TWI342637B - Polymer electrolyte fuel cell, polymer electrolyte film using it, film electrolyte composite and polymer electrolyte fuel cell - Google Patents

Description

1342637 TECHNICAL FIELD The present invention relates to a polymer electrolyte and a polymer electrolyte membrane using the same, a membrane electrode assembly and a polymer electrolyte fuel cell. [Prior Art] A fuel cell is a power generating device having less emissions, high energy efficiency, and low environmental burden. Therefore, in recent years, attention has been paid to the rise of global environmental protection awareness. Compared with traditional large-scale power generation facilities, it can be used as a power generation device for small-scale distributed power generation facilities, mobile devices such as automobiles or ships, and is a promising power generation device. On the other hand, it has also attracted attention as a power source for small mobile devices and portable devices, and has been used in portable phones or personal computers instead of secondary batteries such as nickel-metal hydride batteries or lithium-ion batteries. High hopes. In a polymer electrolyte fuel cell (PEFC: Polymer Elecuolyte Fuel CeH), a polymer electrolyte fuel cell (hereinafter referred to as PEFC) is used as a fuel, and a fuel such as methanol is directly supplied. Direct fuel cells are also attracting attention. According to the direct fuel cell, the output of the direct fuel cell is lower than that of the previous PEFC. However, since the fuel is liquid and does not require a reformer, the energy density becomes high, so that the portable machine can be used for each time. Long advantage. A polymer electrolyte fuel cell is usually composed of an "electrode" which generates an anode and a cathode for generating a reaction, and a polymer electrolyte membrane which is used as a proton conductor between an anode and a cathode to constitute a membrane electrode complex 1342637. (MEA)", and a cell in which the MEA is obtained by sandwiching the separator is used as a unit. The electrode system includes an electrode substrate (hereinafter also referred to as a "gas diffusion electrode" or a "collector") for promoting gas diffusion and performing current collection, and actually functions as an electrode for electrochemical reaction. Floor. Therefore, for example, at the anode of the PEFC, a fuel such as hydrogen will react in the catalytic layer of the anode to generate protons and electrons, and conduct electrons to the electrode substrate to conduct protons to the polymer electrolyte. Therefore, it is required to have good gas diffusibility, electron conductivity and proton conductivity for the anode. Relatively at the cathode, an oxidizing gas such as oxygen or air generates water by reacting a catalytic layer of the cathode with a proton transmitted from the polymer electrolyte and electrons transferred from the electrode substrate. Therefore, in addition to gas diffusibility, electron conductivity, and proton conductivity, the cathode is required to have an ability to efficiently extract water generated. Furthermore, even if it belongs to PEFC, it is also required for a direct fuel cell fueled with methanol or the like, which is different from the previously used hydrogen fueled PEFC. In other words, in a direct fuel cell, a fuel such as an aqueous methanol solution reacts in the anode catalytic layer to generate protons, electrons, and carbon dioxide, and electrons are conducted to the electrode substrate to conduct protons to the polymer electrolyte. Carbon dioxide is emitted outside the system through the electrode substrate. Therefore, in addition to the required characteristics of the prior PEFC anode, fuel permeability or carbon dioxide discharge property such as an aqueous methanol solution is also required. In addition, in the cathode of the direct fuel cell, in addition to the same reaction as the previous PEFC, a fuel such as methanol permeating the electrolyte membrane and an oxidizing gas such as oxygen or air are generated in the catalytic layer of the cathode. 1342637 The reaction of carbon oxide with water makes the produced water more than the previous PEFC, so it is more necessary to allow the water to be effectively discharged. In the past, a polymer electrolyte has been a perfluoro-based proton conductive polymer typified by NAFION (trade name, manufactured by DuPont). However, these perfluoro-based proton conductive polymers have a problem that the fuel such as methanol has a large permeation, resulting in insufficient battery output or energy efficiency. In addition, due to the need for fluorine in the perfluoro-based proton-conducting polymer, the price is also very expensive. A non-perfluoro-based proton conductive polymer different from the conventional perfluoro-based proton conductive polymer, for example, a polymer electrolyte obtained by introducing an anionic group into a non-fluorine-based aromatic polymer A number of proposals are disclosed in U.S. Patent Application Publication No. 2002/9 1 225, the specification of which is incorporated herein by reference to U.S. Patent No. 5,403,67, the disclosure of which is incorporated herein by reference. However, when such a polymer electrolyte is to increase the conductivity and increase the amount of anionic group introduction, there is a cluster-like compound which causes water to easily enter the interior, causing large water to be generated in the polymer electrolyte. The content of low-melting water as defined in this patent specification is increased so that the amount of antifreezing water defined in this patent specification becomes less, and the fuel such as methanol crosses (cl_〇ss_〇ver). The disadvantage of getting bigger. This is because the fuel such as methanol easily passes through the low-melting water. Furthermore, 'there has been a proposal for a composite of a proton conductive polymer and another polymer', for example, a composite film comprising a sulfonated polyphenylene ether and a polyvinylidene fluoride (U.S. Patent No. 6,103,414) has been All know. Further, a composite film comprising a sulfonated polystyrene and a polyvinylidene fluoride (a special publication No. 9 1342637 No. 2001-504,636) is also well known. However, the polymer electrolyte membrane in these documents is a blending membrane of an ion conductive polymer and polyvinylidene fluoride, which has poor compatibility and is easy to form a large phase separation structure of a micro order. Low-melting water or bulk water (defined in the present specification) may exist between the phases, so that the amount of anti-freezing water in the electrolyte is also small, so that it is difficult to make the conductivity and the fuel cross-inhibition coexist. In addition, there is also a composite of a proton conductive polymer and a copolymer of a siloxane having a nitrogen atom-containing group and a metal oxide (Japanese Patent Laid-Open Publication No. 2002-110,200) Everyone knows. In addition to this, there is also a complex of NAFI0N and a siloxane ("Polymers", Vol. 43, pp. 23 1 1 ~ 2320 (2002), "J. M ater. Chem.", Vol. 12, pp. 834-837. (2002)] The film formed by the like is well known. 'But the film in these documents uses NAFI0N which is a perfluoro-based proton conductive polymer, so that it is difficult to make it even if it is compounded with other polymers. High proton conductivity coexists with low fuel crossover. SUMMARY OF THE INVENTION The polymer electrolyte of the present invention is characterized in that a proton conductive polymer (A) and a polymer (B) different from (A) are mixed together, and the polymer is as described above. The antifreeze amount expressed by the mathematical formula (S1) in the electrolyte is 40 to 100% by weight. (Frozen water rate) = (anti-freezing water amount) / (low-melting water amount + anti-freezing water amount) x 100 (%) (S1) The present inventors have found that proton conductive polymer (Α) and (与) are different. The t-electrolyte produced by the t (Β) mixing is effective for the coexistence of the high conductivity with the 10 1342637 fuel crossover, and the performance of the polymer electrolyte as described above depends on the moisture contained in the polymer electrolyte. The present invention, and its content, complete the present invention. In the present specification, the water in the polymer electrolyte is classified into "the main water J at a temperature of 0 ° C or higher, and the "low melting water" at a temperature below 0 ° C and above -30 ° C. ", and the "freezing water" of the melting point is not seen above -30 UC. The inventors of the present invention have found that the ratio of the antifreeze water has a great influence on the performance of the electrolyte. The polymer electrolyte of the present invention has a freeze water resistance ratio of 40 to 1% by weight, preferably 50 to 99.9% by weight, and more preferably 60 to 99.9% by weight, expressed by the mathematical formula (S1). (anti-freeze water rate) = (anti-freeze water) / (low melting point water + antifreeze water) χ 100 (%) _____ (S1) where the amount of antifreeze and low melting water should be measured according to the method described below Prevail. Fuels such as methanol mainly pass through low-melting water, and if the ratio is large, the fuel crossover will also increase. The relatively antifreeze water is presumed to be present in the vicinity of the ionic group and the polar group, and a fuel such as methanol is less likely to permeate through the antifreeze water. Therefore, the polymer electrolyte that achieves such a large antifreeze water content can make the high proton conductivity and the low fuel cross, and the high output and high energy capacity can be achieved in the polymer electrolyte fuel cell. If the antifreeze rate is less than 4% by weight, it will lead to a negative result of proton conductivity or fuel cross-inhibition. Although the rate of antifreeze water is as close as possible to 100% by weight of 1342637, but there is no concern about the decrease in conductivity when there is no low-melting water at all. Therefore, the upper limit of 9 9 · 9 % is appropriate. Further, the ratio of the amount of the antifreeze water in the polymer electrolyte represented by the mathematical formula (S2) to the dry weight of the polymer electrolyte (the content of the antifreeze water) is preferably 20% to 200%. (Anti-freeze water content) = (anti-freeze water in polymer electrolyte) / (polymer electrolyte dry weight) x 1 〇〇 (%) ----- (S2) where the amount of antifreeze in the polymer electrolyte is high The dry weight of the molecular electrolyte should be based on the enthalpy measured according to the method described below. If the freeze water content is less than 20% by weight, the proton conductivity is insufficient, and when it exceeds 200%, the fuel cross-inhibition effect tends to decrease. The antifreeze water content is preferably from 25% to 150%, more preferably from 30% to 100%.

The antifreeze water rate expressed by the mathematical formula (S1) and the antifreeze water content expressed by the mathematical formula (S2) shall be determined based on the differential scanning calorimetry (DSC). In other words, 'after immersing the polymer electrolyte in water at 20 ° C for 12 hours, 'take it out of the water', wipe off the excess surface-attached water with gauze as quickly as possible, and put it into the previously measured weight (Gp) and apply it. After the shrinkage (C1, imp) was applied to the aluminum-sealed sealed sample container, the total weight (G w) of the sample and the sealed sample container was measured as soon as possible, and then the DSC measurement was immediately performed. The temperature measurement program is cooled from room temperature to -3 〇 °C at a rate of 10 ° C / min. 'The temperature is raised to 5 at 0.3 ° C / min. The DSC curve according to the temperature rise process uses the following mathematical formula. (n 1) Calculate the main body water amount W f and calculate the low melting point water amount wfc using the mathematical formula (n2), and then calculate the antifreeze water amount wnf from the total water rate deduction 12 1342637 (the mathematical formula (η 3) ). Dq 丨' #

Wf= Γ-^-dt (n1) *^° mAHo dq_

Wjc- Γ ————dt (n2) mAH(T)

Wnf = Wt-~Wf-WfC (n3) where Wf, Wfc, Wnf and Wt are the moisture weight per unit weight of the dry sample 'm is the weight of the dry sample' dq/dt is the heat flux signal of the DSC (heat flux Signal) '△ H0 is the enthalpy of the fusion under TO, and TO is the melting point of the main water. In addition, after the DSC measurement, a small hole was opened in the closed and closed sample containers, and vacuum drying was performed in a vacuum dryer at 1 Torr <=c, and the sample and the sealed test were measured as soon as possible. The total weight of the sample container (Gdh, therefore, the dry sample weight (m) is m = Gd - Gp' The total moisture content (W t) is W t = (G w - G d) / m. The conditions are as follows: DSC device ·· ΤΑ Instrument company "dsc qi〇〇" Data processing device: Toray Research Center "trcthadapdsc" Measurement temperature range: -50 to 5 °C Scanning speed: 0.3 °C / minute Sample size: about 5 mg sample dish: aluminum sealed sample container 13 1342637 temperature, heat correction: water melting point (〇, 〇 ° c, heat of fusion 7 9.7 calories / gram) according to this method by Toray The developers of the research center are the most reliable according to the measurement of the Toray Research Center. If the measurement is based on other organizations, the reliability may not be sufficient to implement the invention. The situation, so it should be based on the determination of the Toray Research Center In the past, when a proton conductive polymer is used as a polymer electrolyte, if the amount of anionic group is increased to obtain high proton conductivity, the water content of the polymer electrolyte will increase, resulting in a polymer electrolyte. Since the low-melting water and the main body water become large, the fuel crossover becomes large, and the result that the high proton conductivity and the fuel crossover are prevented from coexisting cannot be obtained. Conversely, the polymer electrolyte of the present invention polymerizes protons. The product (A) is mixed with the polymer (B) different from (A). Therefore, the molecular chain of the proton conductive polymer (A) is restrained by the polymer (B) to suppress the low melting water and the host. The amount of water increases the ratio of antifreeze water, so that the high proton conductivity and the low fuel cross each other. The proton conductive polymer (A) is described below. The proton conductive polymer (A) can be full The fluorine-based proton conductive polymer may be a non-perfluoro-based proton conductive polymer. The "perfluoro-proton conductive polymer" refers to a proton conductive polymer and the alkane in the polymer And/or most of the hydrogen or all of the alkylene group is replaced by a fluorine atom. In the present specification, proton conduction is replaced by a fluorine atom substituted by more than 85 % of the hydrogen of the alkyl group and/or the alkylene group in the polymer. Polymer 1 14342637 is defined as a "perfluoro-type proton conductive polymer". Representative examples of perfluoro-based proton conductive polymers include: NAFION (made by DuPont), FULEMION (made by Asahi Glass Co., Ltd., transliteration products) Name) and ASIPLEX (made by Asahi Glass Co., Ltd., transliteration product name), etc. The structure of these perfluoro-based proton conductive polymers is as shown in formula (1): —(CF2CF2)n1—(CF2CF)n2— (1)

(OCF2CF) k1-〇-(CF2) k2 - S03H CF3 [In the formula (1), n, n2 each independently represent a natural number: k, and k2 each independently represents an integer of 0 to 5. 〕

The perfluoro-based proton conductive polymer forms a water channel called a cluster in the polymer in a water-containing state because it forms a phase-separated structure in which the hydrophobic portion and the hydrophilic portion of the polymer are clearly defined. The water passage is mainly formed of low-melting water, and fuel such as methanol can be easily moved therein, so that it is not necessarily suitable for fuel cross-reduction. Therefore, in the present invention, it is more preferable to use a non-perfluoro-based proton conductive polymer. When a non-perfluoro-based proton conductive polymer is used, it is easier to make the high proton conductivity and the low fuel cross. Here, the "non-perfluoro-type proton conductive polymer" means a proton conductive polymer other than the perfluoro-based proton conductive polymer. The non-perfluoro-type proton conductive polymer is described in more detail below. The non-perfluoro-based proton conductive polymer can be used in various combinations at the same time. Non-perfluoro-based proton conductive polymers are polymerized with anionic groups 15 1342637

Things are appropriate. The term "anionic group" means a substituent which can be cleaved in the presence of water to produce an anion and a proton (or a cation if it is a salt). Preferably, the anionic group is a sulfonic acid group, a sulfonium imino group, a sulfuric acid group, a phosphonic acid group 'phosphoric acid group, or a carboxylic acid group. Wherein the sulfonic acid group may be represented by the formula (π), and the sulfonimide group may be a group represented by the formula (f 2) (wherein R represents an arbitrary atomic group), and the sulfate group may be represented by the formula (f3) The group, the phosphonic acid group may be a group represented by the formula (f4), the phosphate group may be a group represented by the formula (f5) or the formula (f6), and the carboxylic acid group may be a group represented by the formula (f7). Further, if it is a salt for this purpose, it is equivalent to an anionic group.

0 —S-OH (ί1) II ' 〇0 U〇μ Η π /f~ —SNSR f2 II II 〇〇0 —OS-OH (f3) 0 o —〒-〇H (f4) OH 0 —0- Early-〇H (i5) OH 〇-〇-〒-〇H (f6) 0 I -C-OH (f7) 〇 Even if it belongs to these anionic groups, it is considered from the viewpoint of high proton conductivity. It is preferred that at least one member selected from the group consisting of a sulfonic acid group, a sulfonimide group, and a sulfate group is more preferably a sulfonic acid group or a sulfonium imide group from the viewpoint of hydrolysis resistance. These anionic groups may be contained in two or more kinds of the proton conductive polymers of the non-perfluoro-based proton conductive polymer as described above. The preferred non-all 16 1342637 fluorine-based proton conductive polymers (E_1 and E j ) having an anionic group as described above are specifically exemplified below. (E-1) is a sensible molecule obtained from an ethylene polymerization monomer, for example, having acrylic acid, methacrylic acid, vinyl benzoic acid, vinyl sulfonic acid 'allyl sulfonic acid, styrene sulfonic acid An anionic group of ethylene polymerized monomers represented by maleic acid, 2-propenylamine-2-methylpropanesulfonic acid, thiopropyl (meth)acrylate, ethylene glycol methacrylate, and the like The polymer produced. A polymer obtained by copolymerizing an ethylene polymerizable monomer having an anionic group as described above and a monomer having no anionic group can also be used. The monomer having no anionic group is not particularly limited as long as it is a compound having an ethylene polymerizable functional group. Preferred are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (2-ethyl)hexyl (meth)acrylate, ( (meth) acrylate compounds such as lauryl methyl methacrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; styrene, α-methyl styrene, amino styrene , styrene compounds such as chloromethyl styrene; (meth)acrylonitrile, (meth) acrylamide hydrazine, hydrazine-dimethyl methacrylate, hydrazine-propylene hydrazinomorph, hydrazine-methyl (Meth) acrylamide derivatives such as acrylamide; Ν-phenyl maleimine, Ν-benzylmaleimine' Ν-cyclohexylmaleimide, Ν-isopropyl Maleic imine compounds such as maleic imine. Further, a polymer obtained by introducing an anionic group into an ethylene polymerization monomer having no anionic group is also suitable. Regarding the method of introducing an anionic group, a well-known method can be used, for example, the introduction of a phosphonic acid group can be based on 17 1342637, for example, " Ρ ο 1 ymer P reprints ", J apa η, 5J_, 7 5 0 (2 0 0 2) The method described in the above. The introduction of a phosphate group can be carried out, for example, by phosphorylation of a polymer having a hydroxyl group. The introduction of the carboxylic acid group can use, for example, oxidation of a polymer having an alkyl group or a hydroxyl group. The introduction of the sulfate group can be sulphuric acid sulfonation using, for example, a polymer having a hydroxyalkyl group. The method of introducing a sulfonic acid group is, for example, a method described in Japanese Laid-Open Patent Publication No. Hei 2- No. Hei. Specifically, for example, the host molecule can be sulfonated by reacting it with a sulfonating agent such as chloropropionate in a halogenated hydrocarbon solvent such as chloroform or by reacting it in concentrated sulfuric acid or fuming sulfuric acid. The sulfonating agent is not particularly limited as long as it can sulfonate the polymer. In addition to the above, sulfur trioxide or the like can also be used. Further, for example, in the case of a polymer having an epoxy group, it can be sulfonated according to the method described in "J. Electriochem. Soc.", 143 ffi}, pp. 2795-2799 (1996). When the polymer is sulfonated by such a method, the degree of sulfonation can be easily controlled depending on the amount of the sulfonating agent used, the reaction temperature, and the reaction time. The introduction of the sulfonimide group of the aromatic polymer can be carried out, for example, by a method of reacting a sulfonic acid group with a sulfonium imide group. The proton conductive polymer is advantageous in terms of fuel cross-linking as long as it belongs to a crosslinked polymer. When the polymer obtained by the ethylene polymerization monomer is to be crosslinked, the copolymerization of the polymerizable monomer having a plurality of polymerizable functional groups in the ethylene polymerization monomer may be carried out as a crosslinking agent. Here, a part of the ethylene polymerizable functional group having a plurality of ethylene polymerizable functional groups in the ethylene polymerization monomer is exemplified as follows. That is, for example, ethylene glycol di(meth)acrylate 'di(methyl)propyl 18 1342637 diethylene glycol dicarboxylate diethylene glycol di(meth)acrylate methyl) Alcohol ester, dipropylene glycol di(meth)acrylate dimethacrylate, di(meth)acrylate, propylene glycol poly(meth)acrylate, tris(methyl) hydroxymethylpropane ester, four Styrene such as (meth)acrylic acid pentaerythritol ester, or dipentaerythritol acrylate, such as (meth) acrylate-based vinyl benzene, divinyl naphthalene or divinyl biphenyl; methylene double (Methyl) propylene oxime (meth) propylene oxime: maleic imine compound such as phenyl bismaleimide, ρ, ρ' oxy bis(phenyl-N-amine) Wait. In order to produce a polymer composition obtained by using an ethylene polymerization monomer, a polymerization agent represented by a peroxide or an azo or a photopolymerization initiator is added to cause a polymerization reaction to proceed easily. When the thermal polymerization is applied, the one is selected for the desired reaction temperature decomposition characteristics. In general, it is preferred to use a peroxide-based initiator having a half-life of 4 Torr to 1 ° C for 1 hour, and a crack-free polymer electrolyte can be further produced by using an agent. The photopolymerization initiator may be used in combination with a carbonyl amine system such as benzophenone, a thiol compound, a disulfide compound or the like. These polymerization initiators may be used singly or in combination, and may be used in an amount of about 1% by weight or so. The polymerization method and the molding method can be carried out by a well-known method. Polymerization under a gas or a reduced pressure atmosphere, an alcohol ester, a tri-tripropylene glycol acrylic acid trimer (methyl compound; a two-type compound amine compound, Malayan, which has an optimum temperature for the single thermal polymerization. A method of forming a monomer composition having a film shape by using a method such as an interlamellar polymerization method and a coating method, such as an interlaminar polymerization method, and a coating method, etc. The interlayer polymerization method will be described below. The monomer composition is filled in the gap between the two plate-shaped molds, and then photopolymerized or thermally polymerized to form a film. The plate-shaped mold is made of resin, glass 'ceramic, metal, etc. For the polymerization, an optically transparent material should be used, usually a resin or glass, and if necessary, a pad having a thickness which can impart a certain thickness to the film and prevent the liquid leakage function of the charged monomer composition. The plated mold of the monomer composition is immersed in a void, and irradiated with an active light such as ultraviolet rays or heated in an oven or a liquid tank to be polymerized. However, it may also be used after the first photopolymerization. A method in which heating polymerization is carried out, or vice versa, and then photopolymerization is carried out. When photopolymerization is carried out, it is generally irradiated with a mercury lamp or a trap for a short time (usually 1 hour or less), and the lamp is used as a light source. Multi-ultraviolet light. When performing thermal polymerization, in order to maintain

