JP2002194125A - Method of modifying surface and water repellent or hydrophilic polymeric material by the method, and clothing, paper, rubber and separator for battery using them - Google Patents
Method of modifying surface and water repellent or hydrophilic polymeric material by the method, and clothing, paper, rubber and separator for battery using themInfo
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- JP2002194125A JP2002194125A JP2000394984A JP2000394984A JP2002194125A JP 2002194125 A JP2002194125 A JP 2002194125A JP 2000394984 A JP2000394984 A JP 2000394984A JP 2000394984 A JP2000394984 A JP 2000394984A JP 2002194125 A JP2002194125 A JP 2002194125A
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- Prior art keywords
- polymer material
- gas
- synthetic
- bond
- rubber
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Classifications
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- 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
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Paper (AREA)
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、合成若しくは天然
高分子材料を撥水性若しくは親水性にする表面改質方
法、また、表面改質された合成若しくは天然高分子材料
並びにこれらを用いた衣料、紙、ゴム及び電池用セパレ
ータに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface modification method for making a synthetic or natural polymer material water-repellent or hydrophilic, a surface-modified synthetic or natural polymer material and clothing using the same. The present invention relates to paper, rubber, and battery separators.
【０００２】[0002]
【従来の技術】従来より、合成高分子及び天然高分子材
料に表面処理を施し、撥水性、親水性にする合成高分子
及び天然高分子材料の表面処理方法が検討されている。2. Description of the Related Art Conventionally, surface treatment methods for synthetic polymers and natural polymer materials which are made water-repellent and hydrophilic by subjecting synthetic polymers and natural polymer materials to surface treatment have been studied.
【０００３】例えば、撥水化処理方法としては特開昭５
６−１２６１４６号公報に開示されている成形ゴム材料
の表面処理方法がある。この方法は、成形ゴム材料を約
１０〜１５０℃の温度においてフッ素ガス若しくはフッ
素ガスと不活性キャリアガスとの混合ガス気流中に保持
し成形ゴムの表面を撥水化処理する方法である。[0003] For example, Japanese Patent Laid-Open No.
There is a surface treatment method for a molded rubber material disclosed in JP-A-6-126146. In this method, a molded rubber material is held at a temperature of about 10 to 150 ° C. in a flow of a fluorine gas or a mixed gas of a fluorine gas and an inert carrier gas, and the surface of the molded rubber is subjected to a water-repellent treatment.
【０００４】また、親水化処理方法としては、例えば、
特開平６−１１６４３６号公報に開示されている多孔質
高分子膜の処理方法がある。この方法は、多孔質高分子
膜をフッ素ガスと酸素ガスの混合ガスに反応させて多孔
質高分子膜の表面を親水化処理する方法である。[0004] In addition, as a hydrophilic treatment method, for example,
There is a method for treating a porous polymer membrane disclosed in JP-A-6-116436. In this method, the surface of the porous polymer film is subjected to a hydrophilic treatment by reacting the porous polymer film with a mixed gas of fluorine gas and oxygen gas.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
従来の撥水化処理や、親水化処理でも、撥水性や親水性
の機能を効率よく付与できない場合があった。However, these conventional water-repellent treatments and hydrophilic treatments have sometimes failed to provide water-repellent and hydrophilic functions efficiently.
【０００６】そこで、本発明は、合成若しくは天然高分
子材料を表面処理し、確実に撥水性または親水性を付与
することのできる表面改質方法及びその方法による撥水
性若しくは親水性の高分子材料並びにこれらを用いた衣
料、紙、ゴム及び電池用セパレータを提供することを目
的とする。Accordingly, the present invention provides a surface modification method capable of reliably imparting water repellency or hydrophilicity to a synthetic or natural polymer material by surface treatment, and a water repellent or hydrophilic polymer material by the method. Another object of the present invention is to provide clothing, paper, rubber, and battery separators using the same.
【０００７】[0007]
【課題を解決するための手段】前記課題を解決するため
の本発明の合成若しくは天然高分子材料に撥水性を付与
する表面改質方法は、合成若しくは天然高分子材料にフ
ッ素ガスと不活性ガスを含むガスによる処理を行って撥
水性を付与する表面改質方法であって、前記合成若しく
は天然高分子材料として、比重が１．６以下であって、
且つエーテル結合、カーボネート結合、アミド結合、ウ
レタン結合の何れも含まない材料を選択することを特徴
とする。The surface modification method for imparting water repellency to a synthetic or natural polymer material according to the present invention for solving the above-mentioned problems is achieved by adding fluorine gas and inert gas to the synthetic or natural polymer material. A surface modification method for imparting water repellency by performing a treatment with a gas containing, wherein the synthetic or natural polymer material has a specific gravity of 1.6 or less,
In addition, a material that does not contain any of an ether bond, a carbonate bond, an amide bond, and a urethane bond is selected.
【０００８】また、本発明の合成若しくは天然高分子材
料に親水性を付与する表面改質方法は、合成若しくは天
然高分子材料にフッ素フッ素ガスと酸素を含むガスによ
る処理を行って親水性を付与する表面改質方法であっ
て、前記合成若しくは天然高分子材料として、比重が
１．６以下であって且つエーテル結合、カーボネート結
合、アミド結合、ウレタン結合の何れも含まない材料を
選択することを特徴とする。In the surface modification method of the present invention for imparting hydrophilicity to a synthetic or natural polymer material, the synthetic or natural polymer material is treated with a fluorine gas and a gas containing oxygen to impart hydrophilicity to the synthetic or natural polymer material. Surface modifying method, wherein a material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond is selected as the synthetic or natural polymer material. Features.
【０００９】また、前記合成高分子材料は、熱硬化性樹
脂、熱可塑性樹脂、ゴム状高分子のうちより選ばれた材
料であることが好ましい。また、前記天然高分子材料
は、天然ゴム、セルロース、セルロースエステル、綿、
絹、亜麻のうちより選ばれた材料であることが好まし
い。The synthetic polymer material is preferably a material selected from a thermosetting resin, a thermoplastic resin, and a rubber-like polymer. The natural polymer material is natural rubber, cellulose, cellulose ester, cotton,
The material is preferably selected from silk and flax.
