JPS58204030A - Bonding of membrane - Google Patents
Bonding of membraneInfo
- Publication number
- JPS58204030A JPS58204030A JP57087319A JP8731982A JPS58204030A JP S58204030 A JPS58204030 A JP S58204030A JP 57087319 A JP57087319 A JP 57087319A JP 8731982 A JP8731982 A JP 8731982A JP S58204030 A JPS58204030 A JP S58204030A
- Authority
- JP
- Japan
- Prior art keywords
- exchange membrane
- cation exchange
- acid type
- perfluorosulfonic acid
- membrane
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、陽イオン交換膜とフッ素系樹脂シートの接合
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for joining a cation exchange membrane and a fluororesin sheet.
イオン交換膜法によシ食塩な電気分解して水酸化ナトリ
ウムと塩素を製造する際の隔膜として、耐薬品性、機械
的強度等に優れたフッ素系陽イオン交換膜が使用され、
特に陽イオン交換樹脂としてスルフォン酸基を有するパ
ーフルオロスルフォン酸型陽イオン交換膜が汎用されて
いる。このパーフルオロスルフォン酸型陽イオン交換漠
ハ邂解電圧が低くてすむという利点がある反面、陰極室
から拡散する水酸イオンが透過しやすく、′１ｔＩＬ効
率が低くなるという欠点があった。この欠点を屏消する
ために前記膜の陰極側にパーフルオロカルボン酸型陽イ
オン交換膜を複合させ、あるいは化学処理を施して陰極
側の面をパーフルオロカルボン酸型とし、て電流効率を
高くするとともに、機械強度をも向上させるようにした
陽イオン交換膜が提案されている。また、この陽イオン
交換膜の両層の中間、あるいはパーフルオロスルフォン
酸型陽イオン交換膜中に陽イオン交換膜の強度を向上さ
せる丸めに網状の補強材を介在させることが通常打なわ
れている。A fluorine-based cation exchange membrane with excellent chemical resistance and mechanical strength is used as a diaphragm when producing sodium hydroxide and chlorine by electrolyzing common salt using the ion exchange membrane method.
In particular, perfluorosulfonic acid type cation exchange membranes having sulfonic acid groups are widely used as cation exchange resins. Although this perfluorosulfonic acid type cation exchange solution has the advantage that the decomposition voltage is low, it has the disadvantage that hydroxyl ions diffusing from the cathode chamber easily permeate, resulting in a low '1tIL efficiency. In order to eliminate this drawback, a perfluorocarboxylic acid type cation exchange membrane is combined on the cathode side of the membrane, or the cathode side is made into a perfluorocarboxylic acid type by chemical treatment, thereby increasing the current efficiency. At the same time, cation exchange membranes with improved mechanical strength have been proposed. In addition, a reinforcing material in the form of a round net is usually inserted between the two layers of the cation exchange membrane or in the perfluorosulfonic acid type cation exchange membrane to improve the strength of the cation exchange membrane. There is.
この陽イオン交換膜の食塩１屏用性能は非常に優秀であ
るが、価格が非常に高く、膜の低廉化が望まれていると
ころである。Although this cation exchange membrane has excellent performance for one layer of common salt, it is very expensive, and there is a desire to make the membrane cheaper.
たとえば、第１図の通り、この陽イオン交換膜を袋状に
成形し、袋状体Ａの内部に陽極Ｂ′ｔ−１外部に陰曳（
図示略）を配置する方法が提案されているが（特開昭５
３−９５８９９号、特開昭５３−１０６６７９号等）、
この型式の陽イオン交換膜において有効に機能するのは
陽極と陰極とに挾まれた部分のみであり、他の部分は、
電解には寄与しない。For example, as shown in FIG. 1, this cation exchange membrane is formed into a bag shape, and a negative electrode (
(not shown) has been proposed.
3-95899, JP-A-53-106679, etc.),
In this type of cation exchange membrane, only the part sandwiched between the anode and cathode functions effectively; the other parts are
Does not contribute to electrolysis.
そのため、第２図及び第３図に示すように、陽極と陰極
とに挾まれる部分Ｃのみを陽イオン交換膜で成形し、そ
の他の部分りを比較的安価で、耐久性に富むフッ素系樹
脂で成形して、膜の単価を下げることが検討されている
。Therefore, as shown in Figures 2 and 3, only the part C sandwiched between the anode and the cathode is molded with a cation exchange membrane, and the other parts are made of a relatively inexpensive and durable fluorine-based membrane. Consideration is being given to lowering the unit price of the membrane by molding it with resin.
