JP2002371471A - Porous base material made of hydrophilicity-given polyolefin resin and method for producing the same - Google Patents
Porous base material made of hydrophilicity-given polyolefin resin and method for producing the sameInfo
- Publication number
- JP2002371471A JP2002371471A JP2001175878A JP2001175878A JP2002371471A JP 2002371471 A JP2002371471 A JP 2002371471A JP 2001175878 A JP2001175878 A JP 2001175878A JP 2001175878 A JP2001175878 A JP 2001175878A JP 2002371471 A JP2002371471 A JP 2002371471A
- Authority
- JP
- Japan
- Prior art keywords
- porous substrate
- polyolefin resin
- acid amide
- vinylcarboxylic acid
- electron beam
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリオレフィン系樹
脂からなる多孔質性基材、例えば、織布または不織布を
改質し、優れた保水性を持たせる方法、及び、優れた保
水性を持たせたポリオレフィン系樹脂からなる織布また
は不織布に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying a porous substrate made of a polyolefin resin, for example, a woven or non-woven fabric, so as to have excellent water retention, and to provide excellent water retention. And a woven or non-woven fabric made of a polyolefin resin.
【０００２】更に、本発明で得られた、優れた保水性を
有するポリオレフィン系樹脂からなる織布または不織布
は、電池用セパレータ、保湿剤、衛生食品等に用いられ
る。Further, the woven or nonwoven fabric made of a polyolefin resin having excellent water retention obtained by the present invention is used for battery separators, humectants, sanitary foods and the like.
【０００３】[0003]
【従来の技術】ポリオレフィン系の樹脂は化学的に安定
で、耐薬品性にも優れることから、それを構成材料とす
る基材は、種々の用途に使用されている。しかし、ポリ
オレフィン系の基材は、疎水性が大きいため、保水性を
必要とする、電池用セパレータ、保湿剤、衛生用品等に
使用し難いという問題点があった。2. Description of the Related Art Polyolefin-based resins are chemically stable and have excellent chemical resistance. Therefore, base materials comprising the same are used for various purposes. However, since the polyolefin-based substrate has a large hydrophobicity, there has been a problem that it is difficult to use it for a battery separator, a humectant, a sanitary article, etc., which requires water retention.
【０００４】保水性を高める手段として、特開平２−８
７４６０号にはプラズマ処理による親水性を持つ官能基
をを付与する方法が示されている。また特開平５−１８
６９６４号にはポリオレフィン樹脂からなる不織布をス
ルホン化して親水化する方法が示されている。しかし、
プラズマ処理による方法では工程が複雑となり、生産性
が低いという問題がある。スルホン化法では反応率が低
く、コントロールも難しいという問題がある。[0004] As means for increasing water retention, Japanese Patent Laid-Open No. 2-8 / 1990
No. 7460 discloses a method of imparting a hydrophilic functional group by plasma treatment. Japanese Patent Laid-Open No. 5-18
No. 6964 discloses a method of sulfonating a non-woven fabric made of a polyolefin resin to make it hydrophilic. But,
The plasma processing method has a problem that the process is complicated and productivity is low. The sulfonation method has a problem that the reaction rate is low and control is difficult.
【０００５】特開平８−１３３３７には、ポリオレフィ
ンに不飽和カルボン酸またはその誘導体を放射線の照射
でグラフト重合する方法が示されている。しかし、不飽
和カルボン酸またはその誘導体のグラフト処理では、そ
れらの親水性のモノマーの他にジビニルベンゼンを添加
しなければ、十分なグラフト率と保水性が得られない。JP-A-8-13337 discloses a method in which an unsaturated carboxylic acid or a derivative thereof is graft-polymerized to a polyolefin by irradiation with radiation. However, in the grafting of an unsaturated carboxylic acid or a derivative thereof, a sufficient graft ratio and water retention cannot be obtained unless divinylbenzene is added in addition to those hydrophilic monomers.
