JP2002038361A - Radical-resistant fiber structure and hydrogen ion- conducting polymer membrane reinforced therewith - Google Patents
Radical-resistant fiber structure and hydrogen ion- conducting polymer membrane reinforced therewithInfo
- Publication number
- JP2002038361A JP2002038361A JP2000223998A JP2000223998A JP2002038361A JP 2002038361 A JP2002038361 A JP 2002038361A JP 2000223998 A JP2000223998 A JP 2000223998A JP 2000223998 A JP2000223998 A JP 2000223998A JP 2002038361 A JP2002038361 A JP 2002038361A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen ion
- polymer membrane
- radical
- fiber structure
- conductive polymer
- 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.)
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は主としてポリ塩化ビ
ニル繊維からなる繊維構造物に関する。さらに詳しく
は、主としてポリ塩化ビニル繊維からなる耐ラジカル性
を有する繊維構造物、及びこれを用いた固体高分子型燃
料電池用に好適な水素イオン伝導性高分子膜に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure mainly comprising polyvinyl chloride fibers. More specifically, the present invention relates to a radical resistant fiber structure mainly composed of polyvinyl chloride fiber and a hydrogen ion conductive polymer membrane suitable for a polymer electrolyte fuel cell using the same.
【０００２】[0002]
【従来の技術】従来から電気分解、一次電池や二次電池
におけるセパレータ、あるいは燃料電池に用いられる水
素イオン伝導性高分子膜の補強材に合成繊維の不織布、
織布、短繊維等の繊維質基材を使用することが検討され
ている。特に近年、環境問題からクリーンで高効率な電
源として燃料電池が注目されている背景もあり、低温作
動や小型化の観点から自動車用途を中心に固体高分子型
燃料電池(PEFC)の開発が活発におこなわれているが、こ
れに用いられる水素イオン伝導性高分子膜の補強技術の
開発も重要になっている。2. Description of the Related Art Conventionally, a nonwoven fabric of synthetic fiber is used as a separator in a primary battery or a secondary battery or a reinforcing material of a hydrogen ion conductive polymer membrane used in a fuel cell.
The use of fibrous base materials such as woven fabrics and short fibers has been studied. In particular, in recent years, fuel cells have been attracting attention as clean and highly efficient power sources due to environmental issues, and the development of polymer electrolyte fuel cells (PEFCs) has been active mainly in automotive applications from the viewpoint of low-temperature operation and miniaturization. However, the development of a technique for reinforcing the proton conductive polymer membrane used for this purpose is also important.
【０００３】PEFCの用いる高分子電解質膜はナフィオン
(Nafion、デュポン社の登録商標。以下同様。)に代表さ
れるパーフルオロアルキルスルホン酸膜や米国特許第
５，３６２，８３６号に記載されているスルホン酸基で
置換したポリエーテルエーテルケトン、特開平１０−４
５９１３号公報に記載されているポリエーテルスルホン
等がある。[0003] The polymer electrolyte membrane used by PEFC is Nafion.
(Nafion, a registered trademark of DuPont; hereinafter the same). A perfluoroalkylsulfonic acid membrane represented by US Pat. No. 5,362,836, and a polyetheretherketone substituted with a sulfonic acid group described in US Pat. Kaihei 10-4
And polyethersulfone described in JP-A-5913.
【０００４】上記のような高分子膜において、水素イオ
ン伝導性を発現させるためには水による膨潤が必須であ
る。しかし、水により膨潤させると十分な機械的強度が
保てないという問題がある。また、水素イオン伝導性を
向上させるためにはスルホン酸基をより多く導入する必
要があるが、高いスルホン酸基置換量においては膜が溶
解してしまうという問題も有している。以上のような理
由から上記のような高分子膜単独では、燃料電池を作製
した際耐久性が悪く、十分な性能が引き出せないという
のが実情である。[0004] In the above-mentioned polymer membrane, swelling with water is essential for developing hydrogen ion conductivity. However, there is a problem that sufficient mechanical strength cannot be maintained when swelled with water. Further, in order to improve the hydrogen ion conductivity, it is necessary to introduce more sulfonic acid groups, but there is a problem that the membrane is dissolved at a high sulfonic acid group substitution amount. For the above reasons, it is a fact that the polymer membrane alone as described above has poor durability when a fuel cell is manufactured, and cannot provide sufficient performance.