S is a condition of 'quality, and reproducibility is improved by taking a temperature rise slowly from around room temperature' and increasing to a temperature of 60 to 200 ° C over a period of hours or tens of hours. A polymer having an anionic group and having an aromatic ring in the main chain. This is a polymer having an aromatic ring in the main chain (hereinafter also referred to as an aromatic polymer) and having an anionic group. The main chain structure is not particularly limited as long as it has an aromatic ring, but it is preferably, for example, a mechanical strength sufficient for use as an engineering plastic. For example, U.S. Patent No. 5,403,6, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, 9 The polyphenylene high score 20 1342637 as disclosed in et al. is the best example. Further, a polymer having at least one polar group different from the anionic group in the main chain is preferred. It is presumed that the reason is to promote the coordination of water in the vicinity of the main chain and increase the amount of antifreeze water, thereby imparting high proton conductivity and reducing fuel crossover. Although the polar group is not particularly limited, it is preferably a functional group which is water-coordinating. Such a polar group is preferably a sulfonyl group represented by the formula (g 1 ), an oxy group represented by the formula (g2), a thio group represented by the formula (g3), a carbonyl group represented by the formula (g4), A phosphine oxide group represented by the formula (g5) (wherein R1 represents a monovalent organic group), a phosphonate group represented by the formula (g6) (wherein R2 represents a monovalent organic group), and a formula (g 7) The ester group represented by the formula (§8) can be an amine group (wherein R3 represents a monovalent organic group), and the quinone imine group represented by the formula (S9) and the phosphorus represented by the formula (gi0) A nitrogen alkenyl group (wherein R4 and R5 represent a monovalent organic group) and the like. 1 ο -2 OMPIR I ο 0 0 II 〜S— (91) —co— (97) II 〇0 —0—(92) —C—N — R3 (g8) ~s— (93) 〇II 0 — 6, m a (TN-II (g9) Weng Weng - C~ (g4) 〇〇Μ (g5) R5 - P = N - r4 (a10) R1 Γ λ 1342637 Even a polymer belonging to the polar group as described above Nie Hao is an aromatic polymer selected from the group consisting of a repeating unit represented by the formula (P1) shown below, and a polyimine selected from a repeating unit represented by the formula (P2) shown below. z1—Y1——Ζ2-γ2——(Ρ1) Ja b (wherein Z1 and Z2 represent an organic group containing an aromatic ring, each of which may also represent two or more groups; Y1 represents an electron attracting group; Y2 It means 0 or s; a and b each independently represent an integer from 〇 to 2, and a and b are not simultaneously 0 0) 〇〇AA 4 —N Z3 N-Z4—(P2) ϊ ¥ 〇〇( Wherein z3 and z4 represent an organic group containing an aromatic ring, and each of them may represent two or more groups.) A preferred organic group of Z3 is an organic group represented by the formula (Z3-1) to S (Z3-4). And in terms of hydrolysis resistance, it is preferred to be (Z3-1) The organic group shown. These hydrogens on the aromatic nucleus may be alkyl, cycloalkyl, alkoxy, aryloxy, nitro, cyano 'ester group to a monovalent radical functional group. 221342637

XX (Z3-2)

A preferred organic group of Z4 is an organic group represented by the formula (Z4-1) to the formula (Z4-l〇). The hydrogen on the aromatic nucleus may also be substituted with a monovalent functional group such as a substituent, a ring, an alkoxy group, an aryloxy group, a nitro group, a cyano group or an ester group.

(Z4-2)

(Z4-7)

(Z4-3)

(Z4-8) H3C CH

(Ζ4-10)

0- 高分子 The polymer electrolyte is superior in hydrolysis resistance, and is preferably an aromatic polymer having a repeating unit represented by the formula (Ρ1). However, in the aromatic polymer having a repeating unit represented by the formula (pi) in 23 1342637, it is also an aromatic polymer having a repeating unit represented by the formula (P1) to S(Pl-9). It is better. In view of the proton conductivity level and ease of production, it is preferable to use an aromatic polymer having a repeating unit represented by the formula (P1-6) to the formula (Pi_9). 〇—Z1_S—Z2 η 〇-s— (P1-1) — 'Z2-0—(P1-6) 〇-Z1~S~Z2" II -〇一(P1-2) ^z1-c-z2- O-z2-o——(P1-7) 〇〇-Z1-C—z2- -〇一(P1-3) o II il 〇—21-S-Z2-〇-Z2-〇—〇(P1- 8) R1 I ——Z1-P—z2-^ Ή Δ 〇一(P1-4) R1 〇一z^rz2-o-z2-o——〇(P1-9) —z2-s- (P1- 5) A preferred organic group of Z1 is a phenylene group or a naphthylene group. These can also be replaced. Further, a preferred organic group of Z2 is a phenylene group, a naphthylene group, and an organic group represented by the formula (Z2-(i)~(Z2-14). These may also be substituted. The organic group represented by the formula (Z2-7) to the formula (Z2- 4) is excellent in the fuel permeation suppressing effect, and the z2 of the polymer electrolyte of the present invention is preferably in the formula (Z2_7). The organic group represented by ~s(Z2-l4) contains at least one species. It can be represented by the formula (Z2.7) to the formula (Z2.l4m, and the most important one is the formula (Z2-8). Organic base. 1342637

(22-5)

(Z2-6)

(Z2-13)

(Z2-7)

(Z2-14) 25 1342637 Preferred examples of the organic group represented by R1 in the formula (P]-4) and the formula (PI-9) are, for example, methyl, ethyl, propyl, isopropyl , cyclopentyl, cyclohexyl, norbornyl, vinyl 'allyl, benzyl, phenyl, naphthyl, biphenyl, and the like. In terms of industrial difficulty, the best of R | is phenyl. In addition, a method of introducing an anionic group into the aromatic polymer may be a method in which a monomer having an anionic group is used for polymerization, and a method in which an anionic group is introduced by a reaction with a polymer. When a monomer having an anionic group is used for polymerization, a monomer having an anionic group in the repeating unit may be used, and if necessary, an appropriate protecting group may be introduced and polymerized, followed by deprotection treatment. This method has been disclosed, for example, in "Journal of Membrane Science", 197 (2002) 231-242. The method of introducing an anionic group by a polymer reaction is exemplified as follows. The introduction of a phosphonic acid group into an aromatic polymer can be achieved, for example, according to the method disclosed in "Polymer Preprints", Japan, ϋ, 750 (2002), and the like. The introduction of a phosphate group into an aromatic polymer can be achieved, for example, by phosphorylation of an aromatic polymer having a hydroxyl group. The introduction of a carboxylic acid group into an aromatic polymer can be achieved, for example, by using an aromatic polymer having an oxide group or a hydroxyalkyl group. The introduction of a sulfate group into an aromatic polymer can be achieved, for example, by sulfation of an aromatic polymer having a hydroxyl group. A method of sulfonating an aromatic polymer, that is, a method of introducing a sulfonic acid group, is disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei. No. 2-16,126, or Japanese Patent Application Laid-Open No. Hei-2-208,322-26 The methods disclosed are well known. Specifically, for example, an aromatic polymer can be reacted with a sulfonating agent such as chlorosulfonic acid in a solvent such as chloroform or expanded in a concentrated sulfuric acid or fuming sulfuric acid. The sulfonating agent is not particularly limited as long as it can sulfonate the aromatic polymer, and sulfur trioxide or the like can be used in addition to the above. When the aromatic polymer is sulfonated by this method, the degree of sulfonation can be easily controlled depending on the amount of the sulfonating agent used, the reaction temperature, and the reaction time. The introduction of the sulfonimide group into the aromatic polymer can be achieved, for example, by a method in which a phosphonic acid group and a fluorinated imine group are reacted. The non-perfluoro-based proton conductive polymer may also be a crosslinked polymer. If the non-perfluoro-based proton conductive polymer is a crosslinked polymer, it is advantageous in controlling fuel crossover. The polymer electrolyte of the present invention is a polymer electrolyte obtained by mixing a proton conductive polymer (A) and a polymer (B) different from (A). In the present invention, the combination of the proton conductive polymer (A) and the polymer (B) different from (A) means that (A) and (B) are substantially mixed to be uniform, or A) and (B) are in a state in which a phase separation structure having a size of 1 μm or more is not formed and is mixed. Whether (A) and (B) are substantially homogeneously mixed, or (A) and (B) are substantial and do not form a phase separation structure of a size of 100 μm or more, and are confirmed by mixing together. Obtained by optical microscopy of the electrolyte. If the phase separation is not confirmed by observing the polymer electrolyte with an optical microscope, and the size of the phase separation is 90 or more of the non-human, and 90 or more of them are less than 100 μm, it is judged as (A) and ( B) is mixed together. In order to make the phase separation state easy to confirm, the polymer electrolyte can be appropriately dyed while observing the optical microscope 27 1342637. If (A) and (B) are mixed together, the molecular chain motion of (A) may be restricted by the interaction with (B), that is, (the chain of magical molecules is constrained. In the polymer electrolyte of the present invention, as described above, the proton conductive polymer (A) and the polymer (B) as described above are preferably substantially uniformly mixed in the fuel cross-inhibition. (A) The state in which (B) is substantially uniformly mixed means that (A) and (B) are substantially in a state in which a phase separation structure having a size of 1 μm or more is not formed and mixed together. Regarding (A) and (B) The confirmation that the substance is uniformly mixed together can be obtained by electron microscopic observation of the polymer electrolyte. If the polymer electrolyte is observed by an optical microscope, phase separation cannot be confirmed, and the size of the phase separation is non-human. When 90 or more of the 00 is less than 1 μm, it is judged that (A) and (B) are mixed together. In order to make the phase separation state easy to confirm, the polymer can be appropriately observed when observing the optical microscope. Electrolyte is dyed. In (A) with B) In a state of being uniformly mixed together, the polymer chains of each other may be in a state of being sufficiently entangled, and the restraining moves with each other', thereby hindering the permeation of the fuel. The formation makes (A) and (B) substantially homogeneously mixed in In the method of the state together, a method of preparing a polymer electrolyte by mixing at least one of the precursors (monomer or oligomer) in (A) and (B) and then applying a polymerization reaction Next, the "polymer (B) different from (A)" will be described above. 28 1342637 The molecule (B) is effective for suppressing fuel permeation, and therefore it is preferably 40 ° C. The 10 M aqueous methanol solution is insoluble. The so-called insoluble system means that the polymer electrolyte membrane is immersed in a 4 〇»c aqueous methanol solution for 8 hours, and then filtered by a filter paper to detect a polymer (Β) from the filtrate. The amount 'is 5% by weight or less of the total amount of the polymer (Β) contained in the polymer electrolyte membrane. In addition, 'the fuel is assumed to be an aqueous methanol solution, but the behavior of the aqueous methanol solution is still for other combustion. Commonly similar. Examples of polymers (Β) are, for example, polyimine, polyamine, polyurethane, polyurea, vinyl polymer, melamine polymer, phenol. An inorganic crosslinked polymer such as a resin polymer, polyorganosiloxane, titanium oxide, cerium oxide or aluminum chloride, but the present invention is not limited thereto. Further, a plurality of polymers may be used in combination. (Β) In addition, it is preferable to use a crosslinked polymer in a polymer (Β). In this case, the molecular chain entanglement ratio with the proton conductive polymer can be increased to exhibit a large molecular chain. The restraining effect is particularly advantageous for the coexistence of high proton conductivity and low fuel crossover. In the present invention, cross-linking may be chemically cross-linked or physically cross-linked. The term "crosslinking" as used in the present invention means a state in which the solvent is substantially insoluble or in another state. The crosslinked polymer in the present invention means a polymer which is substantially insoluble to a solvent. Further, the determination of whether or not the polymer electrolyte of the present invention contains a crosslinked polymer is carried out by the method described below. The polymer electrolyte (about 0.1 g) of the sample was washed with pure water, and vacuum-dried at 40 ° C for 24 hours, and then measured to a weight of 29 1342637. The polymer electrolyte was immersed in a solvent of 1 Torr and heated in a closed vessel at 70 ° C for 40 hours with stirring. Then, it was filtered using a filter paper (No. 2) made by ADVANTEKK. When the furnace is overheated, the filter paper and the residue are washed with the same solvent as the weight of the crucible, and the eluted matter is completely dissolved in the solvent. The filtrate was dried and the dissolved weight was calculated. If the eluted weight is less than 95% of the initial weight, it is judged that the solvent contains substantially insoluble components. The test is carried out in five solvents such as toluene, hexane, N-methylpyrrolidone, methanol, and water, and as a result, if it is determined that all the dissolution|j substantially contains an insoluble component, the polymer electrolyte is used. It was judged that f had a crosslinked polymer. The amine to be used or the use of an amine or three can be used in the above cross-linking. The use of a cyanate ester is (methacrylic acid hexyl ester, and the polyethylenimine of the polymer (B) as described above has a trifunctional or higher functional group. The above-mentioned carboxylic acid can be used as a raw material to obtain a crosslinked polymer. As described above, the polyamine of the polymer (B) is obtained by using a carboxylic acid having a trifunctional or higher functional group or more as a raw material to obtain a crosslinked polymer. As described above, the polyethyl urethane of the polymer (B) is a polymer obtained by using a hetero-acid vinegar of ～ or a difunctional or higher polyhydric alcohol as a raw material. The polymer (B) is as described above. The polyurea can be obtained by using the above-mentioned fee as a raw material to obtain a crosslinked polymer as the above-mentioned polymer (B) ethylene polymer polymer. , methacrylate, ethyl propyl (meth) acrylate methyl) butyl acrylate, methyl (meth) acrylate lauryl methacrylate, benzyl methacrylate propylene -2- (Methyl) cholenoate esters such as hydroxyethyl ester: 30 1342637; benzene Styrene compounds such as olefin, α-methylstyrene, acetophenone, gas methyl styrene; (meth)acrylonitrile, (meth) propyl;) 3⁄4 n amine, hydrazine, hydrazine-dimethyl (meth)acrylamide compounds such as acrylamide, hydrazine-acryloyl morpholine, hydrazine-methyl propyl amide, and hydrazine-phenyl-maleimide, hydrazine-benzylmethyl A (co)polymer such as a quinone imine, a fluorene-cyclohexylmaleimide, an N-isopropylmaleimine or the like. These ethylene-based polymerization system molecular groups can be cross-linked by copolymerizing a plurality of polymerizable functional groups having a plurality of polymerizable functional groups as a crosslinking agent. For example, a part of the ethylene polymerizable monomer having a plurality of ethylene polymerizable monomers in the ethylene polymerization monomer is as follows. That is, for example: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, •triethylene glycol di(ethylene)acrylate, poly(di)(meth)acrylate B Glycol ester, di(meth)acrylic acid propylene glycol vinegar, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, propylene poly(meth)acrylate, tris(methyl) a (meth) acrylate compound such as trimethylolpropane acrylate, neopentyl glycol tetra(meth)acrylate, or neopentyl glycol (meth)acrylate; divinylbenzene, divinyl a styrene compound such as a naphthalene or a divinylbiphenyl; a (meth) acrylamide compound such as methylene bis(meth) acrylamide; a phenyl bis-imine, ρ, ρ, a maleimide compound such as oxy bis(phenyl_31 1342637 N-maleimide). Specific examples of the epoxy-based polymer which can be used for the polymer (B) as described above are, for example, bisphenol A type epoxy resin, tetramethyl bisphenol A type epoxy resin, and Si Mo Shuang A Type epoxy resin; bisphenol f type epoxy resin, tetramethyl biguanide F type epoxy resin; bisphenol 5 type epoxy resin, tetramethyl bisphenol type epoxy resin; bisphenol AF type epoxy resin 'Bisphenol z-type epoxy resin; double-type soil-oxygen resin' bisphenol type epoxy resin, tetramethyl bisphenol type epoxy resin, naphthalene dioxime type epoxy resin, bisphenoxyethanol type Epoxy resin, dicyclopentene type epoxy resin, trisphenol methane type epoxy resin 'tetraphenol ethane type epoxy resin. These may be used singly or in combination of two or more. The polyorganosiloxane which can be used for the inorganic crosslinked polymer of the polymer (B) as described above can be obtained by a condensation reaction of a decane compound. The decane compound is preferably selected from the group consisting of at least one compound of the group represented by the following formula (dj) (· and the following formula (d2): J1 J1 J6 ^ J2 -Si-J4 (d1) J2-Si-Q-Si-J5 (d2) ringing [in the general formula (dl) and formula (d2), 'j1~ broadly, each independently indicates that it can be replaced by The aryl group, the thiol group which may also be substituted, the alkoxy group which may be substituted, the aryloxy group which may be substituted, and the substituent of the awakening oxy group and the halogen group which may be substituted; At least one of the broad meanings is selected from the group consisting of: alkoxy groups which may be substituted with a hydroxyl group, or a substituent of a methoxy group and a halogen group which may be substituted with 32 134,637, aryl groups; Q It is a divalent organic group.] The 1 in the formula each independently represents an aryl group which may be substituted with an alkyl group which may also be substituted, or a hydroxyl group which may be substituted. An aryloxy group which may also be substituted, or a substituent of a decyloxy group and a halogen group which may be substituted; and at least one of: r~]6, An aryloxy group which may be substituted with an hydroxy group or a substituted alkoxy group, or a substituent of a decyloxy group and a halogen group which may be substituted, and specific examples thereof are, for example, a methyl group or an ethyl group. , vinyl, isopropyl 't-butyl and the like alkyl; chloropropyl, 3,3,3-dichloropropyl and other halogenated hospital bases; glycidoxypropyl, hydrazine - (3,4 -Epoxy group-containing allyl group such as epoxy-cyclohexyl)ethyl group: (meth)acryloyl group containing T-methyl propyl ethoxylated propyl group, 7-propyl oxypropyl group Acryl sulfhydryl; others have a thiol group, a cyano group, an amine group, and the like, a phenyl group, a phenyl group, a phenylethyl group, etc., an aryl group, a hydroxyl group, a methoxy group An alkoxy group such as an ethoxy group or a methoxyethoxy group which may be substituted, an ethoxy group which may be substituted by an ethoxy group, an aryloxy group such as a phenoxy group, a chloro group or a bromo group. The halogen group or the like may be independent of each other, and may be the same or different from each other. The Q system represents a divalent organic group, and even if it contains a carbon atom such as a hydrogen atom or an oxygen atom or hydrogen, There is no problem with it. In addition, the organic group can also be chain-like, and even if a hydrogen atom exists in the form of an epoxy ring, it will not cause any problem, but it will act as a function when hardened. Base, so it has a positive effect. 33 1342637 Examples thereof are, for example, an ethylidene group, a methylene group, an ethyl group, a propyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, Heptanediyl, octanediyl, decanediyl, decanediyl, undecanediyl, dodecanediyl, octadienyl; and formula (grl)~S as shown below Gr9) indicates the base is equal to ~V / one 〇-ch2ch2-^ Y )—ch2ch2—(gri) ο-7 Y-〇-ch2ch2 CH2CH2— (gr2)

