WO2006126313A1

WO2006126313A1 - Fuel cell system

Info

Publication number: WO2006126313A1
Application number: PCT/JP2006/302548
Authority: WO
Inventors: Mitsuru Nozue
Original assignee: Kurita Water Industries Ltd.
Priority date: 2005-05-24
Filing date: 2006-02-14
Publication date: 2006-11-30
Also published as: JP2006331751A; TWI373878B; TW200642155A

Abstract

A fuel cell system where only a fuel composition is placed in a cartridge to enable fuel for fuel cells to be safely carried, where the fuel can be easily supplied to the fuel cells, and which is thin to enable it to be installed in various apparatuses. The fuel cell system (1) has a plate-like frame body (2) having square installation openings (3) formed in it, fuel cells (4) individually installed on the underside of the installation openings (3) of the frame body (2), and thin plate-like fuel cartridges (5) with a rectangular shape, received in the installation openings (3). A fuel cartridge (5) is of the shape and size exactly fitting in an installation opening (3), and a water discharge member (6) is placed on the underside of the fuel cartridge (5). A lid body (10) as a pressing member is installed on the upper side of the frame body (2).

Description

Specification

Fuel cell system

Technical field

[0001] The present invention relates to a fuel cell system.

Background art

[0002] A solid polymer electrolyte fuel cell is formed by using a solid electrolyte membrane such as a perfluorosulfonic acid membrane as an electrolyte, and a fuel electrode and an oxidant electrode are joined to both surfaces of the membrane, and hydrogen or It is a device that generates oxygen by electrochemical reaction by supplying oxygen to methanol and power sword. The electrochemical reaction that occurs at each electrode is as follows:

CH OH + H 0 → 6H + + CO + 6e "'· · [1]

3 2 2

And in the power sword,

3/20 + 6H ⁺ + 6e "→ 3H O---[2]

twenty two

It is. In order to cause this reaction, both electrodes are composed of a mixture of fine carbon particles carrying a catalyst material and a solid polymer electrolyte.

In such a solid polymer electrolyte fuel cell, when methanol is used as the fuel, the methanol supplied to the anode reaches the catalyst through the pores in the electrode, and the methanol is decomposed by the catalyst. Then, electrons and hydrogen ions are generated by the reaction of the above reaction formula [1]. The hydrogen ions reach the cathode through the electrolyte in the anode and the solid electrolyte membrane between the electrodes, react with oxygen supplied to the force sword and electrons flowing from the external circuit, as shown in the above reaction formula [2]. Produces water. On the other hand, electrons released from methanol are led to the external circuit through the catalyst carrier in the anode, and flow into the force sword from the external circuit. As a result, in the external circuit, electrons flow from the anode to the force sword and power is extracted.

[0004] In recent years, direct methanol fuel cells using methanol as a fuel are likely to be applicable as portable small fuel cells. In recent years, development is actively underway as next-generation secondary batteries for portable computers and mobile phones. It's becoming.

[0005] However, the fuel of the direct methanol fuel cell uses methanol as a liquid. As a result, there are many handling problems that are very dangerous. As a method for safely storing such fuel, a method in which the fuel is a molecular compound (see Patent Document 1), a method in which the fuel is absorbed into a polymer and gelled (see Patent Document 2), or a fuel that contains a large amount of fuel. A method of blending with a fatty acid ester of a monohydric alcohol (see Patent Document 3) has been reported. In addition, as a method for releasing fuel cell fuel from those fuel cell fuels having a stable composition, a method in which water is discharged through the fuel composition has been reported.

Patent Document 1: International Publication No. 2004Z000857 Pamphlet

Patent Document 2: JP 2004-127659 A

Patent Document 3: Japanese Patent Application Laid-Open No. 8-231970

Disclosure of the invention

Problems to be solved by the invention

[0006] However, in the conventional fuel discharge device, the water passing through the container containing the fuel composition for the fuel cell exists as a liquid, and the water leaks. There is a risk of doing it.

[0007] On the other hand, direct methanol fuel cells are difficult to obtain a large voltage with a single fuel battery cell due to operational characteristics, and thus it is necessary to use a plurality of direct methanol fuel cells connected in series. There is a problem that there is a limit to the shape that can be installed in a device for portable use.

[0008] The present invention aims to solve these problems, and by using only the fuel composition as a cartridge, the fuel for the fuel cell can be safely carried and easily supplied to the fuel cell. It aims at providing the fuel cell system which can supply. Another object of the present invention is to provide a fuel cell system that is thin and can be installed in various devices.

Means for solving the problem

[0009] The fuel cell system of the present invention includes a frame in which a plurality of fuel battery cells are installed in a mounting portion arranged in a planar direction, and a fuel cartridge that can be detachably accommodated in the mounting portion of the frame. A water discharge member is provided between the fuel cartridge and the fuel cell, and the fuel cell is provided so that a fuel electrode is on the water discharge member side. (Invention 1) As a result, the fuel cells are arranged in the plane direction. Therefore, even if a large number of fuel cells are arranged according to the desired voltage, the thickness of the fuel cell system can be minimized, greatly increasing the degree of freedom of installation in various devices. Can be improved. In addition, the liquid fuel component can be carried and stored by solidifying the liquid fuel component. Further, when the fuel cell is in operation, the cartridge is accommodated so that the cartridge presses the water discharge member to release the liquid fuel component. In addition, fuel can be supplied to the fuel electrode of the fuel cell to generate electricity.

[0010] In particular, it is preferable to include a pressing member that presses the fuel cartridge housed in the attachment portion of the frame toward the water release member (Invention 2). As a result, the fuel cartridge is pressed against the water discharge member by the pressing member, the liquid fuel component is discharged, and the fuel is supplied to the fuel electrode of the fuel cell, thereby generating electric power.

[0011] According to the fuel cell system of the present invention having the above-described configuration, the liquid component can be absent in the fuel cartridge (Invention 3). As the liquid fuel component, one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals can be used (Invention 4).

[0012] The fuel cell system of the present invention is characterized in that the fuel composition includes a molecular compound of a liquid fuel component and an opposite compound (Invention 5). Molecular compound power of the fuel composition A clathrate compound formed from the fuel for a fuel cell and a host compound (Invention 6), wherein the host compound is composed of an organic compound, an inorganic compound, and an organic'inorganic composite compound One or more selected (Invention 7). On the other hand, the host compound is one or more selected from the group power consisting of monomolecular, polymolecular and polymeric host compounds (Invention 8). Further, as the fuel composition, one containing a fatty acid ester of a polyhydric alcohol and a fuel for a fuel cell can be used (Invention 9).

The invention's effect

[0013] Since the fuel cell system of the present invention has the fuel cells arranged in a plane direction, the thickness of the fuel cell system can be minimized even when a plurality of fuel cells are used according to the desired voltage. The degree of freedom of installation in various devices can be greatly improved. In addition, a fuel composition in which a liquid fuel component is solidified is put in a case to form a fuel cartridge, and this fuel cartridge is detachable, so that the liquid fuel component is solidified and held. In addition, when the fuel cell is in operation, the cartridge is accommodated so that the cartridge is pressed against the water discharge member, thereby releasing the liquid fuel component and supplying the fuel electrode to the fuel electrode of the fuel cell. Fuel is supplied and power can be generated.

[0014] Also, by setting the maximum possible number of fuel cells in the frame to be large, the number of fuel cells to be provided is determined according to the desired voltage, so that different voltages can be set. If it is possible to respond freely to various devices, there is also an effect.

Brief Description of Drawings

FIG. 1 is an exploded perspective view schematically showing a fuel cell system according to an embodiment of the present invention.

FIG. 2 is a longitudinal sectional view of a fuel cell system according to one embodiment of the present invention. Explanation of symbols

[0016] 1 ... Fuel cell system

2 ... Frame

3 ... Mounting port (mounting part)

4 ... Fuel cell

5 ... Fuel cartridge

6… Water release member

7 ... Fuel electrode

10 ··· Lid (Pressing member)

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is an exploded perspective view schematically showing a fuel cell system according to an embodiment of the present invention, and FIG. 2 is a longitudinal sectional view of FIG.