【０００５】また、経済的な観点及び性能の面から高分
子膜はより薄膜化した方が好ましいが、機械的強度の問
題から高分子膜単独では限界がある。Further, it is preferable to make the polymer film thinner from the viewpoint of economy and performance, but there is a limit to the polymer film alone due to the problem of mechanical strength.
【０００６】このような背景から高分子膜を補強する技
術が重要であり、膜補強技術としてテトラフルオロエチ
レン延伸多孔膜(特開平8-162132号公報)と複合化させる
というものがある。また、第三回国際燃料電池会議（１
９９９年）要項集Ａ４−１、Ａ４−２等に記載されてい
るように、テトラフルオロエチレンの織物、短繊維分散
による補強技術が検討されている。[0006] Against this background, the technique of reinforcing a polymer membrane is important, and as a membrane reinforcing technique, there is a technique of combining with a tetrafluoroethylene stretched porous membrane (Japanese Patent Laid-Open No. 8-162132). In addition, the 3rd International Fuel Cell Conference (1
(1999) As described in essential points A4-1, A4-2, etc., a reinforcing technique by dispersion of woven fabric and short fibers of tetrafluoroethylene is being studied.
【０００７】しかし、テトラフルオロエチレンによる補
強は燃料電池を普及させることを考えると経済的に困難
であり、また表面張力が小さいことによる濡れ性の問題
から電解質ドープの含浸が難しいという問題を有してい
る。However, reinforcement with tetrafluoroethylene is economically difficult considering the spread of fuel cells, and has the problem that it is difficult to impregnate with an electrolyte dope due to the problem of wettability due to low surface tension. ing.
【０００８】しかし、PEFC用水素イオン伝導性高分子膜
補強基材には耐久性といった観点から耐ラジカル性に対
する要求は強く、テトラフルオロエチレンに代表される
フッ素系樹脂しか用いられていないのが現状である。However, there is a strong demand for radical resistance from the viewpoint of durability in the hydrogen ion conductive polymer membrane reinforcing substrate for PEFC, and only a fluororesin represented by tetrafluoroethylene is currently used. It is.
【０００９】[0009]
【発明が解決しようとする課題】上記のような理由か
ら、燃料電池用水素イオン伝導性高分子膜補強基材とし
てテトラフルオロエチレンに代表されるようなフッ素系
ポリマーを用いることは好ましくない。For the reasons described above, it is not preferable to use a fluorine-based polymer such as tetrafluoroethylene as the hydrogen ion conductive polymer membrane reinforcing substrate for a fuel cell.
【００１０】我々はこのような課題に対して、耐熱性の
高いアラミド樹脂からなる基材にポリテトラフルオロエ
チレン微粒子を添着後、ポリテトラフルオロエチレンの
溶融温度以上に加熱し添着粒子を溶解して均一に塗膜化
する技術を検討している。[0010] In order to solve such a problem, after adhering polytetrafluoroethylene fine particles to a substrate made of aramid resin having high heat resistance, the mixture is heated to a temperature higher than the melting temperature of polytetrafluoroethylene to dissolve the adhered particles. We are studying a technique for forming a uniform coating.
【００１１】また、我々は、有機極性溶媒にフッ素化ポ
リアルキレンを溶解した溶液を用いて非フッ素系高分子
重合体繊維からなる繊維質基材を被覆することも提案し
ている。We have also proposed coating a fibrous substrate made of non-fluorinated high molecular weight polymer fibers with a solution of a fluorinated polyalkylene dissolved in an organic polar solvent.
【００１２】本発明の目的は、耐ラジカル環境下におい
ても十分に機械的強度を維持できるような非フッ素系ポ
リマーからなる補強基材を提供し、燃料電池用水素イオ
ン伝導性高分子膜補強基材に用いることである。An object of the present invention is to provide a reinforcing substrate made of a non-fluorinated polymer capable of maintaining sufficient mechanical strength even in a radical-resistant environment, and a hydrogen ion conductive polymer membrane reinforcing substrate for a fuel cell. It is used for materials.
【００１３】また本発明の目的は、上記補強基材を用い
た燃料電池用として好適な水素イオン伝導性高分子膜を
提供することにある。It is another object of the present invention to provide a hydrogen ion conductive polymer membrane suitable for a fuel cell using the above-mentioned reinforcing substrate.