【００１０】そして、本発明は表面が撥水性若しくは親
水性を有した高分子材料であり、衣料、紙、ゴムとして
使用することができ、また親水性の高分子材料は、電池
セパレータとして使用することが好適である。The present invention is a polymer material having a water-repellent or hydrophilic surface, and can be used as clothing, paper, and rubber. The hydrophilic polymer material is used as a battery separator. Is preferred.
【００１１】本発明で使用する合成高分子材料として
は、フェノール樹脂、キシレン樹脂、エポキシ樹脂等の
熱硬化性樹脂や、ポリエチレン、塩化ポリエチレン、エ
チレン酢酸ビニル共重合樹脂、エチレンアクリル酸エチ
ル共重合樹脂、ポリプロピレン、ポリメチルペンテン、
ポリスチレン、アクリルニトリル−ブタジエン−スチレ
ン（ＡＢＳ）樹脂、アクリルニトリル−スチレン（Ａ
Ｓ）樹脂、アクリルニトリル−塩化ポリエチレン−スチ
レン（ＡＣＳ）樹脂、メタクリル酸メチル樹脂、メタク
リルスチレン共重合樹脂、塩化ビニル樹脂、塩化ビニル
酢酸ビニル共重合樹脂、塩化ビニル塩化ビニリデン共重
合樹脂、塩化ビニルアクリル酸エステル共重合樹脂、塩
化ビニルメタクリル酸共重合樹脂、塩化ビニルアクリル
ニトリル共重合樹脂、エチレン塩化ビニル共重合樹脂、
プロピレン塩化ビニル共重合樹脂、酢酸ビニル樹脂、ポ
リエチレンテレフタレート、ポリブチレンテレフタレー
ト、ポリフェニレンオキサイド、ポリスルフォン、エチ
レン−４フッ化エチレン共重合樹脂、ポリブチレン等の
熱可塑性樹脂が例示できる。The synthetic polymer material used in the present invention includes thermosetting resins such as phenol resin, xylene resin and epoxy resin, polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer resin and ethylene-ethyl acrylate copolymer resin. , Polypropylene, polymethylpentene,
Polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (A
S) Resin, acrylic nitrile-polyethylene chloride-styrene (ACS) resin, methyl methacrylate resin, methacryl styrene copolymer resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, vinyl chloride vinylidene chloride copolymer resin, vinyl chloride acrylic Acid ester copolymer resin, vinyl chloride methacrylic acid copolymer resin, vinyl chloride acrylonitrile copolymer resin, ethylene vinyl chloride copolymer resin,
Examples thereof include thermoplastic resins such as propylene vinyl chloride copolymer resin, vinyl acetate resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, ethylene-tetrafluoroethylene copolymer resin, and polybutylene.
【００１２】また、ゴム状高分子としては、ブタジエン
スチレン共重合体（スチレンブタジエンゴム）、ブタジ
エンアクリルニトリル共重合体（ニトリルゴム）、ブチ
ルゴム、ポリイソブチレン、クロロスルフォン化ポリエ
チレン、ポリブタジエン（ブタジエンゴム）、クロロプ
レンゴム、エチレンプロピレンゴム、アクリルゴム等
が、例示できる。Examples of the rubbery polymer include butadiene styrene copolymer (styrene butadiene rubber), butadiene acrylonitrile copolymer (nitrile rubber), butyl rubber, polyisobutylene, chlorosulfonated polyethylene, polybutadiene (butadiene rubber), Examples thereof include chloroprene rubber, ethylene propylene rubber, and acrylic rubber.
【００１３】また、天然高分子としては、天然ゴム、セ
ルロース、セルロースエステル、綿、絹、亜麻等が例示
できる。Examples of the natural polymer include natural rubber, cellulose, cellulose ester, cotton, silk, flax and the like.
【００１４】ここで、比重が１．６以下の合成若しくは
天然高分子材料は、材料中のフッ素フッ素ガスの拡散が
極めて良く被表面改質物の反応サイトに容易に行き渡
る。このため、被表面改質物の表面は、容易に改質され
る。また、比重が１．６よりも大きいと合成若しくは天
然高分子材料では結晶構造が発達しているのでフッ素フ
ッ素ガスの拡散も容易でないため表面改質の機能が発現
しにくい。[0014] Here, a synthetic or natural polymer material having a specific gravity of 1.6 or less diffuses fluorine gas in the material very easily and easily spreads to the reaction site of the surface-modified product. For this reason, the surface of the surface-modified product is easily modified. On the other hand, if the specific gravity is greater than 1.6, the crystal structure of a synthetic or natural polymer material has been developed, and it is difficult to diffuse fluorine gas.
【００１５】また、エーテル結合、カーボネート結合、
アミド結合、ウレタン結合を有するものは、フッ素フッ
素ガスとの接触で容易に分解し、撥水性や親水性の機能
を付与しにくくなるため、好ましくない。これら、合成
若しくは天然高分子材料の表面のエーテル結合、カーボ
ネート結合、アミド結合、ウレタン結合は、日本分光社
製のフーリエ変換式赤外分光光度計（ＦＴ−ＩＲ）５３
００型装置を用いて各結合の有無を測定した。Further, an ether bond, a carbonate bond,
Those having an amide bond or a urethane bond are not preferred because they are easily decomposed by contact with fluorine and fluorine gas, and it is difficult to impart water repellency and hydrophilicity. The ether bond, carbonate bond, amide bond, and urethane bond on the surface of the synthetic or natural polymer material are formed by a Fourier transform infrared spectrophotometer (FT-IR) 53 manufactured by JASCO Corporation.
The presence or absence of each bond was measured using a 00 type apparatus.
【００１６】以下、これら合成高分子材料若しくは天然
高分子材料を、撥水性又は親水性にする夫々の表面改質
方法について説明する。Hereinafter, the respective surface modification methods for making these synthetic polymer materials or natural polymer materials water-repellent or hydrophilic will be described.