-CH2CH2CH2-C-^ ^-c-ch2ch2ch2— (g“3) o o

——CH2CH2CH2-O-C-O-CHCH2OCH2CH3—〇-C-〇-CH2CH2CH2—(gr4) 〇 O CH2 —ch2—c-ch2—(g“5)—CH2CH2CH2—SSSS—CH2CH2CH2— (gr6)

H ^ CH2CH2CH2—N-C-N—CH2CH2CH2— (gr7)

〇 H

H-CH2CH2CH2-N--CH2CH2CH2-(gr8)-CH2CH2CH2-NHCH2CH2NH-CH2CH2CH2-(gr9) 34 1342637 A specific representative example of the compound represented by the formula (d1) and the formula (d2) is, for example, tetramethoxy Decane, tetraethoxydecane, tetrabutoxydecane, tetrachlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltrimethoxy-4-methoxyethoxysilane, methyltriethoxysilane Base decane, methyl tripropoxy decane, methyl tributoxy decane, methyl trichloro decane, ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, vinyl triethoxy decane, vinyl trimethoxy ethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triethoxy decane, y -chloropropyltrimethoxydecane, r-chloropropyltriethoxydecane'r-chloropropyltriethoxydecane, *r-methacryloxypropyltrimethoxydecane, > r-Aminopropyltrimethoxydecane, r-Aminopropyltriethoxydecane, r-thiolpropyltrimethoxydecane R-thiolpropyltriethoxydecane, ® N- /3 · (aminoethyl)-γ-aminopropyltrimethoxydecane, /3-cyanoethyltriethoxydecane, Methyltriphenoxydecane, chloromethyltrimethoxydecane, chloromethyltriethoxydecane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane' α - Glycidoxyethyltrimethoxydecane, α-glycidoxyethyltriethoxydecane, 35 1342637 cold-glycidoxyethyltrimethoxydecane, /?-glycidoxyethyl three Ethoxy decane, «-glycidoxypropyl trimethoxy decane, < « - glycidoxypropyl triethoxy decane ' /3 - glycidoxypropyl trimethoxy decane, /3 - glycidoxypropyl triethoxy decane, r-glycidoxypropyl trimethoxy decane, 7-glycidoxypropyl triethoxy decane, τ-glycidoxypropyl tripropyl Oxydecane, Lu T-glycidoxypropyl tributoxy decane, r-glycidoxypropyltrimethoxyethoxy decane, 7 - Glycidoxypropyltriphenoxydecane, *α-glycidoxybutyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, /3-glycidyloxy Trimethoxy decane, cold-glycidoxybutyl triethoxy decane, hydrazine-glycidoxy butyl trimethoxy decane, ® r-glycidoxy butyl triethoxy decane, δ - Glycidoxybutyl trimethoxy decane, δ-glycidoxy butyl triethoxy decane, (3,4-epoxycyclohexyl)methyltrimethoxy decane, (3,4-epoxy Cyclohexyl)ethyltrimethoxydecane, /3 - (3,4-epoxycyclohexyl)ethyltrimethoxydecane, /3 - C 3,4-epoxycyclohexyl)ethyltriethyl Oxydecane, 36 1342637 yS - (3,4-epoxycyclohexyl)ethyltripropoxydecane, -(3,4-epoxycyclohexyl)ethyltributoxydecane, /5 - (3,4·epoxycyclohexyl)ethyltrimethoxyethoxydecane, /5-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxydecane, /9 - (3 , 4-epoxycyclohexyl)ethyltriphenyloxide Baseline, r-(3,4-epoxycyclohexyl)propyltrimethoxydecane, r-(3,4-epoxycyclohexyl)propyltriethoxydecane, (5-(3, 3-alkoxycyclodecyl)butyltrimethoxydecane, tris-oxydecane such as fluorene-(3,4-epoxycyclohexyl)butyltriethoxydecane, trimethoxy decane Or triphenyloxydecane, or a hydrolyzate thereof; and dimethyldimethoxy fluorene, phenylmethyldimethoxydecane 'dimethyldiethoxydecane, phenylmethyldiethyl Oxydecane, · r-chloropropylmethyldimethoxydecane, r-chloropropylmethyldiethoxydecane, dimethylacetoxydecane, r-methylpropenyloxypropyl Methyldimethoxy oxime, r-methacryloxypropylmethyldiethoxylate, τ-thiol propyldimethoxy decane, r-thiol propyl Methyldiethoxydecane, 7-aminopropylmethyldimethoxydecane, styryltrimethoxydecane, styryltriethoxydecane, r-aminopropylmethyldiethyl Oxydecane, 37 methyl ethyl ketone monomethoxy sand, A Vinyl diethoxydecane' glycidoxymethylmethyldimethoxydecane, glycidoxymethylmethyldiethoxydecane, α-glycidoxyethylmethyldimethoxy Decane, α-glycidoxyethylmethyldiethoxydecane, lyo-glycidoxyethylmethyldimethoxydecane, /5-glycidoxyethylmethyldiethoxydecane , α-glycidoxypropylmethyldimethoxydecane, 0-glycidoxypropylmethyldiethoxydecane, /3-glycidoxypropylmethyldimethoxydecane, /3-glycidoxypropylmethyldiethoxydecane, glycidoxypropylmethyldimethoxydecane, glycidoxypropylmethyldiethoxydecane, τ-glycidyloxy Propylmethyldipropoxydecane, γ-glycidoxypropylmethyldibutoxydecane, τ-glycidoxypropylmethylmethoxyethoxydecane, τ-glycidoxy Propylmethyldiphenoxydecane, f-glycidoxypropylmethyldiethoxymethoxydecane, glycidoxypropyl Dimethoxyoxane, 7-glycidoxypropylethyldiethoxydecane, f•glycidoxypropylvinyldimethoxydecane, γ-glycidoxypropylvinyldiene Alkoxy decane such as ethoxy decane, hydrazine-glycidoxypropyl phenyl dimethoxy decane, 38 1342637 τ-glycidoxy propyl phenyl diethoxy decane _, diphenoxy a decane, or a dimethoxy decane, or a hydrolyzate thereof; and bis(trichlorodecyl)methane, 1,2-bis(trichlorodecanealkyl)ethane, 1.4-bis(trichlorodecyl)butyl Alkane, 1.6-bis(trichlorodecanealkyl)hexane, 1.8-bis(trichlorodecanealkyl)octane' 1,2-bis(trimethoxydecylalkyl)ethene 1,2-bis(triethoxy)矽alkyl)ethylene, bis(trimethoxydecyl)methane, 1,2-bis(trimethoxydecyl)ethane, 1.4-bis(trimethoxydecyl)butane, 1.6-bis(trimethoxy)矽alkyl)hexane ' . , 1.8-bis(trimethoxydecyl)octane' bis(triethoxydecyl)methane ' 1,2-bis(triethoxydecyl)B Alkane, 1.4-bis(triethoxydecyl)butane, ® 1,6-bis(triethoxydecyl)hexane, 1,8-bis(triethoxydecyl)octane, 1 ,1-bis(trichlorodecylmethyl)ethene bis(trimethoxydecyl)-1,7-octadiene, bis(triethoxydecyl)-1,7-octadiene, double [3-(Trimethoxydecyl)propyl]tetrasulfide, bis[3-(triethoxydecyl)propyl]tetrasulfide ' 39 1342637 bis[3-(trimethoxydecyl)propyl Urea, bis[3-(triethoxydecyl)propyl]urea, bis[3-(trimethoxydecyl)propyl]amine, bis[3-(triethoxydecyl)propyl Amine

N,N-bis[3-(triethoxydecyl)propyl]Exetylene can improve the proton conductivity and the proton conductive polymerization. The polyorganosiloxane can also have an anion. It is preferred that the sulfonic acid group, the carboxylic acid group, and the phosphonic acid group are used in combination of two or more kinds, and in this case, the effect of improving durability is improved as compared with the case of using alone. In the case of an anionic polyorganosiloxane, the crosslinking density can be increased without conductivity and the fuel can be used only for compatibility. The polyorganosiloxane having an anionic group, which may be an anionic group or a protected anionic group, may be prepared from a decane compound having or protected an anionic group, for example, by the following formula (cl)~ The compound i diamine of the formula (C9) and the like. The ionic group of the compatibility of the substance. Yin base. In the case of such an anisotropy, it is sometimes used so as to cause a decrease in the proton fork, so that it has an anionic basis. Applicable to alkane compounds, then

1342637 [G 1 ~ G6 is an alkoxy group which may be independently selected from the group consisting of an alkyl group which may be substituted, a hydroxyl group which may be substituted, or a substituted alkoxy group, and a substituent of a halogen group; and at least one of them is a substituent selected from the group consisting of a hydroxyl group, an alkoxy group which may be substituted, an anthracene group which may also be substituted, and a halogen group; and E1 and E2 represent each It is independently selected from the group consisting of a hydrocarbon group, a substituted mercaptooxy group, an alkoxy group which may be substituted, an epoxy group which may be substituted, and a substituent of a halogen group. Among these decane compounds having an anionic group, the compound represented by the formula (c4) is particularly preferable from the viewpoint of availability and proton conductivity. Further, in terms of the cross-reduction effect of the fuel such as methanol, 1342637, it is preferable that the compound represented by the formula (c 1 ) is preferable. These decane compounds having an anionic group may be used singly or in combination with a decane compound having no anionic group. In order to lower the hardening temperature of these decane compounds, it is preferred to carry out the hardening. The hydrolysis can be carried out by mixing an acidic aqueous solution of hydrochloric acid, acetic acid or nitric acid, and stirring. Further, the degree of hydrolysis can be controlled by adjusting the mixing amount of pure water or acidic aqueous solution. When the hydrolysis is carried out, it is preferred to mix the pure water or the acidic aqueous solution having a hydrolyzable group in the decane compound to be equal to or higher than three moles or less, to accelerate the hardening. In the case of hydrolysis, since alcohol or the like is formed, hydrolysis may be carried out without a solvent, but in order to obtain uniform hydrolysis, it is preferred to carry out hydrolysis after mixing the decane compound and the solvent. Further, it is also possible to carry out hydrolysis by subjecting the hydrolyzed alcohol or the like to an appropriate amount under heating and/or reduced pressure, or by adding an appropriate solvent. The solvent which can be used for hydrolysis is, for example, an alcohol, an ester 'ether, a ketone, a halogenated hydrocarbon or an aromatic hydrocarbon such as toluene or dimethyl benzene; N,N-dimethylformamide, hydrazine, hydrazine- Dimethylacetamide 'Ν-methylpyrrolidone, dimethylimidazolidinone, dimethyl alum, and the like. These solvents may be used in combination of two or more kinds as needed. Further, in order to promote the hydrolysis reaction in accordance with the purpose, and further accelerate the reaction such as pre-condensation, it may be heated to room temperature or higher, or may be carried out by suppressing the pre-condensation and lowering the hydrolysis temperature to room temperature or lower. Further, other inorganic crosslinked polymers which can be used for polymers (including ruthenium), including titanium oxide, zirconium oxide, aluminum oxide, and the like, each of which can be obtained by a condensation reaction of a corresponding alkoxy metal. 42 1342637 In the polymer electrolyte of the present invention, the composition ratio of the proton conductive polymer (A) as described above to the polymer (B) as described above is preferably 0.05 to 20 in terms of a weight ratio. If the ratio is less than 0.05, sufficient proton conductivity may not be obtained. If it exceeds 20, a perfect fuel cross-reduction effect may not be obtained. Next, a method of producing a polymer electrolyte membrane using the polymer electrolyte of the present invention will be exemplified as follows, but it is not intended to limit the present invention. In order to obtain the polymer electrolyte membrane of the present invention, a method of forming a membrane from a solution state, a method of forming a membrane from a molten state, or the like can be employed. In other words, the film forming system is a raw material of the polymer electrolyte membrane, that is, at least one of the proton conductive polymer (A) and the polymer (B) as described above or a precursor thereof (monomer, oligomer, etc.). It is used in a solution state or a molten state. When (A) and/or (B) is composed of a crosslinked polymer, it is preferred to use a precursor to form a film, and to form a film and then convert the polymer into a polymer. The method of forming a film from a solution state, for example, may be carried out by applying a solution to the plate or film by a suitable coating method, and then removing the solvent to form a film. The coating method can be applied to a spraying method, a brush coating method, a dip coating method, a die coating method, a curtain coating method, a shower coating method, an & E coating method, a screen printing method, and the like, but is not limited thereto. The solvent which can be used for film formation, as long as it can dissolve the raw material and can be removed by heating or decompression thereafter, is not particularly limited, and for example, dimethyldiethylamine, N,N-di can be used. An aprotic polar solvent such as methylformamide, N-methylpyrrolidone, methylmerazide, cyclobutylidene, tris-dimethyl-2-imidazolidinone or trimethylamine hexamethylphosphate. Ethylene glycol monomethyl ether 'ethylene II 43 1342637 alcohol-monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other alkylene glycol monoalkyl ethers, or methanol, ethanol, iso An alcohol solvent such as propanol. The film thickness can be controlled by the solution concentration or the coating thickness on the substrate. When the film is formed from a molten state, a melt press method, a melt extrusion method, or the like can be used. Further, when the raw material is used as a precursor, it may be melted at room temperature. Therefore, in this case, it may be formed by coating on a flat plate or a film. When the precursor is formed into a film, the reaction is completed by applying heat, light, energy rays or the like to convert the precursor into a polymer. The thickness of the film is usually from 3 to 2,000 μm. If the film strength is to be practical, the thickness is preferably 3 μm or more. If the film resistance is to be reduced, that is, the power generation performance is improved, the thickness is 2,000. Those below the micrometer are suitable. The optimum film thickness ranges from 5 to 1,000 microns. Next, a method of mixing the proton conductive polymer (A) as described above with the polymer (B) as described above to produce the polymer electrolyte membrane of the present invention will be exemplified. The same method can be applied to the case where the polymer electrolyte according to the present invention is applied to a catalytic layer. However, these are merely illustrative of the invention, and other suitable methods can be employed to form the film. The first method is a method in which a proton conductive polymer (A) or a precursor thereof in a molten state or a molten state is mixed with a polymer (B) in a molten state or a molten state or a precursor thereof to form a film. The second method is a method in which a film composed of a proton conductive polymer (A) or a polymer (B) is brought into contact with a polymer in a solution state or a molten state or a precursor thereof to form a film. 44 1342637 Further, in the case of producing the ruthenium molecular electrolyte of the present invention, an additive such as a plasticizer for the use of a high molecular compound, a release agent, or the like can be used as long as it does not deviate from the object of the present invention. The anionic group density in the polymer electrolyte of the present invention is preferably m Μ 5.0 mmol/g, more preferably 0.5 to 3.5 mA/g, from the viewpoints of proton conductivity and anti-alcohol solution. If the anionic group is less than ^ mmol/g, the proton conductivity tends to decrease. On the contrary, if the anion group is higher than 5.0 mmol/g, it is used for the polymer electrolyte type.