しかしながら、上記陽イオン交換膜とフッ素系樹脂シー
トを直接接合する有効な方法が存在せず、従来第２図あ
るいは第′−５図に示す袋状体を前記陽イオン交換膜と
フッ素系樹脂シートとで構成することは実用上回ｌであ
った。However, there is no effective method for directly bonding the cation exchange membrane and the fluororesin sheet, and conventionally the bag-like body shown in FIG. It was practical to configure it with the following.
本発明者らは、上記欠点に鑑み、前記陽イオン交換、漢
とフッ素系樹脂シートの接合方法について糧々検討した
ところ、両者の側縁間にパーフルオロスルフォン敗凰陽
イオン交換膜を介在させて両者を熱融着させることによ
り、両者を十分な強度をもって接合できることを見い出
した。In view of the above-mentioned drawbacks, the present inventors have extensively studied the method of joining the cation exchange and fluororesin sheets, and found that a perfluorosulfone cation exchange membrane is interposed between the side edges of both. It has been discovered that by thermally fusing the two together, the two can be joined with sufficient strength.
すなわち、本発明は、一方の面にパーフルオロスルフォ
ン酸基を、他方の面にパーフルオロカルボン酸基を有し
、内部に網状の補強材を埋め込んでなる陽イオン交換膜
の側縁とフッ素系樹脂シートの側縁との間に、少なくと
もその一部が前記陽イオン交換膜のパーフルオロスルフ
ォン酸基側及びフッ素系樹脂シートと重なるようにパー
フルオロスルフォン酸型陽イオン交換膜から成る接合片
を介在させ、この重ね合わせ部を加熱融着して陽イオン
交換膜とフッ素系樹脂シートとを接合する方法である。That is, the present invention has a perfluorosulfonic acid group on one surface, a perfluorocarboxylic acid group on the other surface, and a cation exchange membrane having a mesh reinforcing material embedded therein. A joint piece made of a perfluorosulfonic acid type cation exchange membrane is placed between the side edge of the resin sheet and at least a portion thereof overlaps with the perfluorosulfonic acid group side of the cation exchange membrane and the fluororesin sheet. In this method, the cation exchange membrane and the fluororesin sheet are bonded by interposing the cation exchange membrane and the fluororesin sheet by heating and fusing the overlapping portion.
以下、第４図及び第５図に基いて、本発明方法の実施要
領を説明する。Hereinafter, the implementation procedure of the method of the present invention will be explained based on FIGS. 4 and 5.
第４図及び第５図は陽イオン交換膜とフッ素系樹脂シー
トとをパーフルオロスルフォン酸型陽イオジ交換膜を用
いて接合した状態を示す断面図であるう
１は、方形シート状のパーフルオロカルボン酸屋陽イオ
ン交換膜で、２は、この膜１と同一形状ヲナスパーフル
オロスルフォン酸型陽イオン交換膜である。この両イオ
ン交換膜１，２の中間には図示を省略したフッ素系樹脂
等から成る網状の補強体が介在し、この３部材により陽
イオン交換膜３が形成されている。Figures 4 and 5 are cross-sectional views showing a state in which a cation exchange membrane and a fluororesin sheet are joined using a perfluorosulfonic acid type cation exchange membrane. This is a carboxylic acid cation exchange membrane, and 2 is a Wona perfluorosulfonic acid type cation exchange membrane having the same shape as this membrane 1. A net-like reinforcing body made of fluororesin or the like (not shown) is interposed between the two ion exchange membranes 1 and 2, and the cation exchange membrane 3 is formed by these three members.
４は、パーフルオロスルフォン酸を陽イオン交換膜から
成る接合片で、５は、テトラフルオロエチレン、ヘキサ
フルオロプロピレン、フッ化ビニリデン等の１種又は２
種以上を重合させて成るフッ素系樹脂シートである。4 is a bonded piece made of perfluorosulfonic acid and a cation exchange membrane, and 5 is a bonded piece made of one or two of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, etc.
This is a fluororesin sheet made by polymerizing more than one species.
