JP2007087646A - Fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell system which can be carried safely by turning a fuel composition into a cartridge, capable of simply supplying fuel to a fuel battery cells. <P>SOLUTION: The fuel cell system 1 is composed of a fuel discharging structure 2 and the fuel battery cells 3 arranged adjacent to the fuel discharging structure 3. The fuel discharging structure 2 has a fuel cartridge 4 housing methanol inclusion compound, a water container 5 arranged adjacent to the fuel cartridge 4, and a blade-shaped member 10 opening the water container 5. A sponge 6 is arranged between the fuel cartridge 4 and the water container. By the above, when the water container 5 is opened by the blade-shaped member 10 and the water is supplied, aqueous solution of methanol is discharged and supplied to the fuel battery cells 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fuel cell system.

A solid polymer electrolyte fuel cell has 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 sides of the membrane. Hydrogen or methanol is used for the anode and oxygen is used for the cathode. Is a device that generates electricity through an electrochemical reaction. The electrochemical reaction that occurs at each electrode is as follows:
CH ₃ OH + H ₂ O → 6H ⁺ + CO ₂ + 6e ⁻ [1]
And at the cathode,
3 / 2O ₂ + 6H ⁺ + 6e ⁻ → 3H ₂ O [2]
It is. In order to cause this reaction, both electrodes are composed of a mixture of carbon fine 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. Electrons and hydrogen ions are generated by the reaction of reaction formula [1]. The hydrogen ions reach the cathode through the electrolyte in the anode and the solid electrolyte membrane between the two electrodes, react with oxygen supplied to the cathode and electrons flowing from the external circuit, and water as shown in the above reaction formula [2]. Occurs. 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 cathode from the external circuit. As a result, in the external circuit, electrons flow from the anode to the cathode and electric power is taken out.

  This direct methanol fuel cell using methanol as a fuel has a high possibility of being applicable as a portable small fuel cell, and in recent years, development has been activated as a next-generation secondary battery such as a portable computer or a mobile phone.

However, the direct methanol fuel cell fuel is used as it is in liquid form, for example, by impregnating or absorbing methanol in a sponge or other absorbent material. High and has many handling problems. As a method of safely storing such a fuel, a method of using a fuel as a molecular compound (see Patent Document 1), a method of absorbing a polymer into a gel (see Patent Document 2), a fatty acid ester of a polyhydric alcohol, A method of blending (see Patent Document 3) has been reported. In addition, the present applicants have previously proposed a method for releasing fuel cell fuel from a fuel cell fuel having a stable composition (see Patent Document 4).
International Publication No. 2004/000857 Pamphlet JP 2004-127659 A JP-A-8-231970 JP 2005-203335 A

  However, in the conventionally reported fuel release mechanism, water that passes through the container containing the fuel composition for the fuel cell exists as a liquid, and the water may leak. Therefore, as described in Patent Document 4, it is conceivable to adopt a method of supplying a necessary amount of water using only the fuel composition as a cartridge, but there is still room for improvement in the specific structure. is there.

  The present invention has been made in view of the above problems, and by using the fuel composition as a cartridge, the fuel for the fuel cell can be safely carried and can be easily supplied to the fuel cell. The purpose is to provide a system.

  A fuel cell system according to the present invention comprises a fuel release mechanism and a fuel cell arranged close to the fuel release mechanism, wherein the fuel release mechanism is a fuel composition obtained by solidifying a liquid fuel component. And a water container provided close to the fuel cartridge, and an opening member for the water container, wherein the fuel cartridge is disposed on the fuel cell side. (Claim 1). Thereby, since the liquid fuel component is solidified, it can be carried and stored. Further, when the water container is opened by the opening member and water is supplied to the fuel cartridge, the liquid fuel component is released and is supplied to the fuel cell. Fuel is supplied and power can be generated.

  In the said invention (invention 1), the fuel cartridge is provided so that the said water container can be pressed, and the said opening member is a blade shape or a needle-like member, Comprising: It is provided so that a pressure contact is possible to the said water container. (Claim 2). By adopting such a configuration, it is possible to release water by opening the water container by pressing the water container with the blade or the needle-like member by simply pressing the water container with the fuel cartridge.

  In the said invention (invention 2), it is preferable to have a stopper which hold | maintains the said fuel cartridge in the state which pressed the said water container (invention 3). In particular, the fuel cartridge is preferably provided with a compression elastic member that urges the fuel cartridge in a direction away from the water container. Thus, the state in which the water container is pressed by the opening member can be maintained, and the water container can be opened by separating the fuel cartridge by the compression elastic member simply by releasing the stopper.

  In the above inventions (inventions 2 to 4), an elastic water absorbing member is provided between the fuel cartridge and the water container, and the elastic water absorbing member is reduced when the water container is pressed by the fuel cartridge, Preferably, when the water container is opened by the fuel cartridge, the elastic water absorbing member is restored by the compression elastic member to absorb moisture. By adopting such a configuration, when the water container is opened by the fuel cartridge, the compression elastic member is restored and absorbs moisture, so that leakage of the liquid fuel component from the fuel cell system can be prevented. Moreover, if the water container is pressed again by the fuel cartridge, the elastic water absorbing member is reduced, so that the liquid fuel component can be released.

  Such a fuel cell system can be used by housing the fuel release mechanism and the fuel cell in a casing (Claim 6). 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 during storage (claim 7).

  As the liquid fuel component, one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals can be used (Claim 8). In the fuel cell system of the present invention, it is preferable that the fuel composition includes a molecular compound of a liquid fuel component and a counterpart compound (Claim 9), and the molecular compound of the fuel composition includes the fuel for the fuel cell. An inclusion compound formed from a host compound is preferred (claim 10). Moreover, what contains the fatty acid ester of a polyhydric alcohol and the fuel for fuel cells as said fuel composition can also be used (Claim 11).

  In the fuel cell system of the present invention, the fuel composition obtained by solidifying the liquid fuel component is put into a case to form a fuel cartridge. Therefore, the liquid fuel component can be solidified and stored, and further, blade-like, needle-like, etc. By simply abutting and pressing the opening member on the water container, the water container can be opened to reliably supply water to the fuel cartridge, and the liquid fuel component can be released from the fuel cartridge. Power can be reliably generated by supplying fuel.

Embodiments of the present invention will be described below with reference to the drawings.
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 perspective view showing a usage state of the fuel cell system of FIG. 4 is a longitudinal sectional view showing different usage states, and FIG. 5 is a longitudinal sectional view showing a power supply stop state in the fuel cell system of FIG.