【０００６】ポリオレフィンに対する電子線照射により
Ｎ−ビニルカルボン酸アミドをグラフト重合する方法
は、特開平９−２７８８３４号にポリオレフィン系のフ
ィルム、シートにグラフト重合する方法が示されている
が、織布または不織布の様な多孔質性基材にグラフト重
合する方法は示されていない。Japanese Patent Application Laid-Open No. 9-278834 discloses a method for graft polymerization of N-vinyl carboxylic acid amide by electron beam irradiation on polyolefin. The method includes graft polymerization on polyolefin-based films and sheets. No method is disclosed for graft polymerization on a porous substrate such as a nonwoven fabric.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、疎水性の大
きいポリオレフィン系樹脂からなる多孔質性基材、例え
ば、織布または不織布の親水性を向上させ、保水性を必
要とする電池用セパレータ、保湿材、衛生用品等に好適
な材料とすることを課題とする。特に電池用セパレータ
用に好適な材料である、ポリオレフィン系樹脂の不織布
を提供することを課題とする。SUMMARY OF THE INVENTION The present invention relates to a battery separator which requires a water-retaining property by improving the hydrophilicity of a porous substrate made of a polyolefin resin having high hydrophobicity, for example, a woven or nonwoven fabric. It is an object to provide a material suitable for a humectant, a hygiene article, and the like. In particular, it is an object of the present invention to provide a nonwoven fabric of a polyolefin resin, which is a material suitable for a battery separator.
【０００８】また、Ｎ−ビニルカルボン酸アミドの存在
下、電子線を照射することにより、ポリオレフィン系樹
脂からなる織布または不織布に親水性を向上させる方法
を提供することを課題とする。Another object of the present invention is to provide a method for improving the hydrophilicity of a woven or nonwoven fabric made of a polyolefin resin by irradiating an electron beam in the presence of N-vinylcarboxylic acid amide.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、前記課題
を解決するため鋭意検討した結果、ポリオレフィン系樹
脂からなる多孔質性基材に親水性モノマーであるＮ−ビ
ニルカルボン酸アミドを特に電子線照射処理によりグラ
フト重合することにより、親水性に優れたポリオレフィ
ン系樹脂からなる多孔質性基材が得られることを見出し
本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the N-vinylcarboxylic acid amide, which is a hydrophilic monomer, has been particularly applied to a porous substrate made of a polyolefin resin. The present inventors have found that a porous base material made of a polyolefin-based resin having excellent hydrophilicity can be obtained by performing graft polymerization by electron beam irradiation treatment, and completed the present invention.
【００１０】また、Ｎ−ビニルカルボン酸アミドをポリ
オレフィン系樹脂からなる多孔質性基材にグラフト重合
処理する場合に、電子線照射処理をすることにより、効
率的にグラフト重合できることを見出し、本発明を完成
した。この際より好ましくは、ポリオレフィン系樹脂か
らなる多孔質性基材にＮ−ビニルカルボン酸アミド溶液
を含浸した後に電子線処理することにより、より効率よ
くグラフト重合処理可能である。In addition, it has been found that, when N-vinylcarboxylic acid amide is graft-polymerized to a porous substrate made of a polyolefin resin, the graft polymerization can be efficiently performed by electron beam irradiation. Was completed. In this case, more preferably, the graft polymerization treatment can be performed more efficiently by impregnating the porous substrate made of a polyolefin resin with the N-vinylcarboxylic acid amide solution and then performing the electron beam treatment.
【００１１】更に、Ｎ−ビニルカルボン酸アミドをグラ
フト重合処理したポリオレフィン系樹脂の多孔質性基材
は、優れた化学的安定性、耐薬品性と優れた吸水性を併
せ持つため、電池用セパレータ、保湿材、衛生用品等に
好適であり、特に電池用セパレータ用に有用である。Further, the porous base material of the polyolefin resin obtained by graft polymerization of N-vinylcarboxylic acid amide has excellent chemical stability, chemical resistance and excellent water absorption. It is suitable for humectants, sanitary articles, etc., and is particularly useful for battery separators.
【００１２】すなわち、本発明は下記の多孔質性基材、
その製造方法、その多孔質性基材を用いる電池用セパレ
ータを提供する。That is, the present invention provides the following porous substrate:
Provided are a manufacturing method thereof and a battery separator using the porous substrate.