【００１４】[0014]
【課題を解決するための手段】我々はこの課題について
検討をかさねた結果、ポリ塩化ビニルが十分な耐ラジカ
ル性を有することを見出した。しかし、ＰＥＦＣ用水素
イオン伝導性高分子膜補強材として好適に用いることが
できるようなポリ塩化ビニルの形態は厚さ等の点で望ま
しくなかった。そこで、我々はポリ塩化ビニルを主体と
する繊維を主体とした厚さが薄い繊維構造物が、ＰＥＦ
Ｃ用水素イオン伝導性高分子膜の補強基材として重要で
あることを見出し開発することで本発明に至った。As a result of studying this problem, we have found that polyvinyl chloride has sufficient radical resistance. However, a form of polyvinyl chloride that can be suitably used as a hydrogen ion conductive polymer membrane reinforcing material for PEFC is not desirable in terms of thickness and the like. Therefore, we have developed a thin fiber structure mainly composed of polyvinyl chloride fibers, PEF.
The present invention has been achieved by finding out and developing it as important as a reinforcing base material of the hydrogen ion conductive polymer membrane for C.
【００１５】すなわち本発明は、主としてポリ塩化ビニ
ルからなる繊維を主体とした厚さ１０〜５０μｍであ
り、透気度（ＪＩＳ Ｐ８１１７）が１０ｓｅｃ／１０
０ｃｃ・ｉｎ2以下であることを特徴とした繊維構造物
である。また、上記繊維構造物が不織布である繊維構造
物である。さらに、上記繊維構造物により補強されたこ
と水素イオン伝導性高分子膜である。That is, the present invention has a thickness of 10 to 50 μm mainly composed of fibers mainly composed of polyvinyl chloride and an air permeability (JIS P8117) of 10 sec / 10.
It is a fiber structure characterized by being 0 cc · in 2 or less. Further, the fibrous structure is a nonwoven fabric. Further, it is a hydrogen ion conductive polymer membrane reinforced by the fiber structure.
【００１６】[0016]
【発明の実施の形態】以下、本発明の耐ラジカル性繊維
構造物及びそれにより補強された水素イオン伝導性高分
子膜複合体を詳細に説明する。本発明の繊維構造物は、
耐ラジカル性を有し、ポリ塩化ビニルを主体にした繊維
を主体とした厚さが１０〜５０μｍであり、透気度（Ｊ
ＩＳ Ｐ８１１７）が１０ｓｅｃ／１００ｃｃ・ｉｎ2
以下であることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a radical-resistant fiber structure of the present invention and a hydrogen ion conductive polymer membrane composite reinforced by the same will be described in detail. The fiber structure of the present invention,
It has radical resistance, a thickness mainly composed of a fiber mainly composed of polyvinyl chloride is 10 to 50 μm, and an air permeability (J
IS P8117) is 10 sec / 100 cc in 2
It is characterized by the following.
【００１７】ここで耐ラジカル性とはヒドロキシルラジ
カルのような活性なラジカル存在かで物性が低下しない
ことを意味する。この特性はPEFC用水素イオン伝導性高
分子膜補強基材としては重要な特性である。燃料電池作
動時に該高分子膜中にはヒドロキシルラジカルが発生
し、このヒドロキシルラジカルによる劣化が燃料電池の
耐久性に悪影響を及ぼすからである。故に該高分子膜補
強基材はヒドロキシルラジカル存在下においても物性を
維持する必要がある。Here, radical resistance means that physical properties do not decrease due to the presence of an active radical such as a hydroxyl radical. This property is an important property as a hydrogen ion conductive polymer membrane reinforcement base material for PEFC. This is because hydroxyl radicals are generated in the polymer membrane during operation of the fuel cell, and the deterioration due to the hydroxyl radicals adversely affects the durability of the fuel cell. Therefore, it is necessary for the polymer film reinforcing substrate to maintain physical properties even in the presence of a hydroxyl radical.