  1 to 4, a fuel cell system 1 includes a fuel release mechanism 2 and a fuel cell 3, and the fuel release mechanism 2 includes a fuel cartridge 4 and a water container provided on the upper side of the fuel cartridge 4. 5 and a sponge 6 which is an elastic water absorbent disposed between the fuel cartridge 4 and the water container 5. This fuel cartridge 4 is a box body in which the upper and lower sides of a rectangular frame 4A having upper and lower openings are covered with mesh members 7 and 8, and a granular methanol clathrate compound 9 as a fuel composition is filled therein. The amount of methanol in the fuel cartridge 4 can be easily controlled by filling the methanol clathrate compound 9 with glass beads or the like and adjusting the density of the methanol clathrate compound 9. Further, in this fuel cartridge 4, three pairs of rod-like blade members 10 which are open members having a sharp blade at the tip end stand corresponding to water filling portions 5A, 5B, 5C of the water container 5 described later. It is installed. And the water container 5 has three water filling part 5A, 5B, 5C in the composite film made from a synthetic resin excellent in water vapor | steam barrier property and mechanical strength. In FIG. 1, the sponge 6 and the mesh member 7 are represented by a two-dot chain line for convenience of explanation.

  The fuel cartridge 4, the water container 5, and the sponge 6 are accommodated in a first casing 11 having a slightly lower size than the fuel cartridge 4, but at the four corners of the fuel cartridge 4 are compression coils that are compression elastic members. A spring 12 is erected via a guide pin (not shown). Further, guide recesses 13 are formed at two locations on the front and rear sides of the fuel cartridge 4, and a receiving plate member 14 of the guide recess 13 is projected on the inner surface side of the first casing 11. The fuel cartridge 4 is slidable in the vertical direction with respect to the first casing 11 by fitting the guide recess 13 into 14. Thus, in a no-load state, the compression coil spring 12 is in an extended state, and the fuel cartridge 4 is in a retracted limit with respect to the water container 5 and the water container 5 and the blade member 10 are not in contact with each other via the sponge 6. It has become. Reference numeral 15 denotes a stopper having a locking projection 15 </ b> A formed at the tip, and reference numeral 16 denotes a receiving recess of the blade-like member 10 formed on the inner top surface of the first casing 11.

  On the other hand, the fuel cell 3 includes current collecting plates 21 and 21 made of a fuel electrode side mesh member fixed to the metal plate 21A, current collecting plates 22 and 22 made of an air electrode side mesh member, and a space between them. MEA (membrane electrode assembly) 23 provided in The MEA 23 is a thin plate member in which a fuel electrode, an electrolyte membrane, and an air electrode are integrally laminated. The fuel electrode and the air electrode are brought into contact with the current collector plates 21 and 22, respectively, to take out electrons. For this reason, conductive plates 24 and 25 for wiring connection to electric devices and the like are attached to the metal plate 21A and the current collecting plates 22 and 22, respectively. These current collecting plates 21, 21, 22, 22 and MEA 23 are accommodated in the second casing 26. The second casing 26 has a thickness sufficiently larger than the thickness of the current collector plates 21, 21, 22, 22 and the MEA 23, so that the first casing 11 described above can be stored perfectly. The box has a slightly large opening, and an opening 27 corresponding to the current collector plates 22 is formed on the bottom surface. Reference numeral 28 denotes a stopper receiver that receives the locking projection 15A of the stopper 15, and 29 denotes a release plate.

  The first casing 11 and the second casing 26 are provided with a waterproof mechanism (not shown) such as an O-ring and packing so that liquid does not leak to the outside.

  The effect | action is demonstrated about the said structure. First, as shown in FIG. 3, the first casing 11 is set in a state of covering the second casing 26 from the fuel cartridge 4 side. At this time, the stopper 15 is in a position removed from the second casing 26, and the compression coil spring 12 is in the extended state and the water container 5 and the blade member 10 are not in contact with each other, so that no water is released from the water container 5. Therefore, no fuel is supplied to the fuel cell 3 and no electric power is generated.

  Next, when the electric device is used, the first casing 11 is pushed into the second casing 26. Then, the stopper 15 enters the second casing 26, and when the fuel cartridge 4 comes into contact with the metal plate 21A, the locking projection 15A is locked and held in the stepped portion of the stopper receiver 28. Since the upper portion of the water container 5 is regulated by the first casing 11, the compression coil spring 12 is gradually compressed, and the distance between the water container 5 and the fuel cartridge 4 is reduced, and the blade is relatively moved. The shaped member 10 is raised. As a result, the blade 6 penetrates the sponge 6 while being compressed by the fuel cartridge 4, and finally penetrates the water container 5 (FIG. 4). At this time, the blade-like member 10 becomes the rising limit, and the tip of the blade-like member 10 is accommodated in the receiving recess 16 so that the water container 5 is completely penetrated.

By opening the water container 5 in this way, water leaks out. At this time, since the sponge 6 is contracted, water does not absorb moisture and water enters the fuel cartridge 4 and comes into contact with the methanol clathrate compound in the fuel cartridge 4 so that methanol is released and is made of a methanol aqueous solution. Fuel is generated. The aqueous methanol solution that is the fuel solution for the fuel cell is smoothly pressed against the MEA 23 of the fuel cell 3 because the fuel cartridge 4 is pressed against the current collector plates 21 and 21 and the metal plate 21A by the elastic force of the compression coil spring 12. Is supplied and converted into hydrogen ions (H ⁺ ), carbon dioxide (CO ₂ ), and electrons (e ⁻ ) by the catalyst component of the fuel electrode of the MEA 23, and the electrons (e ⁻ ) are electrically connected to hydrogen ions (H ⁺ ) Is introduced into the air electrode of the MEA 23 by passing through the MEA 23. On the other hand, air or oxygen (O ₂ ) is supplied to the air electrode, and this oxygen (O ₂ ) reacts with hydrogen ions (H ⁺ ) and electrons (e ⁻ ) generated at the fuel electrode to generate water. In such a reaction, by connecting the conductive plates 24 and 25 to the wiring of the electric device, a circuit is formed through the current collecting plates 21 and 22 and electric power is taken out.

  Then, when stopping the supply of power, as shown in FIG. 5, the release plate 29 is pressed to bend the stopper 15 inward, and the locking projection 15A and the stepped portion of the stopper receiver 28 are locked. To release. Then, the first casing 11 is raised by the elastic force of the compression coil spring 12, the fuel cartridge 4 and the water container 5 are separated from each other, and the sponge 6 is restored to return to the state shown in FIG. At this time, since the sponge 6 absorbs the excess methanol aqueous solution, the supply of the methanol aqueous solution is stopped and the supply of electric power is stopped. Moreover, when supplying electric power again, the sponge 6 is compressed by similarly pushing the 1st casing 11 into the 2nd casing 26, and what is necessary is just to discharge | release the absorbed methanol aqueous solution.

