JPH01292174A - Graft polymerization - Google Patents
Graft polymerizationInfo
- Publication number
- JPH01292174A JPH01292174A JP12109788A JP12109788A JPH01292174A JP H01292174 A JPH01292174 A JP H01292174A JP 12109788 A JP12109788 A JP 12109788A JP 12109788 A JP12109788 A JP 12109788A JP H01292174 A JPH01292174 A JP H01292174A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- graft polymerization
- base material
- gas phase
- polyolefin
- 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.)
- Granted
Links
- 238000010559 graft polymerization reaction Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 8
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 7
- 239000002759 woven fabric Substances 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims abstract description 5
- 239000002861 polymer material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 7
- -1 polyethylene Polymers 0.000 abstract description 7
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polymerisation Methods In General (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高分子材料の改質および高機能化等の手段とし
て、その有効性が確認されつつある電離性放射線を用い
てグラフト重合する方法、即ち放射線グラフト重合方法
に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method of graft polymerization using ionizing radiation, whose effectiveness is being confirmed as a means of modifying and enhancing the functionality of polymeric materials. , that is, it relates to a radiation graft polymerization method.
（従来の技術）
放射線グラフト−重合は基材の特長を生かしながら他の
性質を付与することができるので、素材の高機能化を図
る先端産業分野で最近注目を浴びている重合方法である
０
従来の放射線グラフト重合方法は、基材をモノマー液中
で反応させる液相グラフト重合法が一般的であるが、七
ツマ−および洗浄薬品量を多く必要とするためランニン
グコストが高くなる欠点を有する。しかも、基材の形状
により洗浄薬品量は大きく異なる。例えば繊維状の基材
を使用すると液切れが非常に悪く、ロールプレス、遠心
分離、ろ過等の固液分離操作が必要となる。また、多孔
質の基材の場合は、微細孔からの薬品のリークが長時間
続くので、多量の洗浄薬品が必要であり洗浄時間も長く
かかる。更に洗浄排液の処理に注意を払う必要がある。(Conventional technology) Radiation graft polymerization is a polymerization method that has recently been attracting attention in the cutting-edge industrial field that aims to improve the functionality of materials because it can impart other properties while taking advantage of the characteristics of the base material. The conventional radiation graft polymerization method is generally a liquid phase graft polymerization method in which the base material is reacted in a monomer solution, but it has the disadvantage of high running costs because it requires a large amount of chemicals and cleaning chemicals. . Moreover, the amount of cleaning chemicals varies greatly depending on the shape of the base material. For example, when a fibrous base material is used, liquid drainage is extremely difficult, and solid-liquid separation operations such as roll pressing, centrifugation, and filtration are required. In addition, in the case of a porous base material, leakage of chemicals from micropores continues for a long time, so a large amount of cleaning chemicals are required and cleaning time is also long. Furthermore, it is necessary to pay attention to the treatment of cleaning waste liquid.
したがりて実際は非多孔性の粒子、膜以外はランニング
・コストがかなり高い。Therefore, in reality, running costs for non-porous particles and membranes are quite high.
（発明が解決しようとする課題）
一方、モノマーを気体状態で基材と接触させる気相グラ
フト重合法は、重合装置の密閉性に多少の配慮を必要と
するがモノマー量が非常に少なく、洗浄工程も不要であ
り、コスト的に有利である。さらに、気相グラフト重合
は反応に必要なモノマー量を所定量使用するだけで、グ
ラフト率のコントロールも可能である。(Problems to be Solved by the Invention) On the other hand, the gas phase graft polymerization method, in which monomer is brought into contact with the base material in a gaseous state, requires some consideration for the sealing of the polymerization equipment, but the amount of monomer is very small, and cleaning No process is required and it is advantageous in terms of cost. Furthermore, in gas phase graft polymerization, it is possible to control the grafting ratio by simply using a predetermined amount of monomers necessary for the reaction.