【００１３】［１］下記一般式（１）のＮ−ビニルカル
ボン酸アミドがグラフト重合していることを特徴とす
る、ポリオレフィン系樹脂からなる多孔質性基材。 ＣＨ2＝ＣＨ−Ｎ（Ｒ1）−ＣＯ−Ｒ2 （１） （式中、Ｒ1、Ｒ2は互いに独立して、水素原子またはメ
チル基を示す。）[1] A porous substrate comprising a polyolefin resin, wherein an N-vinylcarboxylic acid amide represented by the following general formula (1) is graft-polymerized. CH 2 ＣＨCH—N (R 1 ) —CO—R 2 (1) (In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
【００１４】［２］Ｎ−ビニルカルボン酸アミドをグラ
フト重合処理する際に、その処理方法が電子線照射する
手段である、［１］に記載される多孔質性基材。[2] The porous substrate according to [1], wherein, when the N-vinylcarboxylic acid amide is subjected to the graft polymerization treatment, the treatment method is a means for irradiating an electron beam.
【００１５】［３］グラフト重合処理するに際し、ポリ
オレフィン系樹脂からなる多孔質性基材にＮ−ビニルカ
ルボン酸アミド溶液を含浸した後に、電子線照射するこ
とを特徴とする［２］に記載される多孔質性基材。[3] The method according to [2], wherein the graft polymerization treatment is performed by impregnating a porous substrate made of a polyolefin resin with an N-vinylcarboxylic acid amide solution and then irradiating with an electron beam. Porous substrate.
【００１６】［４］Ｎ−ビニルカルボン酸アミドがＮ−
ビニルアセトアミドである［１］から［３］のいずれか
に記載される多孔質性基材。[4] N-vinylcarboxylic acid amide is N-
The porous substrate according to any one of [1] to [3], which is a vinylacetamide.
【００１７】［５］多孔質性基材が織布または不織布で
あることを特徴とする［１］から［４］のいずれかに記
載の多孔質性基材。[5] The porous substrate according to any one of [1] to [4], wherein the porous substrate is a woven or nonwoven fabric.
【００１８】［６］下記一般式（１）のＮ−ビニルカル
ボン酸アミドがグラフト重合しているポリオレフィン系
樹脂からなる多孔質性基材を製造する方法において、電
子線照射によりグラフト重合処理することを特徴とする
ポリオレフィン系樹脂からなる多孔質性基材の製造方
法。 ＣＨ2＝ＣＨ−Ｎ（Ｒ1）−ＣＯ−Ｒ2 （１） （式中、Ｒ1、Ｒ2は互いに独立して、水素原子またはメ
チル基を示す。）[6] In the method for producing a porous base material comprising a polyolefin resin on which N-vinylcarboxylic acid amide represented by the following general formula (1) is graft-polymerized, graft-polymerizing treatment by electron beam irradiation: A method for producing a porous substrate comprising a polyolefin-based resin, characterized in that: CH 2 ＣＨCH—N (R 1 ) —CO—R 2 (1) (In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
【００１９】［７］Ｎ−ビニルカルボン酸アミドをグラ
フト重合処理するに際し、ポリオレフィン系樹脂からな
る多孔質性基材にＮ−ビニルカルボン酸アミド溶液を含
浸した後に、電子線照射することを特徴とする［６］に
記載されるポリオレフィン系樹脂からなる多孔質性基材
の製造方法。[7] In the graft polymerization of N-vinyl carboxylic acid amide, a porous substrate made of a polyolefin resin is impregnated with an N-vinyl carboxylic acid amide solution and then irradiated with an electron beam. A method for producing a porous substrate comprising a polyolefin resin according to [6].
【００２０】［８］Ｎ−ビニルカルボン酸アミドがＮ−
ビニルアセトアミドである［６］または［７］に記載の
ポリオレフィン系樹脂からなる多孔質性基材の製造方
法。[8] N-vinylcarboxylic acid amide is N-vinylcarboxylic acid amide
A method for producing a porous substrate comprising the polyolefin resin according to [6] or [7], which is vinylacetamide.
【００２１】［９］［１］から［４］に記載されるポリ
オレフィン系樹脂からなる多孔質性基材を用いた電池用
セパレータ。[9] A battery separator using a porous substrate made of the polyolefin resin described in [1] to [4].
【００２２】[0022]
【発明の実施の形態】以下更に詳しく本発明を説明す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail.