  As described above, in the present embodiment, the fuel cartridge 4 serving as the fuel does not contain water, so it can be safely stored and transported, and only the first casing 11 is pushed into the second casing 26 during use. The methanol aqueous solution as the fuel can be easily supplied to the fuel battery cell 3. Moreover, since the sponge 6 is interposed between the fuel cartridge 4 and the water container 5 as in the present embodiment, there is no risk of leakage of the methanol aqueous solution, and since it is in a dilute methanol aqueous solution state, safety is also improved. It also has the effect of being excellent.

  In the present embodiment as described above, the case where a methanol clathrate compound is used as the fuel composition has been described as an example. However, the following can also be used as the fuel composition. That is, examples of the fuel for fuel cells (or liquid fuel components) include alcohols such as methanol, ethers, hydrocarbons, or acetals, which can be used as fuel for solid polymer fuel cells. However, the present invention is not limited to these. Specifically, hydrogen; alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; ethers such as dimethyl ether, methyl ethyl ether, and diethyl ether; hydrocarbons such as propane and butane; dimethoxymethane, trime Examples include acetals such as toshikimethane, but are not limited thereto, and these may be used alone or in combination of two or more.

  The fuel cell is preferably a polymer electrolyte fuel cell. Among them, a direct methanol fuel cell is suitable as in the above-described embodiment, but is not limited thereto.

  As the fuel for the fuel cell, a fuel composition for a fuel cell solidified or gelled as a molecular compound or polymer of the fuel for the fuel cell can be used.

  A molecular compound is a compound in which two or more kinds of compounds that can exist stably alone are bonded by a relatively weak interaction other than a covalent bond typified by a hydrogen bond or van der Waals force. And hydrates, solvates, addition compounds, inclusion compounds and the like. Such a molecular compound can be formed by a contact reaction between the compound forming the molecular compound and the fuel for the fuel cell, and the fuel for the fuel cell can be changed into a solid compound, which is relatively light and stable. The fuel for the fuel cell can be stored.

  Examples of the molecular compound include an inclusion compound in which a fuel for a fuel cell is included by a contact reaction between a host compound and a fuel for a fuel cell.

  Among molecular compounds, host compounds that form an inclusion compound that includes a fuel for a fuel cell are known, and organic compounds, inorganic compounds, and organic / inorganic composite compounds are known. Molecular systems, multimolecular systems, polymer hosts, and the like are known.

Examples of the monomolecular host include cyclodextrins, crown ethers, cryptands, cyclophanes, azacyclophanes, calixarenes, cyclotriveratrylenes, spherands, and cyclic oligopeptides. Multimolecular hosts include ureas, thioureas, deoxycholic acids, cholic acids, perhydrotriphenylenes, tri-o-thymotides, bianthrils, spirobifluorenes, cyclophosphazenes, mono Alcohols, diols, hydroxybenzophenones, acetylene alcohols, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, Examples include bixanthenes, carboxylic acids, imidazoles, and hydroquinones. In addition, as a polymer host, celluloses, starches, chitins, chitosans, polyvinyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2, -tetrakisphenylethane as a core, α, Examples include polyethylene glycol arm type polymers having α, α ′, α′-tetrakisphenylxylene as a core.
In addition, organophosphorus compounds, organosilicon compounds, and the like are also included.

  Examples of the inorganic host compound include titanium oxide, graphite, alumina, transition metal dicargogenite, lanthanum fluoride, clay mineral (montmorillonite, etc.), silver salt, silicate, phosphate, zeolite, silica, porous glass, and the like. It is done.

  Furthermore, some organometallic compounds exhibit properties as host compounds. For example, organoaluminum compounds, organotitanium compounds, organoboron compounds, organozinc compounds, organoindium compounds, organogallium compounds, organotellurium compounds, organotins. Examples thereof include compounds, organic zirconium compounds, and organic magnesium compounds. Further, it is possible to use a metal salt of an organic carboxylic acid, an organic metal complex, or the like, but it is not particularly limited as long as it is an organic metal compound.

  Of these host compounds, multimolecular hosts whose inclusion ability is less affected by the molecular size of the guest compound are more effective.

Examples of the multimolecular host compound include urea, 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol, 1,1-bis (2,4-dimethylphenyl)- 2-propyn-1-ol, 1,1,4,4, -tetraphenyl-2-butyne-1,4-diol, 1,1,6,6, -tetrakis (2,4-dimethylphenyl) -2 , 4-hexadiyne-1,6-diol, 9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis (4-methylphenyl) -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′-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonylbisphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 4,4′-ethylidenebisphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethylene, 1,1,2,2-tetrakis (3-methyl- 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, α, α, α ′, α′-tetrakis (4 -Hydroxyphenyl) -p-xylene, 3,6,3 ', 6'-tetramethoxy-9,9'-bi-9H-xanthene, 3,6,3', 6'-tetraacetoxy-9,9 ' -Bi-9H-xanthene, gallic acid, methyl gallate, catechin, bis-β-naphthol, α, α, α ′, α′-tetraphenyl-1,1′-biphenyl-2,2′-dimethanol, Diphenic acid bis (dicyclohexylamide), fumarate bis (dicyclohexylamide), cholic acid, deoxycholic acid, 1,1,2,2-tetrakis (4-carboxyphenyl) ethane, 1,1,2,2-tetrakis ( 3-carboxyphenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenylimidazole, 1,2,4,5-tetraphenylimidazole, 2-phenylphenanthro [9, 0-d] imidazole, 2- (o-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (m-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (p-cyanophenyl) Examples include phenanthro [9,10-d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4-dimethylphenyl) hydroquinone, and the like. A phenolic host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane is advantageous in that it is easy to use industrially.

  These host compounds may be used individually by 1 type, and may use 2 or more types together. These host compounds may be compounds of any shape as long as they form a solid clathrate compound with the fuel for the fuel cell.

  Furthermore, the organic host compound described above can also 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 silica, zeolites, activated carbons, intercalation compounds such as clay minerals and montmorillonites, but are not limited thereto. Absent. As a method for producing such an organic / inorganic composite material, the above-mentioned organic host compound is dissolved in a solvent capable of dissolving, the solution is impregnated in an inorganic porous material, and the solvent is dried, dried under reduced pressure, or the like. Can be manufactured. 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 with respect to the inorganic porous material.

  As a method of synthesizing a fuel cell fuel clathrate compound using a host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane described above, the fuel cell fuel and the host compound are directly contacted and mixed. Thus, it can be easily synthesized, and it can also be obtained by heating and the like to dissolve the host compound in the fuel for the fuel cell and recrystallizing it. Further, when the fuel for the fuel cell is a gas or liquid, it can be obtained by bringing the fuel into contact with the host compound in a pressurized state.