When the battery is used, perfect fuel cross-inhibition and mechanical strength are sometimes not obtained. The "anionic group density" as described above means the amount of the anionic group introduced per unit gram of the polymer electrolyte. The anionic base density can be determined by nuclear magnetic resonance spectroscopy, elemental analysis or neutralization titration. 9 Because the nuclear magnetic resonance spectroscopy is not affected by the purity of the sample, the anionic base density can be determined, so it can be said to be an ideal method. However, if the anion group Ϊ0 and the degree are difficult to obtain due to the complicated spectrum, it is preferable to use an elemental analysis method which is easy to measure. However, in the case where it is difficult to determine the anionic base density even in the elemental analysis method, the neutralization titration method is preferred. The polymer electrolyte of the present invention has a proton conductivity at room temperature, and is not particularly limited as long as it has a sufficient level when used as a polymer electrolyte fuel cell, but it is ίο at 25r. More preferably, mS/cm or more is more preferably 30 mS/cm or more, and most preferably 60 mS/cm or more. If it is less than 1 〇 ms/cm, it may not be possible to obtain the power generation performance of a high molecular electrolyte fuel cell. 45 1342637 The polymer electrolyte of the present invention is based on the viewpoint of obtaining high output and high energy capacity in a high concentration of a methanol aqueous solution of a fuel in a polymer electrolyte fuel cell produced therefrom, at a temperature of 20 ° C to 1 The fuel crossover in the measurement of M aqueous methanol solution should be preferably below 20 nm/min-min, preferably less than 100 nm/min-min, more preferably 8 〇Nemo/cm-min. . In addition, the lower limit of fuel crossover is best in the case of 〇Nemo/cm-min, but since the extremely low fuel crossover often impairs the proton conductivity, the lower limit of reality is 1 nm/min-min. In the present invention, the polymer electrolyte can also be filled in a porous substrate having a film shape, and the polymer electrolyte membrane obtained in this manner can suppress the front surface of the deformation caused by swelling. The shape of the porous substrate is not particularly limited, and an example thereof is a plurality of pores, but it is preferably a porous substrate having a plurality of independent through-holes or a three-dimensional mesh structure in the thickness direction. A method of fabricating a plurality of independent through holes may be performed by a lithography method, a chemical etching method, a needle punching method, a water jet method, a laser method, a neutron beam method, or the like. The three-dimensional mesh structure means a state in which the polymer constituting the porous substrate has a connection hole that connects the formed body. If the porous substrate has a three-dimensional mesh structure, the pore diameter is preferably in the range of 0.05 to 5 μm, more preferably 0.1 to 1 μm. The aperture can be taken from a photograph of the surface by a scanning electron microscope (SEM) or the like, and is calculated from the average of 20 or more, preferably more than 100, holes, but is usually measured according to 〇〇. For example, the three-dimensional mesh structure obtained by the wet solidification method has a pore size distribution as much as possible, and is obtained from a plurality of pore diameter averages such as 1 〇 〇 to 5 0 〇 46 1342637 as much as possible. The void ratio of the three-dimensional mesh structure is preferably in the range of 10 to 95%, more preferably 1 to 90%. The void ratio is the percentage (%) calculated by subtracting the total volume of the porous substrate from the volume occupied by the polymer and dividing by the total volume of the porous substrate. As the method for producing a porous substrate having a three-dimensional mesh structure as described above, a wet solidification method can be used. When the porous substrate is used for the polymer electrolyte membrane, the shape of the polymer film is as follows: the center of the porous portion is formed as shown in Fig. 1 and the periphery is made of a fine polymer film. In order to be able to form such a shape, for example, the method described below can be employed, but the method is not limited thereto. The first method is a method in which a fine film having only a peripheral portion is prepared in advance, and then a central porous portion is produced. The fine film is obtained, for example, by coating a polymer solution on a substrate and drying it in a conventional manner. It is also possible to adopt a method in which the center portion of the porous portion is removed after the fact that it is not coated by the mask at the time of coating. Then, after the polymer solution is applied to the center, the porous treatment is applied. The second method is a method of making a film which is made porous as a whole, and then blocking the pores in the peripheral portion. The plugging of the pores may be carried out by a method of crushing with a heating press, or a method of filling an aprotic conductive polymer in a pore, or the like, but is not limited thereto. The polymer which can be used in the porous substrate of the present invention is not particularly limited, but is preferably used, for example, polyimine (PI), polyvinylidene fluoride (PVDF), or polyphenylsulfide (ppss). ), polytetrafluoroethylene (PTFE), poly maple (psF), bismuth ether (PES), polycarbonate (ρ〇, polyethene (pE), polyamine, etc., 47 1342637 or copolymers of these Copolymers with other monomers (hexafluoropropylene-vinylidene fluoride copolymer, etc.), plus blends, etc. can also be used. These polymers are easy to oxidize, strength, and wet. The method of filling the porous substrate with the molecular electrolyte as described above is not particularly limited. For example, the polymer electrolyte is made into a solution, and by coating or impregnating the porous substrate, It can be used to fill in the gap. In order to make it easy to carry out the charging in the gap, it is also possible to use ultrasonic or decompression treatment, and if it is used during coating or dipping, it can make the charging efficiency more efficient. Improve the positive effect. In addition, it is also possible to take the front of the polymer electrolyte A method in which a monomer of a bulk is filled in a space, and then polymerized in a space, or a monomer is vaporized and subjected to plasma polymerization. In the present invention, a form of a polymer electrolyte fuel cell and a polymer electrolyte type are used. The manufacturing method of the fuel cell is not particularly limited. The manufacturing method of the polymer electrolyte fuel cell will be described in detail by taking the side-by-side structure as follows. The term "parallel structure" as used herein refers to a single polymer electrolyte membrane surface. In the planar direction, only two or more cells are arranged by a pair of opposing electrodes. According to this configuration, two or more adjacent connections are connected by an electron conductive material that penetrates the polymer electrolyte membrane. The anode and the anode of the battery cell can connect the battery cells in series, whereby the polymer electrolyte membrane of the side-by-side configuration will have a structure in which the proton conducting portion and the electron conducting portion interact. An example of the side-by-side configuration is shown in the first 2 and Fig. 3. Fig. 2 is a schematic view showing a stereoscopic 48 1342637 of the polymer electrolyte membrane of the present invention having a side-by-side configuration. A schematic cross-sectional view showing part of the process. Although two battery cells are arranged laterally as illustrated in FIG. 2 'Fig. 3, three or more of the plurality of cells may be arranged in a planar direction in the same side-by-side configuration. The following description is for two battery cells. In Fig. 2, the proton conducting portion 6 is filled with a polymer electrolyte (not shown) in the porous portion 1, and is charged in the conductive portion 4 in the electron conducting portion. The electron conductive material is a non-porous portion 2 in which the porous portion of the proton conducting portion 6 and the membrane conductive portion 4 of the electron conducting portion are non-porous portions 2 in which protons or cells are not conducted, and is a fine polymer film. The porous substrate is formed into a polymer electrolyte membrane by the method illustrated in Fig. 3. In Fig. 3, the electron conduction portion is charged in advance in the membrane, and then the proton conducting portion 6 is charged. Polymer electrolytes, but the order can be reversed. Further, it is also possible to form a proton-transporting portion 6 by first filling a polymer electrolyte, and then providing an electrode, and finally forming the electron-conducting portion 5. The electron conducting portion of the side-by-side configuration as described above penetrates the structure of the polymer electrolyte membrane. Here, the portion through which the polymer electrolyte membrane is passed through as the electron conduction portion is referred to as a "membrane conductive portion". The film conductive portion has a function different from that of the porous portion for supplying the polymer electrolyte. The size, shape, and the like of the film conductive portion are not particularly limited. The larger the membrane conductive portion, the lower the resistance of the battery cell and the battery cell, so it is expected that the voltage in series will increase. However, the larger the membrane conductive portion, the higher the possibility that the fuel such as hydrogen or methanol on the anode side leaks toward the anode side, or the possibility that the air on the anode side leaks toward the anode side, and as a result, the performance is deteriorated. In view of this, the resistance and leakage resistance of the electron conducting material used in the electron conducting portion must be considered to determine the size or shape of the film conducting portion 49 1342637. Further, the electron conducting portion may pass through the outside without passing through the polymer electrolyte membrane. The electron conductive material of the film conductive portion 4 as described above is not particularly limited, but is preferably a conductive paste. The conductive paste is preferably one in which a conductive agent such as graphite, silver, nickel, copper, platinum or palladium is dispersed in a polymer, so that the resistance can be reduced and the leakage resistance can be improved. Especially in direct fuel cells, it is extremely important to prevent leakage of liquid fuel such as methanol. Therefore, in addition to dispersing graphite or silver in a general conductive paste of enamel resin or polyester 'epoxy resin, it is also possible to use carbon black. , silver, platinum, etc. dispersed in a conductive paste of polyvinylidene fluoride (PVDF) or polyimine. The electron conducting portion 5 is electrically interconnected to the electrode substrate of the battery cell or the electrode catalyst layer, but a conductive paste may be used in order to lower the contact resistance. Further, as the electron conducting portion 5, a metal foil or a metal wire such as nickel stainless steel, aluminum or copper may be used, or these metal foils or wires may be used in combination with a conductive paste. The polymer electrolyte of the present invention can be used as a polymer electrolyte membrane in combination with an electrode 7 including an electrode substrate and an electrode catalyst layer, or as a proton conductor in an electrode catalyst layer to form a membrane electrode assembly ( MEA) is used in polymer electrolyte fuel cells. The electrode catalyst layer of the electrode 7 of the polymer electrolyte fuel cell of the present invention is not particularly limited and can be used. The electrode catalyst layer refers to a layer containing a catalyst or an electrode active material (which is a substance which will be oxidized or reduced) which is necessary for the electrode reaction, and which contains electrons which promote the electrode reaction or which are involved in proton conduction. Further, when the electrode active material is a liquid or a gas of 50 1342637, it is necessary to have a structure in which a liquid or a gas can be easily transmitted, and a discharge structure of a substance which can be produced by the reaction of the electrode is required. In the polymer electrolyte fuel cell of the present invention, the electrode active material is preferably a fuel such as hydrogen or methanol, or oxygen. The catalytic layer is preferably a metal particle such as platinum. Further, it is preferable to contain a material which can improve the conductivity of the electrode catalyst layer, and the form thereof is not particularly limited, but preferably has, for example, conductive particles. As the conductive particles, carbon black can be used, and in particular, platinum-supporting graphite or the like which can be used as a carbon black supporting a catalyst can be used. The electrode catalyst layer requires a catalytic layer 'electron conductor (e.g., carbon black) and a proton conductor (e.g., proton conductive polymer) to be in contact with each other, so that the electrode active material and the reaction product can efficiently enter and exit. Further, the polymer compound is effective for improving proton conductivity or improving material adhesion or for improving hydrophobicity. Therefore, it is preferable that the electrode catalyst layer contains at least catalyst particles, conductive particles and a polymer compound. In the polymer electrolyte fuel cell of the present invention, a catalyst which is well-known in the catalyst of the electrode catalyst layer can be used, and although it is not particularly limited, it is preferably a noble metal catalyst such as platinum, palladium, rhodium, iridium or gold. . Further, alloys, mixtures and the like of such precious metal catalysts may contain two or more elements. The electron conductive material (conductive material) contained in the electrode catalyst layer is not particularly limited, but an inorganic conductive material is preferably used based on the problems of electron conductivity and corrosion resistance. Among them, carbon black, black lead or carbonaceous carbon material, or metal or semimetal is preferably used. Among them, carbon materials include: black, hot black, furnace black, acetylene black and other carbon blacks, which are suitable for use due to their electronic conductivity and surface area of 51 1342637. The furnace black is, for example, the Vulcan XC-72' Vulcan P, Black Pearls 880, Black Pearls 1100' Black Pearls 1300, Black Pearls 2000, Regal 400, KECHEN BLACK · INTERNATIONAL Kechen Black EC, manufactured by CABOT Corporation. Mitsubishi Chemical Corporation manufactures #315〇, #325〇, etc., and acetylene black is Denkablack manufactured by Denki Chemical Industries. Further, in addition to carbon black, natural black lead, pitch, artificial black lead or carbon obtained from an organic compound such as polyacrylonitrile, phenol resin or furan resin can also be used. The form of the carbon material is not particularly limited, and a fibrous form may be used in addition to the granular form. In addition, carbon materials which have been subjected to post-treatment processing of carbon materials can also be used. Among such carbon materials, Vulcan XC-72 manufactured by CABOT Co., Ltd. is preferable because of its electron conductivity. The amount of such electron-conducting substances to be added should be appropriately determined depending on the desired characteristics or the specific surface area or electronic resistance of the substance to be used, but the weight ratio in the electrode catalyst layer should preferably be in the range of 1 to 80%. Preferably, it is 20 to 60%. When the electron conductivity is small, the electronic resistance will become high, and when it is large, the gas permeability or the utilization of the catalytic layer may be hindered, which may cause deterioration of the electrode performance. Since the electron conduction system is based on the performance of the electrode, it should be dispersed uniformly with the catalytic particles. Therefore, it is important that the catalytic particles and the electron conductive material are prepared in advance and sufficiently dispersed. It is also an embodiment in which the electrode catalyst layer is formed by using a catalyst and an electron conductor to form an integrated catalyst-supporting carbon. By using the catalyst to carry carbon, the catalyst utilization efficiency can be improved and the cost can be reduced. In the case where the electrode catalyzed 52 1342637 layer also uses a catalyst-supporting carbon, a conductive agent may be further added. As such a conductive agent, carbon black as described above can be used. Proton conductors which can be used in the electrode catalyst layer are well known. In general, although proton conductive materials are known as various organic and inorganic materials, when used in a polymer electrolyte fuel cell, it is preferred to use a sulfonic acid group or a carboxylic acid which improves proton conductivity. A polymer having an anionic group such as an acid group or a phosphoric acid group, wherein a polymer having an anionic group including a fluoroalkyl ether side chain and a fluoroalkyl main chain is preferably used, for example, manufactured by DuPont, NAFION, and Asahi Glass Co., Ltd. ASIPLEX, FULEMION, etc. by Asahi Glass Co., Ltd. The proton conductors are provided in the electrode catalyst layer in the form of a solution or a dispersion. In this case, the solvent for dissolving or dispersing the polymer is not particularly limited, but it is preferable to use a polar solvent based on the solubility of the proton conductive material. The proton conductive material is preferably applied to the coating layer of the electrode catalyzed particles and the electron conductive material as a main constituent material in the state of being uniformly dispersed, in order to prepare the electrode catalytic layer. However, it is also possible to apply a proton conductor after applying the electrode catalyst layer. The method of coating the proton conductor in the electrode catalyst layer is, for example, a spray coating method, a brush coating method, a dip coating method, a die coating method, a curtain coating method, a shower coating method, or the like, but is not limited thereto. The amount of the proton conductor contained in the electrode catalyst layer should be determined depending on the desired electrode characteristics or the conductivity of the proton conductor used, and although it is not particularly limited, it is preferably in the range of 1 by weight. To 80%, more preferably 5 to 50%. If there are too few proton conductors, the proton conductivity is low. If too much, 53 1342637 will hinder the gas permeability. In either case, the electrode performance may be degraded. In addition to the catalyst 'electron conductor, proton conductor as described above, the electrode catalyst layer ' may contain other various substances. Particularly, in order to improve the adhesion of the substance contained in the electrode catalyst layer, it is preferable to contain a polymer other than the proton conductor as described above. As the polymer, a fluorine atom-containing polymer can be used, and although it is not particularly limited, for example, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polyhexafluoropropylene (FEP), polytetrafluoroethylene can also be used. Ethylene, polyperfluoroalkyl vinyl ester (PFA) or the like, or a copolymer thereof, is used to form a copolymer of monomer units of such polymers with other monomers such as ethylene or styrene, and blends and the like. The content of such polymers in the electrode catalyst layer is preferably in the range of 5 to 40% by weight. If the content of the polymer is too large, the electron and ion resistance will increase and the electrode performance tends to decrease. It is also an embodiment in which the electrode catalyst layer has a three-dimensional network structure in which the catalyst-polymer composite has to have a three-dimensional network structure. The catalyst-polymer composite is a polymer composite containing catalyst particles, and the composite system has a three-dimensional mesh structure. In other words, it has a state in which the catalyst-polymer composite is connected to the connection hole of the formed body. If the porous substrate has a three-dimensional mesh structure, the pore diameter is preferably in the range of 0.05 to 5 μm, more preferably 0.1 to μ μm. The aperture can be calculated from an average of 20 or more, preferably more than 100, apertures by a photograph of a photographic surface such as a scanning electron microscope (SΕΜ), but is usually measured according to one measurement. Since the porous structure obtained by the wet solidification method has a wide pore size distribution 54 1342637, it is taken as much as possible from a plurality of pore diameters of, for example, from 100 to 500 pore diameter average 〇 three-dimensional mesh structure. It is 10 to 95%. More preferably, it is from 10 to 90%. The void ratio refers to the percentage (%) obtained by subtracting the total volume of the catalyst layer from the total volume of the electrode catalyst layer by the volume occupied by the catalyst-polymer composite. The electrode catalyst layer having a three-dimensional mesh structure is usually subjected to wet solidification by applying a catalyst layer to an electrode substrate "ion exchange film" or a substrate other than the electrode substrate. If it is difficult to measure the porosity of the electrode catalyst layer by a single method, the void ratio of the electrode substrate, the ion exchange membrane, and the other substrate may be determined in advance, and thus the substrate and the electrode catalyst layer are calculated to be included. After the void ratio, a method of calculating the void ratio of the electrode catalyst layer alone is calculated. The electrode catalyst layer having a three-dimensional mesh structure has a large void ratio, good gas diffusion or generation of water, and good electron conductivity or proton conductivity. The previous method of porosification is to increase the particle size of the catalyst or the particle size of the added polymer, or to use a pore former to form voids. However, if such a porous method is used, the catalyst will support the carbon. Or the contact resistance between the proton conductors is greater than the electrode catalyst layer. In contrast, according to the three-dimensional mesh structure of the wet solidification method, since the polymer composite system containing the catalyst-supporting carbon has a three-dimensional network shape, electrons or protons are easy to conduct the polymer composite, and since it is microporous The structure is such that it has a gas diffusing property or a structure in which water is discharged well, and thus has a positive effect. When the electrode catalyst layer has a three-dimensional mesh structure, the substance which can be used for the catalyst 55 1342637 or the electron conductor or the proton conductor can also be used in the same manner as the previous one. The main component of the catalyst-polymer composite is a catalyst-supporting carbon and a polymer' and the ratio thereof is not particularly limited, and may be appropriately determined depending on the characteristics of the target electrode, but the weight of the catalyst-supporting carbon/polymer The ratio meter is preferably 5/95 to 95/5. In particular, when used as an electrode catalyst layer for a polymer electrolyte fuel cell, it is preferably 40/60 to 85 Å by weight based on the weight ratio of the catalyst-supporting carbon/polymer. Various additives can also be added to the catalyst-polymer composite. There are, for example, a conductive agent such as carbon for improving electron conductivity, a polymer for improving adhesion, an additive for controlling a pore size of a three-dimensional mesh, etc., but are not limited thereto, and the addition amount of such additives is The ratio is preferably from 0.1 to 50%, more preferably from 1 to 20%, based on the weight ratio of the catalyst-polymer composite. The method for producing a catalyst-polymer composite having a three-dimensional mesh structure is preferably a wet solidification method. Here, after the catalyst-polymer solution composition is applied, the coating layer is brought into contact with a condensing solvent for the polymer, so that the coagulation precipitation of the catalyst-polymer solution composition proceeds simultaneously with the solvent extraction. The catalyst-polymer solution composition is such that the catalyst-supporting carbon is uniformly dispersed in the polymer solution. The catalyst-supporting carbon and the polymer may be used as described above, and the solvent for dissolving the polymer is not particularly limited and should be appropriately determined depending on the polymer to be used. It is important that the polymer solution be such that the catalyst-supporting carbon is sufficiently dispersed. If the dispersion state is not good, the wet coagulation will cause a negative result that the catalyst 56 1342637 does not form a complex with the polymer. The coating method of the catalyst-polymer solution composition is not particularly limited, and a coating method depending on the viscosity of the catalyst/polymer solution composition or a solid component can be selected, but a knife coating method, a rod coating method, or the like is generally used. Spraying method, dip coating method, spin coating method, roll coating method, die coating method, curtain coating method, and the like. Further, the solidifying solvent for wet-solidifying the polymer is not particularly limited, but it is preferably a solvent which is easy to coagulate and precipitate the polymer to be used and which has compatibility with the polymer solution. The method of contacting the substrate with the solidifying solvent is not particularly limited, and a method in which the substrate is immersed in the solidifying solvent together, a method in which only the coating layer is brought into contact with the liquid surface of the solidifying solvent, and a coagulating solvent is sprayed or sprayed may be used. A method of coating a layer or the like. Regarding the substrate to which the catalyst-polymer solution composition is applied, any of the electrode substrate or the polymer electrolyte may be subjected to wet coagulation after application. In addition, it may be applied to a substrate other than the electrode substrate or the polymer electrolyte (for example, a transfer substrate), and then subjected to wet coagulation to obtain a three-dimensional mesh structure, and then the electrode catalytic layer is transferred. Or a method of clamping on an electrode substrate or a polymer electrolyte. The transfer substrate at this time may be a sheet of polytetrafluoroethylene (PTFE) or a glass plate or a metal plate treated with a fluorine or a bismuth-based release agent. In the polymer electrolyte fuel cell of the present invention, the electrode substrate is not particularly limited and can be used. In addition, there are cases where the electrode substrate cannot be used to save space. The electrode substrate which can be used in the present invention is not particularly limited as long as it is low in electrical resistance and can be used as a collector. As the material of the electrode substrate, a conductive inorganic substance can be used. The conductive inorganic substance is, for example, a burned material of polyacrylonitrile, a burned material of pitch, black carbon or a black material such as black lead, stainless steel, molybdenum, titanium or the like. The special limitation, for example, the need for transparency, in particular, the use of a base material, a weaving fabric, a twill fabric such as a carbon cloth made of Toray Co., a method of making a satin fabric, a spunbond method, and a fabric. These cloths are to be made of a flammable woven fabric, and the cloth is processed and then applied to a burning filament or a carbonized cloth. In particular, in the form of a conductive inorganic material using a non-woven electrical fiber, a PAN-based carbon-green carbon fiber phase electrode substrate in carbon or phenol-based carbon fibers is not particularly useful in a fibrous form or in a granular form, but is based on a gas. A fibrous conductive inorganic material (inorganic conductive fiber carbon fiber is preferable. Any of electric or non-woven fabrics using inorganic conductive fibers can be used. For example, Carbon Paper TGP series 'SO series, E-TEK can be used. The cloth is not particularly limited, and a plain weave fabric, a weave fabric, a jacquard fabric, a woven fabric, etc. can be used. Further, it is not limited, and for example, a paper-making method, a needle-punching method, and a melt-blown method can be used. It is also possible to use the weaving in the weaving process, in particular, when the carbon fiber is used, it is preferably a woven fabric made of a spun yarn and a carbonized or black lead-formed flame-resistant filament is applied by a needle punching method or a water jet perforation method. Or a non-woven fabric made of black lead-based fabrics which are made according to the paper-making method using silk or black-lead silk, which can be made into a thin and strong fabric. In the case of the electrode substrate, if an inorganic conductive fiber made of carbon fiber is used, for example, polyacrylonitrile (PAN)-based carbon fiber, vinas, pitch, carbon fiber, fluorene-based carbon fiber, etc. can be used. In general, PAN carbon fiber and leaching 58 1342637 shape, compressive strength 'stretch fracture elongation is large and not easy to break. If you want to make carbon fiber that is not easy to break, carbon fiber carbonization should be The temperature is set to 2,500 ° C or less, and more preferably 2,000 ° C or less. The electrode substrate used in the polymer electrolyte fuel cell of the present invention is used to prevent gas diffusion and permeability deterioration caused by water retention. The hydrophobic treatment, the partial hydrophobicity or hydrophilic treatment to form the water discharge path, or the addition of carbon powder to reduce the electric resistance, etc., is also an applicable embodiment. It is a side-by-side configuration of Lu's, which promotes the inflow of fuel or air such as hydrogen or methanol aqueous solution, and the discharge of carbon dioxide and other products in the water. It is also an embodiment that can be used. In such a diffusion layer, the electrode substrate as described above also has its * function 'but a better effect can be obtained by using a non-conductive cloth as a diffusion layer. The constituent material of the fabric is not particularly limited, and it can be used as long as it is a non-conductive fiber. - For a non-conductive fabric which can be used as a non-conductive fabric constituting a diffusion layer, for example, polytetrafluoroethylene (PTFE) can be used. Tetrafluoroethylene-hexafluoroethylene copolymer θ (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) , Polyfluorovinyl (PVF), Polychlorotrifluoroethylene (CTFE), Chlorinated Polyethylene, Flame Resistant Polyacrylonitrile 'Polyacrylonitrile, Polyester, Polyamide, Polyethylene, Polypropylene, etc. Among these non-conductive fibers, a fiber composed of a fluorine-containing atomic polymer such as PTFE'FEP, PFA, ETFE, PVDF'PVF or CTFE is preferable because it is required for corrosion resistance at the time of electrode reaction. 59 1342637 Non-conductive fabric of the diffusion layer, either woven or non-woven fabric. The woven fabric is not particularly limited, and a plain weave, a twill weave fabric, a satin fabric, a jacquard weave fabric, and the like can be used. Further, the non-woven fabric is not particularly limited, and for example, a paper-making method, a needle punching method, a spunbonding method, a water jet perforation method, or a melt-blown method can be used. In addition, a braid can also be used. Among these fabrics, a plain weave, a non-woven fabric using a needle punching method or a water jet perforating method, and a bottom mat non-woven fabric according to a papermaking method are preferably used. In particular, the use of non-woven fabrics should be used in the viewpoint of being able to produce a thin and strong fabric.