【００２３】本発明で用いるポリオレフィン系樹脂とし
ては、種々のポリマーが使用できる。たとえば高圧法ポ
リエチレン、中低圧法ポリエチレン、はポリプロピレ
ン、ポリプロピレン−エチレン共重合体、ポリブテン−
１、ポリ３メチルブテン−１、ポリ４−メチルペンテン
−１、エチレン−酢酸ビニル共重合体、エチレン−アク
リル酸共重合体、エチレン−アクリル酸エステル共重合
体などがあげられる。これらのポリマーはそれぞれ単独
で或いは２種類以上を組み合わせて用いても良い。また
本発明の目的を損なわない範囲で通常用いられる添加
剤、たとえば、滑剤、帯電防止剤、可塑剤、酸化防止剤
等を含んでいても良い。Various polymers can be used as the polyolefin resin used in the present invention. For example, high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, polypropylene-ethylene copolymer, polybutene-
1, poly-3-methylbutene-1, poly4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer and the like. These polymers may be used alone or in combination of two or more. Further, additives which are usually used within a range not to impair the object of the present invention, for example, a lubricant, an antistatic agent, a plasticizer, an antioxidant and the like may be contained.
【００２４】本発明で用いる基材としては柔軟で、強度
にすぐれた多孔質性基材が使用される。多孔質性基材と
しては、例えば、織布、不織布があげられる。特に電池
用セパレータとしては不織布が好ましい。多孔質性基材
のの製法としては特に限定はないが不織布としては繊維
材料からメルトブロー法で製造されたものが微細孔を有
するため好ましい。これらの多孔質性基材の厚さは、そ
の用途によって適宜選択できるが、たとえば電池セパレ
ータ用に使用される場合には目付が１０〜３００ｇ／ｍ
２、厚みは０．０１〜５mm、好ましくは０．１〜１ｍｍ
である。厚さが０．１ｍｍ以下では十分な量の電解液保
持ができず、機械的強度も不足する。また１ｍｍを超え
ると電池用セパレータとして十分な機能を発揮できな
い。As the substrate used in the present invention, a porous substrate having flexibility and excellent strength is used. Examples of the porous substrate include a woven fabric and a nonwoven fabric. In particular, a nonwoven fabric is preferable as the battery separator. The method for producing the porous substrate is not particularly limited, but a nonwoven fabric produced by a melt-blowing method from a fiber material is preferable because it has fine pores. The thickness of these porous substrates can be appropriately selected depending on the application. For example, when used for a battery separator, the basis weight is 10 to 300 g / m 2.
2. The thickness is 0.01 to 5 mm, preferably 0.1 to 1 mm
It is. If the thickness is 0.1 mm or less, a sufficient amount of electrolyte cannot be held, and the mechanical strength is also insufficient. On the other hand, if it exceeds 1 mm, a sufficient function as a battery separator cannot be exhibited.
【００２５】本発明で用いるＮ−ビニルカルボン酸アミ
ドは下記一般式で示される。 ＣＨ2＝ＣＨ−Ｎ（Ｒ1）−ＣＯ−Ｒ2 （１） （式中、Ｒ1，Ｒ2は互いに独立して水素原子またはメチ
ル基を示す。）The N-vinylcarboxylic acid amide used in the present invention is represented by the following general formula. CH 2 ＣＨCH—N (R 1 ) —CO—R 2 (1) (In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
【００２６】具体的には、Ｎ−ビニルアセトアミド、Ｎ
−メチル−Ｎ−ビニルアセトアミド，Ｎ−メチル−Ｎ−
ビニルホルムアミド、Ｎ−ビニルホルムアミドがあげら
れ、特にＮ−ビニルアセトアミドが好ましい。Specifically, N-vinylacetamide, N
-Methyl-N-vinylacetamide, N-methyl-N-
Examples thereof include vinyl formamide and N-vinyl formamide, and N-vinyl acetamide is particularly preferred.
【００２７】これらのＮ−ビニルカルボン酸アミドはそ
れぞれ単独で、あるいは二種以上を組み合わせて用いて
もよい。さらに本発明の目的である親水性化を損なわな
い限りにおいて、共重合可能な他のモノマー、たとえば
アクリル酸、アクリル酸塩、アクリルアミド誘導体、ア
クリル酸エステル、酢酸ビニルなどと併せて用いてもよ
い。These N-vinylcarboxylic acid amides may be used alone or in combination of two or more. Further, as long as the object of the present invention does not impair the hydrophilicity, it may be used in combination with other copolymerizable monomers such as acrylic acid, acrylate, acrylamide derivative, acrylate, vinyl acetate and the like.