  The temperature at which the fuel for the fuel cell is brought into contact with the host compound is not particularly limited, but is preferably from room temperature to about 100 ° C. 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.

  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, the fuel for the fuel cell and other components are used. And a mixed liquid.

  The clathrate compound thus obtained varies depending on the type of the host compound used, the contact conditions with the fuel for the fuel cell, etc., but usually 0.1 to 10 fuel molecules for the fuel cell per mole of the host compound. It is an clathrate compound that clathrates a mole.

  This clathrate compound can stably store fuel for fuel cells over a long period of time in a normal temperature / normal pressure environment. Moreover, since this inclusion compound is lightweight and excellent in handleability and is solid, it can be easily stored in a container such as glass, metal, plastic, etc., and the problem of liquid leakage is also eliminated. . In addition, since the liquid fuel is usually solidified by inclusion, the property as a deleterious substance or a dangerous substance can be avoided. Furthermore, the chemical reactivity of the fuel cell fuel can be reduced, and for example, the corrosiveness to metals can be alleviated.

  The fuel composition contains a constituent unit having a carboxyl group and / or a sulfonic acid group in the molecule in an amount of 20 to 100% by weight based on the polymer (1), and the carboxyl group and / or the sulfonic acid group. A fuel composition for a fuel cell comprising a polymer (1) crosslinked product (A) in which 30 to 100 mol% of protons 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 / or sulfonic acid group in the molecule, and the carboxyl group and / or sulfonic acid group The cross-linked product (A) of the polymer (1) obtained by substituting a certain amount of proton with a predetermined amount of onium cation is used.

  As the structural unit (a) having a carboxyl group and / or a sulfonic acid group constituting the crosslinked body (A), a monomer having a carboxyl group [for example, (meth) acrylic acid, ethacrylic acid, crotonic acid, sorbic acid, Maleic acid, itaconic acid, fumaric acid, cinnamic acid, and their anhydrides]; monomers having sulfonic acid groups [for example, aliphatic vinyl sulfonic acids [vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene] Sulfonic acid etc.], (meth) acrylate type sulfonic acid [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate etc.], and (meth) acrylamide type sulfonic acid [acrylamido-2-methylpropane sulfonic acid etc.] etc. These are one or more of these constituents in the polymer (1). It can be. Preferably, it is a structural unit having a C 3-30 carboxyl group and / or a sulfonic acid group.

  Further, as a method for obtaining a polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, in addition to a method of polymerizing a predetermined amount of the monomer (a), for example, A monomer that can be easily changed to a carboxyl group or a sulfonic acid group, such as an esterified product or an amidated product of the carboxyl group or sulfonic acid group-containing monomer, is polymerized, and a predetermined amount of the carboxyl group is obtained using a method such as hydrolysis. And structural units having sulfonic acid groups introduced into the molecule, carboxyl groups represented by carboxymethyl cellulose, polysaccharide polymers containing sulfonic acid groups, and graft copolymers of the polysaccharide polymers and other monomers In the end, a polymer containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group is obtained. As long as it is not particularly limited.

  Content in the polymer (1) of the structural unit which has a carboxyl group and / or a sulfonic acid group is 20-100 mass% normally, Preferably it is 40-100 mass%, More preferably, it is 60-100 mass%. If the content is less than 20% by mass, the amount of absorption with respect to the liquid fuel of interest will decrease even if the proton of a carboxyl group or sulfonic acid group is replaced with an onium cation described later, or the liquid fuel can be gelled with a small amount. There may be no.

Examples of the copolymerizable monomer (b) forming a structural unit other than the structural unit having a carboxyl group and / or a sulfonic acid group include, for example, (meth) alkyl acrylate (C1-30) esters [(meth) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Stearyl acid, phenyl (meth) acrylate, octylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.]; (meth) acrylic acid oxyalkyl (1 to 4 carbon atoms) [hydroxyethyl (meth) acrylate , (Meth) acrylic acid hydroxypropyl, (meth) acrylic acid mono (polyethylene group) Cole) ester (PEG number average molecular weight: 100 to 4000), (meth) acrylic acid mono (polypropylene glycol) ester (PPG number average molecular weight: 100 to 4000), (meth) acrylic acid monomethoxypolyethylene glycol (PEG number average molecular weight) : 100-4000), (meth) acrylic acid monomethoxypropylene glycol (PPG number average molecular weight: 100-4,000), etc.]; (meth) acrylamides [(meth) acrylamide, (di) methyl (meth) acrylamide, (Di) ethyl (meth) acrylamide, (di) propyl (meth) acrylamide, etc.]; allyl ethers [methyl allyl ether, ethyl allyl ether, propyl allyl ether, glycerol monoallyl ether, trimethylolpropane triallyl Ether, pentaerythritol monoallyl ether, etc.]; α-olefins having 4 to 20 carbon atoms [isobutylene, 1-hexene, 1-octene, isooctene, 1-nonene, 1-decene, 1-dodecene, etc.]; ~ 20 aromatic vinyl compounds [styrene, t-butylstyrene, octylstyrene, etc.]; other vinyl compounds [N-vinylacetamide, vinyl caproate, vinyl laurate, vinyl stearate, etc.]; amino group-containing monomers [ Dialkyl (carbon number of alkyl: 1 to 5) aminoethyl (meth) acrylate, meth (acryloyl) oxyethyltrialkyl (alkyl carbon number: 1 to 5) ammonium chloride, bromide, sulfate, etc.] and the carboxyl group, sulfonic acid An alkali metal salt of a monomer having a group, To tertiary amine salt or an alkanolamine salt, and the like. One or more of these monomers (b) may be copolymerized with the above (a) within a predetermined amount range (less than 80% of the polymer structural unit) as necessary.

  As the monomer (b), (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, allyl ethers, α-olefins, from the viewpoint of the polymerizability of the monomer and the stability of the produced polymer, etc. It is preferable to use aromatic vinyl compounds.

  It is better to select the monomer (b) whose difference between the SP value of the solvent and the monomer (b) is 5 or less according to the SP value (solubility parameter) of the solvent to be absorbed or gelled by the liquid fuel. It is preferable because the amount of absorption and gelling power are likely to increase, and it is more preferable to select one having a difference between the SP value of the target solvent and the SP value of the monomer (b) of 3 or less.

