JPH082994B2 - Method for producing modified open-cell polyolefin foam - Google Patents
Method for producing modified open-cell polyolefin foamInfo
- Publication number
- JPH082994B2 JPH082994B2 JP62057742A JP5774287A JPH082994B2 JP H082994 B2 JPH082994 B2 JP H082994B2 JP 62057742 A JP62057742 A JP 62057742A JP 5774287 A JP5774287 A JP 5774287A JP H082994 B2 JPH082994 B2 JP H082994B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- polyolefin foam
- foam
- monomer
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は親水性連続気泡型ポリオレフイン発泡体の製
造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a hydrophilic open-cell type polyolefin foam.
（従来の技術および発明が解決しようとする問題点） 連続気泡型ポリオレフイン発泡体は耐薬品性に優れて
いるが樹脂の持つ性質として種々の液体に対し大きい接
触角を示し濡れ性に欠ける。従来、連続気泡型ポリオレ
フイン発泡体をクロム酸混液等で表面処理し若干の濡れ
性向上を計つた技術（例えば、特開昭61−281,139号）
があるが、連続気泡型ポリオレフイン発泡体が変色する
事や廃液処理の困難さを伴うものであつた。(Problems to be Solved by Conventional Techniques and Inventions) The open-celled polyolefin foam is excellent in chemical resistance, but the resin has a large contact angle with various liquids and lacks wettability. Conventionally, a technique of surface-treating an open-cell type polyolefin foam with a chromic acid mixture or the like to slightly improve wettability (for example, JP-A-61-281,139).
However, this was accompanied by discoloration of the open-celled polyolefin foam and difficulty in waste liquid treatment.
（問題点を解決するための手段） 本発明の目的はかかる欠点を解消し連続気泡型ポリオ
レフイン発泡体に親水性を与えるために親水性モノマー
の少なくとも１種、例えばアクリル酸，メタクリル酸，
アクリル酸エステル，メタクリル酸エステル，アクリル
アミド，ビニルピロリドンを放射線によりグラフト重合
させる方法を提供することにある。(Means for Solving the Problems) The object of the present invention is to eliminate such drawbacks and to impart hydrophilicity to the open-celled polyolefin foam, at least one hydrophilic monomer, for example, acrylic acid, methacrylic acid,
An object of the present invention is to provide a method for radiation-induced graft polymerization of acrylic acid ester, methacrylic acid ester, acrylamide, and vinylpyrrolidone.
本発明方法において連続気泡型ポリオレフイン発泡体
にアクリル酸等モノマーをグラフト重合する方法は電離
性放射線を用いる前照射法と同時照射法がある。すなわ
ち、前者の前照射法は次の通りである。In the method of the present invention, the method of graft-polymerizing a monomer such as acrylic acid onto the open-celled polyolefin foam includes a pre-irradiation method using ionizing radiation and a simultaneous irradiation method. That is, the former pre-irradiation method is as follows.