1 and 2, the fuel cell system 1 according to the present embodiment includes a plate-like frame in which a total of six square attachment ports 3 are formed, two in the vertical direction and three in the horizontal direction. A body 2, six fuel cells 4 each attached to the lower side of the attachment port 3 of the frame 2, and a fuel cartridge 5 fitted into the attachment port 3 are provided. A water discharge member 6 is disposed below the fuel cartridge 5. This water discharge member 6 is provided in the base body which also has a sponge force. It has a structure filled with microcapsules that have power such as silicon containing water.

On the other hand, the fuel cell 3 includes a fuel electrode 7, an electrolyte membrane 8, and an air electrode 9, and the fuel electrode 7 is in contact with the water release member 6. A thin plate-like lid 10 as a pressing member is attached to the upper surface of the frame 2. The lid 10 has a convex portion 11 formed downward corresponding to the mounting port 3! And not shown in the figure, and is held by the upper body that is in contact with the upper surface of the edge of the frame 2 by a stopper. It has a structure. In the fuel cell system 1, the fuel cartridge 5 is filled with a methanol clathrate compound in which methanol, which is a liquid fuel component, is solidified in a water-permeable casing only on the lower surface.

[0020] In the fuel cell system 1 of the present embodiment as described above, the water discharge member 6 is preliminarily installed on the fuel cell 4 of the attachment port 3, and the attachment port 3 is provided from there. The fuel cartridge 5 is fitted, and the convex portion 11 of the lid body 10 is pushed into the attachment port 3 from above, and the lid body 10 is covered and fixed by a stopper (not shown). As a result, the fuel cartridge 5 in the attachment port 3 is pushed downward, and the water discharge member 6 is compressed. Then, the microcapsules in the water discharge member 6 are crushed, so that water is oozed out, water enters the fuel cartridge 5, and comes into contact with the methanol clathrate compound in the fuel cartridge 5. The fuel for the fuel cell made of methanol aqueous solution is generated.

The aqueous methanol solution that is the fuel for the fuel cell is supplied to the fuel electrode 7 by the pressure at which the water release member 6 is pressed against the fuel electrode 7 of the fuel cell 4, and hydrogen ions are generated by the catalyst component of the fuel electrode 7. Converted to (H +), carbon dioxide (CO) and electrons (e_).

2

Hydrogen ions (H +) are introduced into the air electrode 9 by passing through the electrolyte membrane 8 from an external circuit (not shown) by electrical connection. On the other hand, in the air electrode 9, air or oxygen (O 2)

2 is supplied, and this oxygen (O) and hydrogen ions (H +) and electrons (e_) generated at the anode 7

2

Reaction produces water.

In such a reaction, electrons flow from the fuel electrode 7 toward the air electrode 9 and electric power is taken out. When electric power is required again, the lid 10 is opened and the water discharge member 6 and the fuel cartridge 5 are replaced. On the other hand, when stopping the supply of power, the supply of the methanol aqueous solution is stopped by releasing the stopper of the lid 10 and restoring the water discharge member 6 by the elastic force of the sponge that is the base of the water discharge member 6. Yeah. At this time water discharge Since extra water is absorbed when the sponge as the base material is restored by the member 6, there is also an advantage that no water leakage occurs.

As described above, according to the present embodiment, the fuel cartridge 5 serving as the fuel does not contain water, and thus can be safely stored and transported. By simply setting the fuel cartridge 5 and closing the lid 10, the methanol aqueous solution as fuel can be easily supplied to the fuel cell 4. Moreover, normally, when six fuel cells 4 and fuel cartridges 5 are stacked, the thickness becomes very thick, and the installation location is very limited. The fuel cell system 1 according to the present embodiment has a thickness of approximately fuel. The thickness of the battery cell 4, fuel cartridge 5 and lid 10 is very thin, and it can be mounted on the bottom and back of the casing of various devices. It does not impair the out-of-comparation of various devices with a wide range of applications. In the present embodiment, the force of attaching six fuel cells 4 to each of the six attachment ports 3 The fuel cell 4 according to the voltage of the fuel cell 4 and the desired voltage. By limiting the number of attachments, a fuel cell system with a desired voltage can be obtained.

In the present embodiment as described above, examples of the fuel (or liquid fuel component) for the fuel cell include hydrogen, alcohols, ethers, hydrocarbons, and acetals. However, the present invention is not limited to these as long as it can be used as a fuel for a polymer electrolyte fuel cell. Specifically, hydrogen; alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; ethers such as dimethyl ether, methyl ethyl ether, and jetyl ether; hydrocarbons such as propane and butane; Examples include acetals such as dimethoxymethane and trimethoxymethane, but are not limited thereto, and these may be used alone or in combination of two or more.

[0025] The fuel cell is preferably a polymer electrolyte fuel cell, and among them, a power suitable for a direct methanol fuel cell is not limited thereto.

[0026] The fuel cell fuel may be a fuel cell fuel composition that is solid or gelled as a molecular compound or polymer of the fuel cell fuel.

[0027] The molecular compound includes two or more kinds of compounds that can exist stably alone. It is a compound that is bonded by relatively weak interactions other than covalent bonds, such as hydrogen bonds and van der Waals forces. This molecular compound includes hydrates, solvates, adducts, and inclusion compounds. included. Such a molecular compound can be formed by a contact reaction between a compound forming the molecular compound and a fuel for a fuel cell. According to such a molecular compound, since the fuel for the fuel cell can be changed to a solid compound, the fuel for the fuel cell can be stably stored with a relatively light weight.

[0028] Examples of the molecular compound include clathrate compounds in which the fuel for the fuel cell is clathrated by the contact reaction between the host compound and the fuel for the fuel cell.

[0029] Among the molecular compounds, examples of the host compound that forms the clathrate clathrate fuel cell fuel include organic compounds, inorganic compounds, and organic / inorganic composite compounds, and organic compounds. Examples thereof include monomolecular, multimolecular, and polymeric host compounds.

[0030] Examples of monomolecular host compounds include cyclodextrins, crown ethers, cryptands, cyclophanes, azacyclophanes, calixarenes, cyclotributylatrilens, spherands, and cyclic oligopeptides. Can be mentioned. Examples of the multi-molecular host compounds include ureas, thioureas, deoxycholic acids, cholic acids, perhydrotriphenylenes, tri-o-thymotides, bianthryls, spirobifluorenes, cyclophosphazenes. , Monoalcohols, diols, hydroxybenzophenols, acetylene alcohols, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenol methanol Carboxylic acids amides, thioamides, bixanthenes, carboxylic acids, imidazoles, hydroquinones and the like. Examples of the high molecular weight host compound include celluloses, starches, chitins, chitosans, polybutyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2-tetrakisphenol as a core, and polyethylene glycol arm type polymers having a, a, α ′, α, monotetrakisphenylxylene as a core. In addition, organophosphorus compounds, organocatheter compounds, and the like are also included.

[0031] Examples of inorganic host compounds include titanium oxide, graphite, alumina, and transition gold. Examples include the genus dichalcogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, and porous glass.

[0032] Furthermore, some organometallic compounds exhibit properties as host compounds. Examples of organometallic compounds include organoaluminum compounds, organotitanium compounds, organoboron compounds, organozinc compounds, and organoindium compounds. , Organic gallium compounds, organic tellurium compounds, organic tin compounds, organic zirconium compounds, and organic magnesium compounds. In addition, it is possible to use a metal salt or organic metal complex of an organic carboxylic acid as a host compound.

[0033] Of these host compounds, multi-molecular host compounds whose inclusion ability is not easily influenced by the molecular size of the guest compound are more effective.

