CN103668319B

CN103668319B - Amberplex, the manufacture method of amberplex and electrolytic cell

Info

Publication number: CN103668319B
Application number: CN201310399065.3A
Authority: CN
Inventors: 角佳典; 服部行久
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2012-09-14
Filing date: 2013-09-05
Publication date: 2016-09-07
Anticipated expiration: 2033-09-05
Also published as: CN103668319A; JP5868300B2; JP2014058707A

Abstract

The present invention relates to amberplex, the manufacture method of amberplex and electrolytic cell.It is an object of the invention to provide impurity in electrolyte on the impact of electrolysis performance less, the amberplex of electrolysis performance of playing stably.The amberplex of the present invention is the amberplex with film main body and coating, described film main body comprises the fluorinated polymer with ion-exchange group, described coating is arranged at least one face of this film main body, and wherein, above-mentioned coating contains particles of inorganic material and adhesive；The specific surface area of above-mentioned coating is 0.1m²/ g～10m²/g。

Description

Amberplex, the manufacture method of amberplex and electrolytic cell

Technical field

The present invention relates to amberplex, the manufacture method of amberplex and possess the electrolytic cell of amberplex.

Background technology

The excellences such as the heat resistance of fluorine-containing cation exchange membrane and chemical proofing, are therefore used as by alkalescence chlorine Electrically decompose (electrolysis) of compound etc. manufactures the electrolysis cation-exchange membrane of chlorine and alkali.In addition, its also by with Make the various electrolysis barrier films etc. such as ozone generation barrier film, fuel cell, water electrolysis and electrolysis of hydrochloric acid.

Wherein, in the electrolysis electrically decomposing the alkaline chloride that salt solution etc. manufactures NaOH and chlorine and hydrogen, logical Often use following cation-exchange membrane, this cation-exchange membrane by anion exclusion high using carboxylic acid group as ion The carboxylic layer of exchange base and the such at least 2 layers of structure of low-resistance sulphonic layer with sulfonic group as ion-exchange group Become.This cation-exchange membrane directly can contact with 80 DEG C～the chlorine of 90 DEG C or NaOH etc. when electrolysis, therefore will The fluorinated polymer that chemical proofing is high is used as the material of cation-exchange membrane.

But, during merely with this fluorinated polymer, not there is as cation-exchange membrane sufficient mechanical strength, because of This is embedded in film strengthen as strengthening core by weaving cotton cloth of will being made up of polytetrafluoroethylene (PTFE) (PTFE) etc. Deng.

Additionally, during merely with this fluorinated polymer, the gas such as the chlorine produced due to the electrolysis of alkaline chloride etc. or hydrogen Body is attached to the surface of amberplex, makes decomposition voltage significantly increase, thus the painting that coating is made up of inorganic particles etc. Layer.

Such as, proposing the amberplex being coated with following coating in patent document 1, this coating is containing once Oxide, nitride or the carbide of the periodic table of elements Group IV that average grain diameter is 0.01 μm～0.2 μm of grain.

It addition, propose the ion exchange of the porous layer being provided with gas and liquid permeability in patent document 2 Film, its contain titanium, zirconium, niobium, tantalum, hafnium, tin, vanadium, manganese, molybdenum, tungsten, aluminium, chromium, gallium, cerium, thorium, selenium, Iron, yttrium, terres rares, indium, nickel, silver, cobalt, the oxide of beryllium, nitride, carbide and their mixing Thing, does not have cathode activity.

Prior art literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 3-137136 publication

Patent document 2: Japanese Patent Publication 59-40231 publication

Summary of the invention

Invent problem to be solved

Generally, there is metal impurities in the alkaline chloride aqueous solution, this impurity can make the electrolyte of amberplex Can reduce.

Herein, as use amberplex electrolysis in electrolysis performance, can enumerate: in view of productivity ratio, High relative to the production efficiency of the electric current of circulation；Decomposition voltage in view of economy is low；In view of product quality, Impurity (salt etc.) concentration in alkali (NaOH etc.) is low；Etc..Particularly in salt electrolysis, implementing industry In the case of the electrolysis of level, if its decomposition voltage (even if the amplitude of reduction is faint) can be reduced, can improve electric current Efficiency (even if increase rate is faint), the most also can realize the most energy-conservation.

It addition, for amberplex, in order to persistently play its high electrolysis performance, it is desirable to electrolysis performance will not be by Impurity in electrolyte used in electrolysis and reduce.Electrolyte exists Ca, Mg, Ba, Sr, I, SiO₂, the impurity such as Al, Fe, when these impurity are accumulated in the inside of cation-exchange membrane, decomposition voltage can be caused The increase of impurity concentration in increase, the reduction of current efficiency, alkali.Particularly the cation impurity such as I Yu Ca, Mg is not With, even if it is that electrolyte processes impurity in advance that be not easy to cut down, thus require to be not easily susceptible to the impact of I Cation-exchange membrane.

But, the amberplex described in patent document 1 and 2 is the most insufficient for the patience of this impurity, and ion exchanges The electrolysis performance of film is the most insufficient for the stability of impurity.

The present invention proposes in view of the foregoing, its object is to provide the impurity in electrolyte to electrolysis performance Impact is less, playing stably is electrolysed the amberplex of performance.

Solve the means of problem

The present inventor has been repeated further investigation to solve above-mentioned problem, it was found that by making in the past for anti- The gas that only electrolysis produces be attached to amberplex surface purpose and on amberplex Coating be specific Inorganic particles, it is possible to solve above-mentioned problem, thus complete the present invention.That is, the present invention is as described below.

[1] a kind of amberplex, it is the amberplex with film main body and coating, and described film main body comprises Having the fluorinated polymer of ion-exchange group, described coating is arranged at least one face of this film main body, wherein, Above-mentioned coating contains particles of inorganic material and adhesive；

The specific surface area of above-mentioned coating is 0.1m²/ g～10m²/g。

[2] amberplex as described in [1], wherein, the average grain diameter of above-mentioned particles of inorganic material be 0.90 μm～ 2μm。

[3] amberplex as described in [1] or [2], wherein, above-mentioned particles of inorganic material is for containing selecting free element week The oxide of phase table Group IV element, the nitride of periodic table of elements Group IV element and periodic table of elements Group IV The particle of at least one inorganic matter in the group of the carbide composition of element.

[4] amberplex as described in any one of [1]～[3], wherein, above-mentioned particles of inorganic material is zirconic Grain.

[5] amberplex as described in any one of [1]～[4], wherein, above-mentioned adhesive contains fluorinated polymerization Thing.

[6] amberplex as described in any one of [1]～[5], wherein, above-mentioned coating contain 40 mass %～ The above-mentioned adhesive of the above-mentioned particles of inorganic material of 90 mass %, 10 mass %～60 mass %.

[7] amberplex as described in any one of [1]～[6], wherein, above-mentioned adhesive comprise have ion exchange The fluorinated polymer of base, described ion-exchange group is from carboxyl or sulfo group.

[8] amberplex as described in any one of [1]～[7], wherein, being shaped as of above-mentioned particles of inorganic material is not advised Then shape.

[9] amberplex as described in any one of [1]～[8], wherein, above-mentioned particles of inorganic material is by by inorganic The particles of inorganic material that thing is pulverized and produced.

[10] amberplex as described in [9], wherein, above-mentioned particles of inorganic material is by by under inorganic matter utilization The particles of inorganic material that the method for stating carries out pulverizing and produces, the method for select free ball mill, ball mill, colloid mill, Taper grinding machine, disc mill, edge runner, powder process grinding machine, hammer crusher, particle grinding machine, VSI grinding machine, dimension At least a kind of method in the group of Li Shi flour mill, roller mill and jet pulverizer composition.