【００１８】この耐ラジカル性は次のように評価するこ
とができる。まず、ラジカル処理であるが、これは
「膜」１０（１）（１９８５年）４２頁に記載されてい
るように、ヒドロキシルラジカルを発生するフェントン
試薬中に基材を浸漬するという、ラジカル劣化促進処理
により行うことができる。具体的には、まず、３０重量
％濃度の過酸化水素１００重量部に第二鉄イオンが２０
ｐｐｍとなるように硫酸鉄（II）・七水和物を０．００
９９６重量部添加溶解してフェントン試薬を調製し、そ
して評価材料をその試薬に浸漬し、６８℃で２４時間放
置する。なお、フェントン試薬のヒドロキシルラジカル
発生量は時間と共に低下するため、途中の５時間経過し
た時点で、新たなフェントン試薬に浸漬し直して６８℃
で１９時間放置する。このようにラジカル劣化促進処理
を行った後、評価材料を充分な超純水中で洗浄し、過剰
に付着した水分を拭き取り、劣化度を評価する。The radical resistance can be evaluated as follows. First, the radical treatment is performed. As described in “Membrane” 10 (1) (1985), p. 42, the substrate is immersed in a Fenton reagent that generates hydroxyl radicals. It can be performed by processing. Specifically, first, 20 parts of ferric ion was added to 100 parts by weight of hydrogen peroxide having a concentration of 30% by weight.
ppm iron (II) sulfate heptahydrate to 0.00 ppm
The Fenton reagent is prepared by adding and dissolving 996 parts by weight, and the evaluation material is immersed in the reagent and left at 68 ° C. for 24 hours. Since the amount of hydroxyl radical generated by the Fenton reagent decreases with time, when 5 hours have passed on the way, the Fenton reagent is immersed again in a new Fenton reagent and the temperature is reduced to 68 ° C.
And leave for 19 hours. After the radical deterioration promotion treatment is performed as described above, the evaluation material is washed in a sufficient amount of ultrapure water, excess moisture is wiped off, and the degree of deterioration is evaluated.
【００１９】劣化度は各種の手段で評価できるが、ここ
では引張試験による機械強度から評価した。この引張試
験による劣化度の測定は以下にようにして行う。引張試
験は、ＪＩＳ規格Ｋ７１２７に準じて、２５℃で１０ｃ
ｍ／分の引張速度で行い、測定サンプルは測定方向に、
長さ２０ｃｍになるように切り出し、１０ｃｍ間隔で引
張試験を実施する。この測定における最大点荷重をパラ
メータにし、ラジカル劣化促進処理前の値に対する処理
後の値の割合をラジカル処理後維持率とし劣化度の指標
とした。ここでは、このラジカル処理後維持率が９０％
以上のもの耐ラジカル性材料と定義する。このとき、ポ
リ塩化ビニルは耐ラジカル性材料の部類に含まれる。The degree of deterioration can be evaluated by various means. Here, the degree of deterioration is evaluated from mechanical strength by a tensile test. The measurement of the degree of deterioration by the tensile test is performed as follows. Tensile test is 10c at 25 ° C according to JIS K7127.
The measurement is performed at a tensile speed of m / min.
Cut out to a length of 20 cm, and a tensile test is performed at 10 cm intervals. The maximum point load in this measurement was used as a parameter, and the ratio of the value after the treatment to the value before the radical deterioration promotion treatment was taken as the maintenance rate after the radical treatment and used as an index of the degree of deterioration. Here, the maintenance rate after the radical treatment is 90%.
These are defined as radical-resistant materials. At this time, polyvinyl chloride is included in the class of radical-resistant materials.
【００２０】織物や不織布といった繊維構造物は水素イ
オン伝導性高分子膜複合体を製膜する際に、水素イオン
伝導性高分子を溶解したドープ含浸が容易であるため、
PEFC用水素イオン伝導性高分子膜の補強基材として
は、このような繊維構造物が好適である。When a hydrogen ion conductive polymer membrane composite is formed into a fibrous structure such as a woven or nonwoven fabric, it is easy to impregnate a dope in which the hydrogen ion conductive polymer is dissolved.
Such a fiber structure is suitable as a reinforcing base material of the hydrogen ion conductive polymer membrane for PEFC.
【００２１】該繊維構造物は厚さが１０〜５０μｍのシ
ート状が好適である。５０μｍを超えると内部抵抗が大
きくなり電池特性が低下する。また、燃料電池スタック
をより小型化するという観点からも厚さが大きいことは
好ましくない。また、１０μｍ未満であるとガスリーク
の問題が顕著になり十分な燃料電池特性が得られない。
また、水素イオン伝導性高分子膜と電極を一体化すると
き加熱プレスするが、厚さが薄すぎると短絡の問題が生
じ燃料電池作製が困難となる。The fibrous structure is preferably a sheet having a thickness of 10 to 50 μm. If it exceeds 50 μm, the internal resistance increases and the battery characteristics deteriorate. Further, it is not preferable that the thickness is large from the viewpoint of further reducing the size of the fuel cell stack. On the other hand, if it is less than 10 μm, the problem of gas leak becomes remarkable and sufficient fuel cell characteristics cannot be obtained.