[0034] Specific examples of the multimolecular host compound include urea, 1, 1, 6, 6-tetraphenylhexa-2, 4 diyne-1, 6 diol, 1, 1-bis (2, 4 Dimethylphenol) — 2—Propine 1 ol, 1, 1, 4, 4-Tetraphenolic leu 2 Butyne 1,4-diol, 1, 1, 6, 6—Tetrakis (2, 4 Dimethinolevenore) 2, 4 Xadiyne 1,6 diol 9,10 diphenol 9,10 dihydroanthracene 9,10 diol 9,10 bis (4-methylphenol) 9,10 dihydroanthracene 9,10 diol 1, 1, 2, 2-tetraphenylethane 1,2 diol, 4-methoxyphenol, 2,4 dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahi Droxybenzophenone, 1,1-bis (4hydroxyphenyl) cyclohexane, 4,4'-sulfo-rubi Sufenol, 2, 2, monomethylene bis (4-methyl 6-t-butyl phenol), 4, 4, ethylidene bisphenol, 4, 4, thiobis (3-methyl-6-t-butyl phenol), 1, 1 , 3 Tris (2-methyl-4hydroxy-5-t-butylphenol) butane, 1, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane, 1, 1, 2, 2-tetrax ( 4-hydroxyphenyl) ethylene, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, a , a, α ', α, 1 tetrakis (4-hydroxyphenol) 1 ρ xylene, 3, 6, 3', 6 '-tetramethoxy 9, 9' b 9Η-xanthene, 3, 6, 3 ' 6 '—Tetracetoki 9, 9, 1B 9H-xanthene, gallic acid, methyl gallate, catechin, bis β-naphthol, a,, ', α, 1 tetraphenyl 1, 1, 1, 1 biphenyl 1, 2, 2, 1 dimethanol, Diphenic acid bis (dicyclohexylamide), fumarate bis (dicyclohexylamide), cholic acid, deoxycholic acid, 1, 1, 2, 2-tetrakis (4 carboxyphenol) ethane, 1, 1, 2, 2 —Tetrakis (3-carboxyphenol) ethane, acetylene dicarboxylic acid, 2, 4, 5 triphenylimidazole, 1, 2, 4, 5—tetraphenyl-loumidazol, 2 phenol ant port [9, 10 d] imidazole, 2— (o cyanophane) phenant mouth [9, 10—d] imidazole, 2 -— (m-sianophenol) phenol mouth [9,10—d] imidazole, 2 -— (p cyanophane- Le) The port of the fernant [9, 10—d] Imidazo , Hydroquinone, 2-t-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis (2,4-dimethylphenol) hydroquinone, etc. 1, 1-bis (4 hydroxyphenol- (I) Phenolic host compounds such as cyclohexane are preferred because they are easy to use industrially.

[0035] These host compounds may be used alone or in combination of two or more.

As long as these host compounds form a solid clathrate compound with the fuel for the fuel cell, compounds of any shape can be used.

[0036] Further, the above-mentioned organic host compound can be used as an organic / inorganic composite material supported on an inorganic porous material. In this case, examples of the porous material supporting the organic host compound include intercalation compounds such as clay minerals and montmorillonites in addition to silicas, zeolites, and activated carbons, but are not limited thereto. Absent.

[0037] As a method for producing such an organic / inorganic composite material, the above-mentioned organic host compound is dissolved in a solvent that can be dissolved, and the solution is impregnated in an inorganic porous material. Can be produced by distilling off the product by drying, drying under reduced pressure, or the like. The amount of the organic host compound supported on the inorganic porous material is not particularly limited, but is usually about 10 to 80% by mass relative to the inorganic porous material.

[0038] The inclusion compound of a fuel cell fuel using a host compound such as 1,1 bis (4 hydroxyphenol) cyclohexane described above is obtained by combining a fuel cell fuel and a host compound. It can be easily synthesized by direct contact and mixing, and the host compound can be used for fuel cells. It can also be obtained by a method of dissolving and recrystallizing the fuel by heating or the like. If the fuel for the fuel cell is a gas or liquid, it can be obtained by contacting the fuel with the host compound in a pressurized state.

[0039] The temperature at which the fuel for the fuel cell and the host compound are brought into contact with each other is not particularly limited, but is preferably from room temperature to about 100 ° C. Further, the time for contacting the fuel cell fuel with the host compound is not particularly limited, but is preferably about 0.01 to 24 hours from the viewpoint of work efficiency and the like.

[0040] The fuel for the fuel cell to be brought into contact with the host compound is preferably a high-purity fuel. However, when a host compound having the selective inclusion ability of the fuel for the fuel cell is used. It may be a liquid mixture of fuel for fuel cells and other components.

[0041] The clathrate compound thus obtained varies depending on the type of the host compound, the contact condition between the host compound and the fuel for the fuel cell, etc. An inclusion compound in which 0.1 to 10 moles of fuel molecules for a fuel cell are included.

[0042] The clathrate compound thus obtained can stably store fuel for fuel cells over a long period of time in a normal temperature / normal pressure environment. However, this inclusion compound is lightweight, easy to handle, and solid, so it can be easily stored in glass, metal, plastic, etc. containers, and there is a problem of liquid leakage. It will be resolved. In addition, normally liquid fuel becomes solid due to the inclusions, which makes it possible to avoid the properties of deleterious substances and dangerous goods. Furthermore, the chemical reactivity of the fuel for fuel cells is reduced, and for example, the corrosiveness to metals can be alleviated.

[0043] The fuel composition contains 20 to LOO% by mass of a structural unit having a carboxyl group and Z or sulfonic acid group in the molecule based on the polymer (1), and the carboxyl group and / or the A fuel composition for a fuel cell comprising a cross-linked product (A) of the polymer (1) in which 30 to 100 mol% of protons of a sulfonic acid group are substituted with an onium cation and a fuel for a fuel cell can also be used. . In order to absorb and gel a fuel for a fuel cell (hereinafter simply referred to as fuel), it contains a predetermined amount of a structural unit having a carboxyl group and Z or sulfonic acid group in the molecule, and the carboxyl group and Z or sulfonic acid. The cross-linked product (A) of the polymer (1) in which the proton of the group is substituted with a predetermined amount of an organic cation is used. [0044] The structural unit (a) having a carboxyl group and a Z or sulfonic acid group constituting the cross-linked product (A) includes a monomer having a carboxyl group [for example, (meth) acrylic acid, etaatalic acid, crotonic acid, Sorbic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, and anhydrides thereof]; monomers having a sulfonic acid group [for example, aliphatic vinyl sulfonic acid [bululsulfonic acid, allylic sulfonic acid, butyltoluenesulfone] Acid, styrene sulfonic acid, etc.], (meth) acrylate sulfonic acid [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, etc.) and (meth) acrylamide type sulfonic acid [acrylamide-2-methylpropane sulfone]. Acid or the like]], etc., and one or more of these should be the structural unit in the polymer (1) Can do. Preferably, it is a structural unit having a carboxyl group having 3 to 30 carbon atoms and Z or a sulfonic acid group.

[0045] As a method for obtaining a polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and Z or a sulfonic acid group in the molecule, in addition to a method of polymerizing the monomer (a) in a predetermined amount. For example, a monomer that can be easily changed to a carboxyl group or a sulfonic group, such as an esterified product or an amidated product of the carboxyl group or sulfonic acid group-containing monomer, is polymerized, and a method such as hydrolysis is used. Quantitative carboxyl group or sulfonic acid group-containing structural unit introduced into the molecule, carboxyl group typified by carboxymethylcellulose, sulfonic acid group-containing polysaccharide polymer, and the polysaccharide polymer and other monomers A polymer containing a predetermined amount of structural units having a carboxyl group and Z or a sulfonic acid group. If even the a is obtained it is not particularly limited.

[0046] The content of the polymer (1) of the constituent unit having a carboxyl group and Z or sulfonic acid group, usually. 20 to: LOO mass ^_0/0, preferably 40 to: LOO mass ^_0/0, more preferably Is 60: LO 0% by mass. If the content is less than 20% by mass, even if the protons of the carboxyl group or sulfonic acid group are replaced with a cation cation described later, the amount of absorption of the target liquid fuel is reduced, or the liquid fuel is used in a small amount. There are times when you can't do it.