[11] manufacture method of a kind of amberplex, wherein, the method possesses following operation:

Preparing the operation of coating fluid, this coating fluid contains particles of inorganic material and adhesive, and described particles of inorganic material is to pass through Inorganic matter is pulverized and obtains；

The operation of above-mentioned coating fluid it is coated with on the surface of amberplex；And

Form the operation of coating, make the above-mentioned coating fluid being coated on above-mentioned amberplex surface be dried, thus form painting Layer.

[12] a kind of electrolytic cell, it possesses the amberplex described in any one of [1]～[10].

The effect of invention

In accordance with the invention it is possible to impurity in offer electrolyte on the impact of electrolysis performance less, electrolysis performance of playing stably Amberplex.

Accompanying drawing explanation

Fig. 1 is the sectional view of the embodiment schematically showing amberplex.

Fig. 2 is the schematic diagram of the percent opening strengthening core for illustrating to constitute amberplex.

Fig. 3 is the sectional view of the embodiment schematically showing electrolytic cell.

Fig. 4 is the schematic diagram of the forming method of the intercommunicating pore for amberplex is described.

Symbol description

1 ... amberplex, 2 ... carboxylic layer, 3 ... sulphonic layer, 4 ... strengthen core, 10 ... film main body, 11a, 11b ... coating, 21,22 ... strengthen core, 100 ... electrolytic cell, 200 ... anode, 300 ... negative electrode, 52 ... increase Strong line, 504a ... victim line, 504 ... intercommunicating pore 504.

Detailed description of the invention

Below the detailed description of the invention (hereinafter referred to " present embodiment ") of the present invention is described in detail.Need Illustrating, the present invention is not limited to following present embodiment, can carry out various deformation in the range of its main points Implement.As long as it should be noted that not special declaration, then accompanying drawing wait position relationship based on accompanying drawing up and down Shown in position relationship.Further, the dimension scale of accompanying drawing is not limited to the ratio of diagram.

[amberplex]

The amberplex of present embodiment has film main body and coating, and this film main body comprises and has ion-exchange group Fluorinated polymer, this coating is arranged at least one face of this film main body.Additionally, in the present embodiment, it is coated with Layer is containing particles of inorganic material and adhesive, and the specific surface area of coating is 0.1m²/ g～10m²/g.The ion of this structure is handed over Change in film, impurity contained in produced or electrolyte in electrolysis on the impact of electrolysis performance less, can give play to Stable electrolysis performance.

Fig. 1 is the sectional view of the embodiment schematically showing amberplex.The ion of present embodiment is handed over Changing film 1 to have: film main body 10, it comprises the fluorinated polymer with ion-exchange group；And it is formed at film master Coating 11a on the two sides of body 10 and 11b.

In amberplex 1, film main body 10 possesses: have the ion-exchange group (-SO from sulfo group₃ ^-Represented base Group, hereinafter also referred to as " sulfonic group ") sulphonic layer 3 and there is the ion-exchange group (-CO from carboxyl₂ ^-Institute The group represented, hereinafter also referred to as " carboxylic acid group ") carboxylic layer 2, utilize and strengthen core 4 and strengthen intensity and chi Very little stability.Owing to amberplex 1 possesses sulphonic layer 3 and carboxylic layer 2, thus it is suitable for use as cation exchange Film.

It should be noted that the amberplex of present embodiment can also only have appointing of sulphonic layer and carboxylic layer One of meaning.Additionally, the amberplex of present embodiment need not utilize enhancing core to strengthen, strengthen core The configuration status of material is also not limited to the example of Fig. 1.

(film main body)

First the film main body 10 constituting present embodiment amberplex 1 is illustrated.

For film main body 10, if having selectively through cation function, comprise there is ion-exchange group Fluorinated polymer, to its constitute or material be not particularly limited, can suitably select suitable composition and material Material.

The fluorinated polymer with ion-exchange group in film main body 10 such as can be by having ion-exchange group precursor Fluorinated polymer obtains, and this ion-exchange group precursor can form ion-exchange group by hydrolysis etc..Specifically, example As, it is possible to use before following polymer (hereinafter sometimes called " fluorinated polymer (a) ") makes film main body 10 Body, is converted to ion-exchange group precursor ion-exchange group afterwards, thus obtains film main body 10；Described fluorine-containing birds of the same feather flock together The main chain of compound (a) is made up of fluorinated hydrocarbons, has and can be converted into the group (ion of ion-exchange group by hydrolysis etc. Exchange base precursor) as pendant side chain and melt-processed can be carried out.

Fluorinated polymer (a) such as can by by selected from following 1st group at least one monomer and selected from the following 2nd At least one monomer copolymerization of group and/or following 3rd group manufactures.In addition also by selected from following 1st group, under The homopolymerization stating a kind of monomer in any one group of the 2nd group and following 3rd group manufactures.

As the monomer of the 1st group, such as fluorinated vinylether compound can be enumerated.As fluorinated vinylether compound, permissible Enumerate such as ethylene fluoride, tetrafluoroethene, hexafluoropropene, vinylidene fluoride, trifluoro-ethylene, CTFE, Perfluor (alkyl vinyl ether) etc..Particularly using the amberplex of present embodiment as alkaline electrolysis film In the case of, fluorinated vinylether compound is preferably perfluorinated monomers, is preferably selected from by tetrafluoroethene, hexafluoropropene, complete Perfluorinated monomers in the group that fluorine (alkyl vinyl ether) forms.

As the monomer of the 2nd group, can enumerate such as to have and can be converted to carboxylic acid type ion-exchange group (carboxylic acid group) The vinyl compound of functional group.As having the vinyl compound of the functional group that can be converted to carboxylic acid group, permissible Enumerate such as CF₂=CF(OCF₂CYF)_s-O(CZF)_t(herein, s represents 0～2 to monomers represented by-COOR etc. Integer, t represents the integer of 1～12, Y and Z represents F or CF independently of one another₃, R represents low alkyl group.Low Level alkyl e.g. carbon number is the alkyl of 1～3).

Among these, preferably CF₂=CF(OCF₂CYF)_n-O(CF₂)_mCompound represented by-COOR.Herein, n Representing the integer of 0～2, m represents the integer of 1～4, and Y represents F or CF₃, R represents CH₃、C₂H₅Or C₃H₇。

It should be noted that the amberplex of present embodiment is made as alkaline electrolysis cation-exchange membrane In the case of with, preferably at least use perfluorochemical as monomer, but due to the alkyl (with reference to above-mentioned R) of ester group Can lose from polymer in the moment of hydrolysis, thus alkyl (R) may not be whole hydrogen atom and is substituted by fluorine atom Perfluoroalkyl.

As the monomer of the 2nd group, in above-mentioned substance, the most following shown monomer.

CF₂=CFOCF₂-CF(CF₃)OCF₂COOCH₃、

CF₂=CFOCF₂CF(CF₃)O(CF₂)₂COOCH₃、

CF₂=CF[OCF₂-CF(CF₃)]₂O(CF₂)₂COOCH₃、

CF₂=CFOCF₂CF(CF₃)O(CF₂)₃COOCH₃、

CF₂=CFO(CF₂)₂COOCH₃、

CF₂=CFO(CF₂)₃COOCH₃。

As the monomer of the 3rd group, can enumerate and such as there is the official that can be converted to sulfone type ion-exchange group (sulfonic group) The vinyl compound that can roll into a ball.As having the vinyl compound that can be converted to sulfonic functional group, the most excellent Select CF₂=CFO-X-CF₂-SO₂Monomer (herein, X represents perfluorinated alkylidene) represented by F.Concrete as them Example, can enumerate monomer etc. shown below.