【００２８】本発明においてはポリオレフィン系樹脂か
らなる織布または不織布を構成材料とする基材にＮ−ビ
ニルカルボン酸アミドを電子線照射する手段によりグラ
フト重合処理される。電子線照射する手段によるグラフ
ト処理は、基材に電子線を照射し、活性点を生成させた
後、Ｎ−ビニルカルボン酸アミドを接触させることもで
きる。また基材とＮ−ビニルカルボン酸アミドを接触共
存下で電子線を照射する方法でも可能である。この時、
Ｎ−ビニルカルボン酸アミドを溶かす溶媒としては、Ｎ
−ビニルカルボン酸アミドの重合を阻害しないものが好
ましい。具体的には、水、酢酸エチル、酢酸ブチル等の
カルボン酸エステル類、シクロヘキサン等の炭化水素、
メタノール、ブタノール、エチレングリコール等のアル
コール類等である。In the present invention, a substrate made of a woven or nonwoven fabric made of a polyolefin resin is subjected to graft polymerization by means of electron beam irradiation with N-vinyl carboxylic acid amide. In the grafting treatment by means of electron beam irradiation, the substrate may be irradiated with an electron beam to generate active sites, and then contacted with N-vinylcarboxylic acid amide. Alternatively, a method in which an electron beam is irradiated in the presence of a substrate and N-vinyl carboxylic acid amide in contact and coexistence is also possible. At this time,
Solvents for dissolving N-vinylcarboxylic acid amide include N
Those which do not inhibit the polymerization of vinylcarboxylic acid amide are preferred. Specifically, water, ethyl acetate, carboxylic acid esters such as butyl acetate, hydrocarbons such as cyclohexane,
Alcohols such as methanol, butanol and ethylene glycol.
【００２９】グラフト量はＮ−ビニルカルボン酸アミド
濃度により調製することができる。Ｎ−ビニルカルボン
酸アミド濃度としては１〜９０質量％が望ましい。１質
量％未満であるとグラフト化が十分に行なわれず、９０
質量％を超えると均一なグラフト化が行なわれず、局所
的にゲル状物が発生するようになり好ましくない。The amount of grafting can be adjusted by the concentration of N-vinylcarboxylic acid amide. The N-vinylcarboxylic acid amide concentration is preferably from 1 to 90% by mass. When the amount is less than 1% by mass, grafting is not sufficiently performed, and
If the amount is more than mass%, uniform grafting is not performed, and a gel-like substance is locally generated, which is not preferable.
【００３０】本発明で用いる電子線の加速電圧は、用い
る多孔質性基材樹脂の種類に応じて適宜かえることがで
きるが、通常、５０ｋＶ〜１０００ｋＶ、好ましくは１
００ｋＶ〜４００ｋＶで、空気雰囲気下または不活性ガ
ス（窒素、アルゴン等）雰囲気下にて行なわれる。また
照射線量としては１０〜５００ｋＧｙ、好ましくは５０
〜２００ｋＧｙが適当である。１０ｋＧｙ未満ではグラ
フト化が十分行なわれず、５００ｋＧｙを超えると基材
の劣化が著しくなるので好ましくない。The accelerating voltage of the electron beam used in the present invention can be appropriately changed according to the kind of the porous base resin used, but is usually 50 kV to 1000 kV, preferably 1 kV to 1000 kV.
It is carried out at 00 kV to 400 kV under an air atmosphere or an inert gas (nitrogen, argon, etc.) atmosphere. The irradiation dose is 10 to 500 kGy, preferably 50 kGy.
~ 200 kGy is appropriate. If it is less than 10 kGy, the grafting will not be sufficiently performed, and if it exceeds 500 kGy, the deterioration of the substrate will be remarkable, which is not preferable.
【００３１】[0031]
【実施例】以下実施例及び比較例により本発明を具体的
に説明するが、本発明はこれらの限定されるものではな
い。なお以下の各例における物性測定は、次の方法で行
なった。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The measurement of physical properties in the following examples was performed by the following methods.
【００３２】１）グラフト率：グラフト反応後の試料を
水洗し、６０℃、２４時間真空乾燥後に秤量し、グラフ
ト反応前に対する質量増加率をグラフト率とした。1) Graft ratio: The sample after the graft reaction was washed with water, dried under vacuum at 60 ° C. for 24 hours, weighed, and the rate of mass increase relative to that before the graft reaction was defined as the graft ratio.