発泡体を電離性放射線で照射した後、モノマー水溶液
あるいはさらにこれに二塩化エチレン等ポリエチレンに
対して膨潤性を持つ有機溶剤を加えた混合液に接触させ
て発泡体にモノマーをグラフト重合させる。この場合、
二塩化エチレンはモノマーの発泡体中へ拡散するのを促
進する作用があり、グラフト重合速度を増大させる。こ
の方法において、電離性放射線としては、加速器よりの
電子線、コバルト60線源よりのγ線、Ｘ線発生装置より
のＸ線等が便利に用いられるが、特に加速器よりの電子
線が好ましい。線量率は特に制限がないが、電子線の場
合は１×104〜５×107rad/秒、線量は１〜20Mradが好ま
しく用いられる。照射後、それに接触させてグラフト重
合を行うモノマー水溶液、又はそれに二塩化エチレンを
加えたものには、グラフト重合に伴っておこるホモポリ
マーの生成を抑制するため少量のモール塩などの水溶性
第一鉄塩、硫酸銅等の水溶性第二銅塩、塩化第一銅等の
水溶性第一銅塩を溶液基準101mol/1までの濃度になるよ
うに添加する方が、アクリル酸のように重合速度の大き
いモノマーを用いる場合には好ましい。重合温度は特に
制限はないが、例えば室温から80℃が好ましく用いられ
る。After irradiating the foam with ionizing radiation, the foam is contacted with an aqueous solution of a monomer or a mixed solution of an organic solvent having swelling property against polyethylene such as ethylene dichloride to graft-polymerize the monomer on the foam. in this case,
Ethylene dichloride has the effect of promoting the diffusion of monomers into the foam and increases the rate of graft polymerization. In this method, as the ionizing radiation, an electron beam from an accelerator, a γ-ray from a cobalt 60-ray source, an X-ray from an X-ray generator, etc. are conveniently used, but an electron beam from an accelerator is particularly preferable. The dose rate is not particularly limited, but 1 × 10 4 to 5 × 10 7 rad / sec and a dose of 1 to 20 Mrad are preferably used in the case of an electron beam. After irradiation, a monomer aqueous solution which is brought into contact with it for graft polymerization, or one in which ethylene dichloride is added, contains a small amount of a water-soluble primary salt such as Mohr salt in order to suppress the formation of a homopolymer accompanying the graft polymerization. It is more like acrylic acid to add a water-soluble cupric salt such as iron salt or copper sulfate, or a water-soluble cuprous salt such as cuprous chloride to a concentration of 10 1 mol / 1 It is preferable to use a monomer having a high polymerization rate. The polymerization temperature is not particularly limited, but for example, room temperature to 80 ° C. is preferably used.
前記の後者の同時照射法は、連続気泡型ポリオレフイ
ン発泡体をモノマー水溶液あるいはそれに二塩化エチレ
ン等のポリオレフインの膨潤剤を加えた混合液に浸漬
し、あるいは含浸させて、電離性放射線を照射し、モノ
マーをグラフト重合させる方法である。モノマー溶液に
はグラフト重合に伴っておこるホモポリマーの生成を抑
制するため前述のホモ重合を抑制する作用を持つモール
塩等を104〜101mol/1添加するのが好ましい。電離性放
射線としては、電子線、γ線、Ｘ線等が便利に用いられ
る。線量率は電子線の場合104〜107rad/秒、γ線、Ｘ線
の場合103〜106rad/時が線量は１×103〜107rad、特に
１×104〜５×106radが好ましく用いられる。照射温度
については特に制限はないが室温より80℃までの温度が
便利に用いられる。The latter simultaneous irradiation method described above, the open-celled polyolefin foam is immersed in an aqueous solution of a monomer or a mixed solution containing a swelling agent of a polyolefin such as ethylene dichloride, or impregnated with the solution, and then irradiated with ionizing radiation, It is a method of graft-polymerizing a monomer. To the monomer solution, it is preferable to add 10 4 to 10 1 mol / 1 of the Mohr salt or the like having the action of suppressing the homopolymerization in order to suppress the formation of the homopolymer accompanying the graft polymerization. Electron beams, γ rays, X rays, etc. are conveniently used as the ionizing radiation. The dose rate is 10 4 to 10 7 rad / sec for electron beams and 10 3 to 10 6 rad / hr for γ rays and X-rays, the dose is 1 × 10 3 to 10 7 rad, especially 1 × 10 4 to 5 × 10 6 rad is preferably used. The irradiation temperature is not particularly limited, but a temperature from room temperature to 80 ° C is conveniently used.
本発明に用いる連続気泡型ポリオレフイン発泡体とは
ポリオチレン、ポリ1,2−ブタジェン、エチレン−プロ
ピレン共重合体、エチレン−ブテン共重合体、エチレン
−酢酸ビニル共重合体、エチレン含有量45％までのメチ
ル−、エチル−、プロピル−、ブチル−の各アクリレー
トもしくはメタアクリレートとの共重合体，またはこれ
らをそれぞれ塩素化したもの（塩素含有量60重量％ま
で）、あるいはこれらの２種以上の混合物またはこれら
とアタクチツクもしくはアイソタクチツク構造を有する
ポリプロピレンとの混合物等であるポリオレフインから
なるみかけ密度が0.02〜0.2g/cm3の発泡体である。The open-celled polyolefin foam used in the present invention means polyethylene, poly-1,2-butadiene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene content up to 45%. Methyl-, ethyl-, propyl-, butyl-copolymers with acrylates or methacrylates, or chlorinated products of these (chlorine content up to 60% by weight), or mixtures of two or more of these. A foamed product having an apparent density of 0.02 to 0.2 g / cm 3 comprising polyolefin, which is a mixture of these and polypropylene having an atactic or isotactic structure.