In addition, when the hydrogen ion conductive polymer membrane and the electrode are integrated with each other, they are heated and pressed. However, if the thickness is too small, a short circuit problem occurs, and it becomes difficult to manufacture a fuel cell.
【００２２】このような範囲の厚さの繊維構造物を得る
ためには不織布の形態が好適である。ただ、織物でもこ
のような厚さになればよいので特に不織布には限定しな
い。In order to obtain a fibrous structure having a thickness in such a range, the form of a nonwoven fabric is preferable. However, the fabric is not particularly limited to a non-woven fabric as long as it has such a thickness.
【００２３】この繊維構造物は、ＪＩＳ Ｐ８１１７に
準拠した測定法で測定された透気度が１０ｓｅｃ／１０
０ｃｃ・ｉｎ2以下であることも特徴である。この透気
度が１０ｓｅｃ／１００ｃｃ・ｉｎ2を超えると目がつ
まり過ぎているため水素イオン伝導性高分子との複合化
が困難になるばかりでなく、該繊維構造物で補強された
ことにより複合化された水素イオン伝導性高分子膜にお
いても実用的な水素イオン伝導性が得られない。This fiber structure has an air permeability of 10 sec / 10 measured by a measuring method according to JIS P8117.
It is also a feature that it is 0 cc · in 2 or less. If the air permeability exceeds 10 sec / 100 cc · in 2 , the eyes are too clogged, which makes it difficult to form a composite with the hydrogen ion conductive polymer, and also makes the composite reinforced by the fiber structure. Practical hydrogen ion conductivity cannot be obtained even with the hydrogenated proton conductive polymer membrane.
【００２４】上記のようなポリ塩化ビニルを主体にした
繊維構造物を得るには例えば以下に示すような方法があ
る。ただし、以下に示すものはあくまで例であり、本発
明を限定するものではない。To obtain a fibrous structure mainly composed of polyvinyl chloride as described above, for example, there are the following methods. However, what is shown below is merely an example and does not limit the present invention.
【００２５】例えば、不織布の製造法としては、例えば
カードとニードル加工を組みあわせたニードルパンンチ
法や接着剤で繊維を結合するケミカルボンド法、熱可塑
性樹脂を用いるサーマルボンド法、エアーを用いるエア
ーレイ法、高圧ジェット水流で繊維を絡ませるスパーン
レース法、繊維を吹き出しながら直接不織布を作製する
メルトブローン法、湿式抄造法等種々の方法が知られて
いるがこれらに限定されるものではない。For example, the nonwoven fabric may be produced by, for example, a needle punching method in which carding and needle processing are combined, a chemical bonding method in which fibers are bonded with an adhesive, a thermal bonding method using a thermoplastic resin, or an airlay using air. Various methods are known, including, but not limited to, a spunlace method in which fibers are entangled with a high-pressure jet stream, a melt blown method in which a nonwoven fabric is directly produced while blowing fibers, and a wet papermaking method.
【００２６】湿式抄造法においてはバインダー繊維を用
いることも可能であるが、用いなくても作製可能であ
る。また、バインダー繊維としてはポリエステル繊維、
ポリエチレン等のオレフィン系繊維等が好適に用いられ
る。ここで、バインダー繊維の含有量は５０重量％以下
が好適であり、さらに好適には２５重量％以下が好適で
ある。バインダー繊維は一般にポリ塩化ビニルより耐ラ
ジカル性が低いため、５０重量％を超えるとラジカル環
境化に曝されたとき十分な物性を維持することが困難と
なる。In the wet papermaking method, it is possible to use a binder fiber, but it is possible to produce without using a binder fiber. Also, polyester fibers as binder fibers,
Olefin fibers such as polyethylene are preferably used. Here, the content of the binder fiber is preferably 50% by weight or less, more preferably 25% by weight or less. Since binder fibers generally have lower radical resistance than polyvinyl chloride, if the content exceeds 50% by weight, it becomes difficult to maintain sufficient physical properties when exposed to a radical environment.