【００１７】撥水性を付与する場合は、合成若しくは天
然高分子材料を処理容器に入れて処理容器を数１００Ｐ
ａ以下に減圧する。次いで、不活性ガスに雰囲気を置換
する。ここで、不活性ガスとは、窒素ガス、ヘリウムガ
ス、アルゴンガス等をいう。その後、フッ素ガスが２０
〜９５ｖｏｌ５〜９５ｖｏｌ％となるように容器内に導
入する。フッ素ガスと接触させる処理時間は１秒〜１０
日、好ましくは１０分〜数時間である。処理温度は０〜
２００℃、好ましくは室温〜１００℃である。When imparting water repellency, a synthetic or natural polymer material is placed in a processing container and the processing container
Reduce the pressure to a or less. Next, the atmosphere is replaced with an inert gas. Here, the inert gas refers to a nitrogen gas, a helium gas, an argon gas, or the like. After that, the fluorine gas becomes 20
９５95 vol 5 to 95 vol% are introduced into the container. Processing time for contact with fluorine gas is 1 second to 10
Days, preferably 10 minutes to several hours. Processing temperature is 0
The temperature is 200 ° C, preferably room temperature to 100 ° C.
【００１８】また、本発明でいうところの「撥水」と
は、撥水化処理前の合成若しくは天然高分子材料の水に
対する接触角（θ）よりも、フッ素ガスで撥水化処理し
た後の合成若しくは天然高分子材料の水に対する接触角
（θ1）の方が、１０°以上大きくなるものをいうもの
と定義するし、θとθ1の関係は、式１のように表せ
る。 θ1−θ≧１０°……（式１）The term “water repellency” as used in the present invention refers to the water or water repellency of a synthetic or natural polymer material before the water repellency treatment, which is greater than the contact angle (θ) with water. The contact angle (θ 1 ) of water of the synthetic or natural polymer material with respect to water is defined to be 10 ° or more, and the relationship between θ and θ 1 can be expressed as in Equation 1. θ 1 −θ ≧ 10 ° (Equation 1)
【００１９】また、親水性を付与する場合は、合成若し
くは天然高分子材料を処理容器に入れて処理容器を数１
００Ｐａ以下に減圧する。次いで、窒素ガス、ヘリウム
ガス、アルゴンガス等の不活性ガスや、酸素ガス、二酸
化硫黄ガス、二酸化炭素ガス、一酸化炭素ガス等の酸素
を含むガスに雰囲気を置換する。不活性ガスで置換した
場合は、置換その後、酸素を含むガスを導入する。この
際ここで、酸素を含むガスとしては、酸素ガス、二酸化
硫黄ガス、二酸化炭素ガス、一酸化炭素ガスを単独で
も、これらに、窒素ガス、ヘリウムガス、アルゴンガス
等の不活性ガスを混合したガスや、酸素ガスに二酸化硫
黄ガス、二酸化炭素ガス、一酸化炭素ガス等のガスとを
混合したガス状態のいずれであってもよい。そして、フ
ッ素ガスが、５〜１５ｖｏｌ％となるように容器内に導
入する。フッ素ガスと酸素を含むガスと接触させる処理
時間は１秒〜１０日、好ましくは１０分〜数時間であ
る。処理温度は０〜２００℃、好ましくは室温〜１００
℃である。When imparting hydrophilicity, a synthetic or natural polymer material is placed in a processing vessel, and
The pressure is reduced to 00 Pa or less. Next, the atmosphere is replaced with an inert gas such as nitrogen gas, helium gas, or argon gas, or a gas containing oxygen such as oxygen gas, sulfur dioxide gas, carbon dioxide gas, or carbon monoxide gas. When the gas is replaced with an inert gas, a gas containing oxygen is introduced after the replacement. At this time, as the gas containing oxygen, an oxygen gas, a sulfur dioxide gas, a carbon dioxide gas, a carbon monoxide gas alone, or an inert gas such as a nitrogen gas, a helium gas, or an argon gas was mixed with them. The gas may be in a gas state or a gas state in which an oxygen gas is mixed with a gas such as a sulfur dioxide gas, a carbon dioxide gas, and a carbon monoxide gas. Then, the fluorine gas is introduced into the container so as to be 5 to 15 vol%. The treatment time for contacting the gas containing fluorine gas and oxygen is 1 second to 10 days, preferably 10 minutes to several hours. The treatment temperature is 0 to 200 ° C, preferably room temperature to 100
° C.
【００２０】また、本発明でいうところの「親水」と
は、親水化処理前の合成若しくは天然高分子材料の水に
対する接触角（θ）よりも、フッ素ガスと酸素を含むガ
スで親水化処理した後の合成若しくは天然高分子材料の
水に対する接触角（θ2）の方が１０°以上小さくなる
ものをいうものと定義するし、θとθ2の関係は式２の
ように表せる。 θ−θ2≧１０°……（式２）The term “hydrophilic” as used in the present invention means that the contact angle (θ) of a synthetic or natural polymer material before water treatment with water is higher than that of a gas containing fluorine gas and oxygen. The contact angle (θ 2 ) of the synthetic or natural polymer material after water becomes smaller than that by 10 ° or more, and the relationship between θ and θ 2 can be expressed as in Equation 2. θ−θ 2 ≧ 10 ° (Equation 2)
【００２１】ここで、水との接触角の測定方法は、エル
マ社製のＧ−１型装置を用い、厚みが１ｍｍの高分子材
料を１０×２０（ｍｍ）に切り、１つの試料に直径０．
５ｍｍ位の水滴を１０個注射器で作り、それぞれの接触
角を上記装置で測定し、その平均値を求めた。この操作
を１０回繰り返し、その平均値をもって１試料の接触角
の測定値とした。Here, the contact angle with water was measured by using a G-1 type device manufactured by Elma, cutting a polymer material having a thickness of 1 mm into 10 × 20 (mm), and applying a diameter to one sample. 0.
Ten water drops of about 5 mm were formed with a syringe, and each contact angle was measured with the above-mentioned device, and the average value was obtained. This operation was repeated 10 times, and the average value was used as the measured value of the contact angle of one sample.
【００２２】また、比重の測定は、プラスチック−非発
泡プラスチックの密度及び比重の測定方法（ＪＩＳ Ｋ
７１１２（１９９９））のうちのピクノメーター法によ
り測定した。The specific gravity is measured by measuring the density and specific gravity of plastic-non-foamed plastic (JIS K
7112 (1999)).
【００２３】なお、これら合成高分子材料若しくは天然
高分子材料を、撥水性又は親水性にする際に、フッ素ガ
ス若しくはフッ素ガスを含む混合ガスと接触させる方法
は、前記のように、各処理物ごとに処理容器設置するバ
ッチ式処理方法のほかに連続式処理方法とすることもで
きる。連続式処理方法とは、フッ素ガス若しくはフッ素
ガスを含む混合ガス中に合成高分子材料若しくは天然高
分子材料を通過させて接触させる方法である。The method of bringing these synthetic polymer materials or natural polymer materials into contact with fluorine gas or a mixed gas containing fluorine gas when making them water-repellent or hydrophilic is as described above. In addition to the batch-type processing method in which a processing container is installed every time, a continuous-type processing method may be used. The continuous treatment method is a method in which a synthetic polymer material or a natural polymer material is passed through fluorine gas or a mixed gas containing fluorine gas and brought into contact therewith.