【００３３】２）保液率 ：幅５０ｍｍ、長さ１００
ｍｍの試料を用い、グラフト反応後の試料を水洗し、６
０℃、２４時間真空乾燥後、２３℃で水に１０分間浸漬
し、水から引き上げ１０分後の試験片の質量を浸漬前の
質量と比較し、質量増加率を求めた。2) Liquid retention rate: width 50 mm, length 100
mm, the sample after the graft reaction was washed with water,
After vacuum drying at 0 ° C. for 24 hours, the test piece was immersed in water at 23 ° C. for 10 minutes, pulled up from the water, compared with the weight of the test piece after 10 minutes with the weight before immersion, and the rate of mass increase was determined.
【００３４】［実施例１］Ｎ−ビニルアセトアミド（以
下ＮＶＡと略す）を水に表１に示す組成比率で溶解して
ＮＶＡ溶液を調整する。本溶液にメルトブローン法によ
るＰＰ不織布（繊維径１０．３μm、目付け５２．０ｇ
／ｍ２、厚さ４００μｍ、幅５０ｍｍ、長さ１００ｍ
ｍ）を５分間浸漬させ、液から引き上げてクリアランス
３００μｍの絞りロールではさみ含浸溶液量を均一にし
た後、窒素雰囲気下で表１に示した照射条件で電子線照
射法によりグラフト処理を行なった。得られた不織布に
ついて、グラフト率、保液率を測定した。その結果を表
１に示した。[Example 1] N-vinylacetamide (hereinafter abbreviated as NVA) is dissolved in water at a composition ratio shown in Table 1 to prepare an NVA solution. To this solution, melt-blown PP nonwoven fabric (fiber diameter 10.3 μm, basis weight 52.0 g)
/ M2, thickness 400μm, width 50mm, length 100m
m) was immersed for 5 minutes, pulled up from the solution, and sandwiched with a squeezing roll having a clearance of 300 μm to uniform the amount of the impregnating solution. . About the obtained nonwoven fabric, the graft ratio and the liquid retention ratio were measured. The results are shown in Table 1.
【００３５】［実施例２］ＮＶＡと水の組成比率を表1
に示したように以外は実施例１と同様の方法で処理を行
なった。その結果を表1に示した。Example 2 Table 1 shows the composition ratio of NVA and water.
The processing was carried out in the same manner as in Example 1 except as shown in FIG. Table 1 shows the results.
【００３６】［実施例３］ＮＶＡと溶媒をエチレングリ
コールに変え、票１に示すような組成比率にした以外は
実施例１と同様の方法で処理を行なった。その結果を表
1に示した。Example 3 A treatment was carried out in the same manner as in Example 1 except that NVA and the solvent were changed to ethylene glycol and the composition ratio was as shown in Table 1. The results are displayed
Shown in 1.
【００３７】［実施例４］電子線の照射条件を表1に示
したように以外は実施例１と同様の方法で処理を行なっ
た。その結果を表1に示した。Example 4 A treatment was carried out in the same manner as in Example 1 except that the electron beam irradiation conditions were as shown in Table 1. Table 1 shows the results.
【００３８】［比較例１］ＮＶＡを使用せずに水のにみ
浸積して処理を行なった以外は実施例１と同様の不織布
と電子線照射条件で処理を行なった。その結果を表1に
示した。[Comparative Example 1] A nonwoven fabric and an electron beam irradiation condition were the same as in Example 1 except that the treatment was performed by immersion in water without using NVA. Table 1 shows the results.
【００３９】［比較例２］ＮＶＡを使用せずにエチレン
グリコールのにみ浸積して処理を行なった以外は実施例
１と同様の不織布と電子線照射条件で処理を行なった。
その結果を表1に示した。[Comparative Example 2] A nonwoven fabric was treated under the same electron beam irradiation conditions as in Example 1 except that the treatment was performed by immersion in ethylene glycol without using NVA.
Table 1 shows the results.
【表１】 [Table 1]
【００４０】表１に示す結果から、Ｎ−ビニルカルボン
酸アミドでグラフト化することにより、親水性が大幅に
向上させることができることがわかる。From the results shown in Table 1, it can be seen that hydrophilicity can be significantly improved by grafting with N-vinylcarboxylic acid amide.