【００２７】しかして本発明によれば、上記繊維構造物
によって補強された水素イオン伝導性高分子膜が提供さ
れる。すなわち、上記繊維構造物を水素イオン伝導性高
分子膜と複合化することにより、補強された水素イオン
伝導性高分子膜が提供される。補強された水素イオン伝
導性高分子膜複合体の膜厚は１５〜１００μｍの範囲が
好適である。According to the present invention, there is provided a proton conductive polymer membrane reinforced by the above-mentioned fibrous structure. That is, by reinforcing the fibrous structure with a hydrogen ion conductive polymer membrane, a reinforced hydrogen ion conductive polymer membrane is provided. The thickness of the reinforced proton-conductive polymer membrane composite is preferably in the range of 15 to 100 μm.
【００２８】ここで、補強される水素イオン伝導性高分
子としては、「ナフィオン」に代表されるパーフルオロ
アルキルスルホン酸膜やスルホン酸基で置換したポリエ
ーテルエーテルケトン、ポリエーテルスルホン等が挙げ
られる。Here, as the hydrogen ion conductive polymer to be reinforced, a perfluoroalkylsulfonic acid membrane represented by "Nafion", a polyetheretherketone substituted by a sulfonic acid group, a polyethersulfone, and the like can be mentioned. .
【００２９】上記の水素イオン伝導性高分子と該繊維構
造物の複合化は、例えば、該水素イオン伝導性高分子を
溶媒に溶解したドープを該繊維構造物に含浸させ、つい
で乾燥する等の方法がある。The composite of the hydrogen ion conductive polymer and the fibrous structure is performed by, for example, impregnating the fiber structure with a dope in which the hydrogen ion conductive polymer is dissolved in a solvent, and then drying the dope. There is a way.
【００３０】[0030]
【実施例】以下、実施例により本発明を具体的に説明す
る。The present invention will be described below in detail with reference to examples.
【００３１】［実施例１］帝人（株）製のポリ塩化ビニ
ル繊維「テビロン」（５６ｄｔｅｘ）の極細糸を用い、
目付量２０ｇ／ｍ2、厚み４５μｍとなるように平織り
した織物を作製した。この織物の透気度は０．０８ｓｅ
ｃ／１００ｃｃ・ｉｎ2であった。この織物について、
耐ラジカル性を評価した結果、ラジカル処理後維持率は
９２．３％であった。[Example 1] Using an ultra-fine thread of polyvinyl chloride fiber "Tevilon" (56 dtex) manufactured by Teijin Limited,
A plain woven fabric having a basis weight of 20 g / m 2 and a thickness of 45 μm was prepared. The air permeability of this fabric is 0.08 sec
c / 100 cc · in 2 . About this fabric,
As a result of evaluating the radical resistance, the retention rate after the radical treatment was 92.3%.
【００３２】［実施例２］帝人（株）製のポリ塩化ビニ
ル繊維「テビロン」（１．６５ｄｔｅｘ、６ｍｍ）と帝
人（株）製のポリエステル繊維（１．６５ｄｔｅｘ、５
ｍｍ）を重量比で８０：２０になるようにパルパー（又
はリファイナー）を用いて水に混合し、単繊維状に離
解、分散して単繊維濃度が０．２５重量％の均一な湿式
抄造用のスラリーを作成した。次に、当該抄造用スラリ
ーを用いてタッピー式角型手抄き機で抄紙し、重量が約
１３０ｇ／ｍ2の水分を多量に含んだ湿紙を得た、この
湿紙を乾燥して得た不織布状シート（抄造紙）の坪量
（目付量）は１２ｇ／ｍ2であった。次いで、得られた
不織布シートを直径２５０ｍｍの硬質表面金属ロールと
直径３５０ｍｍの耐熱性弾性ロールからなるカレンダー
機を用いて、温度；１４０℃、圧力；１００ｋｇ／ｃｍ
2の条件で加熱、加圧してカレンダー加工を実施し、厚さ
が２３．５μｍ、引張強力が０．４２kg／１５ｍｍであ
る目的とする不織布シートを作製した。この不織布の透
気度は０．０４ｓｅｃ／１００ｃｃ・ｉｎ2であった。
この不織布シートについて耐ラジカル性を評価した結
果、ラジカル処理後維持率は１０１％であった。[Example 2] Polyvinyl chloride fiber "Tevilon" (1.65 dtex, 6 mm) manufactured by Teijin Limited and polyester fiber (1.65 dtex, 5 mm) manufactured by Teijin Limited.
mm) with water using a pulper (or refiner) so that the weight ratio becomes 80:20, and disintegrated and dispersed into single fibers to form a uniform single fiber concentration of 0.25% by weight. Was prepared. Next, using the slurry for papermaking, papermaking was carried out with a tappy-type square-shaped papermaking machine to obtain a wet paper containing a large amount of water having a weight of about 130 g / m 2. The wet paper was obtained by drying. The basis weight (weight per unit area) of the obtained non-woven sheet (papermaking) was 12 g / m 2 . Then, the obtained nonwoven fabric sheet was heated at a temperature of 140 ° C. and a pressure of 100 kg / cm using a calender comprising a hard surface metal roll having a diameter of 250 mm and a heat-resistant elastic roll having a diameter of 350 mm.