【００２４】ここで、本発明で用いられるフッ素ガス
は、通常フッ化水素の電気分解によって得られる。かか
る電気分解で得られたフッ素ガスを直接処理に使用する
ことも可能である。また、ボンベに充填されたフッ素ガ
スを使用することも可能である。The fluorine gas used in the present invention is usually obtained by electrolysis of hydrogen fluoride. It is also possible to use the fluorine gas obtained by such electrolysis for direct treatment. Further, it is also possible to use fluorine gas filled in a cylinder.
【００２５】フッ素ガスを導入する前に処理容器を雰囲
気置換することは、非常に重要で、この順番を逆にする
と、撥水性、親水性の機能が発現しなかったり、基材を
分解・焼失させてしまったりすることがある。It is very important to replace the atmosphere in the processing vessel before introducing the fluorine gas. If the order is reversed, the functions of water repellency and hydrophilicity are not exhibited, or the substrate is decomposed and burned. You may be let go.
【００２６】以上のようにして、合成高分子材料若しく
は天然高分子材料の表面を、その素材の強度、耐薬品
性、耐熱性を損なうことなく、撥水性若しくは親水性に
することが可能となる。このように表面を改質すること
によって、それぞれを衣料、紙、ゴム等に使用すること
ができる。また、親水性にすることによって、電池用セ
パレータとして使用することも可能となる。As described above, the surface of a synthetic polymer material or a natural polymer material can be made water-repellent or hydrophilic without impairing the strength, chemical resistance and heat resistance of the material. . By modifying the surface in this way, each can be used for clothing, paper, rubber and the like. In addition, by making it hydrophilic, it can be used as a battery separator.
【００２７】また、合成高分子材料若しくは天然高分子
材料の表面を部分的にマスキングを行って、撥水性若し
くは親水性に処理することで、部分的に撥水性若しくは
親水性にすることが可能である。これによって、合成高
分子材料若しくは天然高分子材料の表裏面の特性が異な
るものや、傾斜的にその特性が変化するような合成高分
子材料若しくは天然高分子材料とすることができる。例
えば、表面に撥水性を持たせ、裏面は親水性を持たせた
衣服等とすることが可能となる。Further, by partially masking the surface of the synthetic polymer material or the natural polymer material and treating it with water repellency or hydrophilicity, it is possible to make the surface partially water repellent or hydrophilic. is there. As a result, it is possible to use a synthetic polymer material or a natural polymer material having different characteristics on the front and back surfaces, or a synthetic polymer material or a natural polymer material whose characteristics are inclined. For example, it is possible to provide clothes or the like having water repellency on the front surface and hydrophilicity on the back surface.
【００２８】[0028]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、その要旨を越えない限り、以下の実
施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.
【００２９】（実施例１）熱可塑性樹脂として、比重が
０．９１で、エーテル結合、カーボネート結合、アミド
結合、ウレタン結合の何れも含まない低密度ポリエチレ
ンを用い、これを処理容器に入れ、１００Ｐａに減圧し
た後、窒素ガスを導入し、処理容器内のガスを置換した
後、フッ素ガスを導入した。フッ素ガスは、導入後の処
理容器内のガス混合比率が、窒素ガス８０ｖｏｌ％、フ
ッ素ガス２０ｖｏｌ％となるように導入した。その後、
７０℃で６０分間反応させて材料の表面を撥水化処理し
た。(Example 1) As a thermoplastic resin, a low-density polyethylene having a specific gravity of 0.91 and containing no ether bond, carbonate bond, amide bond, or urethane bond was used. Then, nitrogen gas was introduced to replace the gas in the processing vessel, and then fluorine gas was introduced. Fluorine gas was introduced such that the gas mixture ratio in the processing vessel after introduction was 80 vol% of nitrogen gas and 20 vol% of fluorine gas. afterwards,
The material was reacted at 70 ° C. for 60 minutes to make the surface of the material water-repellent.
【００３０】（実施例２）ゴム状高分子材料として、比
重が１．３で、エーテル結合、カーボネート結合、アミ
ド結合、ウレタン結合の何れも含まないクロロプレンゴ
ムを用いたことを除き、実施例１と同様にして、材料の
表面を撥水化処理した。Example 2 Example 1 was repeated except that a chloroprene rubber having a specific gravity of 1.3 and containing no ether bond, carbonate bond, amide bond or urethane bond was used as the rubber-like polymer material. In the same manner as described above, the surface of the material was subjected to a water-repellent treatment.
【００３１】（実施例３）天然高分子材料として比重が
１．５で、エーテル結合、カーボネート結合、アミド結
合、ウレタン結合の何れも含まない綿を用い、これを処
理容器に入れ、１００Ｐａに減圧した後、窒素ガスを導
入し、処理容器内のガスを置換した後、フッ素ガスを導
入した。フッ素ガスは、導入後の処理容器内のガス混合
比率が、窒素ガス９５ｖｏｌ％、フッ素ガス５ｖｏｌ％
となるように導入した。その後、２０℃（室温）で１０
分間反応させて材料の表面を撥水化処理した。Example 3 As a natural polymer material, cotton having a specific gravity of 1.5 and containing no ether bond, carbonate bond, amide bond or urethane bond was used. After that, nitrogen gas was introduced to replace the gas in the processing container, and then fluorine gas was introduced. As for the fluorine gas, the gas mixture ratio in the processing vessel after introduction is 95 vol% of nitrogen gas and 5 vol% of fluorine gas.
It was introduced to become. Then, at 20 ° C (room temperature), 10
After reacting for minutes, the surface of the material was treated for water repellency.