For the non-conductive fabric of the diffusion layer, the hydrophobic treatment to prevent gas diffusion and permeability from being caused by water retention, and the partial hydrophobicity and hydrophilic treatment to form the water discharge path are also applicable. the way. Further practice of heat treatment, extension, stamping, etc., may also be employed. The post-treatment of the field can expect effects such as thin film formation, increased void ratio, and increased strength.

In the polymer electrolyte fuel cell of the present invention, it is preferable that at least a conductive intermediate layer containing an inorganic conductive material and a hydrophobic polymer is provided between the electrode substrate and the electrode catalyst layer. In particular, when the electrode substrate is a carbon fiber woven fabric or a non-woven fabric having a large void ratio, once the conductive intermediate layer is provided, the deterioration of the performance due to the penetration of the electrode catalyst layer into the electrode substrate can be suppressed. When the polymer electrolyte of the present invention is used, for example, in a membrane electrode assembly (MEA), it is preferably processed into a polymer electrolyte membrane to obtain MEA. For example, in order to further reduce the permeation of fuel such as methanol, it is also possible to apply a metal film to the polymer electrolyte. Examples of the metal thin film as described above are palladium, platinum, silver, and the like. In the polymer electrolyte membrane of the present invention, the membrane electrode assembly (Μ E A) formed by using the electrode catalyst layer or the electrode catalyst layer and the electrode substrate is not particularly limited. However, it is preferable to use a hot press to integrate the above, but the temperature or pressure should be appropriately selected depending on the thickness of the polymer electrolyte membrane, the void ratio, the electrode catalyst layer or the electrode substrate. A preferred temperature range is from 40 to 180 ° C and a pressure of from 1 Torr to 80 kgf/cm 2 . The polymer electrolyte of the present invention can be applied to various electrochemical devices such as a fuel cell, a water electrolysis device, a chloralkaline electrolysis device, etc., among which a fuel cell is most suitable. In the fuel cell, a polymer electrolyte fuel cell is most suitable, and it can be divided into hydrogen as a fuel and methanol as a fuel. However, the present invention is particularly suitable for use as a fuel for methanol or the like. Further, the use of the polymer electrolyte fuel cell of the present invention is suitable as a power supply source for mobile equipment. In particular, it can be applied to portable telephones such as portable computers such as personal computers and PDAs (personal digital assistants), household appliances such as vacuum cleaners, and private vehicles such as buses and trucks, and mobile equipment such as ships and rail vehicles. Supply source. [Embodiment] The present invention will be described below by way of examples. However, the examples are only intended to illustrate the invention and are not intended to limit the invention. <Measurement method, test method> Μ 1. The antifreeze water rate and the antifreeze water content of the polymer electrolyte are represented by the mathematical formula (S1) and the antifreeze water content represented by the mathematical formula (S2). The rate 'is measured by differential scanning calorimetry (DSC). The high-altitude 1342637 molecular electrolyte was immersed in water of 20 〇C for 12 hours, and then taken out from the water, and the excess surface-attached water was wiped off with gauze as quickly as possible, and then the pre-measured weight (Gp) was applied and coated. After the wrinkle is applied to the sealed sample container made of alumina in aluminum, the total weight (Gw) of the sample and the sealed sample container is measured as quickly as possible, and then the dSC measurement is immediately performed. The temperature measurement procedure was followed by cooling from room temperature to -3 0 C at a rate of 1 〇 u C /min. c / min is raised to 5 ° C ' and the 〇SC curve of the heating process uses the mathematical formula (η 1) shown below to calculate the main body water amount W f , using the mathematical formula (n 2) to calculate the low melting point water amount Wfc 'Then the dehydrated water amount Wnf is calculated from the total moisture rate [mathematical formula (n3)]. Dq

Wf= (n1) J/,° mAHo dq

Wjc= Γ —-~~dt (n2)

Wnf^Wt-Wf-Wjc (n3) where Wf, Wfc 'Wnf and Wt are the moisture weight per unit weight of the dried sample, m is the dry sample weight, dq/dt is the heat flow signal of DSC, △ H0 is The melting enthalpy at T0, T0 is the melting point of the main water. In addition, after the DSC measurement, a small hole was opened in the sealed sample container, and vacuum drying was performed by applying a vacuum drying machine at 110 ° C for 24 hours, and then the total weight of the sample and the sealed sample container was measured as soon as possible ( Gd). Therefore, the weight (m) of the dried sample is m = G d - G p ' The total moisture content (W t) is W i (G w - G d) / m. 62 1342637 The machine and conditions for DSC measurement are as follows. DSC device·· TA Instrument company ‘DSC Q100” 'Grafting device: Toray Research Center system "TRC-THADAP-DSC"

Measuring temperature range: -5 0 to 5. C Scanning speed: 〇·3 °C/min Sample size: Approx. 5 mg Sample dish: Aluminum sealed sample container temperature • Heat correction: water melting point (〇.〇°C, melting heat 79.7 calories/克鲁This measurement method was carried out in the Toray Research Center. Μ 2 · Microscopic observation The optical polymer was observed using an optical microscope and a transmission electron microscope (ΤΕΜ) to confirm the phase separation state. When the phase separation is not confirmed, and 90 or more of the non-human ones are less than 100 μm, it is judged that (Α) and (Β) are mixed in __. When the phase separation is not confirmed by electron microscopy, and 90 or more of the 100 non-human particles are less than 1 μm, it is judged that (Α) and (Β) are substantially mixed. Μ 3. Whether the polymer electrolyte contains a crosslinked polymer or not, the determination of whether or not the polymer electrolyte contains a crosslinked polymer is carried out as follows: The polymer electrolyte of the sample is washed with pure water (about 0.1)克), applied at 40 ° C, 24 hours The weight was measured after drying, and the polymer electrolyte was immersed in a solvent of 100 times by weight in a closed container and heated at 70 ° C for 40 hours with stirring. Then, ADVANTEKK 63 ^ 42637 filter paper (No. 2) was used. Filtering. When filtering, wash the filter paper and residue 1 with the same solvent as the weight of 1 to dissolve the elution solution thoroughly in the solvent. Dry the filtrate and calculate the dissolved weight. If the dissolution weight is less than the initial weight of 9 When it is 5 %, it is judged that the solvent contains substantially insoluble components. This test is carried out in five solvents of toluene, hexane, N-methylpyrrolidone 'methanol and water, and as a result, it is judged that all the solvents are substantially contained. The polymer electrolyte was determined to contain a crosslinked polymer. Example 1 (1) Preparation of polymer electrolyte membrane φ Dissolving sulfonated polyphenylene sulfide (sulfonic acid base density: 2 mmol/g) In Ν, dimethyl-dimethylformamide (DMF), to obtain a yellow transparent solution (Μ-Al) with a concentration of 20%. Add 0.01 Ν aqueous hydrochloric acid to Toray-Dawkorning, 5 ketone (Tor ay-Dow Corning Silicone) The company made tetrabutoxy oxime 5 g > 4, stirred at room temperature for 30 minutes 'to obtain a colorless transparent hydrolyzate (M-B1) » taken 10 g (Μ-A丨), and added 0.5 g (MB). This solution was infiltrated into a polyimide substrate prepared by lithography with a perforation rate of 10% open pores and a pore size of 12 μm and heated at 100 °C. After 30 minutes, a polymer electrolyte membrane was produced, and the film thickness was 15 μm. The polymer electrolyte membrane was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the Μ 2 method as described above. The polymer electrolyte membrane was further judged by the method of Μ 3 as described above, and as a result, it contained a crosslinked polymer. Moreover, the insoluble matter (crosslinked polymer) under the Μ 3 test does not substantially have proton conductivity. Further, according to the μ ] method as described above, the antifreeze water content of the mathematical formula (S 1 ) is 42%, and the antifreeze water content of the mathematical formula (s 2) 64 1342637 is 43%. (2) Performance of polymer electrolyte membrane The methanol permeation amount and proton conductivity of the polymer electrolyte membrane were evaluated. The membrane was placed in a battery cell manufactured by ELECTROCHEM Co., Ltd., and 1 mol/liter methanol aqueous solution was supplied at 0.2 ml/min on one side, and air was supplied at 50 ml/min on the other side. The methanol permeation amount is measured by measuring the concentration of methanol in the discharged air. The proton conductivity of the membrane is measured by contacting the current and voltage terminals with the membrane surface and measuring the electrical resistance. (3) Preparation of electrode φ After hydrophobic treatment with a 20% polytetrafluoroethylene (PTFE) suspension on a carbon fiber cloth substrate, a carbon black dispersion containing 20% PTFE was applied and fired to obtain Electrode substrate. Applying an anode catalyst coating liquid composed of platinum, -, ruthenium supported carbon and NAFION solution on the electrode substrate, and adding v

After drying, the anode is prepared, and a cathode catalyst coating solution composed of Pt-supported carbon and NAFION solution is applied and dried to obtain a cathode ruthenium (4) membrane electrode composite and a polymer electrolyte fuel. Preparation and Evaluation of Battery The polymer electrolyte membrane of the above step (2) was sandwiched between the anode and the cathode prepared in the above step (3), and heated and stamped to obtain a membrane electrode assembly (MEA). ). The MEA was placed in a battery cell of ELECTROCHEM Co., Ltd., and a 30% aqueous methanol solution was passed through the anode side, and air was passed through the cathode to be subjected to MEA evaluation. The evaluation is a method of measuring the voltage at a constant current flowing through the MEA. The current is measured in order to increase the voltage to 65 1342637 and the voltage drops to 10 mV. The product of the current and the voltage at each measurement point is the output, and the result obtained by the evaluation is that the EA of the polymer electrolyte membrane of Example 1 is higher than that of the EA (Comparative Example 1) using the N AFI ΟN 1 1 7 film. The superior characteristics, that is, 1.4 times the output (m W/cm 2 ) and 1.9 times the energy capacity (Wh). Comparative Example 1 MEA was prepared in the same manner as in Example 1 (4) using a NAFION 1 17 film (manufactured by DuPont). The evaluation was carried out in the same manner as in Example 1 (4). Comparative Example 2 A polymer electrolyte membrane was prepared in the same manner as in Example 1 except that the hydrolyzate of tetrabutoxytitanium was not added in Example 1. ME A and evaluate it. The MEA of Comparative Example 2 is only 0. 4 times higher than the output (m W / c m2), and only 0.7 times the energy capacity (Wh), compared with the EA using the NAFION 1 17 film (Comparative Example 1). After that. The polymer electrolyte was judged by the Μ 3 method as described above, and as a result, it did not contain a crosslinked polymer. Further, according to the above method, the result of the method is that the antifreeze water rate of the mathematical formula (S1) is 22%, and the antifreeze water content of the mathematical formula (S2) is 51%. Comparative Example 3 A polymer electrolyte membrane and MEA were prepared and evaluated in the same manner as in Example 1 except that the 20% D M F solution of the mineralized polyphenylene sulfide of Example 1 was used instead of the 20% NAFION solution. The polymer electrolyte was substantially uniformly mixed together according to the M2 method as described above by optical microscopy and electron microscopy plus 66 1342637. Further, the polymer electrolyte was determined by the method of Μ 3 as described above, and as a result, it contained a crosslinked polymer. Moreover, the insoluble matter (crosslinked polymer) in the M3 test did not have proton conductivity. Further, according to the Μ1 method as described above, the antifreeze rate of the mathematical formula (S1) is 38%, and the antifreeze rate of the mathematical formula (S2) is 15%. The ΜΕΑ 之 本 NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA value. Example 2 φ In addition to the 20% DMF solution of the sulfonated polyphenylene sulfide of Example 1, a 20% DMF solution containing a phosphate-based polyimine (phosphate density: 2 mmol/g) was used and replaced. Titanium tetrabutoxide and tetramethoxy decane to *