CF₂=CFOCF₂CF₂SO₂F、

CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂F、

CF₂=CFOCF₂CF(CF₃)OCF₂CF₂CF₂SO₂F、

CF₂=CF(CF₂)₂SO₂F、

CF₂=CFO[CF₂CF(CF₃)O]₂CF₂CF₂SO₂F、

CF₂=CFOCF₂CF(CF₂OCF₃)OCF₂CF₂SO₂F。

Among these, more preferably CF₂=CFOCF₂CF(CF₃)OCF₂CF₂CF₂SO₂F and CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂F。

The copolymer obtained by these monomers can be by the polymerization developed for homopolymerization and the copolymerization of ethylene fluoride Method, the general polymerization used especially for tetrafluoroethene manufacture.Such as, in non-aqueous method, The atent solvent such as perfluoroparaffin, cfc can be used, at free radicals such as perfluorocarbon peroxide or azo-compounds In the presence of polymerization initiator, temperature be 0 DEG C～200 DEG C, pressure be 0.1MPa～20MPa under conditions of carry out Polymerisation.

In above-mentioned copolymerization, kind and ratio thereof to the combination of above-mentioned monomer are not particularly limited, according to will be to gained To fluorinated polymer give functional group kind and amount select and determine.Such as, formation contains only During the fluorinated polymer of carboxylic acid group, at least one monomer is selected to carry out copolymerization i.e. respectively from above-mentioned 1st group and the 2nd group Can.During it addition, formation contains only sulfonic fluorinated polymer, divide from the monomer of above-mentioned 1st group and the 3rd group At least one monomer is not selected to carry out copolymerization.Additionally, formed, there is carboxylic acid group and the polymerization of sulfonic fluorinated During thing, at least one monomer is selected to carry out copolymerization i.e. from the monomer of above-mentioned 1st group, the 2nd group and the 3rd group respectively Can.In this case, it is also possible to by by above-mentioned 1st group and the 2nd group of copolymer constituted and by the above-mentioned 1st Group and the 3rd group of copolymer constituted are polymerized respectively, mix afterwards, thus obtain target fluoro base polymer. Further, the mixed proportion of each monomer is not particularly limited, in the feelings of the amount of the functional group increasing per unit polymer Under condition, as long as increasing the ratio of the monomer of free above-mentioned 2nd group and the 3rd group of choosing.

The total ion exchange capacity of fluorinated copolymer is not particularly limited, preferably 0.5mg equivalent/g～2.0mg Equivalent/g, more preferably 0.6mg equivalent/g～1.5mg equivalent/g.Total ion exchange capacity herein refers to per unit The equivalent of the cation exchange groups in the dry resin of weight, can be measured by acid-base titration etc..

In the film main body 10 of amberplex 1, make to comprise the sulphonic layer 3 with sulfonic fluorinated polymer with The carboxylic layer 2 comprising the fluorinated polymer with carboxylic acid group carries out lamination.By making the film of such Rotating fields Main body 10, it is possible to improve the selective penetrated property of the cations such as sodium ion further.

In the case of being configured in a cell by amberplex 1, generally it is configured such that sulphonic layer 3 is positioned at electrolysis Groove anode-side, carboxylic layer 2 is made to be positioned at the cathode side of electrolytic cell.

Sulphonic layer 3 is preferably made up of the material that resistance is low, from the aspect of film-strength, and preferably its Film Thickness Ratio carboxylic layer 2 is thicker.The thickness of sulphonic layer 3 is preferably 2～25 times, more preferably 3～15 times of carboxylic layer 2.

Even if the preferred thickness of carboxylic layer 2 is thin also has high anion exclusion.Anion exclusion described herein is Refer to the character hindering the anion immersion to amberplex 1 and passing through.In order to improve anion exclusion, configure from It is effective that sub-exchange capacity is less than the ways such as the carboxylic layer of sulphonic layer.

As fluorinated polymer used in sulphonic layer 3, such as, it is suitably use as the 3rd group of monomer CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂F and the polymer that obtains.

As fluorinated polymer used in carboxylic layer 2, such as, it is suitably use as the 2nd group of monomer CF₂=CFOCF₂CF(CF₂)O(CF₂)₂COOCH₃And the polymer obtained.

(coating)

The amberplex of present embodiment has coating at least one face of film main body.Additionally, such as Fig. 1 institute Show, in amberplex 1, the two sides of film main body 10 form respectively coating 11a and 11b.

Coating contains particles of inorganic material and adhesive, and the specific surface area of coating is 0.1m²/ g～10m²/g.Herein, it is coated with The specific surface area of layer represents the value of the index S utilizing following assay method to calculate.By making this index S low, can drop The impact on electrolysis performance of the impurity in low electrolyte.The specific surface area (index S) of coating is preferably 0.1m²/ g～ 5m²/ g, more preferably 0.1m²/ g～3m²/g。

The concrete assay method of the index S of specific surface area is as described below.

The index S of specific surface area can be tried to achieve as follows.Prepare to be coated with cated amberplex (A) and by profit Eliminated the amberplex (B) of coating by amberplex (A) with sponge wiping, respectively it is carried out little angle X and penetrate Line scattering measures.

Obtained from coating by the small angle X ray scattering measurement result of amberplex (A) Yu amberplex (B) Scatter intensity distribution, carries out absolute intensity correction to obtained scatter intensity distribution.

Now unit conversion is e²/nm³.Carrying out absolute intensity timing, as sample thickness, using by coating The thickness that transmitance calculates.In scatter intensity distribution I so obtained, for I and q^-4Proportional region, Utilize I=2 π Δ ρ²Tq^-4It is fitted (Off ィッティ Application グ), thus obtains the value of T.Herein, Δ ρ uses coating In the poor (1/nm of electron density of particles of inorganic material and adhesive³).During small angle X ray scattering measures, to q scope It is set obtaining I and q^-4(q is the absolute value of Scattering of Vector, and unit is nm in proportional region^-1).Specific surface Long-pending index S can use this T to be tried to achieve by following formula.

S=T/ρ×1000

Herein, ρ is the density (g/cm of inorganic matter³).It should be noted that it is whole at coating tight, inorganic matter Be covered by adhesive, in the case of mineral surfaces has sharp interface, according to Porod law, index S is inorganic Composition granule and the specific interfacial area (m of adhesive²/g)。

The average grain diameter of particles of inorganic material is more preferably more than 0.90 μm.The average grain diameter of particles of inorganic material is 0.90 μm Time above, the durability of impurity there is raising greatly.I.e., in the present embodiment, by increasing particles of inorganic material Average grain diameter and meet above-mentioned specific surface area value simultaneously, available especially significant effect.Such in order to meet Average grain diameter and specific surface area, in the present embodiment, can use irregular particles of inorganic material, preferably aptly Use the particles of inorganic material obtained by carrying out raw ore pulverizing.

Additionally, the average grain diameter of particles of inorganic material can be below 2 μm.The average grain diameter of particles of inorganic material is 2 μm Time following, it is possible to prevent the membrane damage caused by particles of inorganic material.The average grain diameter of particles of inorganic material is more preferably 0.90 μm～1.2 μm.More preferably 1 μm～1.2 μm.

Herein, average grain diameter may utilize size distribution meter (" SALD2200 " Shimadzu Seisakusho Ltd.) and is measured.

Being preferably shaped to of particles of inorganic material is irregularly shaped.Thus, can reduce further specific surface area index S, Improve the patience to impurity further.Additionally, the size distribution of particles of inorganic material preferably has deviation, preferred distribution Wide.

Particles of inorganic material preferably comprises and selects the oxide of free periodic table of elements Group IV element, periodic table of elements iv At least one in the group of the nitride of race's element and the carbide composition of periodic table of elements Group IV element is inorganic Thing.From the aspect of durability, more preferably zirconia particles.

This particles of inorganic material is preferably by the inorganic matter pulverized the raw ore of particles of inorganic material and produce Grain.It was to manufacture particles of inorganic material, by grain diameter by being melted by the raw ore of particles of inorganic material, carry out refining in the past Consistent spherical particle is used in coating as particles of inorganic material.On the other hand, in the present embodiment, find to pass through Making specific surface area is the impact that can reduce impurity in above-mentioned scope to electrolysis performance, in order to increase the surface of particles of inorganic material Long-pending, reduction specific surface area, can be used for the particles of inorganic material obtained by carrying out raw ore pulverizing in coating.