【００３２】（実施例４）熱可塑性樹脂として、比重が
０．９５でエーテル結合、カーボネート結合、アミド結
合、ウレタン結合の何れも含まないポリプロピレン系不
織布を用い、これを処理容器に入れ、１００Ｐａに減圧
した後、酸素ガスを導入し、処理容器内のガスを置換し
た後、フッ素ガスを導入した。フッ素ガスは、導入後の
処理容器内のガス混合比率が、酸素ガス８０ｖｏｌガス
９５ｖｏｌ％、フッ素ガス２０ｖｏｌフッ素ガス５ｖｏ
ｌ％となるように導入した。その後、２０℃（室温）で
１分間反応させて材料の表面を親水化処理した。Example 4 As a thermoplastic resin, a polypropylene-based nonwoven fabric having a specific gravity of 0.95 and containing no ether bond, carbonate bond, amide bond, or urethane bond was used. After reducing the pressure, oxygen gas was introduced to replace the gas in the processing vessel, and then fluorine gas was introduced. The mixing ratio of the fluorine gas in the processing vessel after the introduction is 80 vol gas of oxygen gas, 95 vol% of gas, 20 vol of fluorine gas and 5 vol of fluorine gas.
1% was introduced. Thereafter, the material was subjected to a reaction at 20 ° C. (room temperature) for 1 minute to subject the surface of the material to a hydrophilic treatment.
【００３３】（実施例５）ゴム状高分子材料として、比
重が１．０９で、エーテル結合、カーボネート結合、ア
ミド結合、ウレタン結合の何れも含まないニトリルゴム
を用い、これを処理容器に入れ、１００Ｐａに減圧した
後、酸素ガスを導入し、処理容器内のガスを置換した
後、フッ素ガスを導入した。フッ素ガスは、導入後の処
理容器内のガス混合比率が、酸素ガス９０ｖｏｌ％、フ
ッ素ガス１０ｖｏｌ％となるように導入した。その後、
２０℃で１０分間反応させて材料の表面を撥水化処理し
た。Example 5 A nitrile rubber having a specific gravity of 1.09 and containing neither an ether bond, a carbonate bond, an amide bond, nor a urethane bond was used as a rubber-like polymer material. After reducing the pressure to 100 Pa, oxygen gas was introduced, and the gas in the processing container was replaced. Then, fluorine gas was introduced. Fluorine gas was introduced so that the gas mixture ratio in the processing vessel after introduction was 90 vol% for oxygen gas and 10 vol% for fluorine gas. afterwards,
The material was reacted at 20 ° C. for 10 minutes to make the surface of the material water-repellent.
【００３４】（実施例６）天然高分子材料として、比重
が０．９２でエーテル結合、カーボネート結合、アミド
結合、ウレタン結合の何れも含まない天然ゴムを用いた
ことを除き実施例５と同様の操作で材料の表面を親水化
処理した。Example 6 The same as Example 5 except that a natural rubber having a specific gravity of 0.92 and containing no ether bond, carbonate bond, amide bond or urethane bond was used as the natural polymer material. The surface of the material was subjected to a hydrophilic treatment by an operation.
【００３５】（比較例１）熱可塑性樹脂として比重が
２．１５で、エーテル結合、カーボネート結合、アミド
結合、ウレタン結合の何れも含まない四フッ化エチレン
−パーフルオロアルコキシエチレン共重合樹脂（ＰＦ
Ａ）を用い、実施例１と同様な操作手順で材料の表面を
撥水化処理した。COMPARATIVE EXAMPLE 1 A thermoplastic resin having a specific gravity of 2.15 and containing neither an ether bond, a carbonate bond, an amide bond nor a urethane bond, is a tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin (PF).
Using A), the surface of the material was subjected to a water-repellent treatment in the same operation procedure as in Example 1.
【００３６】（比較例２）熱硬化性樹脂として、比重が
１．２１でウレタン結合を含むポリウレタンを用い実施
例１と同様な操作手順で材料の表面を撥水化処理した。(Comparative Example 2) A polyurethane having a specific gravity of 1.21 and containing a urethane bond was used as a thermosetting resin, and the surface of the material was subjected to a water-repellent treatment in the same operation procedure as in Example 1.
【００３７】（比較例３）熱可塑性樹脂として、比重が
１．２でカーボネート結合を含むポリカーボネートを用
い実施例１と同様な操作手順で材料の表面を撥水化処理
した。(Comparative Example 3) As a thermoplastic resin, polycarbonate having a specific gravity of 1.2 and containing a carbonate bond was used, and the surface of the material was subjected to a water-repellent treatment in the same operation procedure as in Example 1.
【００３８】（比較例４）熱硬化性樹脂として、比重が
１．２１でウレタン結合を含むポリウレタンを用い、実
施例５と同様な操作手順で材料の表面を親水化処理し
た。Comparative Example 4 Polyurethane having a specific gravity of 1.21 and containing a urethane bond was used as a thermosetting resin, and the surface of the material was subjected to a hydrophilic treatment in the same operation procedure as in Example 5.
【００３９】（比較例５）合成高分子材料として、比重
が１．８でエーテル結合、カーボネート結合、アミド結
合、ウレタン結合の何れも含まないシリコンゴムを用
い、実施例５と同様な操作手順で材料の表面を親水化処
理した。(Comparative Example 5) As a synthetic polymer material, a silicone rubber having a specific gravity of 1.8 and containing no ether bond, carbonate bond, amide bond, or urethane bond was used. The surface of the material was subjected to a hydrophilic treatment.
【００４０】（比較例６）天然高分子材料として、比重
が１．３で、エーテル結合、アミド結合を含む羊毛を用
い、実施例５と同様な操作手順で材料の表面を親水化処
理した。Comparative Example 6 Wool having a specific gravity of 1.3 and containing an ether bond and an amide bond was used as a natural polymer material, and the surface of the material was subjected to a hydrophilic treatment in the same procedure as in Example 5.
【００４１】実施例１乃至６及び比較例１乃至６の試料
について、合成若しくは天然高分子材料の種類、比重、
撥水性や親水性の機能付与の阻害因子となる結合の有
無、処理条件、接触角等をまとめて表１に示す。With respect to the samples of Examples 1 to 6 and Comparative Examples 1 to 6, the type, specific gravity,
Table 1 summarizes the presence / absence of a bond, a treatment condition, a contact angle, and the like, which serve as an inhibitory factor for imparting water repellency and hydrophilic functions.