第４図においては、陽イオン交換膜６の下方のスルフォ
ン酸基側側豫に接合片４が当接され、かつこの接合片４
の下方にフッ素系樹脂シート７が当接され、この当接部
を加熱融着することにより、陽イオン交換膜３とフッ素
系樹脂シート５が互いに接合されている。In FIG. 4, a bonding piece 4 is brought into contact with the lower side of the sulfonic acid group side of the cation exchange membrane 6, and this bonding piece 4 is shown in FIG.
A fluororesin sheet 7 is brought into contact with the lower part of the cation exchange membrane 3 and the fluororesin sheet 5 are joined to each other by heat-sealing this contact portion.
第５図においては、陽イオン交換膜３の側縁とフッ素系
樹脂シート５の側縁とが整合し、この整合部に下方から
、すなわち、陽イオン交換膜３のスルフォン酸基側から
接合片４を当接させ、この部分を加熱融着することによ
り、陽イオン交換膜３とフッ素系樹脂シート５が互いに
接着されている。なお、この場合、下方からだけでなく
、下方及び上方の両面から接合片を当接するようにして
もよい。In FIG. 5, the side edges of the cation exchange membrane 3 and the side edges of the fluororesin sheet 5 are aligned, and the bonded piece is inserted into this aligned portion from below, that is, from the sulfonic acid group side of the cation exchange membrane 3. The cation exchange membrane 3 and the fluororesin sheet 5 are bonded to each other by bringing them into contact with each other and heat-sealing this portion. In this case, the joining pieces may be brought into contact not only from below, but also from both below and above.
この場合、陽イオン交換膜３のスルフォン酸基と、接合
片４のスルフォン酸基との親和力により、陽イオン交換
膜３と接合片４とが強固に接合され、満足すべき引張シ
強度が得られる。さらに、陽イオン交換膜３が網状の補
強材で補強されているため、融着の際の熱によシ、陽イ
オン交換膜６の樹脂が溶は出しても、補強材の格子内に
補Ｔ足され、形がくずれたシ、強度が低下したシするこ
とがない。In this case, due to the affinity between the sulfonic acid groups of the cation exchange membrane 3 and the sulfonic acid groups of the bonded piece 4, the cation exchange membrane 3 and the bonded piece 4 are firmly bonded, and satisfactory tensile strength can be obtained. It will be done. Furthermore, since the cation exchange membrane 3 is reinforced with a mesh-like reinforcing material, even if the resin of the cation exchange membrane 6 melts due to heat during fusion, it will be compensated within the lattice of the reinforcing material. It will not lose its shape or lose its strength due to T-addition.
なお、第４図及び第５図においては、パーフルオロスル
フォン酸型陽イオン交換膜とパーフルオロカルボン酸型
陽イオン交換膜とを複合させて陽イオン交換膜を形成し
たが、本発明は、これに限定されるものではなく、パー
フルオロカルボン酸型陽イオン交換膜の片面を化学処理
してパーフルオロスルフォン酸型とし走り、あるいは逆
の操作により陽イオン交換膜を形成するようにしてもよ
い。また、接合片に網状の補強材を、埋め込んで、接合
部の強度を向上させるようにしてもよい。In addition, in FIGS. 4 and 5, the cation exchange membrane is formed by combining a perfluorosulfonic acid type cation exchange membrane and a perfluorocarboxylic acid type cation exchange membrane, but the present invention The method is not limited to this, and one side of a perfluorocarboxylic acid type cation exchange membrane may be chemically treated to form a perfluorosulfonic acid type, or a cation exchange membrane may be formed by the reverse operation. Furthermore, a net-like reinforcing material may be embedded in the joint piece to improve the strength of the joint.
また、融着条件は、温度２００〜３５０℃、面圧５〜５
０ ｈ／Ｃｄ、時間５〜１２０秒とすることが好ましく
、上＠を越えると膜の材質が劣化し、又、下限を越える
と、融着が不十分となり、ともに好ましくないっ
本発明によれば、上述のように高価な陽イオン交換膜と
比積的安価なフッ素系樹脂シートとを容易に接合するこ
とができ、必要な部分の′みを陽イオン交換膜とし、他
の部分をフッ素樹脂シートとして所定形状の成形体とす
ることができるため、経済的に有利であるっ
実施例
パーフルオロカルボン酸型陽イオン交換膜シートとパー
フルオロスルフォン酸型陽イオン交換膜シートとを網目
状の補強材を介して複句させてなるデュポン社！！！Ｎ
ａｆ ｉ ｏｎ （登鎌商標）＃９０１のシートの側縁
部と、上部が開口し、両面に角孔状の開口部が形成され
た、テトラフルオロエチレンとへキサフルオロプロピレ
ンの共重合体であるフッ素系樹脂シート（ＦＥＰ）の開
口部の周縁部との間に、パーフルオロスルフォン酸型陽
イオン交換膜から成る１０」字状の接合片を重ね合わせ
、この重ね合わせ部を面圧１３Ｋｆ／ｄ、Ｎａｆｉｏｎ
＠ ９０１側温度２６０℃、ＦＥＰ側温度３１０℃で
６５秒間圧着し、Ｎａｆｉｏｎ ＠ ９０１とＦＥＰを
接合した。単位幅あ走りの引張り強度は、４．０ Ｋｇ
／ｃｔｍ ”幅であった。In addition, the fusion conditions are a temperature of 200 to 350°C and a surface pressure of 5 to 5.