Be not particularly limited as breaking method, can enumerate ball mill, ball mill, colloid mill, taper grinding machine, Disc mill, edge runner, powder process grinding machine, hammer crusher, particle grinding machine, VSI grinding machine, dimension Li Shi abrasive dust Machine, roller mill, jet pulverizer etc..It is then preferred that be carried out after being pulverized, as cleaning method now, Preferably carry out acid treatment.Thus, the impurity such as the iron being attached to particles of inorganic material surface can be cut down.

In the present embodiment, coating contains adhesive.Adhesive is that particles of inorganic material is maintained at amberplex Surface and become the composition of coating.From the aspect of the patience for the product caused by electrolyte or electrolysis, bonding Agent preferably comprises fluorinated polymer.

As adhesive, from for the product caused by electrolyte or electrolysis patience and with amberplex surface The aspect of cementability set out, more preferably there is carboxylic acid group or sulfonic fluorinated polymer.Comprising, there is sulphur In the case of arranging coating on the layer (sulphonic layer) of the fluoropolymer of acidic group, as the adhesive of this coating, more preferably Use has sulfonic fluorinated polymer.Additionally, comprising the layer (carboxylic acid of the fluoropolymer with carboxylic acid group Layer) on coating is set in the case of, as the adhesive of this coating, more preferably use and there is the fluorine-containing of carboxylic acid group birds of the same feather flock together Compound.

The content of the particles of inorganic material in coating be preferably 40 mass %～90 mass %, more preferably 50 mass %～ 90 mass %.Additionally, the content of adhesive be preferably 10 mass %～60 mass %, more preferably 10 mass %～ 50 mass %.

The preferably every 1cm of the distribution density of the coating in amberplex²For 0.05mg～2mg.Additionally, ion exchange Film in the case of surface has concaveconvex shape, the preferably every 1cm of the distribution density of coating²For 0.5mg～2mg.

It is not particularly limited as the method forming coating, it is possible to use known method.Such as can enumerate following Method: be dispersed in the solution containing adhesive by particles of inorganic material, utilizes spraying etc. to be coated the coating of liquid.

(enhancing core)

The amberplex of present embodiment preferably has the enhancing core of the inside being arranged in film main body.

Strengthening core is intensity and the parts of dimensional stability strengthening amberplex.Configure by core will be strengthened Inside in film main body, it is possible to especially by the extension and contraction control of amberplex in desired scope.This ion is handed over Change film and will not stretch more than for necessary amount when electrolysis etc., it is possible to the dimensional stability that long term maintenance is excellent.

It is constructed without being particularly limited to strengthening core, such as, the line being referred to as splicing thread can be spinned and formed. Splicing thread described herein refers to following line: it is the parts constituting and strengthening core, it is possible to give amberplex Desired dimensional stability and mechanical strength, and this line can stable existence in amberplex.By using The enhancing core that this splicing thread is spinned, it is possible to give the most excellent dimensional stability and machine to amberplex Tool intensity.

It is not particularly limited for strengthening core and the material of splicing thread wherein used, is preferably and acid or alkali etc. are had Indefatigable material, from needing long-term heat resistance, the aspect of chemical proofing, is preferably polymerized by fluorinated The fiber that thing is constituted.

As strengthening fluorinated polymer used in core, such as polytetrafluoroethylene (PTFE) (PTFE), tetrafluoro second can be enumerated Alkene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethene-hexafluoro third Alkene copolymer, chlorotrifluoroethylene-ethylene copolymer and vinylidene fluoride polymer (PVDF) etc..Among these, from resistance to Hot and chemical proofing aspect is set out, the fiber being particularly preferably made up of polytetrafluoroethylene (PTFE).

It is not particularly limited for strengthening the line footpath of splicing thread used in core, preferably 20 daniers～300 denier Neil, more preferably 50 daniers～250 daniers.Weave density (the beating radical of per unit length) is preferably 5 Piece/inch～50 pieces/inch.For strengthen core form be not particularly limited, use such as weave cotton cloth, non-woven fabrics, Compile cloth etc., form of preferably weaving cotton cloth.Additionally, for the thickness weaved cotton cloth, use and be preferably 30 μm～250 μm, more It is preferably weaving cotton cloth of 30 μm～150 μm.

Weave cotton cloth or compile cloth and can use monofilament, multifilament or their yarn, cut film silk etc., for woven mode, permissible Use plain weave, leno is knitted, knitting, raised line is knitted, crape striped is thin the various woven modes such as knits.

The woven mode and configuration strengthening core in film main body is not particularly limited, it may be considered that amberplex big Little, shape, physical property desired for amberplex and use environment etc. to carry out suitable configuration aptly.

For example, it is possible to a prescribed direction configuration along film main body strengthens core, but go out in terms of dimensional stability Sending out, the first direction configuration preferably along regulation strengthens core, and along the second party substantially vertical with first direction To configuration, other strengthens core.More than 2 are configured substantially in parallel by the inside of the longitudinal film main body in film main body Enhancing core, it is possible on multi-direction, give the most excellent dimensional stability and mechanical strength.For example, it is preferable to The surface of film main body is woven with along the enhancing core (warp) of longitudinally configuration and the enhancing core (parallel) that transversely configures Configuration.From the aspect of dimensional stability, mechanical strength and ease of manufacturing, warp and parallel is more preferably made to hand over Beat up the plain weave of braiding, on one side 2 warps of twisted while carrying out, with parallel, the leno that inweaves for sink-float Knit, make 2 or many to pull together respectively and the parallel of the equal number that carries out beating up in the warp configured and the side that is made into Plain weave (oblique sub-り)；Etc..

Particularly preferably along MD direction (Machine Direction direction, longitudinal) and the TD direction of amberplex (Transverse Direction direction, laterally) configuration of the two direction strengthens core.I.e., preferably MD direction with TD direction carries out plain weave.Herein, MD direction refer in the manufacturing process of amberplex described later film main body or Various cores (such as strengthening core, splicing thread, victim line described later etc.) carry out the direction (flow direction) transmitted, TD Direction refers to and MD direction generally perpendicular direction.Further, the line knitted along MD direction is referred to as MD line, The line knitted along TD direction is referred to as TD line.Generally, amberplex used in electrolysis is rectangle, length side To mostly being MD direction, width mostly is TD direction.By using as MD line enhancing core with as TD The enhancing core of line inweaves, it is possible in the most excellent dimensional stability of multi-direction imparting and mechanical strength.

To strengthen core configuration space be not particularly limited, it may be considered that physical property desired to cation-exchange membrane and Environment etc. is used to carry out suitable configuration aptly.

The percent opening strengthening core is not particularly limited, preferably more than 30%, more preferably more than 50% 90% Below.From the aspect of the electrochemical properties of amberplex, percent opening is preferably more than 30%；Exchange from ion The aspect of the mechanical strength of film is set out, and it is preferably less than 90%.

The percent opening of enhancing core refers to the material (electricity such as area (A) intermediate ion on any one surface in film main body Solve liquid and cation (such as sodium ion) contained therein) ratio of the gross area (B) on surface that can pass through (B/A).The gross area (B) on the surface that the materials such as ion can pass through refer at amberplex cationic and Electrolyte etc. are not ion exchanged the gross area strengthening the region that core etc. is blocked contained by film.

Fig. 2 is the schematic diagram of the percent opening strengthening core for illustrating to constitute amberplex.In Fig. 2, by ion The part amplification of exchange membrane, illustrate only the configuration strengthening core 21 and 22 in this region, about other parts, Eliminate diagram.

Can pass through from the district impaled by the enhancing core 21 along longitudinally configuration and the enhancing core 22 in landscape configuration Territory, the most also area (A) in the region including the area strengthening core deduct the gross area (C) strengthening core, ask The gross area (B) in the region that the materials such as area (A) intermediate ion going out above-mentioned zone can pass through.That is, percent opening can Obtained by lower formula (I).