一方、本発明に用いるグラフト重合させる親水性モノ
マーとしては、アクリル酸，メタクリル酸，エチレング
リコールアクリレート，エチレングリコールメタアクリ
レート，トリメチロールプロパントリアクリレート，ト
リメチロールプロパントリメタアクリレート，アクリル
アミド，ビニルピロリドン,2−ヒドロキシエチルメタク
リレート，（ポリ）エチレングリコールジアクリレー
ト，（ポリ）エチレングリコールジメタアクリレート等
がある。On the other hand, as the hydrophilic monomer to be graft-polymerized used in the present invention, acrylic acid, methacrylic acid, ethylene glycol acrylate, ethylene glycol methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, acrylamide, vinylpyrrolidone, 2- Examples include hydroxyethyl methacrylate, (poly) ethylene glycol diacrylate, and (poly) ethylene glycol dimethacrylate.
（実施例） 次に、本発明を実施例により更に詳しく説明する。(Example) Next, the present invention will be described in more detail with reference to Examples.
実施例 １ 三和化工株式会社により開発された連続気泡型ポリオ
レフイン発泡体（エチレン−酢酸ビニル共重合体より成
る、商品名オプセルLC−300＃２、みかけ密度0.028g/cm
3）の試験片（５×60×160mm）を、シール付きポリエチ
レン製袋（50μｍ×120mm×200mm）に入れ、５分間窒素
置換し、バンデグラーフ型電子線加速器（米国ハイボル
テージ社製）を用い加速電圧1.5MeV、線量率1.75×105r
ad/secで、コンベヤーを用い（コンベヤースピード0.48
m/min）0.5Mrad/passで5Mrad照射後、試験片を25℃のア
クリル酸20％水溶液中に浸漬、脱器後30分間反応させ
る。更に水洗後、脱水、乾燥させ製品を得る。得られた
製品はアクリル酸のグラフト率が98.1％で、良好な親水
性を有していた。Example 1 Open-cell type polyolefin foam developed by Sanwa Kako Co., Ltd. (composed of ethylene-vinyl acetate copolymer, trade name Opcell LC-300 # 2 , apparent density 0.028 g / cm
3 ) Put the test piece (5 × 60 × 160 mm) in a polyethylene bag with seal (50 μm × 120 mm × 200 mm), replace with nitrogen for 5 minutes, and use a Van de Graaff electron beam accelerator (manufactured by High Voltage, USA). Acceleration voltage 1.5 MeV, Dose rate 1.75 × 10 5 r
Using a conveyor at ad / sec (conveyor speed 0.48
After irradiation with 5 Mrad at 0.5 Mrad / pass, the test piece is dipped in a 20% aqueous solution of acrylic acid at 25 ° C, and after removing the container, react for 30 minutes. Further, after washing with water, dehydration and drying are performed to obtain a product. The obtained product had a graft ratio of acrylic acid of 98.1% and had good hydrophilicity.
実施例 ２〜５ 実施例１と同様にオプセルLC−30＃２の試験片をバン
デグラーフ型電子線加速器を用いて5Mrad照射後、試験
片を禁止剤としてモール塩（８×10-5mol/1）を含む25
℃アクリル酸20％水溶液に浸漬、脱気後６分,15分,20
分,30分間反応させる。更に水洗後、脱水、乾燥させ製
品2,3,4,5を得る。得られた製品のアクリル酸のグラフ
ト率は２が8.6％、３が19.5％、４が30.0％、５が40.9
％でそれぞれ良好な親水性を有していた。Examples 2 to 5 As in Example 1, the test piece of Opcel LC-30 # 2 was irradiated with 5 Mrad using a Van de Graaff electron beam accelerator, and the test piece was treated with Mohr's salt (8 × 10 −5 mol / mol) as an inhibitor. 25 including 1)
℃ Dip in 20% acrylic acid aqueous solution, 6 minutes, 15 minutes, 20 after degassing
React for 30 minutes. After further washing with water, dehydration and drying are performed to obtain products 2, 3, 4, and 5. The graft ratio of acrylic acid of the obtained product is 2 8.6%, 3 19.5%, 4 30.0%, 5 40.9
%, Each had good hydrophilicity.