  It is desirable to substitute 30 to 100 mol% of protons of the carboxyl group and / or sulfonic acid group with an onium cation. The onium cation is selected from the group of cations consisting of a quaternary ammonium cation (I), a tertiary sulfonium cation (II), a quaternary phosphonium cation (III), and a tertiary oxonium cation (IV). Species or two or more can be used. Examples of the quaternary ammonium cation (I) include the following (I-1) to (I-11).

  (I-1) C4-C30 or higher aliphatic quaternary ammonium having an alkyl and / or alkenyl group; tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl Propyl ammonium, tetrapropyl ammonium, butyl trimethyl ammonium, tetrabutyl ammonium and the like.

  (I-2) Aromatic quaternary ammonium having 6 to 30 or more carbon atoms; trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium and the like.

  (I-3) C3-C30 or more alicyclic quaternary ammonium; N, N-dimethylpyrrinium, N-ethyl-N-methylpyrrolidinium, N, N-dimethylmorpholinium N, N-diethylmorpholinium, N, N-dimethylpiperidinium, N, N-diethylpiperidinium and the like.

  (I-4) imidazolinium having 3 to 30 or more carbon atoms; 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl 2-ethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1,2 , 3,4-tetraethylimidazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4 -Acetyl-1,2,3-trimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 4-formyl-1,2, - trimethyl imidazolinium, 3-hydroxyethyl-1,2,3-trimethyl imidazolinium, 1,2 3-hydroxyethyl dimethyl imidazolinium like.

  (I-5) imidazolium having 3 to 30 or more carbon atoms; 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3 , 4-tetramethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 4-methoxy- , 2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium, N, N'-dimethylbenzimidazolium, N, N'- Diethyl benzimidazolium, N-methyl-N′-ethyl benzimidazolium and the like.

  (I-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyltetrahydropyrimidinium, 1,2,3-trimethyltetrahydropyrimidinium, 1,2,3,4-tetra Methyltetrahydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 3- Cyanomethyl-1,2-dimethyltetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium, 4-methylcarboxymethyl-1,2,3-trimethyl-tetrahydropyrimidinium, 3-methoxymethyl -1,2-dimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,3-dimethyltetra Mud pyrimidinium like.

  (I-7) Dihydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyl-2,4- or -2,6-dihydropyrimidinium [these are 1,3-dimethyl-2, This is expressed as 4 (6) -dihydropyrimidinium, and the same expression is used hereinafter. 1,2,3-trimethyl-2,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-2,4 (6) -dihydropyrimidinium, 1,2,3 , 5-tetramethyl-2,4 (6) -dihydropymidinium, 8-methyl-1,8-diazacyclo [5,4,0] -7,9 (10) -undecandienium, 2-cyanomethyl- 1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-2,4 (6) -dihydropyrimidinium, 4-methylcarboxymethyl-1,2 , 3-trimethyl-2,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-2,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2- Dimethyl-2,4 (6) -dihydropi Mijiniumu like.

  (I-8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazole Linium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2- Diethylamino-1,3-diethylimidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl -2H-pyrimido [1,2a] imidazolinium, 2-dimethylamino-3-methylcarboxymethyl-1-methylimidazo 2-dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3- Dimethylimidazolinium etc.

  (I-9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-diethylamino-1,3,4-triethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 1,5,6,7 -Tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido- [1,2a] imidazolium, 2-dimethylamino-3 -Cyanomethyl-1-methylimidazolium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyli Dazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazole Lium etc.

  (I-10) Guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3,4- Trimethyltetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyltetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1 , 2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino- 3-cyanomethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1 3-dimethyltetrahydropyrimidinium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyltetrahydropyrimidinium, 2-dimethyl Amino-3-hydroxyethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium, and the like.

  (I-11) Guanidium having a dihydropyrimidinium skeleton having 4 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2- Diethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-triethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino- 1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-2,4 (6) -dihydropyrimidinium, 1,6,7,8 -Tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethyl Ruamino-4-cyano-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methylcarboxymethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-2,4 (6) -dihydro Pyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-2,4 (6) -dihydropyrimidinium, and the like.

Examples of the tertiary sulfonium cation (II) include the following (II-1) to (II-3).
(II-1) Aliphatic tertiary sulfonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium and the like.

  (II-2) Aromatic tertiary sulfonium having 6 to 30 or more carbon atoms; phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium and the like.

  (II-3) Alicyclic tertiary sulfonium having 3 to 30 or more carbon atoms; methylthiolanium, phenylthiolanium, methylthianium and the like.

Examples of the quaternary phosphonium cation (III) include the following (III-1) to (III-3).
(III-1) Aliphatic quaternary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyl Tripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.

  (III-2) Aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; triphenylmethylphosphonium, diphenyldimethylphosphonium, triphenylbenzylphosphonium and the like.

  (III-3) Alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms; 1,1-dimethylphosphonium, 1-methyl-1-ethylphosphonium, 1,1-diethylphosphonium 1,1-diethyl phosphorinanium, 1,1-pentaethylene phosphorinanium, and the like.

Examples of the tertiary oxonium cation (IV) include the following (IV-1) to (IV-3).
(IV-1) Aliphatic tertiary oxonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethyloxonium, triethyloxonium, ethyldimethyloxonium, diethylmethyloxonium and the like.

  (IV-2) Aromatic tertiary oxonium having 6 to 30 or more carbon atoms; phenyldimethyloxonium, phenylethylmethyloxonium, phenylmethylbenzyloxonium and the like.

  (IV-3) Alicyclic tertiary oxonium having 3 to 30 or more carbon atoms; methyl oxolanium, phenyl oxolanium, methyl oxonium and the like.

  Among these, a preferable onium cation is (I), more preferable are (I-1), (I-4) and (I-5), and particularly preferable are (I-4) and (I I-5). These onium cations may be used individually by 1 type, and may use 2 or more types together.

  Examples of the method for introducing the onium cation into the polymer include a method in which the proton of the carboxyl group and / or the sulfonic acid group of the polymer is substituted with the onium cation. The method for substituting a proton with an onium cation is not particularly limited as long as it is a method capable of substituting a predetermined amount of onium cation. For example, the above onium cation hydroxide salt (for example, tetraethylammonium hydroxide) or monomethyl carbonate is used. Compound salt (for example, 1,2,3,4-tetramethylimidazolinium monomethyl carbonate, etc.) is added to a polymer containing a carboxyl group and / or a sulfonic acid group, and if necessary, dehydration, decarboxylation, demethanolysis -Can be easily replaced by carrying out Moreover, you may substitute similarly in the stage of a monomer.

  Regarding the stage of substitution with an onium cation, for example, a method of polymerizing after the monomer containing a carboxyl group and / or a sulfonic acid group is substituted with an onium cation, or a polymer having a carboxyl group and / or a sulfonic acid group (1 ), After the proton of the acid is replaced with an onium cation, the proton of the carboxyl group and / or the sulfonic acid group of the polymer (1) is finally replaced. It may be performed at any stage.