Except that the polymer electrolyte membrane and MEA were prepared in the same manner as in Example 1 and evaluated. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to contain a crosslinked polymer as a result of the M3 method as described above. Further, the insoluble matter (crosslinked polymer) in the Μ 3 test J does not substantially have proton conductivity. Further, according to the Μ 1 method as described above, the antifreeze water content of the mathematical formula (S1) is 60%, and the antifreeze water content of the mathematical formula (S2) is 49%. Example 3 A sulfonated polyphenoxyphosphazene (sulfonic acid group density: 1.5 mmol/g) was used in place of the 20% DMF solution of the sulfonated polyphenylene sulfide mill of Example 1. The polymer electrolyte membrane and MEA were prepared and evaluated in the same manner as in Example 1 except that the polyacrylamide substrate was not used, and the other was used. The polymer electrolyte was observed by optical ’ micromirror and electron microscopy according to the Μ 2 method as described above, and the result was substantially uniform mixing at ~J. Further, the polymer electrolyte was determined to have a crosslinked polymer as a result of the Μ 3 method as described above. Further, the insoluble matter (crosslinked polymer) in the M3 test did not substantially have proton conductivity. Further, according to the M1 method as described above, the antifreeze water rate of the mathematical formula (S1) is 49%, and the antifreeze water content of the mathematical formula (S2) is 48%. » The MEA of the present embodiment 3 is compared with the MAFION. The MEA of Comparative Film 117 (Comparative Example 1) was 1.5 times the output (mW/cm2) and 1.9 times the energy capacity (Wh). Rich Example 4 - y In addition to replacing the 20% DMF solution of the sulfonated polyphenylene sulfide of Example 1, a 20% DMF solution containing a phosphonic acid-based polyphenylene sulfide (sulfonic acid group density: 1 mmol/g) was used. A polymer electrolyte membrane and ΜEA were prepared and evaluated in the same manner as in Example 1 except that a porous substrate of polyvinylidene fluoride having a three-dimensional mesh structure was used instead of the polyimide substrate. The high molecular electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was determined by the method of Μ 3 as described above, and as a result, it contained a crosslinked polymer. And the insoluble matter (crosslinked polymer) in the Μ 3 test did not substantially have proton conductivity. Further, according to the M1 method as described above, the antifreeze water content of the mathematical formula (S1) is 41%, and the antifreeze water content of the mathematical formula (S2) is 55 %. 68 1342637 Example 5 A 20% DMF solution containing a carboxylic acid-based polyphenylene sulfide (carboxyl density: 1 mmol/g) was used instead of the 2 Ο% DMF solution of the sulfonated polyphenylsulfuron of Example 1. In place of titanium tetrabutoxide, bisphosphonic acid tetraisopropylbis(3-trimethoxydecylpropyl)methane ester is used, and the rest are in the examples! The polymer electrolyte membrane and MEA were prepared in the same manner and evaluated. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, according to the Μ 1 method as described above, the antifreeze water content of the mathematical formula (S 1) is 40%, and the antifreeze water content of the mathematical formula (S2) is 23%. Example 6 In addition to the 20% DMF solution of the sulfonated polyphenylene sulfide of Example 5, a carboxylic acid group-containing polyphenylphenyl decylamine (carboxylic acid group density: 1 mmmol/g) was used. The polymer electrolyte membrane and ΜEA were prepared in the same manner as in Example 5 except for the % DMF solution, and evaluated. Further, the polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the Μ 3 method as described above. Further, according to the Μ 1 method as described above, the antifreeze water content of the mathematical formula (S1) is 42%, and the antifreeze water content of the mathematical formula (S 2) is 43%. Example 7 except that in place of the tetrabutoxy titanium of Example 1, 2 g of divinylbenzene and 0.02 g of azobisisobutyronitrile were added, the remainder was the same as that of Example 1 in the manner of 69 1342637. Preparation of Polymer Electrolyte Membrane and Mea ' and Evaluation" The polymer electrolyte was mixed together as observed by an optical microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to contain a crosslinked polymer as a result of the M3 method as described above. Further, the insoluble matter (crosslinked polymer) in the M3 test did not substantially have proton conductivity. Further, according to the Μ 1 method as described above, the antifreeze water content of the mathematical formula (S) is 43%, and the antifreeze water content of the mathematical formula (S 2) is 38%. The ruthenium of the present Example 7 was 1.4 times the output (mW/cm2) and 1.7 times the energy capacity (Wh), compared with the case of using the NAFION 1 17 film (Comparative Example 1). Example 8 In the same manner as in Example 1, except that the sulfonated polyfluorene (sulfonic acid group density: 2 mmol/g) was used instead of the sulfonated polyphenylene sulfide 20% DMF solution of Example 1. A polymer electrolyte membrane and MEA were prepared and evaluated. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was determined to have a crosslinked polymer as a result of the M3 method as described above. Further, the insoluble matter (crosslinked polymer) in the M3 test did not substantially have proton conductivity. Further, according to the M1 method as described above, the antifreeze water content of the mathematical formula CS1) is .45%', and the antifreeze water content of the mathematical formula (S 2) is 40%. The MEA of the present Example 8 was output (mW/cm, 1.4 times the mass, and 1.7 times the energy capacity (Wh)) than the MEA (Comparative Example 1) using the NAFION 117 film. 1342637 Example i In addition to replacing 10 g of the sulfonated polyphenylene sulfide solution of Example 1, 5 g of a sulfonated polyphenylene sulfide solution and a sulfonated polyfluorene (sulfonic acid base density: 2 mmol/g) solution were used. The polymer electrolyte membrane and the ruthenium were prepared and evaluated in the same manner as in Example 1 except for 5 g. The polymer electrolyte was mixed together as observed by an optical microscope according to the M2 method as described above. The polymer electrolyte was judged to contain a crosslinked polymer as described above by the method of Μ 3, and the insoluble matter (crosslinked polymer) in the Μ 3 test did not substantially have proton conductivity. According to the M1 method as described above, the antifreeze water rate of the mathematical formula (S1) is 41%, and the antifreeze water content of the mathematical formula (S2) is 37%. The MEA of the present embodiment 9 is more than the NAFION 117 film. MEA (Comparative Example 1) is 1.8 times the output (mW/cm2), with energy capacity (Wh) is 1.9 times. Example 1 0 In addition to the substitution of the titanium tetrabutoxide of Example 1, phenoxytrimethoxydecane and diphenoxydimethoxydecane were used in a ratio of 1:1. The remainder of the mixture was the same as in Example 1 to prepare and evaluate the polymer electrolyte membrane and MEA'. The polymer electrolyte was observed by optical microscopy and electron microscopy according to the M2 method as described above, and the result was a substantially uniform mixture. In addition, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above, and the insoluble matter (crosslinked polymer) in the M 3 test did not substantially have a proton. Conductivity. In addition, according to the method described above, the mathematical formula (S 1) has a freeze water resistance rate of 7] 1342637 42%, and the mathematical formula (S2) has a freeze water content of 44%. Example: 〇 ΜΕΑ is more than 1.6 times the output (mW/cm2) and 88. Example 1 1 (1) Synthesis of sulfonated polyphenylene ether at room temperature under nitrogen atmosphere After dissolving polyphenylene ether (丫卩乂-100L) (100 g) in chloroform (1,000 g), chlorosulfonic acid (34 ml) was slowly added dropwise with stirring. After that, the mixture was stirred at room temperature for 30 minutes. After filtering the precipitated polymer, it was pulverized by a mill, washed thoroughly with water, and then vacuum dried to obtain a desired sulfonated polyphenylene ether (sulfonate). Acid base density: 3.0 mmol/g. (2) Preparation of polymer electrolyte membrane The sulfonated polyphenylene ether prepared by the above (1) was dissolved in hydrazine, hydrazine-dimethylacetamide. A 20% by weight solution (Μ-Α2) was obtained. Mixing and oiling SHIELPOXY's double-layer epoxy resin "EPICOAT 827" (0.5 g) and (M-A2) (10 g) were thoroughly stirred. This solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 80 microns. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) The proton conductivity of the polymer electrolyte membrane is measured by the Beidou Electrician Electrochemical Measuring Device HAG5010 [HZ_30〇〇72 1342637 5〇V 10A power unit, HZ-3000 automated polarization spectrophotometer] and * NF circuit design block The frequency response analyzer 5010 is configured to perform a constant potential impedance measurement by a two-terminal method, and the proton conductivity is determined by a Nyquist diagram. The AC amplitude is set to 500 mV. The sample was a film having a width of about 0 mm and a length of about 10 to 30 mm. The sample is used until it is immersed in water until the measurement. The electrode system uses white gold wires (two pieces) having a diameter of 100 μm. The electrodes are arranged parallel to each other on the surface and the back surface of the sample film and orthogonal to the longitudinal direction of the sample film. · Similarly, the proton conductivity of the NAFION 1 17 membrane (manufactured by DuPont) is also measured in the same manner. (4) The fuel cross-assay of the polymer electrolyte membrane sandwiches the sample membrane between the cells as shown in Fig. 4. On the other side, the battery cells were filled with pure water, and on the other side, the battery cells were charged with 1 Torr of methanol. Stir both battery cells at 20 °C. The amount of methanol dissolved in pure water was measured and quantified at a time of 1 hour, 2 hours, and 3 hours using a gas chromatograph (GC-20 10) manufactured by Shimadzu Corporation, and the unit slope was determined from the chart inclination. Crossover of fuel between units and units. The fuel cross per unit time and unit area of the NAFION 1 17 film (manufactured by DuPont) was also measured in the same manner. (5) The antifreeze water rate and the antifreeze water content are measured according to the method described above. (6) Performance of polymer electrolyte membrane The polymer electrolyte membrane prepared by the above (2) has a proton conduction ratio of 73 1342637 of 0.085 S/cm. The proton conductivity of this system and the "NAFION" membrane (0.085) S/cm) is equal.

In addition, the fuel crossover is 84 nm/min-minute, which is 0.70 times that of the NAFION film. Therefore, it has a fuel cross-inhibition effect. The antifreeze water rate is 61%', and the antifreeze water content is 52%, while the nafion 117 has a freeze water rate of 49% and the antifreeze water content of I 8%. (7) Preparation and evaluation of membrane electrode assembly Using the polymer electrolyte membrane of (2) above, a membrane electrode assembly (MEA) and a fuel cell were prepared according to the method of Example 1 (4) and evaluated. As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFI0N 1 17 membrane, that is, the output (mW/cm3) was 1.0 times times, it is 1.3 times the energy capacity (Wh). Example 1 9. (1) Preparation of polymer electrolyte membrane The same procedure as in Example 11 was carried out except that the "EPICOAT type epoxy resin "EPICOAT 1 032H60 manufactured by SHELLEPOXY Co., Ltd. was used instead of "EPICOAT 827". 2) The polymer electrolyte membrane was prepared in the same manner, and the film thickness was 75 μm. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. The electrolyte was judged by the method of Μ 3 as described above, and the result was a crosslinked polymer. (2) Properties of the polymer electrolyte membrane 74 1342637 Proton conductivity, fuel crossover, antifreeze rate, and antifreeze water content were Example 1 The method of (1) to (5) was measured. The obtained result was that the proton conductivity of the polymer electrolyte membrane prepared as described above (1) was 0.070 S/cm, which was combined with NAFION 117. The proton conductivity (0.085 S/cm) of the membrane is approximately equal. In addition, the fuel crossover is 60 nm/min-min, which is 0.5 times of the NA FI Ο N membrane, so it has a fuel cross-inhibition effect. The measurement rate was 63%, and the antifreeze water content was 48%. (3) Preparation and evaluation of the membrane electrode assembly The polymer electrolyte membrane of (1) above was used, and according to Example 1 (4) The method was to prepare and evaluate a membrane electrode assembly (MEA) and a fuel cell. The result obtained was that the MEA of the polymer electrolyte membrane using the above (]) was compared with the MEA using the NAFION] 17 membrane (comparison Example 1) has superior characteristics, i.e., 1,1 times in output (mW/cm2) and 1.4 times in energy capacity (Wh). Example 1 3 (1) Sulfonated polyether Synthesis of ether ketone Polyetheretherketone (PEEK) (3.0 g) manufactured by VICTOLEX Co., Ltd. (3.0 g) was dissolved in concentrated sulfuric acid (150 ml), and reacted at room temperature for 4 days with stirring. The resulting mixture was poured into excess ether. In the middle, the white precipitate is filtered and washed, and then dried to obtain a sulfonated polyether ether ketone. (2) The preparation of the polymer electrolyte membrane is used in addition to the sulfonated polyphenylene ether as described above (1). The obtained sulfonate 1342637 polyetheretherketone was prepared in the same manner as in Example 1 1 (2). Polymer electrolysis The film has a film thickness of 75 μm. The polymer electrolyte is substantially uniformly mixed together as observed by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte is as described above. 3 The result of the determination is that it contains a crosslinked polymer. (3) Performance of polymer electrolyte membrane Proton conductivity, fuel crossover, antifreeze rate and antifreeze water content are as in Example 1 1 (3) to ( The method of 5) is determined. As a result, the proton conductivity of the polymer electrolyte membrane prepared as described above (1) was 0.080 #S/cm, which was substantially equal to the proton conductivity (0.085 S/cm) of the NAFION 117 membrane. In addition, the fuel crossover is 0.65 times (78 nm/min-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 41% and the antifreeze water content is 45%. (4) Preparation and Evaluation of Membrane Electrode Complex The polymer electrolyte membrane of (1) above was used, and a membrane electrode assembly (MEA) and a fuel cell were prepared according to the method of Example 1 (4), and Evaluation. As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFION 117 membrane, that is, the output (mW/cm2) was 1.1 times, 1.4 times the energy capacity (Wh). Excited Example] 4 (1) Preparation of Polymer Electrolyte Membrane 76 1342637 In addition to "E PI C 0 A Τ 8 2 7", a bis-phenoxyethanol oxime type epoxy resin "BPEFG" manufactured by Osaka Gas Co., Ltd. was used. The rest was prepared in the same manner as in Example 2 (2) to prepare a polymer electrolyte membrane. The film thickness is 75 microns. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged by the method of Μ 3 as described above, and the result was a crosslinked polymer. (2) Properties of polymer electrolyte membrane Proton conductivity, fuel crossover, antifreeze rate and freeze water content were measured by the method of Example 1 1 (3) to (5). As a result, the proton conductivity of the polymer electrolyte membrane prepared as described above ()) was 0.075 S/cm, which was approximately equal to the proton conductivity (0.085 S/cm) of the NAFION 117 membrane. In addition, the fuel crossover is 0.65 times (78 nm/min-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate was 58% and the antifreeze water content was 49%. (3) Preparation of Membrane Electrode Complex 'Evaluation Using the polymer electrolyte membrane as described above (并), and according to the method of Example 1 (4), a membrane electrode assembly (MEA) and a fuel cell were prepared and evaluated. . As a result, the MEA using the polymer electrolyte membrane of U) as described above was superior to the MEA (Comparative Example 1) using the NAFION 117 membrane, that is, the output (mw / cm 2 ) was 1 · 2 times '1.4 times the energy capacity (Wh). 77 1342637 Example η (1) Preparation of polymer electrolyte membrane In addition to the substitution of "EPICOAT 827", 1,6-hexane diisocyanate (0.15 g), propylene glycol (molecular weight 1,000) (0.30 g) and C were used. A polymer electrolyte membrane was prepared in the same manner as in Example 1 1 (2) except for the mixture of triol (0.05 g). The film thickness was 80 microns. The polymer electrolyte was observed to be substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the Μ 2 method as described above. Further, the polymer electrolyte was determined by the method of Μ 3 as described above, and as a result, it contained a crosslinked polymer. (2) Properties of polymer electrolyte membrane Proton conductivity, fuel crossover, antifreeze rate and freeze water content were measured by the method of Example 1 1 (3) to (5). As a result, the proton conductivity of the polymer electrolyte membrane prepared as described above (1) was 0.075 S/cm, which was approximately equal to the proton conductivity (0.085 S/cm) of the NAFION 117 membrane. In addition, the fuel crossover is 0.60 times (72 nmer/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 55% and the antifreeze water content is 40%. (3) Preparation of Membrane Electrode Complex 'Evaluation Using the polymer electrolyte membrane of (1) above, and according to the method of Example 1 (4), a membrane electrode assembly (MEA) and a fuel cell were prepared and evaluated. . The result obtained was that the 78 1342637 MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the N AFION Π 7 membrane, that is, the output (m W ) / c m2) is 1.2 times, and energy capacity (Wh) is 1.5 times. Example 1 6 (1) Preparation of proton conductive polymer