【００４２】[0042]
【表１】 [Table 1]
【００４３】表１から明らかなように、比重が１．６以
下であって且つ、エーテル結合、カーボネート結合、ア
ミド結合、ウレタン結合を含まない合成若しくは天然高
分子材料は、フッ素フッ素ガスを含むガスによって撥水
性、親水性が容易に付与できる。As is clear from Table 1, synthetic or natural polymer materials having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond include gas containing fluorine fluorine gas. Thereby, water repellency and hydrophilicity can be easily imparted.
【００４４】[0044]
【発明の効果】本発明では、比重が１.６以下であっ
て、且つフッ素フッ素ガスを含むガスによる撥水性や親
水性の機能付与を阻害するエーテル結合、カーボネート
結合、アミド結合、ウレタン結合を含まない天然若しく
は合成高分子材料を選択して処理するので、容易に撥水
性や親水性の機能を付与できる。また、撥水性の付与に
よって、汚れにくい建築用資材（具体的にいえば壁紙、
カーペット、窓材、袋紙）、さらに酸素や炭化水素の選
択透過性を低下させたゴムキャップ、吸湿性がなく縮ま
ない衣料、耐油性のある紙や容器が簡便に製造できる。
また、親水性の付与によって、印刷が容易な衣料、建築
用資材、電線やケーブル、容器、さらに電解液との均一
な濡れ性と保液性が向上した各種電池用セパレータを簡
便に提供することができ産業に寄与する効果は極めて大
きい。According to the present invention, an ether bond, a carbonate bond, an amide bond, and a urethane bond having a specific gravity of 1.6 or less and inhibiting the function of imparting water repellency and hydrophilicity by a gas containing fluorine and fluorine gas are inhibited. Since a natural or synthetic polymer material not containing is selected and treated, a water repellent or hydrophilic function can be easily provided. In addition, the construction materials (specifically, wallpaper,
Carpets, window materials, sack papers), rubber caps with reduced permeability to oxygen and hydrocarbons, clothing that does not shrink without moisture absorption, and oil-resistant paper and containers can be easily manufactured.
Further, by providing hydrophilicity, it is possible to easily provide clothing, building materials, electric wires, cables, containers, and various battery separators having uniform wettability with an electrolytic solution and improved liquid retention, which are easily printed. The effect that contributes to the industry is extremely large.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１３年１月５日（２００１．１．５）[Submission date] January 5, 2001 (2001.1.5)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００８】また、本発明の合成若しくは天然高分子材
料に親水性を付与する表面改質方法は、合成若しくは天
然高分子材料にフッ素ガスと酸素を含むガスによる処理
を行って親水性を付与する表面改質方法であって、前記
合成若しくは天然高分子材料として、比重が１．６以下
であって且つエーテル結合、カーボネート結合、アミド
結合、ウレタン結合の何れも含まない材料を選択するこ
とを特徴とする。[0008] The surface modification method of imparting synthetic or hydrophilic natural polymer material of the present invention, a synthetic or natural polymer material by performing treatment with gases containing full Tsu-containing gas and oxygen hydrophilic In the surface modification method to be applied, a material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond is selected as the synthetic or natural polymer material. It is characterized by.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１７】撥水性を付与する場合は、合成若しくは天
然高分子材料を処理容器に入れて処理容器を数１００Ｐ
ａ以下に減圧する。次いで、不活性ガスに雰囲気を置換
する。ここで、不活性ガスとは、窒素ガス、ヘリウムガ
ス、アルゴンガス等をいう。その後、フッ素ガスが５〜
９５ｖｏｌ％となるように容器内に導入する。フッ素ガ
スと接触させる処理時間は１秒〜１０日、好ましくは１
０分〜数時間である。処理温度は０〜２００℃、好まし
くは室温〜１００℃である。When imparting water repellency, a synthetic or natural polymer material is placed in a processing container and the processing container
Reduce the pressure to a or less. Next, the atmosphere is replaced with an inert gas. Here, the inert gas refers to a nitrogen gas, a helium gas, an argon gas, or the like. Then, fluorine gas is 5 to
It is introduced into the container so as to be 95 vol%. The treatment time for contacting with fluorine gas is 1 second to 10 days, preferably 1 second.
0 minutes to several hours. The processing temperature is 0 to 200 ° C, preferably room temperature to 100 ° C.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】また、本発明でいうところの「撥水」と
は、撥水化処理前の合成若しくは天然高分子材料の水に
対する接触角（θ）よりも、フッ素ガスで撥水化処理し
た後の合成若しくは天然高分子材料の水に対する接触角
（θ1 ）の方が、１０°以上大きくなるものをいうもの
と定義し、θとθ1 の関係は、式１のように表せる。 θ1 −θ≧１０°……（式１）The term “water repellency” as used in the present invention refers to the water or water repellency of a synthetic or natural polymer material before the water repellency treatment, which is greater than the contact angle (θ) with water. towards the contact angle against synthetic or water natural polymer material (theta 1) is defines as that refers to larger more than 10 °, the relationship between theta and theta 1 can be expressed as equation 1. θ 1 −θ ≧ 10 ° (Equation 1)
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１９】また、親水性を付与する場合は、合成若し
くは天然高分子材料を処理容器に入れて処理容器を数１
００Ｐａ以下に減圧する。次いで、窒素ガス、ヘリウム
ガス、アルゴンガス等の不活性ガスや、酸素ガス、二酸
化硫黄ガス、二酸化炭素ガス、一酸化炭素ガス等の酸素
を含むガスに雰囲気を置換する。不活性ガスで置換した
場合は、置換後、酸素を含むガスを導入する。ここで、
酸素を含むガスとしては、酸素ガス、二酸化硫黄ガス、
二酸化炭素ガス、一酸化炭素ガスを単独でも、これら
に、窒素ガス、ヘリウムガス、アルゴンガス等の不活性
ガスを混合したガスや、酸素ガスに二酸化硫黄ガス、二
酸化炭素ガス、一酸化炭素ガス等のガスとを混合したガ
スのいずれであってもよい。そして、フッ素ガスが、５
〜１５ｖｏｌ％となるように容器内に導入する。フッ素
ガスと酸素を含むガスと接触させる処理時間は１秒〜１
０日、好ましくは１０分〜数時間である。処理温度は０
〜２００℃、好ましくは室温〜１００℃である。When imparting hydrophilicity, a synthetic or natural polymer material is placed in a processing vessel, and
The pressure is reduced to 00 Pa or less. Next, the atmosphere is replaced with an inert gas such as nitrogen gas, helium gas, or argon gas, or a gas containing oxygen such as oxygen gas, sulfur dioxide gas, carbon dioxide gas, or carbon monoxide gas. If it replaced with an inert gas, for introducing a gas containing 換後 location, oxygen. In here,
As the gas containing oxygen, oxygen gas, sulfur dioxide gas,
Even if carbon dioxide gas and carbon monoxide gas are used alone, they are mixed with an inert gas such as nitrogen gas, helium gas, argon gas, or oxygen gas, sulfur dioxide gas, carbon dioxide gas, carbon monoxide gas, etc. Gas mixed with
And any of them. And the fluorine gas is 5