0 h/Cd and a time of 5 to 120 seconds is preferable; if the upper limit is exceeded, the material of the membrane will deteriorate, and if the lower limit is exceeded, the fusion will be insufficient, both of which are undesirable. For example, as mentioned above, it is possible to easily join an expensive cation exchange membrane and a comparatively inexpensive fluororesin sheet. This is economically advantageous because it can be molded into a predetermined shape as a resin sheet. DuPont's compound phrases are made through reinforcing materials! ! ! N
af i on (regular trademark) #901 sheet is open at the side edges and at the top, and is a copolymer of tetrafluoroethylene and hexafluoropropylene with square hole-shaped openings formed on both sides. A 10"-shaped joint piece made of perfluorosulfonic acid type cation exchange membrane is overlapped between the periphery of the opening of the fluoropolymer sheet (FEP), and the overlapping part is subjected to a surface pressure of 13 Kf/d. , Nafion
Pressure bonding was performed for 65 seconds at a temperature of 260° C. on the @901 side and 310° C. on the FEP side to join Nafion @901 and FEP. Tensile strength of unit width running is 4.0 kg
/ctm" width.
次に、この袋状体を陽極を包囲するように食塩電解槽に
装着し、電槽温度８５℃、供給食塩水１１１ｉ ３００
ｆ／ｌ、７ ／ ライ） 食塩水１１に、Ｆｌ ２２
０ ？／ ｅ、水酸化す） ＩＪウム濃度３２％で１年
間運転したところ、引張り強度に変化はなく、接着部分
に問題は生じなかった。Next, this bag-like body was attached to a salt electrolytic cell so as to surround the anode, and the cell temperature was 85°C, and the supplied salt water was 111i 300°C.
f/l, 7/ly) in saline 11, Fl 22
0? / e, hydroxide) When operated for one year at an IJium concentration of 32%, there was no change in tensile strength and no problems occurred in the bonded area.
第１図は、陽イオン交換膜を袋状に成形して電解槽に装
着した状態を示す一部破断斜視図、第２図及び第５図は
、それぞれ一部をフッ素系樹脂で成形した袋状体を示す
斜視図、第４図及び第５図は、それぞれ本発明方法によ
シ陽イオン交換膜とフッ素系樹脂シートを接合した状態
を示す断面図である。
１・・・パーフルオロカルボン酸型陽イオン交換膜２・
・・パーフルオロスルフォン酸型陽イオン交換膜６・・
・陽イオン交換膜
４・・・接合片
５・・・フッ素系樹脂シート
代理人 弁理士 森 浩 之Figure 1 is a partially cutaway perspective view showing a cation exchange membrane molded into a bag shape and attached to an electrolytic cell, and Figures 2 and 5 are bags each partially molded from fluororesin. A perspective view showing the shaped body, and FIGS. 4 and 5 are cross-sectional views showing a state in which a cation exchange membrane and a fluororesin sheet are joined by the method of the present invention, respectively. 1... Perfluorocarboxylic acid type cation exchange membrane 2.