Percent opening=(B)/(A)=((A)-(C))/(A) ... (I)

Strengthening in core, from chemical proofing and the aspect of heat resistance, particularly preferred form is for comprising The tape yarn of PTFE or highly oriented monofilament.Specifically, the most following enhancing core: its use will be by PTFE The high intensity, porous tape yarn being cut into banding constituted or the 50 of the height-oriented monofilament being made up of PTFE Danier～300 daniers, and be weave density be 10 pieces/inch～the plain weave of 50 pieces/inch, its thickness is 50 μm～the scope of 100 μm.The percent opening of the amberplex comprising this enhancing core is more preferably more than 60%.

As the shape of splicing thread, round wires, strip line etc. can be enumerated.Preferably strip line.

(intercommunicating pore)

The amberplex of present embodiment preferably has intercommunicating pore in the inside of film main body.

Intercommunicating pore refers to become the hole of the stream of cation or the electrolyte produced when electrolysis.Additionally, intercommunicating pore is In the hole of the tubulose that film body interior is formed, formed by sacrifice core (or victim line) described later dissolution.Intercommunicating pore Shape or aperture etc. can be by selecting to sacrifice the shape of core (victim line) or line footpath be controlled.

By forming intercommunicating pore at amberplex, it can be ensured that the alkali ion produced during electrolysis or the movement of electrolyte Property.The shape of intercommunicating pore is not particularly limited, can make for forming the sacrificial of intercommunicating pore according to preparation method described later The shape of domestic animal core.

In the present embodiment, intercommunicating pore is preferably according to alternately through anode-side (sulphonic layer side) and the negative electrode strengthening core The mode of side (carboxylic layer side) is formed.By making this structure, define intercommunicating pore at the cathode side strengthening core In part, the cation (such as sodium ion) being transmitted by electrolyte full in intercommunicating pore can also be flow to Strengthen the cathode side of core.Its result, the flowing of cation will not be truncated, it is thus possible to reduces ion further and hands over Change the resistance of film.

Intercommunicating pore can be formed only along a prescribed direction of the film main body constituting present embodiment amberplex, But from the standpoint of having given play to more stable electrolysis performance, preferably in longitudinal direction and the horizontal the two direction of film main body Formed.

[manufacture method]

As the suitable manufacturing methods of the amberplex of present embodiment, can enumerate and there are following (1) operation～(6) The method of operation.

(1) operation: manufacture and there is ion-exchange group or be there is the ion friendship that can be become ion-exchange group by hydrolysis Change the operation of the fluorinated polymer of based precursor.

(2) operation: the most at least inweave more than 2 strengthen core and having be dissolved in acid or alkali character and Form the victim line of intercommunicating pore, thus obtain being configured with the reinforcing material of victim line each other at the adjacent core that strengthens Operation.

(3) operation: by have ion-exchange group or have can by hydrolysis become ion-exchange group ion exchange The operation of the above-mentioned fluorinated polymer membranization of based precursor.

(4) operation: be embedded in above-mentioned film by above-mentioned reinforcing material as required, obtains being configured with above-mentioned increasing in inside The operation of the film main body of strong material.

(5) operation: the operation (hydrolyzing process) that the film main body obtained in (4) operation is hydrolyzed.

(6) operation: the operation (painting process) of coating is set in the film main body obtained in (5) operation.

Being characterized mainly in that of the manufacture method of the amberplex of present embodiment, uses spy in (6) painting process Fixed particles of inorganic material.Below each operation is described in detail.

(1) operation: manufacture the operation of fluorinated polymer

In (1) operation, use the starting monomer described in above-mentioned 1st group～the 3rd group to manufacture fluorinated polymer. In order to control the ion exchange capacity of fluorinated polymer, adjust former in forming the manufacture of fluorinated polymer of each layer The mixing ratio of material list body.

(2) operation: the manufacturing process of reinforcing material

Reinforcing material is weaving cotton cloth of braiding splicing thread.Enhancing core is formed by imbedding reinforcing material in film Material.When making the amberplex with intercommunicating pore, victim line inweaves in reinforcing material the most together.This situation Under the mixed amount of knitting of victim line be preferably 10 overall mass % of reinforcing material～80 mass %, more preferably 30 mass %～70 mass %.By inweaving victim line, still prevent the skew strengthening core.

Victim line has dissolubility under the manufacturing process or electrolytic environments of film, uses artificial silk, poly terephthalic acid Glycol ester (PET), cellulose and polyamide etc..And also preferably there is the thick of 20 daniers～50 daniers Degree, the polyvinyl alcohol etc. being made up of monofilament or multifilament.

It should be noted that in (2) operation, strengthen core or the configuration of victim line by adjusting, can be to perforate The configuration etc. of rate or intercommunicating pore is controlled.

(3) operation: membranization operation

In (3) operation, use the fluorinated polymer membranization that extruder will obtain in above-mentioned (1) operation.Film can be Single layer structure, can also be 2 Rotating fields of sulphonic layer and carboxylic layer, it is also possible to be the multilayer of more than 3 layers as mentioned above Structure.

As the method carrying out membranization, the most following method can be enumerated.

To there is the fluoropolymer of carboxylic acid group, there is the method that membranization each distinguished by sulfonic fluoropolymer.

By the fluoropolymer with carboxylic acid group is out made compound with having sulfonic fluoropolymer co-extrusion The method of film.

It should be noted that film can also be respectively more than two panels.Further, different types of film coextrusion is contributed to Improve the adhesive strength at interface, thus be preferred.

(4) operation: obtain the operation of film main body

In (4) operation, by the reinforcing material obtained in (2) operation being embedded in (3) operation the inside of the film obtained, Obtain inside and there are the film main body of reinforcing material.

It is preferably formed as method as film main body, can enumerate following method: what (i) will be located in cathode side has carboxylic acid group The fluorinated polymer (hereinafter the layer being made up of it being referred to as ground floor) of precursor (such as carboxylate function) with have The fluorinated polymer (hereinafter the layer being made up of it being referred to as the second layer) of sulfonic group precursor (such as sulfonyl fluoride function) Carry out membranization by coetrusion, use heating source and vacuum source as required, there is a large amount of micropore flat from the teeth outwards On plate or cylinder, separate paper sequentially lamination reinforcing material, the second layer/ground floor across the heat resistance with gas permeability are multiple Close film, at a temperature of each polymer melting, carry out integration by the air removing each interlayer that reduces pressure；(ii) With the second layer/ground floor composite membrane the most dividually, the most individually carry out having the fluorinated polymer (the of sulfonic group precursor Three layers) membranization, use heating source and vacuum source as required, there is flat board or the cylinder of a large amount of micropore from the teeth outwards On across the heat resistance with gas permeability separate paper sequentially lamination third layer film, strengthen core, by the second layer/the first The composite membrane that layer is constituted, is carried out by the air removing each interlayer that reduces pressure at a temperature of each polymer melting Integration.

Herein, by the coextrusion of ground floor Yu the second layer, it is favorably improved the adhesive strength at interface.

Additionally, compared with pressurization pressing, the method for the lower integration of decompression has the third layer that can increase on reinforcing material The feature of thickness.Further, owing to reinforcing material is fixed on the inner face of film main body, thus have and can fully protect Hold the performance of the mechanical strength of amberplex.

It should be noted that lamination described herein be changed to an example, it may be considered that the layer structure of desired film main body One-tenth or physical property etc., carry out coextrusion after suitably selecting suitable lamination pattern (combination etc. of the most each layer).

It should be noted that for the purpose of the electric property improving amberplex further, it is also possible at ground floor And exist by the fluorinated polymer structure with carboxylic acid group's precursor and both sulfonic group precursors further between the second layer Become the 4th layer or use and constitute by having carboxylic acid group's precursor fluorinated polymer with both sulfonic group precursors The 4th layer replace the second layer.

The forming method of the 4th layer can be to manufacture the fluorinated polymer with carboxylic acid group's precursor respectively and have sulfonic acid The method carrying out after the fluorinated polymer of based precursor mixing, it is also possible to will have the monomer of carboxylic acid group's precursor for using Method with the copolymer of the monomer copolymerization with sulfonic group precursor.