Under the conditions of 2 , heating and pressurization were performed to perform calendering, thereby producing a target nonwoven fabric sheet having a thickness of 23.5 μm and a tensile strength of 0.42 kg / 15 mm. The air permeability of this nonwoven fabric was 0.04 sec / 100 cc · in 2 .
As a result of evaluating the radical resistance of the nonwoven fabric sheet, the retention rate after the radical treatment was 101%.
【００３３】［比較例１］ポリプロピレン不織布（ユニ
セル製、ＢＴ−１０２、目付量２４ｇ／ｍ2、膜厚７６
μｍ）について耐ラジカル性を評価した結果、ラジカル
処理後維持率は７４．７％であった。[Comparative Example 1] Polypropylene nonwoven fabric (manufactured by Unicell, BT-102, basis weight 24 g / m 2 , film thickness 76)
As a result of evaluating the radical resistance with respect to μm), the retention rate after the radical treatment was 74.7%.
【００３４】［実施例３］実施例２で作製した不織布を
ポリエチレンテレフタレートフィルム上に置き、その上
から１０ｗｔ．％のナフィオン溶液(Ａｌｄｒｉｃｈ社)
を２００μｍのクリアランスのドクターナイフでキャス
トした。風乾することで該不織布で補強された膜厚３０
μｍの水素イオン伝導性高分子膜を作製した。Example 3 The nonwoven fabric prepared in Example 2 was placed on a polyethylene terephthalate film, and 10 wt. % Nafion solution (Aldrich)
Was cast with a doctor knife with a clearance of 200 μm. Thickness 30 reinforced with the nonwoven fabric by air drying
A μm hydrogen ion conductive polymer membrane was produced.
【００３５】［実施例４］ガス拡散電極として０．３８
ｍｇ／ｃｍ2の白金を担持させた米国Ｅ−ＴＥＫＩＮＣ
製の電極を用い、これを３０ｍｍφに打ち抜きガス拡散
電極とした。実施例３にて作製した水素イオン伝導性高
分子膜を沸騰したイオン交換水中に２時間浸漬し、膜を
含水状態とした後、表面の過剰な水を拭き取り、ガス拡
散電極２枚で挟み込み、1１０℃にて１０ＭＰａで3分間
加圧し電極接合体を得た。得られた電極接合体につい
て、加湿水素及び酸素を供給し８０℃加熱下で燃料電池
出力特性を評価した。１０ケの単セルを作製したが、短
絡やガスリークなどの欠陥は一つもなく、０．７Ａ／ｃ
ｍ2で０．６５Ｖの性能が得られた。Example 4 0.38 as a gas diffusion electrode
U.S.A. E-TEKINC supporting mg / cm 2 of platinum
This was punched out to 30 mmφ and used as a gas diffusion electrode. The hydrogen ion conductive polymer membrane prepared in Example 3 was immersed in boiling ion-exchanged water for 2 hours to make the membrane water-containing, and then excess water on the surface was wiped off and sandwiched between two gas diffusion electrodes. Pressure was applied at 110 ° C. and 10 MPa for 3 minutes to obtain an electrode assembly. With respect to the obtained electrode assembly, the output characteristics of the fuel cell were evaluated while supplying humidified hydrogen and oxygen and heating at 80 ° C. Although 10 single cells were produced, there was no defect such as short circuit or gas leak, and 0.7 A / c
A performance of 0.65 V was obtained at m 2 .