次に、実施例１〜５の様にして得られた試験片の66％
及び93％RHでの吸湿率および保水率を表１に示す。何れ
も良好な親水性が得られた。Next, 66% of the test pieces obtained as in Examples 1 to 5
Table 1 shows the moisture absorption rate and water retention rate at 93% RH. In all cases, good hydrophilicity was obtained.
吸湿率の測定は試験片を66％RH及び93％RHのデシケー
ター中に３日間放置した後、試験片の重量増加を測定
し、次式により吸湿率を求めた。The moisture absorption rate was measured by leaving the test piece in a desiccator of 66% RH and 93% RH for 3 days, measuring the weight increase of the test piece, and determining the moisture absorption rate by the following formula.
吸湿率＝（（放置後の試験片重量／試験片の乾燥重量） −１）×100（％） 保水率の測定は試験片を12時間水中に浸漬後、取り出
して水が出なくなるまで手で絞り重量を測定し、次式に
より保水率を求めた。Moisture absorption rate = ((weight of test piece after leaving / dry weight of test piece) -1) x 100 (%) The water retention rate was measured by immersing the test piece in water for 12 hours, and then removing it by hand until water disappeared. The squeezing weight was measured, and the water retention rate was calculated by the following formula.
保水率＝（（浸漬後の試験片重量／試験片の乾燥重量） −１）×100（％） 実施例 ６〜９ 実施例１と同様にオプセルLC−300＃２の試験片をバ
ンデグラーフ型電子線加速器を用いて5Mrad照射後、メ
タクリル酸，アクリルアミド，ビニルピロリドン，又は
２−ヒドロキシエチルメタクリレートをそれぞれグラフ
ト重合させ、得られた試験片の66％RH,93％RHにおける
吸湿率を表２に示す。Water retention rate = ((weight of test piece after immersion / dry weight of test piece) -1) x 100 (%) Examples 6 to 9 As in Example 1, the test piece of Opcel LC-300 # 2 was irradiated with 5 Mrad using a Van de Graaff electron beam accelerator, and then methacrylic acid, acrylamide, vinylpyrrolidone, or 2-hydroxyethyl methacrylate was respectively added. Table 2 shows the moisture absorption rates of the test pieces obtained by graft polymerization at 66% RH and 93% RH.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小原 長二 京都府京都市南区吉祥院西ノ庄東屋敷町93 (56)参考文献 特開 昭56−38333（ＪＰ，Ａ) 特開 昭61−106640（ＪＰ，Ａ) 特開 昭62−83006（ＪＰ，Ａ) 特開 昭62−258711（ＪＰ，Ａ) 特開 昭63−190602（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Choji Ohara 93 Kichijoin Nishinosho Higashiyashikicho, Minami-ku, Kyoto City, Kyoto Prefecture (56) References JP-A-56-38333 (JP, A) JP-A-61- 106640 (JP, A) JP 62-83006 (JP, A) JP 62-258711 (JP, A) JP 63-190602 (JP, A)
Claims (1)
で照射処理し、それと同時に又はその後に、照射された
発泡体を親水性モノマーの少なくとも１種を含有する水
溶液に接触させ、モノマーを発泡体にグラフト重合させ
ることにより表面改質された連続気泡型ポリオレフィン
発泡体を製造する方法において、 （ａ） 前記ポリオレフィン発泡体が、ポリエチレン、
ポリ1,2−ブタジエン、エチレン−プロピレン共重合
体、エチレン−ブテン共重合体、エチレン−酢酸ビニル
共重合体、エチレンと含有量45重量％までのメチル、エ
チル、ブチル若しくはプロピルの各アクリレート若しく
はメタクアリレートとの共重合体、これらをそれぞれ塩
素化したもの（塩素含有量60重量％まで）、これらの２
種以上の混合物、これらとアクタクチック若しくはアイ
ソタクチック構造を有するポリプロピレンとの混合物か
らなり、 （ｂ） 前記モノマーが、アクリル酸、メタクリル酸、
エチレングリコールアクリレート、エチレングリコール
メタアクリレート、トリメチロールプロパンアクリレー
ト、トリメチロールプロパントリメタアクリレート、ア
クリルアミド、ビニルピロリドン、２−ヒドロキシエチ
ルメタクリレート、又は（ポリ）エチレングリコールジ
メタアクリレートからなり、 （ｃ） ポリオレフィン発泡体に対して膨潤性を持つ二
塩化エチレンが、モノマー水溶液に加えられ、且つ （ｄ） グラフト重合に伴って生ずるホモポリマーの生
成を抑制するためのモール塩からなる水溶性第一鉄塩、
硫酸銅からなる水溶性第二銅塩又は塩化第一銅からなる