  The degree of substitution of the proton of the carboxyl group and / or sulfonic acid group with the onium cation (substitution degree) is 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 70 to 100 mol%. When the degree of substitution by the onium cation is less than 30 mol%, the dissociation of the carboxyl group, sulfonic acid group and onium cation of the polymer (1) is too low, and the swelling power and gelling power may be lowered.

  In the present invention, the polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group and having the carboxyl group and / or the sulfonic acid group substituted with a predetermined amount of an onium cation, Specifically, it is crosslinked at any stage to obtain a crosslinked product. The crosslinking method may be a known method, and examples thereof include the following methods [1] to [5].

[1] Cross-linking with a copolymerizable cross-linking agent;
Copolymerizable with the carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, and, if necessary, other monomer (b) to be copolymerized or having two or more double bonds in the molecule Crosslinker [polyvalent vinyl type crosslinker such as divinylbenzene, (meth) acrylamide type crosslinker such as N, N′-methylenebisacrylamide, polyvalent allyl ether type crosslinker such as pentaerythritol triallyl ether, trimethylol A method of copolymerizing and crosslinking a polyvalent (meth) acrylic acid ester type crosslinking agent such as propane triacrylate].

[2] Cross-linking with a reactive cross-linking agent;
Reactive crosslinking agent [4,4′-diphenylmethane having in the molecule two or more functional groups capable of reacting with a carboxyl group and / or a sulfonic acid group or an onium cation substitution product thereof, and a functional group of a monomer to be copolymerized if necessary Polyisocyanate type cross-linking agent such as diisocyanate, polyhydric epoxy type cross-linking agent such as polyglycerol polyglycidyl ether, polyhydric alcohol type cross-linking agent such as glycerol, polyvalent amine such as hexamethylenetetramine and polyethyleneimine, imine type cross-linking agent , A haloepoxy type crosslinking agent such as epichlorohydrin, a polyvalent metal salt type crosslinking agent such as aluminum sulfate, etc.].

[3] Crosslinking with a polymerization reactive crosslinking agent;
The carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, copolymerizable with another monomer (b) to be copolymerized if necessary, or having a double bond in the molecule, and a carboxyl group And / or a sulfonic acid group or an onium cation-substituted product thereof, and a polymerization reactive crosslinking agent having a functional group capable of reacting with a functional group of a monomer to be copolymerized if necessary [glycidyl (meth) acrylate type such as glycidyl methacrylate] Crosslinking using a crosslinking agent, an allyl epoxy type crosslinking agent such as allyl glycidyl ether, etc.].

[4] Cross-linking by irradiation;
A method of crosslinking the polymer (1) by irradiating the polymer (1) with radiation such as ultraviolet rays, electron beams, γ rays, or the like, and simultaneously polymerizing and crosslinking by irradiating the monomers with ultraviolet rays, electron beams, γ rays, etc. How to do etc.

[5] Crosslinking by heating;
A method in which the polymer (1) is heated to 100 ° C. or more and thermally crosslinked between the molecules of the polymer (1) [crosslinking between carbons due to generation of radicals by heating or crosslinking between functional groups].

  Among these crosslinking methods, the preferred ones vary depending on the use and form of the final product, but when considered comprehensively, [1] crosslinking with a copolymer crosslinking agent, [2] crosslinking with a reactive crosslinking agent, and [4] radiation. Cross-linking by irradiation.

  Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide type crosslinking agents, allyl ether type crosslinking agents, and polyvalent (meth) acrylic acid ester type crosslinking agents, and more preferred are allyl ethers. It is a mold cross-linking agent.

  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 crosslinking agent having three or more functional groups in the molecule or It is a polyvalent epoxy type cross-linking agent.

  The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, it is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on all monomers. preferable.

  The amount of addition in the case of using a reactive cross-linking agent varies depending on the shape of the cross-linked product (A), but is preferably 0.001 to 10% by mass. In the case of producing an integrated gel containing fuel, 0.01 to 50% by mass is preferable.

  In the present invention, the carboxyl group and / or sulfonic acid group-containing monomer, the onium cation-substituted product of the monomer, and the other monomer (b) to be copolymerized if necessary may be a known method. Examples thereof include a solution polymerization method in a solvent in which a monomer and a polymer to be generated are dissolved, a bulk polymerization method in which polymerization is performed without using a solvent, and an emulsion polymerization method. Among these, the solution polymerization method is preferable.

  The organic solvent by solution polymerization can be appropriately selected depending on the solubility of the monomer and polymer used. Examples thereof include alcohols such as methanol and ethanol; carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate; γ-butyrolactone, ε- Examples include lactones such as caprolactam; ketones such as acetone and methyl ethyl ketone; carboxylic acid esters such as ethyl acetate; ethers such as tetrahydrofuran and dimethoxyethane; aromatic hydrocarbons such as toluene and xylene; and water. . These solvents may be used alone or in combination of two or more.

  The polymerization concentration in the solution polymerization is not particularly limited and may vary depending on the intended use, but is preferably 1 to 80% by mass, and more preferably 5 to 60% by mass.

  The polymerization initiator may be a normal one, such as an azo initiator [azobisisobutyronitrile, azobiscyanovaleric acid, azobis (2,4-dimethylvaleronitrile), azobis (2-amidinopropane) dihydrochloride, azobis { 2-methyl-N- (2-hydroxyethyl) propionamide} and the like], peroxide initiators [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, succinic peroxide, di ( 2-ethoxyethyl) peroxydicarbonate, hydrogen peroxide, etc.], redox initiator [a combination of the above peroxide-based initiator and a reducing agent (ascorbic acid or persulfate), etc.], and the like. .

  Examples of other polymerization methods include a method of adding a photosensitizing initiator [benzophenone or the like] and irradiating with ultraviolet rays or the like, a method of irradiating with radiation such as γ rays or electron beams, and the like.

  The amount of initiator added when a polymerization initiator is used is not particularly limited, but is preferably 0.0001 to 5% by mass, more preferably 0.001 to 2% by mass, based on the total mass of the monomers used. preferable.

  The polymerization temperature also 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.

  When making a crosslinked body into a particulate form, the particle diameter is 0.1-5000 micrometers in a volume average particle diameter, More preferably, it is 50-2000 micrometers. Further, the portion less than 0.1 μm is 10% by mass or less of the whole, and the portion exceeding 5000 μm is preferably 10% by mass or less, more preferably 5% by mass or less.