・・Perfluorosulfonic acid type cation exchange membrane 6・・
・Cation exchange membrane 4...Joining piece 5...Fluorine resin sheet Agent: Hiroshi Mori, patent attorney
Claims (2)
他方の面にパーフルオロカルボン酸基を有し、内部に網
状の補強材を埋め込んでなる陽イオン交換膜の側縁と７
ノ素系樹脂シートの側縁との間に、少なくともその一部
が前記陽イオン交換膜のパーフルオロスルフォン酸基側
及びフッ素系ｍ 脂シートと重なるようにパーフルオロ
スルフすン酸型陽イオン交換膜から成る接合片を介在さ
せ、この重ね合わせ部を加熱融着して陽イオン交換膜と
フッ素系樹脂シートとを接合することを特徴とする膜の
接合方法。(1) One mK perfluorosulfonic acid group,
A side edge of a cation exchange membrane having a perfluorocarboxylic acid group on the other side and a mesh reinforcing material embedded inside;
A perfluorosulfonic acid type cation is placed between the side edge of the fluorine-based resin sheet and at least a portion thereof overlaps with the perfluorosulfonic acid group side of the cation exchange membrane and the fluorine-based resin sheet. A method for joining membranes, which comprises interposing a joining piece made of an exchange membrane and heat-sealing the overlapping portion to join a cation exchange membrane and a fluororesin sheet.
ｅ／ｍ、時間５〜１２０秒の条件で行なうようにした特
許請求の範囲第（１）項に記載の膜の接合方法。(2) Fusion at a temperature of 200 to 350°C and a surface pressure of 5 to 50 W.
2. The method for bonding films according to claim 1, wherein the bonding is performed under conditions of e/m and time of 5 to 120 seconds.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087319A JPS58204030A (en) | 1982-05-25 | 1982-05-25 | Bonding of membrane |
| GB8313246A GB2121352B (en) | 1982-05-25 | 1983-05-13 | Bonding of cation exchange membrane |
| FR8308327A FR2527516B1 (en) | 1982-05-25 | 1983-05-19 | WELDING OF A CATION EXCHANGE MEMBRANE |
| KR1019830002206A KR860000643B1 (en) | 1982-05-25 | 1983-05-19 | Bonding of cation exchange memerance |
| SE8302911A SE8302911L (en) | 1982-05-25 | 1983-05-24 | BINDING OF THE CATION CHANGE MEMBRANE |
| IT4835983A IT1172262B (en) | 1982-05-25 | 1983-05-24 | METHOD TO BIND A CATION EXCHANGER MEMBRANE WITH A FLUORINATED RESIN SHEET |
| DD83251250A DD209855A5 (en) | 1982-05-25 | 1983-05-25 | CONNECTING A CATION EXCHANGE MEMBRANE |
| PH28958A PH18667A (en) | 1982-05-25 | 1983-05-25 | Bonding of cation exchange membrane |
| DE19833318962 DE3318962A1 (en) | 1982-05-25 | 1983-05-25 | CONNECTING A CATION EXCHANGER MEMBRANE |
| US06/729,082 US4663013A (en) | 1982-05-25 | 1985-05-01 | Cation exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087319A JPS58204030A (en) | 1982-05-25 | 1982-05-25 | Bonding of membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58204030A true JPS58204030A (en) | 1983-11-28 |
Family
ID=13911520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57087319A Pending JPS58204030A (en) | 1982-05-25 | 1982-05-25 | Bonding of membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58204030A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208948A (en) * | 1990-11-27 | 1993-05-11 | Nirei Industry Co., Ltd. | Apparatus for and method of binding electric cables |
| US7404878B2 (en) | 2003-03-31 | 2008-07-29 | Chlorine Engineers Corp., Ltd. | Gas diffusion electrode assembly, bonding method for gas diffusion electrodes, and electrolyzer comprising gas diffusion electrodes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109536A (en) * | 1981-12-23 | 1983-06-29 | Toyo Soda Mfg Co Ltd | Method for bonding cation exchange membrane |
-
1982
- 1982-05-25 JP JP57087319A patent/JPS58204030A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109536A (en) * | 1981-12-23 | 1983-06-29 | Toyo Soda Mfg Co Ltd | Method for bonding cation exchange membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208948A (en) * | 1990-11-27 | 1993-05-11 | Nirei Industry Co., Ltd. | Apparatus for and method of binding electric cables |
| US7404878B2 (en) | 2003-03-31 | 2008-07-29 | Chlorine Engineers Corp., Ltd. | Gas diffusion electrode assembly, bonding method for gas diffusion electrodes, and electrolyzer comprising gas diffusion electrodes |
| US7569083B2 (en) | 2003-03-31 | 2009-08-04 | Chlorine Engineers Corp. Ltd. | Gas diffusion electrode assembly, bonding method for gas diffusion electrodes, and electrolyzer comprising gas diffusion electrodes |
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