【００４１】[0041]
【発明の効果】本発明によれば、比較的容易に、効率よ
く短時間にＮ−ビニルカルボン酸アミドでグラフト化す
ることにより多孔質性基材を親水化することができる。
このようにして得られた親水化された多孔質性基材は水
の保液性に優れるため、電池用セパレータ、保湿材、衛
生用品等に利用可能である。According to the present invention, the porous substrate can be hydrophilized relatively easily, efficiently and in a short time by grafting with N-vinylcarboxylic acid amide.
The hydrophilic porous substrate thus obtained has excellent liquid retention properties, and can be used for battery separators, humectants, sanitary articles, and the like.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L033 AA05 AB05 AB07 AC15 CA11 5H021 BB12 BB15 CC02 EE04 EE07 EE16 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L033 AA05 AB05 AB07 AC15 CA11 5H021 BB12 BB15 CC02 EE04 EE07 EE16
Claims (9)
酸アミドがグラフト重合していることを特徴とする、ポ
リオレフィン系樹脂からなる多孔質性基材。 ＣＨ2＝ＣＨ−Ｎ（Ｒ1）−ＣＯ−Ｒ2 （１） （式中、Ｒ1、Ｒ2は互いに独立して、水素原子またはメ
チル基を示す。）1. A porous substrate comprising a polyolefin resin, wherein an N-vinylcarboxylic acid amide represented by the following general formula (1) is graft-polymerized. CH 2 ＣＨCH—N (R 1 ) —CO—R 2 (1) (In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
重合処理する際に、その処理方法が電子線照射する手段
である、請求項１に記載される多孔質性基材。2. The porous substrate according to claim 1, wherein when the N-vinylcarboxylic acid amide is subjected to the graft polymerization treatment, the treatment method is a means for irradiating an electron beam.
フィン系樹脂からなる多孔質性基材にＮ−ビニルカルボ
ン酸アミド溶液を含浸した後に、電子線照射することを
特徴とする請求項２に記載される多孔質性基材。3. The method according to claim 2, wherein, during the graft polymerization treatment, a porous substrate made of a polyolefin resin is impregnated with an N-vinylcarboxylic acid amide solution, and then irradiated with an electron beam. Porous substrate.
ルアセトアミドである請求項１から３のいずれかに記載
される多孔質性基材。4. The porous substrate according to claim 1, wherein the N-vinylcarboxylic acid amide is N-vinylacetamide.
ことを特徴とする請求項１から４のいずれかに記載の多
孔質性基材。5. The porous substrate according to claim 1, wherein the porous substrate is a woven or non-woven fabric.
酸アミドがグラフト重合しているポリオレフィン系樹脂
からなる多孔質性基材を製造する方法において、電子線
照射によりグラフト重合処理することを特徴とするポリ
オレフィン系樹脂からなる多孔質性基材の製造方法。 ＣＨ2＝ＣＨ−Ｎ（Ｒ1）−ＣＯ−Ｒ2 （１） （式中、Ｒ1、Ｒ2は互いに独立して、水素原子またはメ
チル基を示す。）6. A method for producing a porous substrate comprising a polyolefin resin on which N-vinylcarboxylic acid amide of the following general formula (1) is graft-polymerized, wherein the graft polymerization treatment is performed by electron beam irradiation. A method for producing a porous substrate comprising a characteristic polyolefin resin. CH 2 ＣＨCH—N (R 1 ) —CO—R 2 (1) (In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
重合処理するに際し、ポリオレフィン系樹脂からなる多
孔質性基材にＮ−ビニルカルボン酸アミド溶液を含浸し
た後に、電子線照射することを特徴とする請求項６に記
載されるポリオレフィン系樹脂からなる多孔質性基材の
製造方法。7. The method according to claim 1, wherein, when the N-vinylcarboxylic acid amide is subjected to the graft polymerization treatment, the porous substrate made of a polyolefin resin is impregnated with the N-vinylcarboxylic acid amide solution and then irradiated with an electron beam. A method for producing a porous substrate comprising the polyolefin-based resin according to claim 6.
ルアセトアミドである請求項６または７に記載のポリオ
レフィン系樹脂からなる多孔質性基材の製造方法。8. The method for producing a porous substrate comprising a polyolefin resin according to claim 6, wherein the N-vinylcarboxylic amide is N-vinylacetamide.