このように、気相グラフト重合は多くの利点を有するに
もかかわらず、未だ実用化されていない最大の原因は、
比較的蒸気圧の高いモノマーの場合しか適用できず、し
かもモノマー溶液に近い方の基材のグラフト率が高く、
遠い方が低くなるというグラフトむらができるためであ
る。As described above, although gas phase graft polymerization has many advantages, the main reason why it has not yet been put into practical use is
It can only be applied to monomers with relatively high vapor pressure, and the grafting rate of the base material near the monomer solution is high.
This is because the graft becomes uneven in that it becomes lower at the far end.
このように、従来の放射線グラフト重合方法は多くの問
題点を有しており、これが放射線グラフト重合の普及を
遅らせる原因にもなっていた。As described above, the conventional radiation graft polymerization method has many problems, which have also been the cause of delaying the spread of radiation graft polymerization.
本発明の目的は、気相グラフト重合の利点を維持しなが
ら、いかなる種類の重合性モノマーにおいてもグラフト
むらのないグラフト物が、極めて短時間で得られる実用
的な放射線グラフト重合方法を提供することである。An object of the present invention is to provide a practical radiation graft polymerization method that can obtain a grafted product without uneven grafting using any type of polymerizable monomer in an extremely short time while maintaining the advantages of gas phase graft polymerization. It is.
（課題を解決するための手段）
本発明は、基材である有機系高分子素材に電離性放射線
を照射したのち、減圧下においてグラフト重合反応を行
うにあたり、重合性モノマー溶液と基材とを少くとも一
度接触させることを特徴としている◇
ここで用いる電離性放射線はα、β、ｒ紫外線、電子線
などがあり、限定されるものではないが、ｒ線や電子線
が比較的本発明には適している。(Means for Solving the Problems) The present invention involves irradiating an organic polymer material as a base material with ionizing radiation and then performing a graft polymerization reaction under reduced pressure by combining a polymerizable monomer solution and a base material. ◇ The ionizing radiation used here includes α, β, r ultraviolet rays, and electron beams, and is not limited to them, but r-rays and electron beams are relatively suitable for the present invention. is suitable.
放射線グラフト重合に用いられる基材としては、有機高
分子化合物が適しており特にポリエチレン。As the base material used for radiation graft polymerization, organic polymer compounds are suitable, especially polyethylene.
ポリプロピレン等に代表されるポリオレフィン類。Polyolefins such as polypropylene.
ＰＴＦＥ、塩化ビニル等に代表されるハロゲン化ポリオ
レフィン類、エチレン−テトラフルオロエチレン共重合
体、エチレン−ビニルアルコール共重合体（ＥＶＡ）等
に代表されるオレフィン−ハロゲン化オレフィンの共重
合体類に適しているが、この範囲に限定されるわけでは
ない。Suitable for halogenated polyolefins represented by PTFE and vinyl chloride, and olefin-halogenated olefin copolymers represented by ethylene-tetrafluoroethylene copolymers, ethylene-vinyl alcohol copolymers (EVA), etc. However, it is not limited to this range.
また、モノマーとしてはビニル基を有する重合性単量体
であればいずれも使用可能である。例えば、アクリル酸
、アクロレイン、アクリロニトリル、メタクリル酸メチ
ル等のアクリル系単量体。Moreover, any polymerizable monomer having a vinyl group can be used as the monomer. For example, acrylic monomers such as acrylic acid, acrolein, acrylonitrile, and methyl methacrylate.
スチレン、クロルメチルスチレン等に代表されるスチレ
ン系の単量体、酢酸ビニルやビニルピリジン系の単量体
の他、ジビニルベンゼンに代表されるポリエン化合物も
使用可能であるが、この範囲に限定されるわけではない
。In addition to styrene monomers such as styrene and chloromethylstyrene, vinyl acetate and vinylpyridine monomers, polyene compounds such as divinylbenzene can also be used, but they are limited to this range. It's not like that.