  The particle size was measured using a low-tap test sieve shaker and JIS Z8801-2000 standard sieve, Perry's Chemical Engineers Handbook, 6th edition (McGlow Hill Book Company, 1984, p. 21). (Hereinafter, the particle diameter is measured by this method.).

  The method for obtaining the particulate form is not particularly limited as long as it finally becomes particulate, and examples thereof include the following methods (i) to (iv).

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

(Ii) Polymerization using a solvent, if necessary, to prepare a polymer (1), followed by crosslinking of the polymer (1) by means of the reactive crosslinking agent or irradiation, etc. A method in which the solvent is distilled off by a method and pulverized using a known pulverization method to form particles.

(Iii) After the carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, other monomer (b) are copolymerized using a solvent in the presence of the copolymerizable cross-linking agent and cross-linked to form a polymer. The onium cation compound is added, and the proton of the acid group is replaced with a predetermined amount of onium cation, and then the solvent is distilled off by a method such as drying if necessary, followed by pulverization using a known pulverization method to form particles. Method.

(Iv) The carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, the other monomer (b) are copolymerized using a solvent if necessary in the absence of the copolymerizable crosslinking agent to obtain an uncrosslinked polymer. Thereafter, the onium cation compound and the reactive cross-linking agent and radiation irradiation are used to simultaneously replace the proton of the acid group to cross-link the polymer, and if necessary, the solvent is distilled off by a method such as drying. A method of pulverizing into particles by using a pulverization method.

  The drying performed as necessary in the process of making the shape of the crosslinked body (A) of the fuel cell fuel storage (hereinafter referred to as fuel storage) into particles may be a known drying method, for example, ventilation drying (circulation drying). Etc.), air permeation drying (such as a band-type dryer), vacuum drying (such as a vacuum dryer), contact drying (such as a drum dryer), and the like.

  The drying temperature in the case of drying is not particularly limited as long as the polymer or the like is not deteriorated or excessively cross-linked, but is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The pulverization method when the shape is in the form of particles may be a known method, for example, impact pulverization (pin mill, cutter mill, ball mill type pulverizer, high-speed rotary pulverizer such as ACM pulverizer), air pulverization (jet pulverization) And the like, and freeze grinding.

  In this way, a particulate crosslinked body (A) is obtained. In the present invention, the cross-linked product (A) in the fuel storage of the present invention that is made into particles in this way has the ability to absorb fuel.

  The fuel composition accommodated in the fuel cell system of the present invention can be processed into various forms, and the form is not particularly limited, but is preferably in the form of particles, sheets, and integral gelation.

  Hereinafter, a method for creating a preferable form will be described. However, a method for creating the preferred form, a preferable method, and the like differ slightly depending on the form, and each will be described.

  The particulate fuel storage product may be one in which the particulate crosslinked body (A) has absorbed the fuel, or 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 same volume average particle diameter as that of the crosslinked body (A) is preferable.

  The particulate fuel composition has the ability to absorb fuel. The amount of the crosslinked body (A) absorbed in the fuel storage according to the present invention varies depending on the type of the target fuel, the polymer composition, the gel strength, etc., and the (A) is used as the fuel storage. In this case, it is preferable to design the amount of absorption with respect to methanol to 10 to 1000 g / g, and more preferably to 50 to 900 g / g. If the absorption amount is 10 g / g or more, the liquid retention amount is significantly larger than that of the conventional nonionic absorbent, and if it is 1000 g / g or less, the gel strength of the fuel stock holding liquid fuel is too weak. There is no problem.

  Next, the case where the fuel composition is in the form of a sheet will be described. Examples of the method for forming a sheet include the following methods (v) to (vii).

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

(Vi) After impregnating and / or applying one or more substrates selected from the group consisting of nonwoven fabric, woven fabric, paper and film with the uncrosslinked body of the polymer (1), After cross-linking the polymer (1) using one or two or more cross-linking means selected from the group consisting of cross-linking, cross-linking by radiation irradiation, and cross-linking by heating, and if necessary, after distilling off the solvent and forming a sheet, A method of absorbing fuel.

(Vii) Carboxyl group and / or sulfonic acid group-containing monomer in which 30 to 100 mol% of protons are substituted with the onium cation, and 0 to 80 mass% of other copolymerizable monomers, and the crosslinking After impregnating and / or applying one or more substrates selected from the group consisting of nonwoven fabrics, woven fabrics, papers and films with the mixed solution composed of the agent, the substrate is polymerized with a polymerization initiator and / or radiation, etc. A method of polymerizing by using one or more crosslinking means selected from the group consisting of crosslinking by irradiation and crosslinking by heating, and if necessary, forming a sheet by distilling off the solvent, and then absorbing the fuel.

Among these methods, (vi) or (vii) is preferable from the viewpoint of easy adjustment of the thickness of the prepared sheet (B) and the absorption rate of the prepared sheet. When the shape is a sheet, the thickness of the sheet (B) is preferably 1 to 50000 μm, more preferably 5 to 30000 μm, and particularly preferably 10 to 10000 μm. When the thickness of the sheet is 1 μm or more, the basis weight of the crosslinked body (A) is not too small, and when it is 50000 μm or less, the thickness of the sheet is not too thick. The length and width of the sheet can be appropriately selected depending on the size to be used, and are not particularly limited. However, the preferred length is 0.01 to 10 m, and the preferred width is 0.1 to 300 cm. The weight per unit area of the crosslinked polymer of the present invention in the sheet (B) is not particularly limited, but taking into account the absorption / retention capacity of the target liquid fuel, the thickness not being too thick, and the like. weight per unit area is preferably 10~3000g / ^{m 2,} more preferably 20~1000g / ^{m 2.}

  A base material such as a nonwoven fabric, a woven fabric, paper, or a film that is used as necessary to form the sheet may be a known one. For example, a nonwoven fabric made of synthetic fibers or natural fibers having a basis weight of about 10 to 500 g. Or a woven fabric, paper (quality paper, thin paper, Japanese paper, etc.), a film made of a synthetic resin, two or more substrates thereof, or a composite thereof can be exemplified.

  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.

  Although there is no limitation in particular about the thickness of these base materials, it is 1-50000 micrometers normally, Preferably it is 10-20000 micrometers. When the thickness is less than 1 μm, it is difficult to impregnate or apply the predetermined amount of the polymer (1). On the other hand, when the thickness exceeds 50000 μm, the sheet is too thick and the overall bulk is large when used as a fuel storage. It becomes difficult to use. The coating method or impregnation method of the polymer (1) to the substrate may be a known method, for example, a normal method such as coating or padding may be applied. In addition, after performing a coating or padding process, you may distill away the solvent used for superposition | polymerization, dilution, viscosity adjustment, etc. by drying etc. as needed.