[0047] Examples of the copolymerizable monomer (b) that forms a structural unit other than the structural unit having a carboxyl group and Z or a sulfonic acid group include, for example, an alkyl (meth) acrylate (C1-30) ester. [Methyl (meth) acrylate, Ethyl (meth) acrylate, (Meth) Atari Propyl sulfate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate -L, octyl alcohol (meth) acrylate, cyclohexyl (meth) acrylate, etc.

] (Meth) acrylic acid oxyalkyl (carbon number 1 to 4) class [(meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic acid mono (polyethylene glycol) ester (PEG number average molecular weight: 100-4000), (meth) acrylic acid mono (polypropylene glycol) ester (PPG number average molecular weight: 100-4000), (meth) acrylic acid monomethoxypolyethylene glycol (PEG number average molecular weight: 100-4000), (meth) Monomethoxypropylene glycol acrylate (PPG number average molecular weight: 100 to 4000), etc.]; (meth) acrylamides [(meth) acrylamide, (di) methyl (meth) acrylamide, (di) ethyl (meth) arylamide, (Di) propyl (meth) acrylamide, etc.]; allylic ethers [methyl allylate, ethinorealinore Tenole, propinorealinoreethenole, glyceronomonoarinoreether, trimethylolpropane triallyl ether, pentaerythritol monoallyl ether, etc.] α-olefins with 4 to 20 carbon atoms [isobutylene, 1 to 1] Xene, 1-Otaten, Iso-Otaten, 1-Nonene, 1-Decene, 1-Dodecene, etc.]; Aromatic beryl compounds having 8 to 20 carbon atoms [Styrene, t-butylstyrene, Octylstyrene, etc.]; Compound [N-Bulucacetamide, caproic acid bull, lauric acid bull, stearic acid vinyl, etc.]; Amino group-containing monomer [dialkyl (alkyl carbon number: 1 to 5) aminoethyl (meth) atari RATE, META (ATALILOYL) OXHETIL TRIALKY (ALKYL CARBON: 1-5) Ammonium chloride, bromide or sulfur Etc.] and the alkali metal of the monomer having a carboxyl group or a sulfonic acid group

Examples thereof include salts, primary to tertiary amine salts, and alkanolamine salts. One or more of these monomers (b) may be copolymerized with the monomer (a) within a predetermined range (less than 80% of the polymer constituent units) if necessary!

[0048] Examples of the monomer (b) include viewpoints such as the polymerizability of the monomer and the stability of the produced polymer, (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, aryl ethers, _a- olefins And aromatic vinyl compounds are preferred.

[0049] SP value (Solubility parameter) of solvent subject to absorption and gelation of liquid fuel If the monomer (b) whose difference between the SP value of the solvent and the SP value of the monomer (b) is 5 or less is selected, the amount of absorption and the Gelich force is likely to increase. It is more preferable that the difference between the SP value and the SP value of the monomer (b) is 3 or less.

[0050] The proton of the carboxyl group and Z or sulfonic acid group O - it is desirable to 30-100 mole ^_0/0 substituted with Umukachion. As the cation cation, the quaternary ammonium cation (1), the tertiary sulfo cation (11), the quaternary phospho cation (111), and the tertiary oxo cation (IV) group of cations One or more selected from the above can be used. Examples of the quaternary ammonia cation (I) include the following (1-1) to (1-11).

[0051] (1-1) Aliphatic quaternary ammonia having 4 to 30 or more carbon atoms having an alkyl and Z or alkenyl group; tetramethyl ammonium, ethyl trimethyl ammonium Hum, jetyl dimethyl ammonium, triethyl methyl ammonium, tetraethyl ammonium, trimethyl propyl ammonium, tetrapropyl ammonium, butyl trimethyl ammonium, tetraptyl ammonium- Um etc.

[0052] (1-2) Aromatic quaternary ammonia having 6 to 30 or more carbon atoms; trimethylphenol, dimethylethylphenol, triethylylamine, triethylylamine Mu etc.

[0053] (1-3) Cycloaliphatic quaternary ammonium having 3 to 30 or more carbon atoms; N, N-dimethylpyrrolidinium, Nethylyl N-methylpyrrolidinium, N, N Dimethyl morpholine, N, N Jetyl morpholium, N, N dimethyl piperidium, N, N dimethyl biverium, etc.

[0054] (1-4) imidazolium having 3 to 30 or more carbon atoms; 1, 2, 3 trimethylimidazolium, 1, 2, 3, 4-tetramethylimidazolium, 1, 3, 4 Trimethyl-2 ethylimidazolium, 1,2 dimethyl-3, 4 Jetylimidazolium, 1,2 dimethyl-3 ethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2, 3, 4—Tetratilimidazolium, 1, 2, 3 Triethylimidazolium, 4 Cyan—1, 2, 3 —Trimethylimidazolium, 2 Cyanmethyl 1, 3 Dimethylimidazole, 4--acetylyl 1, 2, 3 Trimethylimidazole, 4-methylcarboxymethyl 1, 2, 3 Trimethylimidazole, 4 Formyl—1, 2, 3 Trimethylimidazole, 3 —Hydroxyethyl 1,2,3 Trimethylimidazole, 3 Hydroxyethyl 1,1,2 Dimethyl Imidazolium etc.

[0055] (1-5) imidazolium having 3 to 30 or more carbon atoms; 1,3 dimethyl imidazolium,

1-Ethinole 1-Methinoreido imidazolium, 1-Metinore 1 ethino-reyl imidazolium, 1, 2, 3, 4-tetramethylimidazole, 1, 2 dimethyl 3-ethyl imidazolium, 1 1-Methinoremidazolium, 1-Methinore 1 ethenoremidazolium, 1, 2, 3 Trier Chile imidazolium, 1, 2, 3, 4-tetraethyl imidazolium, 1, 3 Dimethyl—2 Fe-imidazolium, 1, 3 Dimethyl-1-benzylimidazole, 4 Cyan 1, 2

, 3 Trimethylimidazole, 3 Cyanmethyl 1,2 Dimethylimidazole, 4 Cetinolide 1, 2, 3 Trimethylimidazole, 4-Methoxy-1, 2, 3 Trimethylimidazolium, 3 Formylmethyl-1, 2 Dimethylimidazole, 2 Hydroxyethyl 1,3-Dimethylimidazole, N, N, -Dimethylbenzimidazole, N, N, Monoethylbenzimidazolium, N-Methyl-N, Ichiethyl Benzimidazolium etc.

[0056] (1-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms; 1, 3 dimethyltetrahydropyrimidinium, 1, 2, 3 trimethylenotetrahydropyrimidinium, 1 , 2, 3, 4-tetramethyltetrahydropyrimidium, 8-methyl 1,8 diazabicyclo [5, 4, 0]-7 —undecseum, 5-methyl 1,5 diazabicyclo [4, 3, 0] — 5 Noneum, 3-Cyanomethyl-1, 2 Dimethyltetrahydropyrimidium, 3 Acetylmethyl-1,

2 Dimethyltetrahydropyrimidinium, 4 Methylcarboxymethyl-1,2,3 Trimethyltetrahydropyrimidinium, 3-Methoxymethyl-1,2 Dimethyltetrahydropyrimidinium, 4 Hydroxymethyl-1,3 Dimethyl Tetrahydropyrimidi-um etc.

[0057] (1-7) dihydropyrimidium having 4 to 30 or more carbon atoms; 1,3 dimethyl-2,4 or 2,6 dihydropyrimidium [these are 1,3 dimethyl-2,4 (6) Denoted as “jihido pyrimidum”, the same expression is used hereinafter. ], 1, 2, 3 Trimethyl-2,4 (6) -dihydropyrimidium, 1,2,3,4-tetramethyl-2,4 (6) -dihydropyrimididium, 1, 2, 3, 5—Tetramethinole 2, 4 (6) —Dihydropymidyureum, 8—Methinore 1,8—Diazacyclo [5, 4, 0] — 7, 9 (10) —Undecangeum, 2 Cyanmethyl-1,3 Dimethyl-2,4 (6) —Dihydropyrimidium, 3 Acetylmethyl-1, 2 Dimethyl-2,4 (6) —Dihydropyrimidium, 4-Methylcarboxymethyl-1,2,3 Trimethylol-1,4 ( 6) —Dihydropyrimidinium, 4 Honoremino 1, 2, 3 Trimethinole 1, 4 (6) —Dihydropyrimidium, 3 Hydroxyethyl 1, 2, Dimethyl 2, 4 (6) —Dihydro Pyrimidine- Um etc.

