＜トも
０，１０μｍ以下の精度で制御できる。The range of the pore diameter of the film that can be controlled in the present invention is from 0.01 μm to 1000 μm, and can be controlled with an accuracy of 0.10 μm or less.
以下、実施例によって本発明をさらに詳細に説明するが
１本発明は以下の実施例に限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples.
実施例１
クリストバライトを１０、３０．４０重ｔ％含有するポ
リプロピレン系多孔性フィルムをそれぞれ低温プラズマ
処理した。Example 1 Polypropylene porous films containing 10 and 30.40% by weight of cristobalite were treated with low-temperature plasma, respectively.
そのプラズマ処理条件：
プラズマ処理装置は、高周波発生装置により１３．５８
ＭＨｚの高周波をマツチングボックスを通して一定の電
圧が加わるグロー放電方式の内部電極型を用いた。まず
、前期の試料をガラス製プラズマチャンバー内に吊り下
げ、チャンバー内を十分に脱気した後、０．０５ｔｏｒ
ｒの圧力になるよう酸素ガスまたはフロンガスを導入し
た。その後、出力５０〜３００Ｗで、３０〜６００秒間
プラズマ放電を行った。The plasma processing conditions: The plasma processing equipment uses a high frequency generator to
A glow discharge internal electrode type was used in which a constant voltage was applied through a matching box with a high frequency of MHz. First, the sample from the previous period was suspended in a glass plasma chamber, and after the chamber was sufficiently degassed, the sample was heated to 0.05 Torr.
Oxygen gas or fluorocarbon gas was introduced to the pressure of r. Thereafter, plasma discharge was performed for 30 to 600 seconds at an output of 50 to 300W.
次に、走＊型電子顕微＃ （ＳＥＭ）およびポロシメー
ターによりプラズマ処理された多孔性フィルム、未処理
多孔性フィルムの表面分析を行った。＊た、ガラス製ろ
過装置を用いて、蒸留水、エタノール、ベンゼンを１０
０ｍ１注ぎ、大気圧下、３０分放置後の透過量を測定し
た。Next, the surface of the plasma-treated porous film and the untreated porous film was analyzed using a scanning electron microscope (SEM) and a porosimeter. * Using a glass filtration device, distilled water, ethanol, and benzene were
The amount of permeation was measured after pouring 0ml and leaving it for 30 minutes under atmospheric pressure.
これらの測定の結果を表１〜３に示す。The results of these measurements are shown in Tables 1-3.
比較例
クリストバライトを５重量％含有するポリオレフィン系
多孔性フィルム（市飯名ＮＣフィルム）、ゼオライトを
５重量％含有するポリオレフィン系多孔性フィルム（市
原名ユニエース）、大谷石を５重量％含有させたポリオ
レフィン系多孔性フィルム（市販名ＦＨフィルム）、Ｃ
ａＣＯ５を１５重量％含有するポリオレフィン系フィル
ム（市原名 通気性フィルム）、無機系多孔質材を全く
含有しないポリオレフィン系多孔性フィルム（市販名工
スボアール）を用い、それぞれ実施例１と同様にプラズ
マ処理を行い、溶媒の透過性についても同様に測定した
。その結果を表４に示す。Comparative Examples Polyolefin porous film containing 5% by weight of cristobalite (Ichiiina NC Film), polyolefin porous film containing 5% by weight of zeolite (Ichihara Uniace), polyolefin containing 5% by weight of Oya stone system porous film (commercial name: FH film), C
A polyolefin film containing 15% by weight of aCO5 (Ichihara Breathable Film) and a polyolefin porous film containing no inorganic porous material (commercially available Meiko Suboar) were each subjected to plasma treatment in the same manner as in Example 1. The solvent permeability was also measured in the same manner. The results are shown in Table 4.
以下余白。Margin below.