Using the 4th layer as in the case of the composition of amberplex, ground floor and the co-extrusion of the 4th layer can be molded Membrane, with it respectively by third layer and the independent membranization of the second layer, profit carries out lamination with the aforedescribed process；Also can be simultaneously Carry out this co-extrusion of 3 layers of ground floor/four layer/second layer and out carry out membranization.

In this case, the direction of membrane flow carrying out extruding is MD direction.Thus, can be formed on reinforcing material Comprise the film main body of the fluorinated polymer with ion-exchange group.

Additionally, the amberplex of present embodiment preferably has by having sulfonic group in the face side being made up of sulphonic layer Fluoropolymer constitute ledge, i.e. protuberance.It is not particularly limited for forming the method for such protuberance, The known method forming protuberance at resin surface can be used.Specifically, can enumerate such as at the table of film main body The method of embossing processing is implemented in face.Such as, by will use time integrated to above-mentioned composite membrane and reinforcing material etc. Carry out the separate paper of embossing processing in advance, above-mentioned protuberance can have been formed.In the feelings being processed to form protuberance by embossing Under condition, the height of protuberance and the control of configuration density can be by carrying out the embossed shapes (shape of separate paper) transferred Control to carry out.

(5) hydrolyzing process

In (5) operation, carry out following operation: the film main body that will obtain in (4) operation hydrolyzes, before ion-exchange group Body is converted to ion-exchange group (hydrolyzing process).

Additionally, in (5) operation, remove by utilizing acid or alkali the victim line contained in film main body to be dissolved, permissible Dissolution hole is formed in film main body.Remove and the company of remaining in it should be noted that victim line can also not be completely dissolved In through hole.Further, remain in the victim line in intercommunicating pore to dissolve by electrolyte when amberplex is for electrolysis Remove.

Victim line has relative to acid or the dissolubility of alkali under the manufacturing process or electrolytic environments of amberplex, passes through The dissolution of victim line, forms intercommunicating pore at this position.

(5) operation can be by being immersed in the film main body obtained in (4) operation in the hydrating solution containing acid or alkali OK.As this hydrating solution, such as, can use containing KOH Yu DMSO (dimethyl sulfoxide (DMSO), Dimethyl sulfoxide) Mixed solution.

This mixed solution preferably comprises the KOH of 2.5N～4.0N, containing 25 mass %～the DMSO of 35 mass %.

As the temperature of hydrolysis, preferably 70 DEG C～100 DEG C.Temperature is the highest, and apparent thickness more can be made thicker.More It is preferably 85 DEG C～100 DEG C.

Time as hydrolysis is preferably 10 minutes～120 minutes.Time is the longest, and apparent thickness more can be made thicker. More preferably 20 minutes～120 minutes.

The operation being formed intercommunicating pore by dissolution victim line is described in detail herein.Fig. 4 (a), (b) are For the schematic diagram of the forming method of the intercommunicating pore of the amberplex in present embodiment is described.

In Fig. 4 (a), (b), only illustrate splicing thread 52, victim line 504a and formed by victim line 504a Intercommunicating pore 504, the diagram for other component omission such as film main bodys.

First, the splicing thread 52 strengthening core will be constituted in amberplex and be used in amberplex being formed Victim line 504a of intercommunicating pore 504 is enrolled, and makes reinforcing material.Then, in (5) operation, victim line 504a is made Dissolution, thus form intercommunicating pore 504.

According to said method, as long as according to how configuring enhancing core, intercommunicating pore in the film main body of cation-exchange membrane Adjust the mode of enrolling of splicing thread 52 and victim line 504a, thus easy.

Fig. 4 (a) illustrates and inweaves splicing thread 52 and victim line at paper along vertical and horizontal the two direction The plain weave reinforcing material of 504a, but the splicing thread 52 in reinforcing material and victim line can be changed as required The configuration of 504a.

(6) painting process

In (6) operation, preparation contains the coating fluid of particles of inorganic material and the adhesive pulverized and obtain by raw ore, The surface of the amberplex obtained in (5) operation is coated the coating of liquid and is dried, and thus can form coating.

As adhesive, the most following adhesive: the fluorinated polymer with ion-exchange group precursor is utilized The aqueous solution containing dimethyl sulfoxide (DMSO) (DMSO) and potassium hydroxide (KOH) is hydrolyzed, and being immersed in afterwards in hydrochloric acid will The counter ion counterionsl gegenions of ion-exchange group are replaced into H⁺, obtain this adhesive and (for example, contain carboxyl or the fluorine-containing of sulfo group birdss of the same feather flock together Compound).Thus, it is readily dissolved in water described later and ethanol, thus preferably.

This adhesive is dissolved in the solution that water and ethanol mix.It should be noted that water and ethanol is excellent Selecting volume ratio is 10:1～1:10, more preferably 5:1～1:5, more preferably 2:1～1:2.Utilize Ball mill makes particles of inorganic material be dispersed in so obtained lysate, obtains coating fluid.Now, it is possible to by adjusting Time during dispersion, rotary speed adjust the average grain diameter etc. of particle.It should be noted that particles of inorganic material with The preferred combined amount of adhesive is described above.

About the particles of inorganic material in coating fluid and the concentration of adhesive, though being not particularly limited, but it is preferably made low dense The coating fluid of degree.Thus can carry out even spread on the surface of amberplex.

Additionally, when making particles of inorganic material disperse, surfactant can be added in dispersion liquid.As surfactant, Preferably nonionic surface active agent, can enumerate such as Japan Oil Co HS-210, NS-210, P-210, E-212 etc..

Sprayed by utilization or roller coat by obtained coating solution on amberplex surface, obtain ion exchange Film.

[electrolytic cell]

For the amberplex of present embodiment, can use it to make electrolytic cell and use.Fig. 3 is this reality Execute the schematic diagram of an embodiment of mode electrolytic cell.

The electrolytic cell 100 of present embodiment at least possess anode 200, negative electrode 300 and be arranged in anode 200 with The cation-exchange membrane 1 of the present embodiment between negative electrode 300.Herein, to possess above-mentioned cation-exchange membrane 1 Electrolytic cell 100 illustrates as an example, but is not limited to this, can be in the range of the effect of present embodiment The deformation carrying out various composition is implemented.

This electrolytic cell 100 can use in various electrolysis, below, as representative examples, at alkaline chloride Situation about using in the electrolysis of the aqueous solution illustrates.

Electrolytic condition is not particularly limited, can carry out under the conditions of known.Such as, to anode chamber supply 2.5～ The alkaline chloride aqueous solution of 5.5 equivalents (N), to cathode chamber for feedwater or the alkaline hydrated oxide aqueous solution of dilution, profit Electrolysis is implemented with DC current.

Present embodiment electrolytic cell is constructed without being particularly limited to, for example, it is possible to can also be multipole for acyclic type Formula.It is not particularly limited, such as, as the material of anode chamber, preferably to alkali as the material constituting electrolytic cell 100 Property chloride and chlorine have indefatigable titanium etc.；As the material of cathode chamber, preferably alkaline hydrated oxide and hydrogen are had The nickel etc. of patience.About the configuration of electrode, can arrange between cation-exchange membrane 1 and anode 200 suitable between Every configuring, even if configuring in the way of anode 200 contacts with cation-exchange membrane 1, it is also possible to Do not use with there is no any problem.Additionally, negative electrode generally arranges suitable interval join with cation-exchange membrane Put, even if being that the electrolytic cell (zero space type electrolytic cell) of the not contact-type at this interval can also not have any problem ground Use.

Above the suitable embodiment of the present invention is illustrated, but the present invention is not limited to above-mentioned embodiment.

Embodiment

The present invention is described in detail below by embodiment.It should be noted that the present invention is not limited to following example. It should be noted that as long as no special declaration, the most following unit is based on quality criteria.