[0058] (I 8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; 2 —dimethylamino— 1, 3, 4 trimethylimidazolium, 2 jetylamino—1, 3, 4 —trimethylimidazoli 1-methyl 3,4 dimethyl imidazole, 2 dimethylamino 1,3 dimethyl imidazole, 2 dimethylamino 1,3 dimethyl imidazolium, 2 jetinoreamino 1,3 Tyrimidazolium, 1, 5, 6, 7-tetrahydro-1,2,2 dimethyl-2H-pyrimido [1, 2a] imidazole, 1,5 Dihydro-1,2,2 dimethyl-2H pyrimido [1, 2a ] Imidazole, 2 Dimethylamino 3 Methylcarboxymethyl- 1-Methylimidazolium, 2 Dimethylamino 3-Methoxymethyl-1-methylimidazolium, 2-Dimethylamino 3 Hydro Shechiru 1-methyl imidazolium - © beam, 2 Jimechiruamino one 4-hydroxymethyl-one 1, 3-dimethyl imidazolinium - © beam or the like.

[0059] (I 9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; 2—dimethylamino—1, 3, 4 trimethylimidazolium, 2 jetylamino—1, 3, 4 trimethylimidazolium, 2 Jetylamino-1, 3 Dimethyl-4-ethylimidazolium, 2 Jetylamino— 1, 3, 4 Triethylimidazolium, 2 Dimethylamino— 1, 3- Dimethinoley imidazolium, 1, 5, 6, 7—Tetrahydro 1,2 Dimethylolone 2H—imide [1, 2 a] imidazole, 1,5 dihydro-1,2 dimethyl-2H—pyrimido [1, 2a] imidazole, 2 dimethylamino-3 cyanomethyl-1-methyl imidazolium, 2 Dimethylamino 4 Methylcarboxymethyl-1,3 Dimethylimidazole, 2 Dimethylamino-3 Methoxymethyl-1-Methylimidazolium, 2-Di Chiruamino 3 Horumirumechi Lou 1-methyl imidazo Riu arm, 2 Jimechiruamino one 4-hydroxymethyl-one 1, 3 dimethyl chill imidazolium like.

[0060] (I-10) Gua having a tetrahydropyrimidi-um skeleton having 4 to 30 or more carbon atoms -Dimethyl; 2 dimethylamino-1,3,4 trimethyltetrahydropyrimidium, 2 dimethylamino-1,3,4 trimethyltetrahydropyrimididium, 2 dimethylamino-1,3-dimethyltetrahydropyrimididium, 2 Jetylamino-1,3 dimethyltetrahydropyrimidi-um, 1, 3, 4, 6, 7, 8 Hexahydro 1,2 dimethyl—2H—imide [1, 2 a] pyrimidi-um, 1, 3, 4, 6, 7, 8 Hexahydro-1,2 dimethyl-1,2H pyrimido [1,2a] pyrimidium, 2 dimethylamino-1,3 cyanomethyl 1-methyltetrahydropyrimidium, 2 dimethylamino-4 acetylyl 1,3 dimethyl Tetrahydropyrimidinium, 2 dimethylamino-4 methylcarboxymethyl-1,3 dimethyltetrahydropyrimidium, 2 dimethylamino-3-methoxymethyl-1-methyltetrahydride Ropyrimidium, 2 dimethylamino 3 hydroxyethyl 1-methyltetrahydropyrimidium, 2 dimethylamino 1 4 hydroxymethyl-1,3 dimethyltetrahydropyrimidinium, etc.

[0061] (I 11) Guadium having a dihydropyrimidi-um skeleton having 4 to 30 or more carbon atoms; 2 Dimethinoreamino-1,3,4-trimethinole 2, 4 (6) -Dihydropyrimige 1-, 3- and 4- (3) trimethyl 2,4 (6) —dihydropyrimidium, 2,3,4-triethylinole 2,4 (6) —dihydropyrimidium, 2 jetinoreamino-1 , 3 Dimethyl-2, 4 (6) —Dihydropyrimidinium, 2 Dimethylamino-1, 1-Ethanole 3, 4-Methinole 1, 4 (6) —Dihydropyrimidinium, 1, 6, 7, 8—Tetrahydro 1, 2—Dimethyl-1-2H—imide [1, 2a] pyrimidium, 1,6 Dihydro-1,2 Dimethyl-1-2H —pyrimido [1,2a] pyrimidi-um, 2 Dimethylamino-4 Siano 1, 3 Dimethyl 1, 2, 4 (6) -dihydropyrimidium, 2 dimethylamino 3 acetylmethyl -1-methyl-2,4 (6) -dihydropyrimidium, 2-dimethylamino 3-methylcarboxymethyl — 1-methyl 2,4 (6) -dihydropyrimidi-um, 2 dimethylamino 4-formyl 1,3 Dimethinole 1,4 (6) —Dihydropyrimigeum, 2 Dimethinoreamino-1,3 Honoleminole methyl 1—Methyl 2,4 (6) —Dihydropyrimidium, etc.

[0062] Examples of the tertiary sulfoyuium cation (II) include the following (II 1) to (II 3).

(II-1) Aliphatic tertiary sulfoyuum having alkyl having 1 to 30 or more carbon atoms and Z or alkenyl group; trimethylsulfum, triethylsulfum, ethyldi Methyl sulfome, jetyl methyl sulfome, etc.

[0063] (II 2) Aromatic tertiary sulfone having 6 to 30 or more carbon atoms; Fehr-dimethi nolesnorehonum, Hue-norechinoremethinoresnorehonium, Hue -Noremetino Lebenzinoles Norejo

-Um etc.

[0064] (II 3) Alicyclic tertiary sulfoyuum having 3 to 30 or more carbon atoms; methylthiolaum

, Felt thiolum, methyl thiarum, etc.

[0065] Examples of the quaternary phosphonium cation (III) include the following (III 1) to (III 3).

(III 1) Aliphatic quaternary phosphonium having 1 to 30 or more carbon atoms and Z or alkenyl groups; tetramethylphosphonium, tetraethylphosphonium, tetrapropy Norrephosphonium, Tetrabutinorephosphonium, Methyltritinorephosphonium, Methyltripropylphosphonium, Methyltributylphosphonium, Dimethyljetylphosphonium, Dimethyldibutylphosphonium, Trimethyl Ethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.

[0066] (III—2) Aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; triphenyl methino phospho- um, diphen-noresi methino phospho- um, tri-phenol leveno eno phospho -Um etc.

[0067] (III-3) Cycloaliphatic quaternary phosphorous having 3 to 30 or more carbon atoms; 1, 1-dimethyl phosphorum, 1-methinoleol 1-etinorephosphorum, 1, 1 Getinore phosphorum, 1, 1-jetyl phosphorinum, 1, 1-pentaethylene phosphorinum, etc.

[0068] Examples of the tertiary oxoyuium cation (IV) include the following (IV-1) to (IV-3).

(IV-1) Aliphatic tertiary oxoumo having an alkyl group having 1 to 30 or more carbon atoms and a Z or alkenyl group; trimethylxosium, trityloxosium, ethyldimethyloxosium, jetylmethylo Kiso-um etc.

[0069] (IV-2) Aromatic tertiary oxoyuum having 6 to 30 or more carbon atoms; ferrodimethyl oxomethyl, ferroethylmethyl oxomethyl, ferromethylbenzyl oxo -Um etc.

[0070] (IV-3) Cycloaliphatic tertiary oxoyuum having 3 to 30 or more carbon atoms; methyl oxo-raum, ferro-solum, methyl oxa-um and the like. [0071] Among these, a preferred form cation is (I), more preferred are (1-1), (I 4) and (I 5), and particularly preferred are (I 4) and (I 5). These lithium cations may be used alone or in combination of two or more.