ィン系樹脂からなる多孔質性基材を用いた電池用セパレ
ータ。9. A battery separator using a porous base material comprising the polyolefin resin according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001175878A JP2002371471A (en) | 2001-06-11 | 2001-06-11 | Porous base material made of hydrophilicity-given polyolefin resin and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001175878A JP2002371471A (en) | 2001-06-11 | 2001-06-11 | Porous base material made of hydrophilicity-given polyolefin resin and method for producing the same |
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|---|---|
| JP2002371471A true JP2002371471A (en) | 2002-12-26 |
Family
ID=19016941
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004303983A (en) * | 2003-03-31 | 2004-10-28 | Fuji Photo Film Co Ltd | Polishing pad |
| EP1968792A1 (en) * | 2005-12-30 | 2008-09-17 | 3M Innovative Properties Company | Functionalized substrates |
| GB2456900A (en) * | 2008-01-25 | 2009-08-05 | Gen Electric | Electron beam functionalised hydrophilic polymer coated membrane |
| US8329034B2 (en) | 2009-06-23 | 2012-12-11 | 3M Innovative Properties Company | Functionalized nonwoven article |
| US8377672B2 (en) | 2010-02-18 | 2013-02-19 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US8435776B2 (en) | 2010-03-03 | 2013-05-07 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US8586338B2 (en) | 2008-05-30 | 2013-11-19 | 3M Innovative Properties Company | Ligand functionalized substrates |
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2001
- 2001-06-11 JP JP2001175878A patent/JP2002371471A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004303983A (en) * | 2003-03-31 | 2004-10-28 | Fuji Photo Film Co Ltd | Polishing pad |
| CN101351338B (en) * | 2005-12-30 | 2012-12-05 | 3M创新有限公司 | Method for preparing functional substrate |
| EP1968792A1 (en) * | 2005-12-30 | 2008-09-17 | 3M Innovative Properties Company | Functionalized substrates |
| EP1973738A1 (en) * | 2005-12-30 | 2008-10-01 | 3M Innovative Properties Company | Method of making functionalized substrates |
| EP1973738A4 (en) * | 2005-12-30 | 2009-04-29 | 3M Innovative Properties Co | Method of making functionalized substrates |
| EP1968792A4 (en) * | 2005-12-30 | 2009-04-29 | 3M Innovative Properties Co | Functionalized substrates |
| GB2456900B (en) * | 2008-01-25 | 2011-11-23 | Gen Electric | Permanent hydrophillic porous coatings onto a substrate and porous membranes thereof |
| GB2456900A (en) * | 2008-01-25 | 2009-08-05 | Gen Electric | Electron beam functionalised hydrophilic polymer coated membrane |
| US8846203B2 (en) | 2008-05-30 | 2014-09-30 | 3M Innovative Properties Company | Method of making ligand functionalized substrates |
| US10017461B2 (en) | 2008-05-30 | 2018-07-10 | 3M Innovative Properties Company | Method of making ligand functionalized substrates |
| US9650470B2 (en) | 2008-05-30 | 2017-05-16 | 3M Innovative Properties Company | Method of making ligand functionalized substrates |
| US8586338B2 (en) | 2008-05-30 | 2013-11-19 | 3M Innovative Properties Company | Ligand functionalized substrates |
| US8652582B2 (en) | 2008-05-30 | 2014-02-18 | 3M Innovative Properties Company | Method of making ligand functionalized substrates |
| US9259689B2 (en) | 2009-06-23 | 2016-02-16 | 3M Innovative Properties Company | Functionalized nonwoven article |
| US8329034B2 (en) | 2009-06-23 | 2012-12-11 | 3M Innovative Properties Company | Functionalized nonwoven article |
| US8945896B2 (en) | 2010-02-18 | 2015-02-03 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US9296847B2 (en) | 2010-02-18 | 2016-03-29 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US8377672B2 (en) | 2010-02-18 | 2013-02-19 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US8435776B2 (en) | 2010-03-03 | 2013-05-07 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US9758547B2 (en) | 2010-03-03 | 2017-09-12 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US10005814B2 (en) | 2010-03-03 | 2018-06-26 | 3M Innovative Properties Company | Ligand functionalized polymers |
| US10526366B2 (en) | 2010-03-03 | 2020-01-07 | 3M Innovative Properties Company | Ligand functionalized polymers |
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