35 g of potassium carbonate, 11 g of hydroquinone, 35 g of 4,4,-(9H-indole-9-camtoside) bisphenol, and 44 g of 4,4'-difluorobenzophenone were used, at N- In methylpyrrolidone (NMP) 'at 160. (: Polymerization is carried out. After extraction with water, reprecipitation is carried out with excess methanol, whereby the formula (T1) as described above is purified and quantitatively obtained. After the polymer I was dissolved in chloroform, 14 ml of chlorosulfonic acid was slowly added dropwise under vigorous stirring, and the reaction was carried out for 5 minutes. After the white precipitate was filtered, pulverized, and thoroughly washed with water, The proton conductive polymer was applied to dryness to obtain the target. The sulfonic acid group density of the prepared proton conductive polymer was 2.6 mmol/g via elemental analysis. (2) Preparation of polymer electrolyte membrane The proton conductive polymer prepared as described above (1) was prepared as a N,N-dimethylacetamide 2% by weight solution. This liquid and oily 79 1342637 SHELLEPOXY bisphenol A ring The oxygen resin "EPICOAT 827" (0.5 g) was mixed and thoroughly stirred. The solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane having a film thickness of 240 μm. According to the M2 method as described above, with an optical microscope and As a result of observing with an electron microscope, the mixture was substantially uniformly mixed. In addition, the polymer electrolyte was judged to have a crosslinked polymer as described above by the method of Μ 3 (3) Performance of the polymer electrolyte membrane was carried out. The method of Example 1 1 (3) to (5) was carried out. The obtained result was that the proton conductivity of the polymer electrolyte membrane prepared as described above in U) was 0.090 S/cm 'the proton of this system and the NAFI0N 117 membrane. The conductivity (0.085 S/cm) is approximately equal. In addition, the fuel crossover is 0.22 times (26 nmer/cm-min) of the NAFI0N 1 film, so the fuel cross-inhibition effect is large. The antifreeze water rate is 86%, and the antifreeze water content is 50%. It is known that the ratio of antifreeze water is very large. (4) Preparation and Evaluation of Membrane Electrode Composite The polymer electrolyte membrane of (2) above was used, and a membrane electrode assembly (Mea) and a fuel cell were prepared according to the method of Example 1 (4), and evaluated. . As a result of the above, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFI0N 1 17 membrane, that is, the output (rnW/cm2). It is 1.9 times, and the energy capacity (W h) is 2 · 9 times. 80 1342637 Example 1 7 (1) Hydrolysis of arsenic oxynitride 5 g of tetrabutoxy titanium manufactured by T〇iay-D〇w Corning Silicone Co., Ltd. 5 g of 〇.〇]N hydrochloric acid The aqueous solution was stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. (2) Preparation of polymer electrolyte 0.5 g of the hydrolyzate obtained in (1) was added to 10 g of a 20% aqueous solution of sodium polystyrene sulfonate (manufactured by ALDOLICH). This solution was poured on a glass plate and heated at 100 ° C for 30 minutes to prepare a polymer electrolyte membrane. The polymer electrolyte membrane was ion-exchanged with 1 Torr hydrochloric acid, and then sufficiently washed with pure water. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Properties of polymer electrolyte The measurement was carried out by the methods of Examples 丨] (3) to (5). The obtained result was that the proton conductivity of the polymer electrolyte membrane prepared as described above (1) was 013 S/cm 〇 and the other 'fuel crossover was 0.80 times (96 nmer/cm-min) of the NAFI0N film'. It has a fuel cross-inhibition effect. The antifreeze water rate was 68% and the antifreeze water content was 58%. (4) Preparation and evaluation of the membrane electrode assembly The polymer electrolyte membrane of the above (2) was used, and a membrane electrode assembly (mea) and a fuel cell were prepared according to the method of Example 1 (4), and 81 1342637 Assessment. As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFION 1 17 membrane, that is, the output (mW/cm2). It is 1.2 times, and it is 1.2 times the energy capacity (Wh). Example 1 (1) Preparation of polymer electrolyte and evaluation of film properties A polymer electrolyte membrane was prepared in the same manner as in Example 17 except that tetramethoxysilane was used instead of tetrabutoxytitanium. The polymer electrolyte was mixed in accordance with the M2 method as described above by optical microscopy and electron microscopy. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. Further, the properties of the film were evaluated in the same manner as in the Example 7 (3), and as a result, the proton conductivity was 0.13 S/ciTi. In addition, the fuel crossover is 0.76 times (91 nmer/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate was 59% and the antifreeze water content was 54%. Example 1 9 (1) Preparation of polymer electrolyte, evaluation of film properties A 1:1 (by weight) mixed solution of phenyl methoxy decane and diphenyltrimethoxy decane was used in place of titanium tetrabutoxide. The rest of the procedure was the same as in Example 17 to prepare a polymer electrolyte membrane. The polymer electrolyte was substantially uniformly mixed together as a result of observation by optical microscopy and electron microscopy according to the Μ 2 method as described above. Further, the polymer electrolysis 82 1342637 was judged as described above by the method of Μ 3 to contain a crosslinked polymer. Further, the properties of the film were evaluated in the same manner as in Example 17 (3), and as a result, the proton conductivity was 0.13 S/cm. ~ In addition, the fuel crossover is 0.75 times (90 nm/min-min) of the NAFION film, so it has a fuel cross-inhibition effect. The antifreeze water rate is 66% and the antifreeze water content is 55%. Example 20 (1) Preparation of polymer electrolyte, evaluation of film properties In addition to replacing sodium polystyrene sulfonate, a 20% sulfonated polyphenylene sulfide solution was used, and the opening ratio was 10%, and the pore diameter was 12 μm. The polymer electrolyte membrane was prepared in the same manner as in Example 以外 except that the polyimide substrate prepared by lithography was filled with a polymer electrolyte. The polymer electrolyte was substantially uniformly mixed together as a result of observation by optical microscopy and electron microscopy according to the M2 method as described above. Further, the polymer electrolyte was judged to contain a crosslinked polymer as a result of the M3 method as described above. The properties of the film were evaluated in the same manner as in Example (3), and as a result, the proton conductivity was 0.080 S/cm. In addition, the fuel crossover is 0.62 times (74 nmer/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. Example 2 1 (1) Preparation of a molecular electrolyte and evaluation of film properties A polymer electrolyte was prepared in the same manner as in Example 17 except that tetramethoxyzirconium was used instead of tetrabutoxytitanium. The high 'molecular electrolytes are observed by optical microscopy and electron microscopy according to the M2 method described above. 83 1342637 The results are substantially uniformly mixed together. Further, the polymer electrolyte was judged by the Μ 3 method as described above, and as a result, it contained a cross-linking high score. The properties of the film were evaluated in the same manner as in Example (3), and as a result, the proton conductivity was 0.1 15 S/cm. In addition, the fuel crossover is 0.92 times (10 10 nm/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate was 52% and the antifreeze water content was 43%. Example 22 (1) Preparation of Polymer Electrolyte, Evaluation of Membrane Performance Triethoxylate was used in place of phenyltrimethoxydecane, and the polymer electrolyte was impregnated to have an open cell ratio of 10% and a surface pore diameter. A polymer electrolyte was prepared in the same manner as in Example 20 except for a PVDF porous substrate having a 1 micron and a ternary mesh structure. The polymer electrolyte was substantially uniformly mixed together as a result of observation by optical microscopy and electron microscopy according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. The properties of the film were evaluated in the same manner as in Example 17 (3). 1 The proton conductivity was 0.095 S/cm. In addition, the fuel crossover is 0.83 times (100 nm/min-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 68% and the antifreeze water content is 58%. Example 2 3 (1) Preparation of Polymer Electrolyte 'Evaluation of Membrane Performance 84 1342637 In addition to bisphosphonate, tetraisopropylbis(3-trimethoxydecylpropyl)methane was used instead of tetrabutoxytitanium The rest are with the examples! 7 In the same manner to prepare a polymer electrolyte. The polymer electrolyte was substantially uniformly mixed together as a result of observation by optical microscopy and electron microscopy according to the Μ 2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the above Μ 3 method. The properties of the film were evaluated in the same manner as in Example 17 (3), and as a result, the proton conductivity was 0.12 S/cm. Further, the fuel crossover is 0.7 times (84 nmer/cm-min) of the NAF10N film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 43% ‘the antifreeze water content is 43%. Example 24 (]) Preparation of polymer electrolyte, evaluation of film properties In addition to the substitution of the bisphosphonate tetraisopropyl bis(3-trimethoxydecylpropyl) ketone vinegar, the amount of hydrolysis was changed to 3 g. The polymer electrolyte membrane was prepared in the same manner as in Example 23 except for use. The polymer electrolyte was substantially uniformly mixed together as a result of observation by optical microscopy and electron microscopy according to the M 2 method as described above. The properties of the film were evaluated in the same manner as in Example 7 (3), and as a result, the proton conductivity was 〇.1 〇 S/cm. Further, the fuel parent fork is 0.6 times (72 nmer/cm-min) of the να FI ON film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 41% ‘the antifreeze water content is 45%. Excited Example 25 85 1342637 (1) Synthesis of sulfonated polyphenylene ether The synthesis was carried out in the same manner as in Example 11 U). Dissolving the sulfonated polyphenylene ether in N,N-dimethylacetamide (DMAc) and setting it to 20% by weight of the solution '(2) 3-pentenoic acid trimethyldecane ester A 200 ml three-necked retort of a reflux condenser 'agitator and a nitrogen introduction tube was placed in 4-pentenoic acid (Tokyo Chemical Industry Co., Ltd., 48.48 g). The distillation flask was immersed in an ice bath and nitrogen gas was introduced, and hexamethyldioxane (39.08 g, 0.242 mol) was added dropwise with stirring. The white crystals were precipitated, and the whole was made into a jelly-like jelly, and the gas was distilled off by introducing nitrogen gas, and the reaction was carried out at 100 ° C for about 6 hours. The crystals of the reaction solution are dissolved to become a colorless transparent solution. Purification by vacuum distillation to obtain a colorless transparent liquid of dimethyl pentenoate (7 0.9 g) (gas chromatograph purity: 96.8%) (3) 5-trimethoxy Synthesis of decyl pentenoic acid trimethyl decyl ester Trimethoxy decane (Tokyo Chemical Industry Co., Ltd., 35.50 g) was placed in a 300 ml three-necked retort with a dropping funnel and a stirring wing. Further, a solution of chloroplatinic acid hexahydrate (Wako Pure Chemical Industries, Ltd., 7.3 g) in 2-propanol (〇, 2 ml) was added. Trimethyl decanoate (50.Q6 g) was placed in a dropping funnel and added dropwise at room temperature with stirring. Gastro-stomach heat was found on the way. Therefore, the three-necked retort was immersed in an ice bath to cool it. The dropping liquid funnel was again returned to room temperature and allowed to stand overnight. It was purified by distillation under reduced pressure to obtain a colorless transparent liquid of 3-trimethoxydecylenoic acid trimethyl sulfonate (32.2 g) (purity purity of 96.8%). 86 1342637 (4) Hydrolysis of decane compound (4a) 1 μ hydrochloric acid (0.68 g) was added to Gelest Company under 〇»C, 6-bis(trimethoxydecyl)hexane (].35 g) It was stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. (4b) 1 μ hydrochloric acid (0.37 g) was added to 1,3-trimethoxydecyl pentenoic acid trimethyl decyl ester (1 gram) obtained in (3) above. The hydrolyzate was stirred and stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. (5) Preparation of polymer electrolyte membrane φ The hydrolyzate of (a) and (b) as described above and the DM Ac solution (19.5 g) of the sulfonated polyphenylene ether of (1) above were mixed. This solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness is 1 80 μm·. The polymer electrolyte was substantially uniformly mixed as a result of observation by optical microscopy and electron microscopy according to the M2 method as described above. Further, the polymer electrolyte was determined to have a crosslinked polymer as a result of the Μ 3 method as described above. (6) Evaluation of performance of polymer electrolyte membrane # The performance of this film was evaluated in the same manner as in Example 1 (3), and the proton conductivity was 80 m S/cm. In addition, the fuel crossover is 0.65 times (78 nm/min-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 68% ‘the antifreeze water content is 56%. (7) Preparation and evaluation of the membrane electrode assembly The polymer electrolyte membrane of the above (5) was used, and a membrane electrode assembly (mea) and a fuel cell were prepared according to the method of Example 87 1342637 (4), and Evaluate. As a result, the MEA using the polymer electrolyte membrane of the above (5) was superior to the MEA (Comparative Example 1) using the NAFION 1 17 membrane, that is, the output (m W / c m2 ). 8倍値。 The energy capacity (W h) is 1.8 times the 値. Example 26 (1) Synthesis of trimethyl decyl 3-butenoate A 3-molecular distillation flask of a 200 ml three-necked retort with a reflux condenser, a stirring device and a nitrogen introduction tube was added (ALDORICH, 50.0 g). . The distillation flask was immersed in an ice bath and nitrogen gas was introduced, and hexamethyldioxane (46.9 g) was added dropwise with stirring. White crystals will precipitate and the whole will become milky milk jelly. Under stirring, ammonia was introduced to distill off ammonia, and the reaction was carried out at 100 ° C for about 5 hours. The crystal of the reaction solution was almost dissolved and _ was a slightly brownish transparent solution. It is applied by distillation under reduced pressure. Since the steaming can was mixed with a little white crystal, it was filtered under pressure filtration (PTFE over-furnace, pore size: 0.1 μm) to obtain a colorless transparent liquid of 3-methylbutyric acid trimethyl sulfonate (67.8 g). (Gas chromatograph purity was 95.1% > (2) Synthesis of 3-trimethoxydecylbutanoic acid trimethyldecane ester 3-butyric acid trimethyldecane ester (50.0 g) was placed in the drop _ 4 Stirring wing 300 ml three-necked retort. Add chloroplatinic acid hexahydrate% (Wako Pure Chemical Industries' Πmg) to 2-propanol (0,4 ml) } <i solution. Alkoxydecane (3 8 · 8 g) was placed in a dropping funnel, and the = 蒸馏 distillation flask was immersed in an ice bath to be cooled, and then added dropwise with stirring at about u ' ^ minutes 88 1342637 hours. It was left at room temperature for one night, and purified by distillation under reduced pressure to obtain a colorless transparent liquid of 4-trimethoxydecylbutanoic acid trimethylsilyl ester (47.3 g) (purity of gas chromatograph was 87.1). %) 〇(3) Hydrolysis of decane compound (3a) 1 Μ hydrochloric acid (0.68 g) was added to 1,6-bis(trimethoxydecyl)hexane (1,35 g) manufactured by Gelest at 0 °C. And stirring at room temperature for 30 minutes to obtain a colorless and transparent hydrolyzate. _ (3b) 1 Μ hydrochloric acid (0.40 g) was added to the above at 0 〇C (2) A hydrolyzate of trimethyldecyl 5-trimethoxydecylbutanoate (?.) obtained and stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. 4) Preparation of polymer electrolyte membrane The hydrolyzate of (3a) and (3b) as described above and the DM Ac solution (19.5 g) of the sulfonated polyphenylene ether of Example 12 (1) were poured into the glass. The polymer electrolyte membrane was prepared by heating on a plate at 100 ° C for 3 hours, and the film thickness was 180 μm. The polymer electrolyte was substantially uniform as observed by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (5) Performance evaluation of the polymer electrolyte membrane The properties of the membrane were compared with Example 1 7 (3) The same way, the proton conductivity is 7 9 m S /cm, which is about the same level as the NA FI ◦ N 1 ]7 film. 89 1342637 In addition, the fuel cross is 0.7 times that of the NAFION film (85 Nemo) Ear/cm-minute) 'Therefore there is fuel crossover Effect. 'The rate of antifreeze water is 47%, and the ratio of antifreeze water is 50%.', (6) Preparation and evaluation of membrane electrode assembly using the polymer electrolyte membrane as described above (4), and according to the implementation The method of Example 1 (4) was carried out to prepare a membrane electrode assembly (M ea ) and a fuel cell, and was evaluated. The obtained result was that the MEA of the polymer electrolyte membrane using the above (5) was more than the use of NAFION 1 The MEA of the 17 film (Comparative Example 1) has a superior characteristic of φ, that is, 1.1 times the output (m W / c m1) and 1.9 times the energy capacity (W h). Example 27 (1) Hydrolysis of decane compound (la) 1 Μ hydrochloric acid (0.68 g) was added to 1,6-bis(trimethoxydecyl)hexane (1·35 g) manufactured by Gelest Corporation at 0 °C. In the middle, and stirred at room temperature for 30 minutes 'to obtain a colorless transparent hydrolyzate. (lb) 1 Torr of hydrochloric acid (〇4 g) was added to a compound represented by the formula (Κ1) (manufactured by AZUMAX Co., Ltd., and stirred at room temperature for 30 minutes) at 0 °C. To produce a colorless and transparent hydrolyzate. 〇

II (EtO)3Si-/^^P(〇Et)2 (K1) 90 1 Preparation of polymer electrolyte membrane The hydrolyzate of U a) and (1 b) as described above and Example 1 2 (1) A DMA c solution of sulfonated polyphenylene ether (15.9 · 5 g). This solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 185 μm. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the Μ 2 method as described above. Further, the molecular electrolyte of this office was judged by the method of Μ 3 as described above, and as a result, it contained a crosslinked polymer. (3) Evaluation of performance of polymer electrolyte membrane The properties of this membrane were evaluated in the same manner as in Example 17 (3), and the proton conductivity was 76 mS/cm. In addition, the fuel crossover is 0.65 times (78 nm/min-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate was 53% and the antifreeze water content was 52%. (4) Preparation and Evaluation of Membrane Electrode Complex The polymer electrolyte membrane of (2) above was used, and a membrane electrode assembly (MEA) and a fuel cell were prepared according to the method of Example 1 (4), and evaluated. . As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFI0N 117 membrane, that is, the output (m W / c m2). It is calculated as 1.丨 times, and is 1·8 times the energy capacity (W h). Example @ (1) Hydrolysis of a decane compound (la) 1 μ hydrochloric acid (0.68 g) was added to a 1,6-bis(trimethoxydecyl)hexane (1·35 g) manufactured by Gelest Company 1342637 under the sputum. Medium' and stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. (lb) 1 Torr hydrochloric acid (0.24 g) was added to a solution containing a compound represented by the formula (Κ2) ("0.74 g" manufactured by Gelest Co., Ltd.) and DMAc (0.74 g) at 0 ° C, and was added at room temperature. Stir for 30 minutes' to prepare a hydrolyzate. 0 II CI-S II Ο

SiCI3 (K2)

(2) Preparation of polymer electrolyte membrane A hydrolyzate of (a) and (lb) as described above and a DMAc solution (19.5 g) of the sulfonated polyphenylene ether of Example 12 (1) were mixed. This solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness is 】 95 microns. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Evaluation of performance of polymer electrolyte membrane The properties of this membrane were evaluated in the same manner as in Example 17 (3), and the proton conductivity was 87 mS/cm. In addition, the fuel crossover is 0.80 times (96 nmer/cm-min) of the N AFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 54% and the antifreeze water content is 54%. 92 4 41342637 (4) Preparation and evaluation of membrane electrode assembly Using the polymer electrolyte membrane of (2) above, and according to the method of Example (4), a membrane electrode assembly (MEA) and a fuel cell were prepared. And evaluate it. As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFION 1 17 membrane, that is, the output (mW/cm2). It is 1.1 times, and the energy capacity (Wh) is 1.4 times. Example 29 · (1) Synthesis of sulfonated polyetheretherketone Polyetheretherketone (PEEK) (3,0 g) manufactured by VICTOLEX Co., Ltd. was dissolved in concentrated sulfuric acid (150 ml) and stirred at room temperature under stirring. The reaction was 4 days. The resulting mixture was poured into an excess of ether, filtered to remove a white precipitate and washed, and dried to give a sulfonated polyetheretherketone. The sulfonated polyetheretherketone was dissolved in DM Ac to give a 20% by weight solution. (2) Hydrolysis of decane compound (2a) 1 Torr hydrochloric acid (0.68 g) was added to Gelest Corporation to make 1,6-bis(trimethoxydecyl)hexane (1.35 g) at 0 ° C, and Stirring was carried out for 30 minutes at room temperature to obtain a colorless transparent hydrolyzate. (2b) 1 Μ hydrochloric acid (0.24 g) was added to a solution containing a compound represented by the formula (K3) (0.80 g, manufactured by Gelest) and DM Ac (0.80 g) at 0 ° C and at room temperature It was stirred for 30 minutes to prepare a hydrolyzate. 93