表１ プラズマ処理多孔性フィルム（クリ訃Ａ−ライト
含有）の溶媒透過性表２ プラズマ出力の溶媒透過性に
対する影響・ 試料：クリストへ−ライト３０ｗｔ％１
【有ボリプ゛ｃＩヒ゛レン系多孔性フィルム・プラズマ
処理条件（ガス種＝０２．ガス流量： ２０ｍ１／第１
ｉｎ、処理時間： １８０ｓｅｃ）表３ プラズマ処理
時間の溶媒透過性に対する影響・＊）プラズマ処理条件
（出方： ３００ＩＩＩ、ガス流１ｋ ： ２０ＩＩ第
１／ｍｉｎ、処理時間： １８０ｓｅｃ）・ −測定不
能
・ 試料：クリストバライト３０ｗｔ％１【有ホ゛リフ
゛ロビレン系多孔性フィルム・プラズマ処理条件（ガス
種＝０２．ガス流量： ２０ｍ１／ｌｌｌ１ｎ、出カニ
３ｏｏ第１）・ −刻定不和
表４
プラズマ処理多孔性フィルム（無機系多孔質材含有）の
溶媒透過性・ 実施例１ ：クリストカー９４１３０ｗ
ｔ％含有 １リフ゛ロヒ“リン系多孔性フィルム・ 本
）プラズマ処理条件（ガス種：０２．出カニ３００Ｗ、
ガス流量： ２０第１／Ｕｎ、処理時間： １８０ｓｅ
ｃ）
・表面状態： Ｏ：空孔拡大、Ｏ：多孔質材浮き出る等
の表面形状変化、ｘ：変化なし
以上のことから、 １０重量％以上クリストバライトを
含有する多孔性フィルムは、表面に低温プラズマ処理を
行うと、空孔が拡大し、溶媒の透過性が高まることが確
認された。さらに、プラズマ処理条件の選択により空孔
径の制御が可能であることが判明した。Table 1 Solvent permeability of plasma-treated porous film (containing Krysto A-Lite) Table 2 Effect of plasma output on solvent permeability Sample: Krysto A-Lite 30wt%1
[Porous film with polypropylene] Plasma treatment conditions (gas type = 02. Gas flow rate: 20 m1/1st
in, processing time: 180 sec) Table 3 Effect of plasma processing time on solvent permeability *) Plasma processing conditions (output: 300III, gas flow 1k: 20II 1st/min, processing time: 180 sec) - Unmeasurable - Sample: cristobalite 30 wt% 1 [polypyropylene-based porous film, plasma treatment conditions (gas type = 02, gas flow rate: 20 m1/lll1n, output crab 30 1st) - Engraved discord table 4 Plasma treated porous film ( Solvent permeability of inorganic porous material (containing inorganic porous material) Example 1: Christker 94130w
t% content 1 reflow phosphorus-based porous film) Plasma treatment conditions (gas type: 02. Output 300W,
Gas flow rate: 20 1st/Un, processing time: 180se
c) ・Surface condition: O: expansion of pores, O: change in surface shape such as protrusion of porous material, x: no change. From the above, a porous film containing 10% by weight or more of cristobalite has a low-temperature plasma on the surface. It was confirmed that the treatment enlarges the pores and increases solvent permeability. Furthermore, it has been found that the pore diameter can be controlled by selecting plasma treatment conditions.
また、 ５重量％クリストバライト、 ５重量％ゼオラ
イト、 ５重量％大谷石をそれぞれ含有するポリオレフ
ィン系多孔性フィルムおよび無機多孔質材を含有しない
ポリオレフィン系多孔性フィルムは、表面に低温プラズ
マ処理を行っても空孔拡大が認められず、溶媒の透過性
も高めることは出来なかった。さらに、１５重量％Ｃａ
ＣＯＩ含有ポリオレフィン系多孔性フィルムにおいて
は、空孔拡大が認められたが、実施例１と同様に溶媒透
過性を高めることは出来なかった。In addition, polyolefin porous films containing 5 wt% cristobalite, 5 wt% zeolite, and 5 wt% otani stone, and polyolefin porous films containing no inorganic porous material, do not survive low-temperature plasma treatment on their surfaces. No pore expansion was observed, and it was not possible to increase solvent permeability. Furthermore, 15 wt% Ca
In the COI-containing polyolefin porous film, pore expansion was observed, but as in Example 1, the solvent permeability could not be increased.
及」Ｌ恩」Ｌ基
本発明における多孔性フィルムの加工法は、プラズマ処
理条件を変化させることで、フィルムの孔径を正確に調
整することができ、かつ透水性、非透水性、透湿性、気
体骨ａｎなどの高機能を自由に選択的に付与することが
できる。The processing method for porous film in the basic invention allows the pore size of the film to be precisely adjusted by changing the plasma treatment conditions, and also allows for water permeability, non-water permeability, moisture permeability, and gas permeability. High functions such as bone ant can be freely and selectively imparted.
さらに、 このプラズマ処理は、 ドライプロセスで短
時間に行えるため、省力的である。また、成形量の二次
加工が可能であるため、繰り返し加工を施すこともでき
る。この加工法により目的に合わせて孔径をミクロンオ
ーダーで制御したフィルムは、高い選択的透過性をもつ
分離瞑として、医療用材、衣料材、包装材、燃料電池用
マトリックス、産業資材等へ広く使用できる。Furthermore, this plasma treatment is a dry process that can be performed in a short time, which is labor-saving. In addition, since secondary processing of the amount of molding is possible, repeated processing can be performed. Through this processing method, the pore size is controlled to the micron order according to the purpose, and the film can be widely used as a separating film with high selective permeability in medical materials, clothing materials, packaging materials, fuel cell matrices, industrial materials, etc. .
さらに目的とする大きさの生物学的試料等を固定化でき
る担体としても期待できる。Furthermore, it can be expected to be used as a carrier that can immobilize biological samples of a desired size.