It introduce | transduces into a container so that it may be -15 volume%. The processing time for contacting the gas containing fluorine gas and oxygen is 1 second to 1
0 days, preferably 10 minutes to several hours. Processing temperature is 0
To 200 ° C, preferably room temperature to 100 ° C.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２０】また、本発明でいうところの「親水」と
は、親水化処理前の合成若しくは天然高分子材料の水に
対する接触角（θ）よりも、フッ素ガスと酸素を含むガ
スで親水化処理した後の合成若しくは天然高分子材料の
水に対する接触角（θ2 ）の方が１０°以上小さくなる
ものをいうものと定義し、θとθ2 の関係は式２のよう
に表せる。 θ−θ2 ≧１０°……（式２）The term “hydrophilic” as used in the present invention means that the contact angle (θ) of a synthetic or natural polymer material before water treatment with water is higher than that of a gas containing fluorine gas and oxygen. towards the contact angle (theta 2) with respect to synthetic or water natural polymer material after the define and shall refer to those smaller 10 ° or more, the relationship between theta and theta 2 is expressed as shown in equation 2. θ−θ 2 ≧ 10 ° (Equation 2)
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Correction target item name] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３２】（実施例４）熱可塑性樹脂として、比重が
０．９５でエーテル結合、カーボネート結合、アミド結
合、ウレタン結合の何れも含まないポリプロピレン系不
織布を用い、これを処理容器に入れ、１００Ｐａに減圧
した後、酸素ガスを導入し、処理容器内のガスを置換し
た後、フッ素ガスを導入した。フッ素ガスは、導入後の
処理容器内のガス混合比率が、酸素ガス９５ｖｏｌ％、
フッ素ガス５ｖｏｌ％となるように導入した。その後、
２０℃（室温）で１分間反応させて材料の表面を親水化
処理した。(Example 4) As a thermoplastic resin, a polypropylene-based nonwoven fabric having a specific gravity of 0.95 and containing no ether bond, carbonate bond, amide bond, or urethane bond was used. After reducing the pressure, oxygen gas was introduced to replace the gas in the processing vessel, and then fluorine gas was introduced. Fluorine gas, the gas mixing ratio of the processing vessel after introduction of oxygen gas 9 5 vol%,
Off Tsu was introduced in such a way that hydrogen gas 5vol%. afterwards,
The material was reacted at 20 ° C. (room temperature) for 1 minute to hydrophilize the surface of the material.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４３】表１から明らかなように、比重が１．６以
下であって且つ、エーテル結合、カーボネート結合、ア
ミド結合、ウレタン結合を含まない合成若しくは天然高
分子材料は、フッ素ガスを含むガスによって撥水性、親
水性が容易に付与できる。[0043] As apparent from Table 1, and there is a specific gravity of 1.6 or less, an ether bond, carbonate bond, amide bond, synthetic or natural polymeric materials containing no urethane bond, including full Tsu-containing gas Water repellency and hydrophilicity can be easily imparted by the gas.
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４４[Correction target item name] 0044
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４４】[0044]
【発明の効果】本発明では、比重が１. ６以下であっ
て、且つフッ素ガスを含むガスによる撥水性や親水性の
機能付与を阻害するエーテル結合、カーボネート結合、
アミド結合、ウレタン結合を含まない天然若しくは合成
高分子材料を選択して処理するので、容易に撥水性や親
水性の機能を付与できる。また、撥水性の付与によっ
て、汚れにくい建築用資材（具体的にいえば壁紙、カー
ペット、窓材、袋紙）、さらに酸素や炭化水素の選択透
過性を低下させたゴムキャップ、吸湿性がなく縮まない
衣料、耐油性のある紙や容器が簡便に製造できる。ま
た、親水性の付与によって、印刷が容易な衣料、建築用
資材、電線やケーブル、容器、さらに電解液との均一な
濡れ性と保液性が向上した各種電池用セパレータを簡便
に提供することができ産業に寄与する効果は極めて大き
い。In the present invention, the specific gravity is 1. A 6 or less, an ether bond inhibiting the function imparting water repellency and hydrophilicity by gas including且one full Tsu-containing gas, carbonate bond,
Since a natural or synthetic polymer material containing neither an amide bond nor a urethane bond is selected and treated, a function of water repellency or hydrophilicity can be easily provided. In addition, by providing water repellency, architectural materials (specifically, wallpaper, carpet, window material, sack paper) that are less likely to be stained, rubber caps with reduced permeability to oxygen and hydrocarbons, and no moisture absorption Clothing that does not shrink, oil-resistant paper and containers can be easily manufactured. Further, by providing hydrophilicity, it is possible to easily provide clothing, building materials, electric wires, cables, containers, and various battery separators having uniform wettability with an electrolytic solution and improved liquid retention, which are easily printed. The effect that contributes to the industry is extremely large.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 2/16 Ｃ０８Ｌ 101:00 // Ｃ０８Ｌ 101:00 Ｄ０６Ｍ 11/00 Ｚ (72)発明者 竹林 仁 香川県三豊郡大野原町中姫2181−２ 東洋 炭素株式会社内 Ｆターム(参考） 4F073 AA01 AA02 AA32 BA03 BA04 BA05 BA06 BB01 DA04 DA09 4L031 BA07 DA00 4L055 AF08 AF09 AF10 AF11 AF14 AF30 AF44 EA01 FA19 FA30 GA01 GA05 GA23 GA30 GA48 5H021 BB09 EE02 EE03 EE04 EE05 EE06 EE08 EE09 EE11 EE15 EE18 HH05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01M 2/16 C08L 101: 00 // C08L 101: 00 D06M 11/00 Z (72) Inventor Jin Takebayashi Kagawa 2181-2 Nakahime, Onohara-cho, Mitoyo-gun, Toyo F-term (reference) 4F073 AA01 AA02 AA32 BA03 BA04 BA05 BA06 BB01 DA04 DA09 4L031 BA07 DA00 4L055 AF08 AF09 AF10 AF11 AF14 AF30 AF44 EA01 FA19 FA30 GA01 GA05 GA30 GA48 5H021 BB09 EE02 EE03 EE04 EE05 EE06 EE08 EE09 EE11 EE15 EE18 HH05
Claims (13)
スと不活性ガスを含むガスによる処理を行って撥水性を
付与する表面改質方法であって、前記合成若しくは天然
高分子材料として、比重が１．６以下であって且つエー
テル結合、カーボネート結合、アミド結合、ウレタン結
合の何れも含まない材料を選択することを特徴とする合
成若しくは天然高分子材料の表面改質方法。1. A surface modification method for imparting water repellency by treating a synthetic or natural polymer material with a gas containing fluorine gas and an inert gas, wherein the specific gravity of the synthetic or natural polymer material is A method for modifying the surface of a synthetic or natural polymer material, characterized by selecting a material that is 1.6 or less and does not contain any of an ether bond, a carbonate bond, an amide bond, and a urethane bond.