[0072] Examples of the method for introducing an onion cation into the polymer include a method in which the protons of the carboxyl group and Z or sulfonic acid group of the polymer are substituted with the above-mentioned cation. The method for replacing the proton with the form cation is not particularly limited as long as it can be substituted with a predetermined amount of the sodium cation. For example, a hydroxide salt of the above form cation (for example, tetraethylammonium hydroxide). Side, etc.) and monomethyl carbonate salts (eg 1, 2, 3, 4-tetramethylimidazolium monomethyl carbonate, etc.) are added to the polymer containing carboxyl groups and Z or sulfonic acid groups. Can be easily replaced by dehydration, decarboxylation and demethanol. Further, it may be similarly substituted at the monomer stage.

[0073] With respect to the stage of substitution with the form cation, for example, a method in which the monomer containing the carboxyl group and Z or sulfonic acid group is substituted with the form cation and then polymerized, or the carboxyl group and Z or sulfonic group For example, a method of substituting the proton of an acid with an olum cation after preparing the polymer (1) having a carboxyl group and the proton of the carboxyl group and the Z or sulfonic acid group of the polymer (1) If it is to be replaced, V, it can be done at the shift stage! /.

[0074] The proton of the carboxyl group and Z or sulfonic acid group O - degree of substitution by Umukachion (degree of substitution) is,. 30 to: LOO mol ^_0/0, preferably 50 to: LOO mol ^_0/0, more preferably it is 70: a LOO mole ^_0/0. O - With the degree of substitution Umukachion is less than 30 mole ^_0/0, the carboxyl group of the polymer (1), sulfonic Sanmoto及Bio - dissociation Umukachion is too low, there is a case where swelling mosquito Ya Gerui匕力lower .

[0075] In the present invention, the structural unit having a carboxyl group and Z or a sulfonic acid group is quantitatively contained, and the carboxyl group and the Z or sulfonic acid group are substituted with a predetermined amount of formcatione. The polymer (1) is finally crosslinked at any stage to form a crosslinked product. The crosslinking method may be a known method, for example, the following methods [1] to [5]. [0076] [1] Cross-linking with a copolymerizable cross-linking agent;

Two or more double bonds can be copolymerized with the carboxyl group- and Z- or sulfonic acid group-containing monomer, an cation-substituted product of the monomer, and, if necessary, another monomer (b) to be copolymerized. Copolymerizable cross-linking agent [polyvalent beryl type cross-linking agent such as dibutenebenzene, (meth) acrylamide type cross-linking agent such as N, N, and methylenebisacrylamide, polyvalent allylic ether type such as pentaerythritol triallyl ether A crosslinking agent, a polyvalent (meth) acrylic acid ester type crosslinking agent such as trimethylolpropane tritalylate] and the like.

[0077] [2] Cross-linking with a reactive cross-linking agent;

Reactive cross-linking agents having two or more functional groups in the molecule that can react with carboxyl groups and Z or sulfonic acid groups, or their cation substitution products, and if necessary, functional groups of monomers to be copolymerized [4, 4, polyisocyanate type crosslinking agents such as di-methanemethane diisocyanate, polyvalent epoxy type crosslinking agents such as polyglycerol polyglycidyl ether, polyhydric alcohol type crosslinking agents such as glycerin, hexamethylenetetramine, Crosslinking using a polyvalent amine such as polyethyleneimine, an imine type crosslinking agent, a haloepoxy type crosslinking agent such as epichlorohydrin, a polyvalent metal salt type crosslinking agent such as aluminum sulfate, and the like.

[0078] [3] Crosslinking with a polymerization reactive crosslinking agent;

Copolymerizable with the carboxyl group- and Z- or sulfonic acid group-containing monomer, an cation-substituted cation of the monomer, and other monomer (b) that is optionally copolymerized, or has a double bond in the molecule. In addition, a carboxyl group and a Z or sulfonic acid group, or an cation substitution product thereof, a polymerization reactive crosslinking agent having a functional group capable of reacting with a functional group of a monomer to be copolymerized, if necessary, etc. [glycidyl metatalylate, etc. A glycidyl (meth) acrylate linking agent, an aryl epoxy linking agent such as allylic glycidyl ether, etc.].

[0079] [4] Cross-linking by irradiation;

The polymer (1) is irradiated with radiation such as ultraviolet rays, electron beams, and γ rays, and the polymer (1) is crosslinked. How to do it. [0080] [5] Crosslinking by heating;

Heating the polymer (1) to 100 ° C or higher to thermally crosslink between the molecules of the polymer (1) [crosslinking between carbons by generation of radicals by heating or crosslinking between functional groups], etc. .

[0081] Among these cross-linking methods, the preferred one varies depending on the use and form of the final product, but when considered comprehensively, [1] cross-linking with a copolymer cross-linking agent, [2] cross-linking with a reactive cross-linking agent and [

4] Cross-linking by irradiation.

[0082] Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide type crosslinking agents, aryl ether type crosslinking agents, and polyvalent (meth) acrylic acid ester type crosslinking agents, and more preferred. One is a aryl ether type cross-linking agent.

[0083] Among the reactive crosslinking agents, preferred are a polyvalent isocyanate type crosslinking agent and a polyvalent epoxy type crosslinking agent, and more preferred are a polyvalent isocyanate type having three or more functional groups in the molecule. It is a crosslinking agent or a polyvalent epoxy type crosslinking agent.

[0084] The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, 0.001 to 10% by mass is preferable with respect to all monomers. A mass% is more preferred.

[0085] When a reactive crosslinking agent is used, the amount of addition varies depending on the shape of the crosslinked body (A). In the case of producing an integrated gel containing a liquid fuel for fuel cells, 0.01 to 50% by mass is preferable.

[0086] In the present invention, a polymerization method of the carboxyl group- and Z- or sulfonic acid group-containing monomer, an cation substitution product of the monomer and, if necessary, another monomer (b) to be copolymerized is also a known method. For example, a solution polymerization method in a solvent in which each monomer and a polymer to be generated are dissolved, a bulk polymerization method in which polymerization is performed without using a solvent, an emulsion polymerization method, and the like can be exemplified. Among these, the solution polymerization method is preferable.

[0087] The organic solvent for solution polymerization can be selected as appropriate depending on the solubility of the monomers and polymers used, for example, alcohols such as methanol and ethanol; carbonates such as ethylene carbonate, propylene carbonate, and dimethyl carbonate; γ-butyrolacton , _Ε — Ratatones such as force prolatatam; Ketones such as acetone and methylethylketone; Vinegar Examples thereof include carboxylic acid esters such as acid ethyl; ethers such as tetrahydrofuran and dimethoxyethane; aromatic hydrocarbons such as toluene and xylene; and water. These solvents may be used alone or in a combination of two or more.

[0088] The polymerization concentration in the solution polymerization varies depending on the intended application, and is not particularly limited, but is preferably 1 to 80% by mass, more preferably 5 to 60% by mass.

[0089] The polymerization initiator may be a normal one. , Azobis {2-methyl N- (2-hydroxyethyl) propionamide}, etc.]; peracid-based initiators [peracid-benzoyl, di-t-butyl peroxide, tamen hydroperoxide , Succinic acid peroxide, di (2-ethoxychetyl) baroxydicarbonate, hydrogen peroxide, etc.]; redox initiator [peroxide-based initiator and a reducing agent (ascorbic acid or persulfate)) Etc.].

[0090] Examples of other polymerization methods include a method of adding a photosensitizing initiator [benzophenone, etc.] and irradiating with ultraviolet rays, a method of polymerizing by irradiating radiation such as 7 rays and electron beams, and the like. it can.

[0091] The amount of initiator added when a polymerization initiator is used is not particularly limited, but is 0.0001 to 5% strong relative to the total weight of monomers used, and 0.001 to 2%. Is even more preferred.

[0092] The polymerization temperature varies depending on the target molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent used, etc., but is preferably 20 to 200 ° C, more preferably 0 to 100 ° C.

[0093] When the crosslinked product is in the form of particles, the volume average particle size is preferably 0.1 to 5000 µm, more preferably 50 to 2000 µm. Further, less than 0.1 m is preferably 10% by mass or less, and more than 5000 m is preferably 10% by mass or less, more preferably 5% by mass or less.