第一銅塩が加えられることを特徴とする方法。1. An open-celled polyolefin foam is irradiated with radiation, and at the same time or after that, the irradiated foam is contacted with an aqueous solution containing at least one hydrophilic monomer to form the foam in the monomer. In the method for producing a surface-modified open-celled polyolefin foam by graft polymerization, (a) the polyolefin foam is polyethylene,
Poly 1,2-butadiene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene and methyl, ethyl, butyl or propyl acrylate or meta with a content up to 45% by weight. Copolymers with qualate, chlorinated products of these (chlorine content up to 60% by weight), 2 of these
A mixture of at least one of these and a mixture of these and polypropylene having an atactic or isotactic structure, (b) the monomer is acrylic acid, methacrylic acid,
Ethylene glycol acrylate, ethylene glycol methacrylate, trimethylolpropane acrylate, trimethylolpropane trimethacrylate, acrylamide, vinylpyrrolidone, 2-hydroxyethyl methacrylate, or (poly) ethylene glycol dimethacrylate, (c) polyolefin foam A water-soluble ferrous salt consisting of Mohr's salt, which is added to the aqueous monomer solution, and (d) suppresses the formation of a homopolymer produced by the graft polymerization.
A method comprising adding a water-soluble cupric salt composed of copper sulfate or a cuprous salt composed of cuprous chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057742A JPH082994B2 (en) | 1987-03-12 | 1987-03-12 | Method for producing modified open-cell polyolefin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057742A JPH082994B2 (en) | 1987-03-12 | 1987-03-12 | Method for producing modified open-cell polyolefin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63223046A JPS63223046A (en) | 1988-09-16 |
| JPH082994B2 true JPH082994B2 (en) | 1996-01-17 |
Family
ID=13064363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62057742A Expired - Fee Related JPH082994B2 (en) | 1987-03-12 | 1987-03-12 | Method for producing modified open-cell polyolefin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082994B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090098359A1 (en) * | 2007-10-11 | 2009-04-16 | Waller Jr Clinton P | Hydrophilic porous substrates |
| EP2559806A1 (en) | 2011-08-17 | 2013-02-20 | Center of Excellence Polymer Materials and Technologies (Polimat) | Method for increasing the hydrophilicity of polymeric materials |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3032380A1 (en) * | 1979-09-04 | 1981-03-19 | Celanese Corp., 10036 New York, N.Y. | METHOD FOR PRODUCING HYDROPHILIC MICROPOROESE FILMS |
| JPS61106640A (en) * | 1984-10-30 | 1986-05-24 | Toa Nenryo Kogyo Kk | Hydrophilic microporous polyethylene membrane |
| JPS63190602A (en) * | 1986-01-07 | 1988-08-08 | Mitsubishi Rayon Co Ltd | Hydrophilic porous membrane and its manufacture |
| JPH0822374B2 (en) * | 1986-05-01 | 1996-03-06 | 旭化成工業株式会社 | Method for producing graft membrane |
-
1987
- 1987-03-12 JP JP62057742A patent/JPH082994B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63223046A (en) | 1988-09-16 |
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