【００３６】[0036]
【発明の効果】本発明によれば、非フッ素系ポリマーで
あるポリ塩化ビニルを主体とした繊維構造物は有意な耐
ラジカル性を有し、経済的な燃料電池用水素イオン伝導
性高分子膜補強基材が提供される。According to the present invention, a fibrous structure mainly composed of polyvinyl chloride, which is a non-fluorinated polymer, has significant radical resistance and is an economical hydrogen ion conductive polymer membrane for fuel cells. A reinforced substrate is provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村山 定光 大阪府茨木市耳原３丁目４番１号 帝人株 式会社大阪研究センター内 (72)発明者 河口 健一 山口県岩国市日の出町２番１号 帝人株式 会社岩国事業所内 Ｆターム(参考） 4F100 AK01B AK15A AK42 AK54 AK55 AK56 BA02 BA03 DG10 DG12 DG15A DH00 EJ82 GB48 JB20B JD02A YY00A 4L047 AA15 AB02 BA03 BA04 CB08 CB10 CC12 5H026 AA06 BB03 CX03 CX04 EE18 HH00 HH03 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Sadamitsu Murayama 3-4-1, Amihara, Ibaraki-shi, Osaka Teijin Limited Osaka Research Center (72) Inventor Kenichi Kawaguchi 2-1 Hinodemachi, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Iwakuni Office F-term (reference) 4F100 AK01B AK15A AK42 AK54 AK55 AK56 BA02 BA03 DG10 DG12 DG15A DH00 EJ82 GB48 JB20B JD02A YY00A 4L047 AA15 AB02 BA03 BA04 CB08 C03 H03 C03 H03 CB10 A03H
Claims (3)
主体とした厚さ１０〜５０μｍであり、透気度（ＪＩＳ
Ｐ８１１７）が１０ｓｅｃ／１００ｃｃ・ｉｎ2以下
であることを特徴とした繊維構造物。The present invention has a thickness of 10 to 50 μm mainly composed of fibers mainly composed of polyvinyl chloride, and an air permeability (JIS).
P8117) is 10 sec / 100 cc · in 2 or less.
載の繊維構造物。2. The fiber structure according to claim 1, wherein said fiber structure is a nonwoven fabric.
り補強されたことを特徴とする水素イオン伝導性高分子
膜。3. A proton conductive polymer membrane reinforced by the fibrous structure according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000223998A JP2002038361A (en) | 2000-07-25 | 2000-07-25 | Radical-resistant fiber structure and hydrogen ion- conducting polymer membrane reinforced therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000223998A JP2002038361A (en) | 2000-07-25 | 2000-07-25 | Radical-resistant fiber structure and hydrogen ion- conducting polymer membrane reinforced therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002038361A true JP2002038361A (en) | 2002-02-06 |
Family
ID=18718026
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000223998A Pending JP2002038361A (en) | 2000-07-25 | 2000-07-25 | Radical-resistant fiber structure and hydrogen ion- conducting polymer membrane reinforced therewith |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005529451A (en) * | 2002-04-03 | 2005-09-29 | スリーエム イノベイティブ プロパティズ カンパニー | Laminating apparatus and method |
| WO2007145176A1 (en) * | 2006-06-12 | 2007-12-21 | Toyota Jidosha Kabushiki Kaisha | Electrolyte film and method of selecting the same |
| US8268511B2 (en) | 2003-05-28 | 2012-09-18 | 3M Innovative Properties Company | Roll-good fuel cell fabrication processes, equipment, and articles produced from same |
-
2000
- 2000-07-25 JP JP2000223998A patent/JP2002038361A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005529451A (en) * | 2002-04-03 | 2005-09-29 | スリーエム イノベイティブ プロパティズ カンパニー | Laminating apparatus and method |
| US8309218B2 (en) | 2002-04-03 | 2012-11-13 | 3M Innovative Properties Company | Lamination apparatus and methods |
| US8480838B2 (en) | 2002-04-03 | 2013-07-09 | 3M Innovative Properties Company | Lamination apparatus and methods |
| US8268511B2 (en) | 2003-05-28 | 2012-09-18 | 3M Innovative Properties Company | Roll-good fuel cell fabrication processes, equipment, and articles produced from same |
| US8828620B2 (en) | 2003-05-28 | 2014-09-09 | 3M Innovative Properties Company | Roll-good fuel cell fabrication processes, equipment, and articles produced from same |
| WO2007145176A1 (en) * | 2006-06-12 | 2007-12-21 | Toyota Jidosha Kabushiki Kaisha | Electrolyte film and method of selecting the same |
| JPWO2007145176A1 (en) * | 2006-06-12 | 2009-10-29 | トヨタ自動車株式会社 | Electrolyte membrane and selection method thereof |
| US8128836B2 (en) | 2006-06-12 | 2012-03-06 | Toyota Jidosha Kabushiki Kaisha | Electrolyte membrane and method of selecting the same |
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