[impurity resistance test]

When amberplex obtained by using is electrolysed, the 5N's (equivalent concentration) as electrolyte supply Salt solution adds impurity, measures the performance as cation-exchange membrane and change.As electrolytic cell used in electrolysis be It is configured with the structure of amberplex between anode and negative electrode, the type (forced circulation of the mandatory circulation of electrolyte will be made Type) 4 electrolysis cells be connected in series and use.

In limited pitch (Off ァイ Na イトギャップ) electrolysis is evaluated, by the anode in electrolysis cells and negative electrode it Between distance be set to 1.5mm.Use as negative electrode on the metal lath of nickel, be coated with the nickel oxide as catalyst Electrode.Use as anode on the metal lath of titanium, be coated with the ruthenium as catalyst, iridium and the electrode of titanium.

In zero spacing electrolysis is evaluated, negative electrode contacts with amberplex together with anode, uses at nickel wire as negative electrode It is coated with the electrode of Ru Yu Ce as catalyst on the net.Use as anode and be coated with on the metal lath of titanium Electrode as ruthenium, iridium and the titanium of catalyst.

Make it maintain the concentration of 205g/L at anode-side supply salt solution, make naoh concentration keep at cathode side It is 32 mass % while carrying out the supply of water.Further, the I containing 10ppm and the Ba containing 0.03ppm are used As the salt solution of impurity, the temperature of salt solution is set as 90 DEG C, with 6kA/m²Current density, cloudy at electrolysis cells Electrolysis in 9 days is carried out under conditions of the hydraulic pressure 5.3kPa higher than the hydraulic pressure of anode-side of side, pole.Thereafter, according to electrolysis the 1st The value of it current efficiency measures the increase and decrease of the current efficiency value of the 9th day after electrolysis, obtains the change in units of 1 day Rate.It should be noted that current efficiency refers to the amount ratio relative to the electric current of circulation of generated NaOH Example, by the effect of electric current of circulation, foreign ion or hydroxide ion rather than sodium ion are in cation-exchange membrane Time mobile, current efficiency reduces.

Current efficiency can by by the molal quantity of the NaOH generated in certain time divided by the electric current circulated therebetween The molal quantity of electronics is obtained.The molal quantity of NaOH can be by being recovered to by electrolytically generated NaOH In plastic containers and measure its quality and obtain.

[embodiment 1]

As strengthening core, use and 900 times/m is imposed for polytetrafluoroethylene (PTFE) (PTFE) system, the tape yarn of 100 daniers The thread (hereinafter referred to PTFE line) of twisting.As the victim line of warp, use to 35 daniers, The polyethylene terephthalate (PET) of 8 imposes line (the hereinafter referred to PET of the twisting of 200 times/m Line).Additionally, as the victim line of parallel, use 35 daniers, the polyethylene terephthalate (PET) of 8 Impose the line of the twisting of 200 times/m.First, making PTFE line is 24 pieces/inch, at adjacent PTFE line Between configure 2 victim line carry out plain weave, obtaining thickness is weaving cotton cloth of 100 μm.

Then, CF is utilized₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂COOCH₃Copolymer prepare from Sub-exchange capacity is the polymer (A1) of the dry resin of 0.84mg equivalent/g, utilizes CF₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂It is the dry of 0.98mg equivalent/g that the copolymer of F prepares ion exchange capacity The polymer (B1) of dry resin.Use these polymer (A1) and (B1), obtain polymer (A1) by coextrusion T modulus method The 2 tunic X that thickness is 74 μm that thickness is 18 μm, polymer (B1) layer of layer.It should be noted that it is each poly- The ion exchange capacity of compound represents when the ion-exchange group precursor hydrolysis of each polymer is converted to ion-exchange group Ion exchange capacity.

Additionally, utilize CF₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂The copolymer of F prepare separately from Sub-exchange capacity is the polymer (B2) of the dry resin of 1.05mg equivalent/g.This polymer monolayers is extruded, obtains The film Y of 20 μm.

Then, there is in inside heating source and vacuum source, its surface have on the cylinder of minute aperture the sequentially pre-advanced person of lamination Gone separate paper, film Y, reinforcing material and the film X of embossing processing, barrel temperature be 225 DEG C, vacuum be After carrying out the heating under reduced pressure of 2 minutes under conditions of 0.067MPa, remove separate paper, thus obtain that there is concaveconvex shape Composite membrane.By obtained composite membrane at the dimethyl sulfoxide (DMSO) (DMSO) containing 30 mass %, the hydrogen of 15 mass % The aqueous solution of 90 DEG C of potassium oxide (KOH) impregnates 1 hour so that it is saponification, afterwards at the 0.5N NaOH of 90 DEG C Middle dipping 1 hour, is Na by the ion exchange on ion-exchange group, then washes.And then carry out at 60 DEG C It is dried.

Additionally, CF will utilized₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂The copolymer of F obtains After ion exchange capacity is polymer (B3) hydrolysis of the dry resin of 1.05mg equivalent/g, hydrochloric acid is utilized to make acid type. The polymer (B3) of this acid type is dissolved in 50/50 (mass ratio) mixed liquor of water and ethanol with the ratio of 5 mass %, The zirconia particles that primary particle size is 1.15 μm is added so that polymer (B3) and zirconium oxide in obtained solution The mass ratio of particle is 20/80.Thereafter ball mill is utilized to disperse, until zirconia particles putting down in suspension All particle diameters are 0.94 μm, obtain suspension.It addition, as zirconia particles, use original ore powder to mince.

Utilize spray-on process by this suspension on two surfaces of amberplex, be dried, thus obtain having and contain There is the amberplex of polymer (B3) and the coating of zirconia particles.

Utilizing fluorescent X-ray to measure to be measured dried coating, result coating density is every 1cm²In 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 2.2m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 mass % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in limited pitch electrolysis, result current efficiency be reduced to for 0.23%/day, display Go out higher impurity durability.Its result is listed in table 1.

[embodiment 2]

In embodiment 1, to utilizing ball mill to be dispersed into Row sum-equal matrix, it is dispersed to zirconia particles in suspension Till average grain diameter is 1.12 μm, obtain suspension；In addition, ion exchange is made similarly to Example 1 Film.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 2.2m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 weight % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in limited pitch electrolysis, result current efficiency be reduced to for 0.27%/day, display Go out higher impurity durability.Its result is listed in table 1.

[embodiment 3]

In embodiment 1, zirconia particles is changed to the particle that primary particle size is 2.50 μm, to utilizing ball mill Be dispersed into Row sum-equal matrix, be dispersed to till zirconia particles average grain diameter in suspension is 1.80 μm, be hanged Supernatant liquid；In addition, amberplex is made similarly to Example 1.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 1.8m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 weight % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in limited pitch electrolysis, result current efficiency be reduced to for 0.24%/day, aobvious Show higher impurity durability.Its result is listed in table 1.

[embodiment 4]

In embodiment 1, to utilizing ball mill to be dispersed into Row sum-equal matrix, it is dispersed to zirconia particles in suspension Till average grain diameter is 0.89 μm, obtain suspension；In addition, ion exchange is made similarly to Example 1 Film.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 2.3m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 weight % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in limited pitch electrolysis, result current efficiency be reduced to for 0.50%/day, aobvious Show higher impurity durability.Its result is listed in table 1.

[comparative example 1]

In embodiment 1, zirconia particles is changed to the particle that primary particle size is 0.04 μm, to utilizing ball mill Be dispersed into Row sum-equal matrix, be dispersed to till zirconium oxide average grain diameter in suspension is 1.64 μm, obtain suspension； In addition, amberplex is made similarly to Example 1.It should be noted that oxygen used in comparative example 1 Changing zirconium particle is by the melted particle produced.Further, average grain diameter is considered as the secondary grain of zirconia particles Footpath.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 13.3m²/g。 It should be noted that according to the observation utilizing electron microscope to carry out, primary particle size during cooperation is the oxygen of 0.04 μm Change zirconium particle primary particle size in the coating and be also about 0.04 μm.