基材に放射線を照射する方法としては、あらかじめ基材
を照射した後、モノマーと接触させる前照射法が、同時
照射法と較ベモノマーの単独重合物の生成が少ないので
、好ましいり
基材と七ツマ−との接触の仕方により、液相グラフト重
合と気相グラフト重合があり、コスト的には気相が有利
であるが、七ツマ−の種類によって蒸気圧が異なるので
蒸気圧の低いモノマーの場合には、グラ２トに要すモノ
マーの供給量が、モノマー発生箇所とグラフト部位との
位置関係により均一ではないため、グラフトむらができ
てしまう。さらに、反応時間も比較的長くなる０液相グ
ラフト重合の長所は、モノマーの蒸気圧とは無関係に、
均一なグラフト物が比較的短時間で得られることである
。これは、基材周辺のモノマー濃度が気相の場合に較べ
圧倒的に高いことによる。気相グラフト重合において、
基材周辺の七ツマー濃度を高めるには、モノマー液温を
高め蒸気圧を高めるか、七ツマー蒸発面積を増加させる
等の方法があるが、両者を同時に行っても基材が多量の
場合あまり効果がない０
基材の形状は特に限定する必要はないが、繊維状であり
、かつ成型品の形状が織布や不織布の場合が本発明には
特に適している０それは、織布や不織布は七ツマ−が含
浸し易（高いグラフト率が容易に得られること、および
均一なグラフト物が短時間で得られ、しかも洗浄不要と
いう本発明の効果が最も発揮される素材であるためであ
る。As a method for irradiating the base material with radiation, a pre-irradiation method in which the base material is irradiated in advance and then brought into contact with the monomer is preferable because it produces less homopolymer of the monomer than the simultaneous irradiation method. There are two types of graft polymerization: liquid-phase graft polymerization and gas-phase graft polymerization, depending on the method of contact with the polymer. Gas-phase graft polymerization is advantageous in terms of cost, but since the vapor pressure differs depending on the type of polymer, monomers with low vapor pressure are preferable. In this case, the amount of monomer supplied for grafting is not uniform depending on the positional relationship between the monomer generation location and the grafting location, resulting in uneven grafting. Furthermore, the advantage of zero-liquid phase graft polymerization, which requires a relatively long reaction time, is that regardless of the vapor pressure of the monomer,
A uniform grafted product can be obtained in a relatively short time. This is because the monomer concentration around the base material is overwhelmingly higher than that in the gas phase. In gas phase graft polymerization,
There are methods to increase the concentration of 7-mers around the substrate, such as raising the monomer liquid temperature to increase the vapor pressure, or increasing the 7-mer evaporation area, but even if you do both at the same time, if there is a large amount of the substrate, it will not be very effective. No effect 0 The shape of the base material does not need to be particularly limited, but it is particularly suitable for the present invention if it is fibrous and the shape of the molded product is woven fabric or non-woven fabric 0 It is a woven fabric or non-woven fabric This is because it is a material that can be easily impregnated with nanatsuma (a high grafting rate can be easily obtained), a uniform grafted product can be obtained in a short period of time, and the effects of the present invention are exhibited most, such as not requiring cleaning. .
（作用）
発明者等は、基材自身がモノマー発生源となれば、均一
で高いグラフト率のグラフト物が短時間で得られ、しか
も気相グラフトの特徴である反応後の洗浄不要という利
点がそのまま維持されるのではないか・と考え本発明た
至りた０本発明は基材に電離性放射線を照射したあと、
七ツマー溶液に含浸させ、減圧下で反応させるが、照射
したあと、モノマー溶液と基材を減圧にし、次いで含浸
させるようにしても良い。(Function) The inventors believe that if the base material itself becomes a monomer generation source, a uniform grafted product with a high grafting rate can be obtained in a short time, and there is also the advantage that there is no need for post-reaction cleaning, which is a characteristic of gas phase grafting. I came up with the present invention thinking that it might be maintained as it is.The present invention is based on the idea that after irradiating the base material with ionizing radiation,
Although the substrate is impregnated with a monomer solution and reacted under reduced pressure, the monomer solution and the substrate may be subjected to reduced pressure after irradiation, and then impregnated.