[0094] The particle size was measured using a low-tap test sieve shaker and a JIS Z8801-2000 standard sieve. Perry's Chemical Engineers Handbook 6th edition (McGlow Hill Hill Book Company 1) (1984, p. 21) By law. ).

[0095] The method for obtaining the particulate form is not particularly limited as long as it finally becomes particulate.

Examples thereof include the following methods (i) to (iv).

(i) If necessary, using a solvent, copolymerizing the copolymerizable crosslinking agent to prepare a crosslinked body (A) of the polymer (1), and if necessary, removing the solvent by a method such as drying. A method of pulverizing into particles using the above pulverization method.

[0096] (ii) After polymerization using a solvent as necessary to prepare the polymer (1), the polymer (1) is crosslinked by means such as addition of the reactive crosslinking agent or irradiation of radiation. If necessary, the solvent is distilled off by a method such as drying, and pulverization is performed using a known pulverization method to form particles.

(Iii) The above carboxyl group- and Z- or sulfonic acid group-containing monomer and, if necessary, another monomer (b) in the presence of the copolymerizable cross-linking agent, if necessary, using a solvent to crosslink to form a polymer. Then, the above-mentioned cation cation compound is added to replace the proton of the acid group with a fixed amount cation, and if necessary, the solvent is distilled off by a method such as drying. A method of pulverizing to form particles.

(Iv) The above carboxyl group- and Z- or sulfonic acid group-containing monomer and optionally other monomer (b) are copolymerized using a solvent if necessary in the absence of the copolymerizable crosslinking agent, After forming the molecule, by adding the above-mentioned cation compound and a reactive crosslinking agent or by irradiation, the polymer is crosslinked at the same time as replacing the proton of the acid group, and if necessary, the solvent is distilled off by a method such as drying. A method of pulverizing into particles using a known pulverization method.

[0099] In the process of making the shape of the crosslinked body (A) of the fuel cell fuel stock (hereinafter referred to as "fuel stock" t), into a particulate form, the drying performed if necessary is a known drying method. For example, air drying (circulation dryer etc.), air permeation drying (band type dryer etc.), vacuum drying (vacuum dryer etc.), contact drying (drum dryer etc.) etc. can be mentioned.

[0100] The drying temperature for drying is not particularly limited as long as the polymer or the like is not deteriorated or excessively crosslinked, but is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. When the shape is in the form of particles, the pulverization method may be a known method.For example, impact pulverization (pin mill, cutter mill, ball mill type pulverizer, ACM pulverizer, etc. Etc.), air pulverization (jet pulverizer, etc.), freeze pulverization and the like.

[0101] In this way, the particulate crosslinked body (A) is obtained. In the present invention, the cross-linked product (A) in the fuel storage of the present invention that has been particulated in this way has the ability to absorb fuel.

[0102] The fuel composition accommodated in the fuel cartridge 5 of the present invention can be processed into various forms and is not particularly limited, but preferred forms include a particulate form, a sheet form, and an integrated gel form. it can.

[0103] Hereinafter, a method for creating a preferred form will be described. However, since the creation method and the like and the preferred method vary slightly depending on the form, each will be described in detail.

[0104] The particulate fuel reservoir may be one in which the particulate crosslinked body (A) has absorbed the fuel! /, And may be particulate after the fuel has been absorbed. The method for forming particles may be the same as the method for producing the crosslinked body (A). The volume average particle diameter and the like are preferably the same as those of the crosslinked product (A).

[0105] The particulate fuel composition is capable of absorbing fuel. The amount of the crosslinked product (A) absorbed in the fuel storage of the present invention varies depending on the type of the target fuel, the composition of the polymer, the gel strength, etc., and the crosslinked product (A) is converted into the fuel storage product. When used as, it is preferable to design the absorption amount to 10 to: LOOOgZg, more preferably 50 to 9 OOgZg. If the absorption amount is lOgZg or more, the liquid retention amount is significantly larger than that of conventional nonionic absorbents. If the absorption amount is lOOOgZg or less, the gel strength of the fuel stock holding liquid fuel is too weak! There is a problem!ヽ.

Next, the case where the fuel composition is formed into a sheet shape will be described. In the case of forming a sheet, examples of the method include the following methods (v) to (vii).

(V) A method in which the particulate cross-linked product (A) is sandwiched between non-woven fabrics or papers to form a sandwich sheet and absorb fuel.

(Vi) impregnating and Z or coating the uncrosslinked polymer (1) on one or more substrates selected from the group consisting of nonwoven fabric, woven fabric, paper and film strength, and then crosslinking The polymer (1) is crosslinked using one or more crosslinking means selected from the group consisting of crosslinking by an agent, crosslinking by irradiation with radiation, and crosslinking by heating, and if necessary, the solvent is distilled off and the sheet is removed. The method of absorbing the fuel after it is converted.

[0108] (vii) the proton of 30 to 100 mole ^_0/0 the O - carboxyl substituted with Umukachion Group and Z or sulfonic acid group-containing monomer 20-: LOO% by mass, 0-80% by mass of other copolymerizable monomers, and a mixed solution comprising the above-mentioned crosslinking agent, nonwoven fabric, woven fabric, paper and film After impregnating and Z or coating one or more base materials selected from the group consisting of the following, the base material is selected from the group of cross-linking by irradiation with a polymerization initiator and Z or radiation, and cross-linking by heating 1 or A method in which fuel is absorbed after polymerization using two or more cross-linking means and, if necessary, forming a sheet by distilling off the solvent.

[0109] Among these methods, (vi) or (vii) is preferable from the viewpoint of easy adjustment of the thickness of the produced sheet (B), the absorption rate of the produced sheet, and the like. When the shape is a sheet, the thickness of the sheet (B) is preferably 1 to 50000 111 centimeters, more preferably 5 to 30000 m, and particularly preferably 10 to 10000 m. If the sheet thickness is 1 m or more, the weight per unit area of the crosslinked product (A) does not become too small, and if it is 50000 μm or less, the sheet thickness is not too thick. The sheet length and width can be appropriately selected depending on the size to be used, and are not particularly limited. Force The preferred length is 0.01 to 10 m, and the preferred width is 0.1 to 300 cm.

[0110] The weight per unit area of the crosslinked polymer of the present invention in the sheet (B) is not particularly limited. However, the target liquid fuel can be absorbed and retained, and the thickness is not too thick. In consideration of this, the basis weight is preferably 10 to 3000 g / m ^2, more preferably 20 to L000 g / m ² .

[0111] Substrates such as non-woven fabrics, woven fabrics, papers, films, etc. that are used as necessary to form the sheet may be known ones. For example, synthetic fibers or natural fibers having a basis weight of about 10 to 500 g Examples thereof include non-woven fabrics or woven fabrics made of fibers, paper (quality paper, thin paper, Japanese paper, etc.), films made of synthetic resin, two or more base materials thereof, or composites thereof.

[0112] Among these substrates, preferred are nonwoven fabrics and composites of nonwoven fabrics and plastic films or metal films, and particularly preferred are nonwoven fabrics and composites of nonwoven fabrics and plastic films. is there.

[0113] The thickness of these substrates is not particularly limited, but is usually 1 to 50000 111, preferably 10 to 20000 μm. If the thickness is less than 1 μm, it is difficult to impregnate or apply a predetermined amount of the polymer (1). On the other hand, if the thickness exceeds 50000 m, the sheet is too thick to be used as a fuel storage. It becomes << to use when the mag is big. Coating method of polymer (1) on substrate For example, a conventional method such as coating or padding is applied and the solvent used for polymerization, dilution, viscosity adjustment, etc. is applied after applying coating or padding. What is necessary is just to distill off by methods, such as drying, as needed.