The sodium acid carbonate that the amberplex with dry coating utilizes 2 weight % is moistened, use afterwards this sun from Proton exchange carries out the impurity tolerance determination in limited pitch electrolysis, result current efficiency be reduced to for 0.83%/day, be subject to Arrive the impact that impurity is stronger.Its result is listed in table 1.

Table 1

Owing to comparative example 1 is by the melted particles of inorganic material obtained, thus the index S of specific surface area is high.Averagely Particle diameter and comparative example 1 are that in the embodiment 3 of equal extent, compared with comparative example 1, the index S of specific surface area is low, In the result that impurity patience is high.From result above, by making the numerical value model that index S is the present invention of specific surface area In enclosing, it is possible to realize higher impurity patience.

If it should be noted that by embodiment 1～3 the most relatively, then inorganic matter in embodiment 1～3 The average grain diameter of grain is more than 0.90 μm, and on the other hand, in embodiment 4, the average grain diameter of particles of inorganic material is less than 0.90μm.Accordingly, with respect to embodiment 4, embodiment 1～3 obtains the higher result of impurity patience.

[embodiment 5]

As strengthening core, use polytetrafluoroethylene (PTFE) (PTFE) system, monofilament (the hereinafter referred to PTFE of 90 daniers Line).As victim line, the polyethylene terephthalate (PET) to 40 daniers, 6 is used to impose 200 The line (hereinafter referred to PET line) of the twisting of secondary/m.First, to make PTFE line be 24/inch, adjacent PTFE line between configure 2 victim line carry out plain weave, obtaining thickness is weaving cotton cloth of 100 μm.

Then, CF is utilized₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂COOCH₃Copolymer prepare from Sub-exchange capacity is the polymer (A2) of the dry resin of 0.87mg equivalent/g, utilizes CF₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂It is the dry of 1.03mg equivalent/g that the copolymer of F prepares ion exchange capacity The polymer (B4) of dry resin.Use these polymer (A2) and (B4), obtain polymer (A2) by coextrusion T modulus method The 2 tunic X that thickness is 74 μm that thickness is 18 μm, polymer (B4) layer of layer.

Then, there is in inside heating source and vacuum source, its surface have on the cylinder of minute aperture the sequentially pre-advanced person of lamination Gone separate paper, reinforcing material and the film X of embossing processing, barrel temperature be 240 DEG C, vacuum be 0.067MPa Under conditions of carry out the heating under reduced pressure of 2 minutes after, remove separate paper, thus obtain the composite membrane with concaveconvex shape. By obtained composite membrane at dimethyl sulfoxide (DMSO) (DMSO) containing 30wt%, the potassium hydroxide (KOH) of 15wt% The aqueous solution of 90 DEG C impregnates 1 hour so that it is saponification, impregnates 1 hour in the 0.5N NaOH of 90 DEG C afterwards, It is Na by the ion exchange on ion-exchange group, then washes.And then be dried at 60 DEG C.

CF will be utilized₂=CF₂With CF₂=CFOCF₂CF(CF₃)OCF₂CF₂SO₂The ion exchange that the copolymer of F obtains After capacity is polymer (B5) hydrolysis of the dry resin of 1.05mg equivalent/g, hydrochloric acid is utilized to make acid type.By this acid The polymer (B5) of type is dissolved in 50/50 (mass ratio) mixed liquor of water and ethanol with 5 mass %, obtained molten Liquid adds the zirconia particles that primary particle size is 1.25 μm so that polymer (B5) and the weight ratio of zirconia particles It is 50/50.Ball mill is utilized to disperse afterwards, until the average grain diameter that zirconia particles is in suspension is 1.07 μm, obtain suspension.

Utilize spray-on process by this suspension on two surfaces of amberplex, be dried, thus obtain having and contain There is the amberplex of polymer (B5) and the coating of zirconia particles.

Utilizing fluorescent X-ray to measure to be measured dried coating, result coating density is every 1cm²In 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 0.6m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 mass % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in zero spacing electrolysis, result current efficiency be reduced to for 0.23%/day, demonstrate Higher impurity durability.Its result is listed in table 2.

[embodiment 6]

In embodiment 5, the mass ratio of polymer (B5) Yu zirconia particles is changed to 40/60, utilizes ball mill Carry out disperseing, till zirconia particles average grain diameter in suspension is 1.11 μm, obtaining suspension；Except this In addition, amberplex is made similarly to Example 5.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 1.5m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 mass % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in zero spacing electrolysis, result current efficiency be reduced to for 0.14%/day, demonstrate Higher impurity durability.Its result is listed in table 2.

[embodiment 7]

In embodiment 5, the mass ratio of polymer (B5) Yu zirconia particles is changed to 30/70, utilizes ball mill Carry out disperseing, till zirconia particles average grain diameter in suspension is 1.10 μm, obtaining suspension；Except this In addition, amberplex is made similarly to Example 5.

Utilizing fluorescent X-ray to measure the dried coating to amberplex to be measured, result coating density is Every 1cm²Middle 0.5mg.Additionally, the specific surface area of coating that the scattering measured by SAXS is tried to achieve is 1.3m²/g。

The sodium acid carbonate that the amberplex with dry coating utilizes 2 weight % is moistened, uses this ion afterwards Exchange membrane carries out the impurity tolerance determination in zero spacing electrolysis, result current efficiency be reduced to for 0.34%/day, demonstrate Higher impurity durability.Its result is listed in table 2.

Table 2

Industrial applicibility

The amberplex of the present invention can be used as in middle cation exchanges used such as alkaline chloride electrolysis aptly Film.

Claims

1. an amberplex, it is the amberplex with film main body and coating, and described film main body comprises Having the fluorinated polymer of ion-exchange group, described coating is arranged at least one face of this film main body, wherein,

Described coating contains particles of inorganic material and adhesive；

The specific surface area of described coating is 0.1m²/ g～10m²/ g,

The average grain diameter of described particles of inorganic material is 0.90 μm～2 μm.

2. amberplex as claimed in claim 1, wherein, described particles of inorganic material is for containing selecting free element The oxide of periodic table Group IV element, the nitride of periodic table of elements Group IV element and periodic table of elements iv The particle of at least one inorganic matter in the group of the carbide composition of race's element.

3. amberplex as claimed in claim 1 or 2, wherein, described particles of inorganic material is zirconic Grain.

4. amberplex as claimed in claim 1 or 2, wherein, described adhesive contains fluorinated polymer.

5. amberplex as claimed in claim 1 or 2, wherein, described coating contains 40 mass %～90 matter The amount described particles of inorganic material of %, 10 mass %～the described adhesive of 60 mass %.

6. amberplex as claimed in claim 1 or 2, wherein, described adhesive comprises and has ion exchange The fluorinated polymer of base, described ion-exchange group is from carboxyl or sulfo group.

7. amberplex as claimed in claim 1 or 2, wherein, being shaped as of described particles of inorganic material is not advised Then shape.

8. amberplex as claimed in claim 1 or 2, wherein, described particles of inorganic material is by by inorganic The particles of inorganic material that thing is pulverized and produced.

9. amberplex as claimed in claim 8, wherein, described particles of inorganic material is by by inorganic matter profit The particles of inorganic material carrying out pulverizing by following method and produce, the method is choosing free ball mill, ball mill, colloid Mill, taper grinding machine, disc mill, edge runner, powder process grinding machine, hammer crusher, particle grinding machine, VSI mill At least a kind of method in the group of machine, wiley mill, roller mill and jet pulverizer composition.

10. the manufacture method of the amberplex described in any one of claim 1～9, wherein, under the method possesses State operation:

The operation of described coating fluid it is coated with on the surface of amberplex；And

Form the operation of coating, make the described coating fluid being coated on described amberplex surface be dried, thus form painting Layer.

11. 1 kinds of electrolytic cells, it possesses the amberplex described in any one of claim 1～9.