スと酸素を含むガスによる処理を行って親水性を付与す
る表面改質方法であって、前記合成若しくは天然高分子
材料として、比重が１．６以下であって且つエーテル結
合、カーボネート結合、アミド結合、ウレタン結合の何
れも含まない材料を選択することを特徴とする合成若し
くは天然高分子材料の表面改質方法。2. A surface modification method for imparting hydrophilicity by treating a synthetic or natural polymer material with a gas containing fluorine gas and oxygen, wherein the synthetic or natural polymer material has a specific gravity of 1. 6. A method for modifying the surface of a synthetic or natural polymer material, wherein a material having a molecular weight of 6 or less and not containing any of an ether bond, a carbonate bond, an amide bond, and a urethane bond is selected.
熱可塑性樹脂、ゴム状高分子のうちより選ばれた材料で
ある請求項１または２に記載の表面改質方法。3. The synthetic polymer material is a thermosetting resin,
3. The method according to claim 1, wherein the material is selected from a thermoplastic resin and a rubber-like polymer.
ロース、セルロースエステル、綿、絹、亜麻のうちより
選ばれた材料である請求項１または２に記載の表面改質
方法。4. The surface modification method according to claim 1, wherein the natural polymer material is a material selected from natural rubber, cellulose, cellulose ester, cotton, silk, and flax.
撥水性の高分子材料。5. A water-repellent polymer material surface-treated by the method according to claim 1.
親水性の高分子材料。6. A hydrophilic polymer material surface-treated by the method according to claim 2.
用いた衣料。7. Clothing using the water-repellent polymer material according to claim 5.
用いた紙。8. A paper using the water-repellent polymer material according to claim 5.
用いたゴム。9. A rubber using the water-repellent polymer material according to claim 5.
を用いた衣料。10. Clothing using the hydrophilic polymer material according to claim 6.
を用いた紙。11. Paper using the hydrophilic polymer material according to claim 6.
を用いたゴム。12. A rubber using the hydrophilic polymer material according to claim 6.
を用いた電池用セパレータ。13. A battery separator using the hydrophilic polymer material according to claim 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000394984A JP3585833B2 (en) | 2000-12-26 | 2000-12-26 | Surface modification method of synthetic or natural polymer material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000394984A JP3585833B2 (en) | 2000-12-26 | 2000-12-26 | Surface modification method of synthetic or natural polymer material |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004095877A Division JP3629031B2 (en) | 2004-03-29 | 2004-03-29 | Method for surface modification of synthetic or natural polymer materials |
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| Publication Number | Publication Date |
|---|---|
| JP2002194125A true JP2002194125A (en) | 2002-07-10 |
| JP3585833B2 JP3585833B2 (en) | 2004-11-04 |
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ID=18860524
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| JP2000394984A Expired - Fee Related JP3585833B2 (en) | 2000-12-26 | 2000-12-26 | Surface modification method of synthetic or natural polymer material |
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| JP2004139879A (en) * | 2002-10-18 | 2004-05-13 | Casio Comput Co Ltd | Display panel and manufacturing method of the same |
| WO2009154252A1 (en) * | 2008-06-19 | 2009-12-23 | ステラケミファ株式会社 | Method for modifying fluorine resin film |
| JP2010215718A (en) * | 2009-03-13 | 2010-09-30 | Fujifilm Corp | Method for producing resin molded article, inkjet head and electronic equipment |
| WO2010140603A1 (en) | 2009-06-04 | 2010-12-09 | ステラケミファ株式会社 | Method for producing multilayer film |
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| WO2017209495A1 (en) * | 2016-05-30 | 2017-12-07 | 주식회사 엘지화학 | Lithium secondary battery separator and lithium secondary battery comprising same |
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|---|---|---|---|---|
| JP2004139879A (en) * | 2002-10-18 | 2004-05-13 | Casio Comput Co Ltd | Display panel and manufacturing method of the same |
| JP4517569B2 (en) * | 2002-10-18 | 2010-08-04 | カシオ計算機株式会社 | Manufacturing method of display panel |
| WO2009154252A1 (en) * | 2008-06-19 | 2009-12-23 | ステラケミファ株式会社 | Method for modifying fluorine resin film |
| JP2010024446A (en) * | 2008-06-19 | 2010-02-04 | Stella Chemifa Corp | Method of modifying fluorine resin film |
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| JP2010215718A (en) * | 2009-03-13 | 2010-09-30 | Fujifilm Corp | Method for producing resin molded article, inkjet head and electronic equipment |
| EP2439057A1 (en) * | 2009-06-04 | 2012-04-11 | Stella Chemifa Corporation | Method for producing multilayer film |
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| US9142357B2 (en) | 2011-02-24 | 2015-09-22 | Nec Corporation | Separator for electric storage device and electric storage device |
| WO2017209495A1 (en) * | 2016-05-30 | 2017-12-07 | 주식회사 엘지화학 | Lithium secondary battery separator and lithium secondary battery comprising same |
| CN108140788A (en) * | 2016-05-30 | 2018-06-08 | 株式会社Lg化学 | Partition board for lithium secondary battery and the lithium secondary battery including the partition board |
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