基材をモノマー溶液に含浸させ、液滴がない状態でグラ
フト反応を開始するので、反応速度が早くしかも七ツマ
−を完全に利用でき、単独重合物の生成が極めて少ない
。さらに、反応終了後のグラフト物が乾燥状態であり、
取扱いが容易であるばかりでなく、未反応モノマーを取
除（洗浄工程も不要である。また、本発明では、繊維状
の基材が好適であるが、それ以外の形状の基材において
も１、含浸および反応という工程を複数回繰返すことに
より高いグラフト率を得ることができる。そのためには
、基材とモノマー溶液が同一の減圧容器の内部に存在し
ている方が好都合である。もちろん繊維状や多孔質の基
材でも、より高いグラフト率を得る場合には含浸をさら
に繰返せばよい。Since the base material is impregnated with the monomer solution and the graft reaction is started in the absence of droplets, the reaction rate is fast, the monomer can be fully utilized, and the formation of homopolymers is extremely small. Furthermore, the grafted product is in a dry state after the completion of the reaction,
Not only is it easy to handle, but unreacted monomers are removed (no washing step is required.Also, in the present invention, a fibrous base material is preferred, but base materials of other shapes can also be used. A high grafting rate can be obtained by repeating the steps of , impregnation and reaction multiple times.For this purpose, it is more convenient for the base material and the monomer solution to be present inside the same vacuum container.Of course, the fiber If a higher grafting rate is to be obtained even in the case of a porous or porous substrate, the impregnation may be repeated further.
一方、比較的低いグラフト率を得たい場合や、含浸した
モノマーが全部反応する前に反応を停止させたい場合は
、減圧を破壊して空気を導入し、ラジカルの消滅した後
で、再度真空ポンプ等で吸引すれば、モノマーは容易に
蒸発する。繊維状や多孔質の基材は表面積が大きいので
、特に残留モノマーの蒸発速度が早く吸引除去するのが
容易である０
（実施例）
以下、本発明を実施例に基いて説明する。On the other hand, if you want to obtain a relatively low grafting rate, or if you want to stop the reaction before all the impregnated monomers have reacted, break the reduced pressure and introduce air, and after the radicals have disappeared, pump the vacuum again. If suction is applied, the monomer will easily evaporate. Since a fibrous or porous base material has a large surface area, the evaporation rate of the residual monomer is particularly high and it is easy to remove the residual monomer by suction.Examples The present invention will be explained below based on Examples.
（実施例１）
直径３０μのポリプロピレン製繊維よりなる不織布１０
ｇに加速電子線を２０ Ｍｒａｄ照射した後、クロルメ
チルスチレン溶液に浸漬し、過剰の液を紙でふきとった
。次いで、ガラスアンプルに投入し真空ポンプで吸引し
た後、５０℃の恒温槽に静置した。１．５時間経過後の
クロルメチルスチレンのグラフト率は１４６％であり、
グラフトむらは認められなかった。また、グラフト後の
不織布は完全に乾燥しており、洗浄の必要はなかりだ。(Example 1) Nonwoven fabric 10 made of polypropylene fibers with a diameter of 30μ
g was irradiated with an accelerated electron beam of 20 Mrad, then immersed in a chloromethylstyrene solution, and excess liquid was wiped off with paper. Next, the mixture was poured into a glass ampoule and suctioned with a vacuum pump, and then left in a constant temperature bath at 50°C. The grafting rate of chloromethylstyrene after 1.5 hours was 146%,
No graft unevenness was observed. Additionally, the nonwoven fabric is completely dry after grafting, so there is no need to wash it.
（比較例１）
実施例１と同様の条件で、不織布をクロルメチルスチレ
ンに浸漬させず、気相でグラフト重合を行ったところ、
１２時間後のグラフト率は６８％で、しかもアンプル底
部の基材のみがグラフトしており、グラフトむらが極端
であった。(Comparative Example 1) Graft polymerization was performed in the gas phase under the same conditions as in Example 1, without immersing the nonwoven fabric in chloromethylstyrene.