Claims (1)
媒の透過性を高めることを特徴 とする多孔性フィルムの加工法。 ２、多孔性フィルムが、無機系多孔質材を１０重量％以
上含有する高分子フィルムである特許請求の範囲第１項
記載の多孔性フィルムの加工法。 ３、低温プラズマ処理が、ガス圧０．０１〜１０ｔｏｒ
ｒ無機および有機ガスの存在下に行われる低温プラズマ
照射である特許請求の第１項記載の多孔性フィルムの加
工法。 ４、溶媒が水、水溶液、有機溶媒である特許請求の第１
項記載の多孔性フィルムの加工法。 ５、無機系多孔質材が、クリストバライトを主成分とす
る多孔質材である特許請求の第２項記載の多孔性フィル
ムの加工法。[Scope of Claims] 1. A method for processing a porous film, characterized by subjecting the surface of the porous film to low-temperature plasma treatment to increase solvent permeability. 2. The method for processing a porous film according to claim 1, wherein the porous film is a polymer film containing 10% by weight or more of an inorganic porous material. 3. Low-temperature plasma treatment is performed at a gas pressure of 0.01 to 10 torr.
4. The method of processing a porous film according to claim 1, which comprises low temperature plasma irradiation carried out in the presence of inorganic and organic gases. 4. The first claim in which the solvent is water, an aqueous solution, or an organic solvent
Processing method of porous film described in Section 1. 5. The method for processing a porous film according to claim 2, wherein the inorganic porous material is a porous material containing cristobalite as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9295490A JPH03290446A (en) | 1990-04-07 | 1990-04-07 | Processing of porous film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9295490A JPH03290446A (en) | 1990-04-07 | 1990-04-07 | Processing of porous film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03290446A true JPH03290446A (en) | 1991-12-20 |
Family
ID=14068853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9295490A Pending JPH03290446A (en) | 1990-04-07 | 1990-04-07 | Processing of porous film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03290446A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5552115A (en) * | 1986-02-06 | 1996-09-03 | Steris Corporation | Microbial decontamination system with components porous to anti-microbial fluids |
| JPH11300180A (en) * | 1998-02-20 | 1999-11-02 | Mitsubishi Chemical Corp | Porous resin membrane |
| WO2009127653A1 (en) * | 2008-04-15 | 2009-10-22 | Gelita Ag | Rapidly wetting material containing hydrocolloid, method for the manufacture thereof and use thereof |
| JP2017500185A (en) * | 2013-12-16 | 2017-01-05 | サビック グローバル テクノロジーズ ビー．ブイ． | Plasma-treated polymer membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5293679A (en) * | 1976-02-02 | 1977-08-06 | Sumitomo Chem Co Ltd | Manufacture of semipermeable membrane |
| JPS55746A (en) * | 1978-06-20 | 1980-01-07 | Showa Gomme Kk | Manufacturing of micro-porous material |
| JPS61212303A (en) * | 1985-03-14 | 1986-09-20 | バイエル・アクチエンゲゼルシヤフト | Porous membrane |
| JPS62106806A (en) * | 1985-09-10 | 1987-05-18 | Kanebo Ltd | Filter of superb water permeability and superb resistance to compaction |
| JPH02208333A (en) * | 1989-02-08 | 1990-08-17 | Tonen Corp | Porous hydrophilic polyolefin film and its production |
-
1990
- 1990-04-07 JP JP9295490A patent/JPH03290446A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5293679A (en) * | 1976-02-02 | 1977-08-06 | Sumitomo Chem Co Ltd | Manufacture of semipermeable membrane |
| JPS55746A (en) * | 1978-06-20 | 1980-01-07 | Showa Gomme Kk | Manufacturing of micro-porous material |
| JPS61212303A (en) * | 1985-03-14 | 1986-09-20 | バイエル・アクチエンゲゼルシヤフト | Porous membrane |
| JPS62106806A (en) * | 1985-09-10 | 1987-05-18 | Kanebo Ltd | Filter of superb water permeability and superb resistance to compaction |
| JPH02208333A (en) * | 1989-02-08 | 1990-08-17 | Tonen Corp | Porous hydrophilic polyolefin film and its production |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5552115A (en) * | 1986-02-06 | 1996-09-03 | Steris Corporation | Microbial decontamination system with components porous to anti-microbial fluids |
| US5833935A (en) * | 1994-01-28 | 1998-11-10 | Steris Corporation | Microbial decontamination system with components porous to anti-microbial fluids |
| JPH11300180A (en) * | 1998-02-20 | 1999-11-02 | Mitsubishi Chemical Corp | Porous resin membrane |
| WO2009127653A1 (en) * | 2008-04-15 | 2009-10-22 | Gelita Ag | Rapidly wetting material containing hydrocolloid, method for the manufacture thereof and use thereof |
| JP2017500185A (en) * | 2013-12-16 | 2017-01-05 | サビック グローバル テクノロジーズ ビー．ブイ． | Plasma-treated polymer membrane |
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