[0114] The sheet containing the crosslinked product (A) thus prepared absorbs fuel efficiently, and is used as a sheet-type fuel storage. The amount of fuel absorbed in the sheet-type fuel storage is not particularly limited as long as the fuel supply time is sufficiently long, but is preferably 0.1 to 500 gZcm ² force S, more preferably 1 to 400 g / cm ² . If the absorbed amount is 0.1 lg Zcm ² or more, the liquid fuel can be sufficiently absorbed, and if it is 500 gZcm ² or less, the sheet that has absorbed the liquid fuel does not become too thick.

[0115] The ratio of the crosslinked body (A) Z fuel in the integral gelled fuel storage comprising the crosslinked body (A) and fuel is preferably 0.1 to 99Zl to 99.9% by mass, and preferably 0. 5~50Z50~99. 5 mass ^_0/0, particularly preferably a 1~30Ζ70~99 mass ^_0/0, most preferably from 1~20Ζ80~99 mass%. If the ratio of the cross-linked product (で) is 0.1% by mass or more, the resulting fuel-containing gel may not be able to gel the entire gel strength, while the content is 99% by mass or less. If this is the case, the content of the crosslinked product (体) is too high, so that the required amount of fuel added is not too low, and the discharge time of the battery is not shortened.

[0116] The same fuel as described above can be used as the fuel used for the integral gel fuel storage.

For example, (viii) a method of adding a predetermined amount of fuel to the above-mentioned particulate crosslinked body (A) of the present invention; (ix) the crosslinked body (A However, it is preferable that these fuel-containing gels can be used to produce gels integrated with the following methods (X) and (xi).

[0117] (X) The polymer (1) is dissolved in a fuel, and the polymer (1) is cross-linked by any cross-linking means of cross-linking with the cross-linking agent, cross-linking with radiation, or cross-linking with heating. A method of forming a gel that is integrated by the above method.

[0118] In (xi) in the fuel, the O - 20 to 100% by weight monomer containing 30 to 100 mole ^_0/0 protons Cal was replaced Bokishiru group and Z or sulfonic acid groups at Umukachion, and the necessary A method of forming an integrated gel by polymerizing 0 to 80% by mass of another copolymerizable monomer in the presence of the copolymerizable crosslinking agent. [0119] The form of the crosslinked body and the gel that also has fuel power can be selected as appropriate, and examples of the shape include a sheet shape, a block shape, a spherical shape, and a cylindrical shape. Among these, when used as a fuel storage, a preferable shape is a sheet shape, a block shape or a columnar shape.

[0120] The thickness of the gel in the case of a sheet-like gel is preferably 1 to 50000 111, more preferably 10 to 20000 μm. The width and length of the sheet-like gel may be appropriately selected according to the purpose of use, the location, and the use.

[0121] The method for producing the gel having these shapes is not particularly limited, and for example, a method of gelling in a container or a cell in accordance with the shape of the created cage, a release paper, a film, a nonwoven fabric, etc. Examples thereof include a method of forming a sheet-like gel by laminating or coating a mixture of the polymer (1), monomer and the like and liquid fuel.

[0122] The fuel composition may contain other gelling agents (fatty acid sarcophagus, dibenzal sorbite, hydroxypropyl cellulose, benzylidene sorbitol, carboxyvinyl polymer, polyethylene glycol, polyoxyanolylene, as necessary. Sonorebithonole, nitrocellulose, methinoresenorelose, ethinoresenorelose, acetinolebutinoresenellose, polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylic resin, acetal resin, polycarbonate , Nylon, phenol resin, phenoxy resin, urea resin, alkyd resin, polyester, epoxy resin, diaryl phthalate resin, polyallomer, etc.), adsorbent (dextrin, dextran, silica gel, silica, alumina, molecular sieve) , Force ori , Diatomaceous earth, carbon black, activated carbon, etc.), thickeners, binders, and one or more selected from the group consisting of substances that can be converted into non-fluidized materials by chemical conversion. ,. These are not particularly limited as long as they can exhibit their respective functions, and may be solid or liquid. Moreover, you may mix | blend in the arbitrary steps which produce a fuel store. Example

[0123] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Production Example 1]

1, 1-bis (4-hydroxyphenol) cyclohexane (BHC) 26.8 g (0. lmol) A solid methanol clathrate compound having a BHC: methanol = 1: 1 (molar ratio) and a methanol content of 11% by mass was obtained by heating and dissolving in 50 ml of diol.

[Production Example 2]

1, 1, 2, 2—Tetrakis (4 hydroxyphenol) ethane (THPE) 39.8 g (0. lmol) was dissolved in 100 ml of methanol by heating and recrystallized to obtain THPE: methanol = 1: 2 A solid methanol inclusion complex having a methanol content of 14% by mass (molar ratio) was obtained.

[Production Example 3]

360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether and 40 g of water 11 were placed in a 2 liter adiabatic polymerization tank. After cooling the monomer solution to 0 ° C and reducing the dissolved oxygen through nitrogen in the solution, 2, 2'-azobis (2 amidinopropane) hydride chloride 0.36 g and 35% as a polymerization initiator Polymerization was started by adding 3. lg of peroxyhydrogen water and 0.38 g of L-ascorbic acid. After the polymerization, the resulting hydrous gel was subdivided using a meat chopper, and the gel was mixed with 60% of 1, 2, 3, 4-tetramethylimidazolium cation methyl carbonate (molecular weight: 203). When 1353 g (4 mol) of a methanol solution (manufactured by Sanyo Chemical Industries) was added, decarboxylation and demethanol occurred. Using a band-type dryer (air-permeable dryer, manufactured by Inoue Kinzoku Co., Ltd.), hot air at 100 ° C was passed through the gel with the imidazolinium cation added, and water used as a solvent and by-produced methanol were retained. Left to dry. The dried product was pulverized using a cutter mill to prepare a particulate crosslinked product having an average particle size of 400 m, and methanol was absorbed into 20 g of this to obtain a fuel composition (A1).

[Examples 1 to 3]

The methanol clathrate compound obtained in Production Examples 1 and 2 or the fuel composition (A1) obtained in Production Example 3 is placed in the fuel cartridge 5, and is inserted into the mounting port 3 of the fuel cell system 1 shown in FIGS. When the fuel cartridge 5 was installed, the cover 10 was put on, the fuel cartridge 5 was pushed down, the water discharge member 6 was pressed and compressed, and water was allowed to flow into the fuel cartridge 5. In each case, an aqueous methanol solution was generated. By supplying this aqueous methanol solution to the fuel electrode 7, the fuel cell 4 could be generated.

[0128] Moreover, even if this fuel cell system is dropped from the height of lm, no water leaks occur. The fuel cell was able to generate electric power in the same way even if left at room temperature for an hour.

Claims

The scope of the claims

[1] A fuel cell system comprising a frame in which a plurality of fuel cells are installed in a mounting portion arranged in a plane direction, and a fuel cartridge that can be detachably accommodated in the mounting portion of the frame.

A water discharge member is provided between the fuel cartridge and the fuel battery cell,

The fuel cell system is characterized in that the fuel cell is provided so that the fuel electrode is on the water discharge member side.

2. The fuel cell system according to claim 1, further comprising a pressing member that presses the fuel cartridge accommodated in the attachment portion of the frame body toward the water discharge member.

3. The fuel cell system according to claim 1 or 2, wherein no liquid component is present in the fuel cartridge.

[4] The liquid fuel component according to any one of claims 1 to 3, wherein the liquid fuel component is one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals. The fuel cell system described in 1.

[5] The fuel cell system according to any one of [1] to [4], wherein the fuel composition includes a molecular compound of a liquid fuel component and a counterpart compound.

6. The fuel cell system according to claim 5, wherein the molecular compound of the fuel composition is an inclusion compound formed from the fuel for a fuel cell and a host compound.

7. The fuel cell system according to claim 6, wherein the host compound is one or more selected from the group power consisting of an organic compound, an inorganic compound, and an organic / inorganic composite compound.

8. The fuel cell system according to claim 6 or 7, wherein the host compound is one or more selected from the group consisting of monomolecular, polymolecular and polymeric host compounds. .

[9] The fuel cell system according to any one of [1] to [4], wherein the fuel composition includes a fatty acid ester of a polyhydric alcohol and a fuel for a fuel cell.