The grafting rate after 12 hours was 68%, and only the base material at the bottom of the ampoule was grafted, indicating extremely uneven grafting.
（実施例２）
ポリプロピレン製織布３００ｇに加速電子線を２０Ｍｒ
ａｄ照射した後、スチレン溶液に浸漬し、遠心分離によ
って含浸率１２６チまで液切をした。これを５ノのガラ
ス製真空容器に入れ、真空ポンプで吸引した後、５０℃
の恒温槽に静置した。２時間経過後のグラフト織布は乾
燥しており、重量が６６５ｇであった。即ち、グラフト
率１２２％と含浸率によってグラフト率をコントロール
することが可能であった。(Example 2) 20Mr accelerated electron beam was applied to 300g of polypropylene woven fabric.
After ad irradiation, the sample was immersed in a styrene solution and drained by centrifugation until the impregnation rate was 126 cm. This was placed in a 5-inch glass vacuum container, and after being suctioned with a vacuum pump, it was heated to 50°C.
It was placed in a constant temperature bath. After 2 hours, the grafted fabric was dry and weighed 665 g. That is, it was possible to control the grafting rate by adjusting the grafting rate of 122% and the impregnation rate.
（発明の効果）
本発明により、気相グラフト重合の洗浄不要という長所
をそのまま維持させながら、均一なグラフトおよびグラ
フト反応速度が大という液相グラフト重合の長所が゛極
めて簡単な方法により加味できるようになった。グラフ
ト重合を実用化する上で、技術面およびコスト面での難
題がこれにより一挙に解決された。(Effects of the Invention) According to the present invention, the advantages of liquid phase graft polymerization, such as uniform grafting and high graft reaction rate, can be added by an extremely simple method while maintaining the advantages of gas phase graft polymerization in that no washing is required. Became. This solved all the technical and cost problems in putting graft polymerization into practical use.
Claims (2)
、重合性モノマー溶液を含浸させ気相減圧下で反応させ
ることを特徴とするグラフト重合方法。(1) A graft polymerization method characterized by irradiating an organic polymer material with ionizing radiation, impregnating it with a polymerizable monomer solution, and reacting it under reduced pressure in a gas phase.
布である特許請求の範囲第１項記載のグラフト重合方法
。(2) The graft polymerization method according to claim 1, wherein the organic polymer material is a fibrous woven fabric or nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63121097A JPH0655995B2 (en) | 1988-05-18 | 1988-05-18 | Graft polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63121097A JPH0655995B2 (en) | 1988-05-18 | 1988-05-18 | Graft polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01292174A true JPH01292174A (en) | 1989-11-24 |
| JPH0655995B2 JPH0655995B2 (en) | 1994-07-27 |
Family
ID=14802804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63121097A Expired - Lifetime JPH0655995B2 (en) | 1988-05-18 | 1988-05-18 | Graft polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655995B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000009797A1 (en) * | 1998-08-12 | 2000-02-24 | Ebara Corporation | Base material for radiation graft polymerization and raw material for filter |
-
1988
- 1988-05-18 JP JP63121097A patent/JPH0655995B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000009797A1 (en) * | 1998-08-12 | 2000-02-24 | Ebara Corporation | Base material for radiation graft polymerization and raw material for filter |
| US6659751B1 (en) | 1998-08-12 | 2003-12-09 | Ebara Corporation | Apparatus for radiation-induced graft polymerization treatment of fabric webs |
| US6773654B2 (en) | 1998-08-12 | 2004-08-10 | Ebara Coporation | Polymer substrates for radiation-induced graft polymerization and filter stock |
| US6818038B2 (en) | 1998-08-12 | 2004-11-16 | Ebara Corporation | Polymer substrates for radiation-induced graft polymerization and filter stock |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655995B2 (en) | 1994-07-27 |
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