1342637 (3) Preparation of polymer electrolyte membrane The hydrolyzate of (2 a) and (2 b) as described above and the DMA c solution of sulfonated polyetheretherketone as described above (1·5 g) The solution was placed on a glass plate and heated at 00 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 204 microns. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to contain a crosslinked polymer as described above by the method of Μ3. (4) Performance evaluation of polymer electrolyte membrane The performance of this membrane was evaluated in the same manner as in Example 17 (3). The result was a proton conductivity of 77 mS/cm, which is approximately the same level as NAFION 117. The fuel crossover is 0.81 times (97 nmer/m. minute-minute) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 48% and the antifreeze water content is 51%. (5) Preparation and evaluation of the membrane electrode assembly The polymer electrolyte membrane of the above (3) was used, and a membrane electrode assembly (ME A) and a fuel cell were prepared according to the method of Example 1 (4), and Evaluation. 94 4 41342637 The result obtained is that the MEA using the polymer electrolyte membrane of (3) as described above is superior to the MEA (Comparative Example 1) using the NAFION 1 7 membrane, that is, the output (mW) /cm2) is 1.1 times 'in terms of energy capacity (Wh) is 1.3 times. Example 3 0 (1) Hydrolysis of decane compound (la) 1 Torr hydrochloric acid (0.68 g) was added at 0 ° C to 1,6-bis(trimethoxydecyl)hexane (1.35 g) manufactured by Gelest. Medium' and stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. Lu (lb) 1 Μ hydrochloric acid (0.32 g) was added at 〇 ° C to 3-trimethoxy which was synthesized by the method described in "Electrocinmica", 45, pp. 1 377 - 1 383 (2000). A solution of decylpropane sulfonium chloride (0.97 g) and diethylene glycol dimethyl ether (0.97 g) was stirred at room temperature for 30 minutes to prepare a hydrolyzate. (2) Preparation of polymer electrolyte membrane The hydrolyzate of (la) and (lb) as described above and the DM A c solution (19.5 g) of the sulfonated polyphenylene ether of Example 12 (1) were mixed. This solution was poured on a glass plate, and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness is 1 95 microns. The polymer electrolyte was observed by an optical microscope and an electron microscope according to the M2 method as described above, and was substantially uniformly mixed. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Evaluation of performance of polymer electrolyte membrane The performance of this membrane was evaluated in the same manner as in Example 17 (3), and the proton conductivity of 95 1342637 was 88 mS/cm, which was approximately the same level as NAFION 1 Π. . In addition, the fuel crossover is 0.85 times (102 nmer/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate was 44% and the antifreeze water content was 56%. (4) Preparation and Evaluation of Membrane Electrode Composite The polymer electrolyte membrane of (2) above was used, and a membrane electrode assembly (MEΑ) and a fuel cell were prepared according to the method of Example j (4), and evaluated. . As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example 1) using the NAFION 1 17 membrane, that is, the output (mW/cm2). It is 1 · 1 times and 1.2 times the energy capacity (Wh). Example 3 1 (1) Hydrolysis of decane compound (la) 1 μ hydrochloric acid (〇.37 g) was added to a bis(3-diethoxydecylpropyl)urea (247) manufactured by Gelest Corporation at 0 °C. In gram), and stirring at room temperature for 30 minutes, a colorless transparent hydrolyzate was obtained. (lb) 1 Μ hydrochloric acid (24 g) was added to a solution containing a compound represented by the formula (κ2) (manufactured by GeUst Co., Ltd., 74 g) and DMAc (〇. 74 g) at 0 ° C, and Stir at room temperature for 3 minutes to prepare a hydrolyzate. 96 1342637 ο II Cl-s II 〇

SiCI3 (K2) (2) Preparation of polymer electrolyte membrane The DMA c solution of the sulfonated polyphenylene ether of Example 12) and (lb) as described above (1) and (lb) (1 9 · 5) Gram). This liquid was poured on a glass plate and heated at 00 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness is 195 microns. The smell of the molecular electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Evaluation of performance of polymer electrolyte membrane The properties of this membrane were evaluated in the same manner as in Example 17 (3), and as a result, the proton conductivity was 82 mS/cm, which was approximately the same level as NAFION 117. In addition, the fuel crossover is 0.75 times (90 nm/cm-min) of the NAFION film, thus having a fuel cross-inhibition effect. The antifreeze water rate is 63% and the antifreeze water content is 58%. (4) Preparation of Membrane Electrode Complex 'Evaluation Using the polymer electrolyte membrane of (2) above, and according to the method of Example 1 (4), a membrane electrode assembly (MEA) and a fuel cell were prepared and evaluated. . 97 1342637 The result obtained is that the MEA# using the polymer electrolyte membrane of the above (2) has superior characteristics to the MEA (Comparative Example 1) using the NAFION 117 membrane, that is, the output (mW/Cm2). It is 1.1 times, and the energy capacity (W h) is 1.6 times. Example 3 2 (1) Synthesis of sulfonated polyether ether oxime Polyether ether oxime (3.0 g) was dissolved in concentrated sulfuric acid (15 ml), and reacted at room temperature for 4 days with stirring. The resulting mixture was poured into an excess of ether. After filtering the white precipitate and washing it, it was dried to obtain a sulfonated polyether ether. This was dissolved in DM Ac to become a 20% by weight solution. (2) Hydrolysis of decane compound (2a) 1 Torr hydrochloric acid (〇·24 g) was added to 1,6-bis(trimethoxydecyl)hexane (1.35 g) manufactured by Gelest Corporation at 0 °C. Further, the mixture was stirred at room temperature for 30 minutes to obtain a colorless transparent hydrolyzate. (2b) 1 Torr hydrochloric acid (0.24 g) was added to a solution containing a compound represented by the formula (K3) (0.80 g, manufactured by Gelest) and DM Ac (0.80 g) at 0 ° C, and at room temperature It was stirred for 30 minutes to prepare a hydrolyzate. Ο II a-s II Ο

Si(OEt)3 (K3) (3) Preparation of polymer electrolyte membrane The hydrolyzate of (2 a) and (2 b) as described above and (5) of the above (1) 5 yellowing 98 Ϊ 342637 polyether ether hydrazine DM Ac solution (19.5 g). This liquid was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 1 96 μm. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to contain a crosslinked polymer as described above by the method of Μ3. (4) Evaluation of performance of polymer electrolyte membrane The properties of this membrane were evaluated in the same manner as in Example 17 (3), and as a result, the proton conductivity was 74 ms/cm, which was approximately the same level as NAFION 117. Further, the fuel crossover is 0.79 times (97 nmer/cm-min) of the NAFION film, and thus has a fuel cross-inhibition effect. The antifreeze water rate is 55 % and the antifreeze water content is 50%. (5) Preparation and Evaluation of Membrane Electrode Complex The polymer electrolyte membrane of (3) above was used, and a membrane electrode assembly (MEA) and a fuel cell were prepared according to the method of Example 1 (4), and evaluated. . The result obtained by Lu was that the EA using the polymer electrolyte membrane of the above (3) was superior to the ΜEA (Comparative Example 1) using the NA FI 〇N 1 1 7 film, that is, The output (mW/cm2) is 1.1 times, and the energy capacity (W h) is 15 times. Example 3 3 (1) Hydrolysis of decane compound U a) Right: 0 下 hydrochloric acid (〇. 6 8 g) was added to G e 1 est company 99 1342637 to make 1,6-bis (trimethoxydecane) In the hexane (1. 35 g), & and stirred at room temperature for 30 minutes to obtain a colorless and transparent water solution. _ (lb) Add 1 Μ hydrochloric acid (〇·24 g) to bisphosphonate tetraisopropyl bis(3-trimethoxydecylpropyl)methane (1.0 g) at 〇 ° C, and Stirring at room temperature for 30 minutes to prepare a hydrolyzed % 〇 (2) polymer electrolyte membrane. The preparation of the hydrolyzate of (la) and (lb) as described above and the proton conduction of Example 16 U) The 聚合物 of the polymer, Ν-dimethylacetamide 20% by weight solution, liquid (19.5 g). This liquid was poured on a glass plate and heated at 00 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 220 microns. The polymer electrolyte was substantially uniformly mixed together as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the high molecular electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Performance of polymer electrolyte membrane The measurement was carried out in the same manner as in Example I 1 (3) to (5). As a result, the proton conductivity obtained by the above (1) was 0.090 S/cm, which was substantially the same as the proton conductivity (0.085 S/cm) of the NAFION®7 film. In addition, the fuel crossover is 21 times (25 nm/cm-min) after the NAFION membrane 1 ]7, so the fuel cross-inhibition effect is large. The antifreeze water rate is 82% and the antifreeze water content is 49%. (4) Preparation and evaluation of membrane electrode assembly 100 1342637 A polymer electrolyte membrane as described above (2) was used, and a membrane electrode assembly (MEA) and a fuel cell were prepared according to the method of Example i (4), and Evaluate. As a result, the MEA using the polymer electrolyte membrane of the above (2) was superior to the MEA (Comparative Example) using the NAFION 1 membrane, that is, the output (mW/cm2). It is 2.1 times, and it is 3.0 times the energy capacity (Wh). Example 34 (1) Preparation of polymer electrolyte solution The proton conductive polymer obtained in Example 16 (1) was made into a 20 wt% solution of N,N-dimethyletheneamine. This solution (1 g) was mixed with a bisphenol A type epoxy resin "EPICOAT 827" (0.5 g) manufactured by SHELLEPOXY Co., Ltd., and sufficiently stirred. (2) Preparation of the electrode After the carbon fiber cloth substrate was subjected to hydrophobic treatment with a 22% polytetrafluoroethylene (PTFE) suspension, a carbon black dispersion containing 20% of PTFE was applied and fired to prepare an electrode. Substrate. An anode catalyst coating liquid containing a platinum-ruthenium-supporting carbon and a solution of the above (1) is applied to the electrode substrate, dried to prepare an anode, and coated with Pt-supporting carbon as described above ( The cathode catalyst coating solution of the solution of 1) is dried to obtain a cathode. (3) Preparation of Membrane Electrode Complex The polymer electrolyte membrane obtained in Example 6 (2) was subjected to heating by sandwiching the anode and the cathode prepared as described in (2) above. Stamping to produce a membrane electrode assembly (MEA). 101 1342637 (4) Evaluation of Membrane Electrode Complex Using the EA of (3) as described above to prepare a fuel cell, and evaluating it, the result obtained by using the MEA as described above (3) is better than using N AFIΟN The Μ EA (Comparative Example 1) of 1 1 7 has superior characteristics, that is, the output (m W / c m2) E is 1.8 times that of the energy capacity (wh) is 2.7 times. Comparative Example 4 (1) Preparation of Polymer Electrolyte Membrane According to the method of Example 1 of Japanese Patent Laid-Open Publication No. 2 0 0 - 5 0 4 6 3 6 to prepare divinylbenzene crosslinked sulfonated polystyrene and Composite film of polyvinylidene fluoride The polymer electrolyte was observed by an optical microscope according to the Μ 2 method as described above, and was not mixed. (2) Properties of polymer electrolyte membrane The measurement was carried out by the methods of Examples 3 (3) to (5). The obtained result is that the proton conductivity obtained by the above (1) is 〇〇9 〇 S/cm, which is substantially the same level as the proton conductivity (0.085 s/cm) of the NAFION 丨17 film. . The measurement was carried out in the same manner as in Example 1] (3) to (5). The result obtained was that the proton conductivity obtained in (I) above was 〇 9 〇 S/cm, which was approximately the same as the proton conductivity (0.085 s/cm) of the NAFION 117 film. In addition, the fuel crossover was 1.82 times that of the NAFION membrane (218 Nemo 102 1342637 ears/cm-min), so the fuel crossover was as high as 28% for the frozen water and 58% for the frozen water. Comparative Example 5 (1) Preparation of polymer electrolyte membrane A composite membrane of sulfonated polyphenylene ether and polyvinylidene fluoride was prepared in accordance with the method of Example 1 in the specification of U.S. Patent No. 6,103,414. The polymer electrolyte was observed by an optical microscope according to the Μ 2 method as described above, and was not mixed. Further, the polymer electrolyte was judged by the M3 method as described above, and as a result, it did not contain a crosslinked polymer. (2) Properties of polymer electrolyte membrane The measurement was carried out in the same manner as in Example 1 1 (3) to (5). The result obtained was that the proton conductivity prepared in (1) above was 0.10 S/cm, which exceeded the proton conductivity (0.085 S/cm) of the NAFION 117 film. In addition, the fuel crossover is 1.7 times (205 nm/min-min) of the NAFION film 1 17, so the fuel cross is large. The antifreeze water rate is 36% and the antifreeze water content is 54%. Example 3 5 (1) Preparation of proton conductive polymer

(T2) 103 1342637 using potassium carbonate 35 g, 4,4'-(hexafluoroisopropylidene) diphenol [4,4'-34 g, 4,4-(9^芴-9- citronin) 38 g of biscresol red and 44 g of 4,4-difluorobenzophenone were polymerized in N-methylpredolones (NMP) at 160 UC. After the water was taken out, it was refined by applying an excess amount of methanol to reprecipitate, whereby the polymer represented by the formula (T2) as described above was quantitatively obtained. Then, after dissolving the above-mentioned polymer in chloroform at room temperature under a nitrogen atmosphere, 14 ml of chlorosulfonic acid was slowly added dropwise under vigorous stirring, and the reaction was carried out for 5 minutes. The white precipitate was filtered and pulverized. After washing thoroughly with water, it was dried to obtain a proton conductive polymer of interest. The sulfonic acid group density of the resulting proton conductive polymer was 2.3 mmol/g via the elemental analysis. (2) Preparation of polymer electrolyte membrane The proton conductive polymer obtained by the above U) was made into a 20 wt% solution of hydrazine, hydrazine-dimethylacetamide. This solution (10 g) and an epoxy resin "BPEF-G" (0.5 g) made by Osaka Gas Chemical Co., Ltd. were mixed and sufficiently stirred. This solution was poured on a glass plate and heated at 1 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 240 microns. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Performance of polymer electrolyte membrane

The measurement was carried out in the same manner as in Example 1 1 (3) to (5). As a result, the proton conductivity obtained in the above (1) was 0.085 S/cni, which was the same as the proton conductivity (〇.085 S/cm) of the NAF10N 104 !342637 Π7 film. In addition to λ, the fuel parent fork is NA.2 times (25 nm/min-min) of the NAFION film 117, so the fuel cross-inhibition effect is large. The antifreeze water rate is 8 8 % ‘the antifreeze water content is 52 %, so the ratio of antifreeze water is very large. Example 36 (1) Hydrolysis of decane compound 1 Μ hydrochloric acid (0.68 g) was added to 1,6-bis(trimethoxydecyl) hexane (ία克) manufactured by Gelest at 0 ° C, and Stirring was carried out for 30 minutes at room temperature to obtain a colorless, transparent hydrolyzate. (2) Preparation of polymer electrolyte membrane The proton conductive polymer obtained in Example 35 (1) was made into a 20 wt% solution of N,N-dimethylacetamide. This solution (I gram) and the hydrolyzate (1 gram) as described above (1) were mixed. This solution was poured on a glass plate and heated at 100 ° C for 3 hours to prepare a polymer electrolyte membrane. The film thickness was 240 microns. The polymer electrolyte was substantially uniformly mixed as a result of observation by an optical microscope and an electron microscope according to the M2 method as described above. Further, the polymer electrolyte was judged to have a crosslinked polymer as a result of the M3 method as described above. (3) Properties of polymer electrolyte membranes were measured by the methods of Examples 3 (3) to (5). As a result, the proton conductivity of the polymer electrolyte membrane obtained in the above (1) was 0.083 S/cm, which was substantially the same as the proton conductivity (0.085 S/cm) of the NAFION 117 membrane. 105 1342637 In addition, the fuel crossover is 32 times (38 NM/cm-min) of the enamel film, so the fuel cross-inhibition effect is large. The antifreeze water rate is 81% and the antifreeze water content is 47%, so the ratio of antifreeze water is very large. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polymer electrolyte which can coexist with high proton conductivity and low fuel. Further, the polymer electrolyte membrane, the membrane electrode assembly, and the polymer electrolyte fuel cell comprising the polymer electrolyte of the present invention can achieve high output and high energy density of the polymer electrolyte fuel cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic perspective view of a polymer electrolyte of the present invention. Fig. 2 is a perspective view showing a side-by-side configuration of a polymer electrolyte of the present invention. Fig. 3 is a schematic cross-sectional view showing a part of a process for constructing a fuel cell using a parallel electrolyte of the polymer electrolyte of the present invention. Fig. 4 is a schematic cross-sectional view of a cell cell for measuring the fuel crossover of the polymer electrolyte membrane. Brief Description of Component Symbols 1: Porous portion 2: Non-porous portion 4: Membrane conductive portion 5: Membrane penetrating electron conducting portion 6: Proton conducting portion 106 1342637 7 : Electrode 8 : Sample (Polymer electrolyte membrane) 9 ·. Rubber breeze 1 0 '· Stirrer 1 1 : Pure water 1 2 : Aqueous methanol solution 107

Claims (1)

1342637 Γ-jf "一-吃告本第921 1 7202 "Polymer electrolyte and polymer electrolyte membrane, membrane electrode composite and polymer electrolyte fuel cell using it" patent case (amended on April 8, 2010 Pick up, apply for a patent range 1. A polymer electrolyte, which is a mixture of a proton conductive polymer (A) and a different smelling molecule (B) (A), wherein the proton conductive polymer (A) a non-total gas proton conducting polymer having at least one anionic group selected from the group consisting of a sulfonic acid group, a sulfonium iodide group, a sulfate group, a phosphonic acid group, a pity acid group, and a fumaric acid group, and a polymer (B) at least one selected from the group consisting of a radical polymerizable polymer, an epoxy polymer, a melamine polymer, a phenol resin polymer, a urethane polymer, a urea polymer, and a polyorganic sand. The cross-linked polymer of the oxygen plant, the proton conductive polymer (A) is substantially uniformly mixed with the cross-linked polymer (B), and the polymer electrolyte has the antifreeze rate of the mathematical formula (S1) shown below 40% by weight to " 100% by weight, (freezing water rate ) = (anti-freeze water) / (low melting point water + antifreeze water) X 100 (%) ... (S1). 2. The polymer electrolyte according to claim 1, wherein the ratio of the weight of the antifreeze in the polymer electrolyte represented by the formula (S2) is 20% to the dry weight of the polymer electrolyte. 200%, (freeze water content) = (antifreeze amount in polymer electrolyte) / (polymer electrolyte dry weight) X 100 (%) ... (S2). 3. The polymer electrolyte according to claim 1, wherein the non-perfluoro-type proton conductive polymer is a proton conductive ruthenium 42637 polymer having a polar group in the main chain. The polymer electrolyte according to claim 3, wherein in the proton conductive polymer, the polarity is based on at least one selected from the group consisting of a sulfonyl group, an oxy group, a thio group, a carbonyl 'phosphine oxide group, a phosphate group, and an ester. The group consists of a sulfhydryl group, a quinone imine group and a phosphazene group. The polymer electrolyte according to claim 3, wherein the proton conductive polymer is at least one aromatic polymer selected from the group consisting of repeating units represented by the following formula (P1): -Z1 - Y1 --Z2-Y2--(Ρ1) *3 b wherein z^z2 represents an organic group containing an aromatic ring, each of which may also represent two or more groups; Y1 represents an electron attracting group; Y2 represents 0 or S; b each independently represents an integer of 0 to 2, but a and b are not simultaneously 0 〇6·-type polymer electrolyte membranes, which are polymer electrolytes according to any one of claims 1 to 5. Made into. A membrane electrode assembly obtained by a polymer electrolyte or a polymer electrolyte membrane according to any one of claims 1 to 6. A polymer electrolyte fuel cell comprising a polymer electrolyte or a polymer electrolyte membrane according to any one of claims 1 to 7. 9. The polymer electrolyte fuel cell of claim 8, wherein the fuel is selected from the group consisting of an alcohol selected from the group consisting of carbon atoms 1 to 3, dimethyl ether, and 1342637, and at least one of the mixture with water is used as a fuel. Direct fuel cell. 342637 -1 . Announcement book, drawing 201 Figure 1 1342637 2 1342637 A 5 Figure 3 1342637 Figure 4 4