The sheet containing the cross-linked product (A) thus prepared absorbs fuel efficiently and is used as a sheet-type fuel storage. Absorption for the fuel in the sheet-type fuel reservoir also the supply time of the fuel is not particularly limited as longer enough, preferably 0.1 to 500 g / cm ² sheets further those 1~400g / cm ² preferable. When the absorption amount is 0.1 g / cm ² or more, the liquid fuel can be sufficiently absorbed, and when it is 500 g / cm ² or less, the sheet that has absorbed the liquid fuel does not become too thick.

  The ratio of the crosslinked body (A) / fuel in the integral gelled fuel storage comprising the crosslinked body (A) and fuel is preferably 0.1 to 99/1 to 99.9% by mass, and more preferably. Is 0.5 to 50/50 to 99.5% by mass, particularly preferably 1 to 30/70 to 99% by mass, and most preferably 1 to 20/80 to 99% by mass. When the ratio of (A) is 0.1% by mass or more, the produced fuel-containing gel has a weak gel strength, and there is no case where the entire gel cannot be gelled. On the other hand, when the content is 99% by mass or less, Since the content of (A) is too large, the required amount of fuel added is not too low and the discharge time of the battery is not shortened.

  The same fuel as described above can be used as the fuel used for the integral gelled fuel storage. Examples of a method for preparing an integral gelled fuel storage include: (viii) a method of adding a predetermined amount of fuel to the above-mentioned particulate crosslinked body (A) of the present invention; (ix) containing (A) However, it is preferable that these fuel-containing gels can produce an integrated gel by the methods described in (x) and (xi) below.

(X) The polymer (1) is dissolved in a fuel, and the (1) is integrated by cross-linking by any cross-linking means of cross-linking by the cross-linking agent, cross-linking by radiation irradiation, or cross-linking by heating. How to make a gel.

(Xi) 20 to 100% by mass of a carboxyl group and / or sulfonic acid-containing monomer in which 30 to 100 mol% of protons are substituted with the onium cation in the fuel, and 0 to 80% of other copolymerizable monomers as necessary. A method of forming an integrated gel by polymerizing mass% in the presence of the copolymerizable cross-linking agent.

  The form of the gel composed of the crosslinked body and the fuel can be appropriately selected. 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 column shape.

  1-50000 micrometers is preferable and, as for the thickness of the gel in setting it as a sheet-like gel, 10-20000 micrometers is still more preferable. What is necessary is just to select suitably about the width | variety and length of a sheet-like gel according to the use purpose, a place, a use, etc.

  There are no particular limitations on the method of creating the gel of these shapes, for example, the method of gelling in a container or cell that matches the shape to be created, release paper, film, nonwoven fabric, etc. Examples thereof include a method of preparing a sheet-like gel by laminating or coating a mixture of the polymer (1), the monomer, and the like and a liquid fuel.

  The fuel composition may contain other gelling agents (fatty acid soap, dibenzal sorbite, hydroxypropylcellulose, benzylidene sorbitol, carboxyvinyl polymer, polyethylene glycol, polyoxyalkylene, sorbitol, nitrocellulose, methylcellulose, ethylcellulose as necessary. , Acetylbutyl cellulose, polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylic resin, acetal resin, polycarbonate, nylon, phenolic resin, phenoxy resin, urea resin, alkyd resin, polyester, epoxy resin, diallyl phthalate resin, polyallomer Etc.), adsorbent (dextrin, dextran, silica gel, silica, alumina, molecular sieve, kaolin, diatomaceous earth, carbon bra Click, activated carbon, etc.), a thickener, and a binder, and fuel may be blended with one or more selected from the group consisting of substances which non-fluidized by chemical transformation. 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.

  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 of the present invention is not exceeded.

[Production Example 1]
By re-dissolving 26.8 g (0.1 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (BHC) in 50 mL of methanol by heating and recrystallization, BHC: methanol = 1: 1 (molar ratio). A solid methanol clathrate compound having a methanol content of 11% by mass was obtained.

[Example 1]
In the fuel cell system 1 shown in FIGS. 1 to 5, the fuel cartridge 4 is filled with the methanol clathrate compound 15 obtained in Production Example 1 and 95 g of beads, and the water container 5 is filled with 20 cc of pure water. First, the first casing 11 is pressed and inserted into the second casing, the water container 5 is opened, and when water is introduced into the fuel cartridge 4, a methanol aqueous solution is generated. It was possible to generate electricity by being supplied.

  Further, even when the fuel cell system 1 before use was dropped from a height of 1 m, no water leakage occurred, and the fuel cell was able to generate power even when left at room temperature for 48 hours.

1 is an exploded perspective view schematically showing a fuel cell system according to an embodiment of the present invention. It is a perspective view which shows the state at the time of the electric power supply of the fuel cell system of FIG. It is a longitudinal cross-sectional view which shows the state before the electric power supply of the fuel cell system of FIG. It is a longitudinal cross-sectional view which shows the state at the time of the electric power supply of the fuel cell system of FIG. It is a longitudinal cross-sectional view which shows the electric power supply stop state in the fuel cell system of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Fuel cell system 2 ... Fuel discharge | release mechanism 3 ... Fuel cell 4 ... Fuel cartridge 5 ... Water container 6 ... Sponge (elastic water absorption body)
9 ... Methanol clathrate compound (fuel composition)
10 ... Blade member (opening member)
11: First casing 12: Compression coil spring (elastic member)
15 ... Stopper 23 ... MEA (fuel electrode + electrolytic chamber membrane + air electrode)
26 ... second casing

Claims (11)

A fuel cell system comprising a fuel release mechanism and a fuel cell arranged close to the fuel release mechanism,
The fuel release mechanism includes a fuel cartridge that expropriates a fuel composition obtained by solidifying a liquid fuel component, a water container provided close to the fuel cartridge, and an opening member of the water container,
The fuel cell system, wherein the fuel cartridge is disposed on the fuel cell side.   The said fuel cartridge is provided so that the said water container can be pressed, and the said opening member is a blade shape or a needle-like member, Comprising: The said water container is provided so that press contact is possible. The fuel cell system described in 1.   The fuel cell system according to claim 2, further comprising a stopper that holds the fuel cartridge in a state where the water container is pressed.   4. The fuel cell system according to claim 3, wherein the fuel cartridge is provided with a compression elastic member that urges the fuel cartridge in a direction away from the water container.   An elastic water absorbing member is provided between the fuel cartridge and the water container, and the elastic water absorbing member is contracted when the water container is pressed by the fuel cartridge, while the compression is performed when the water container is opened by the fuel cartridge. The fuel cell system according to claim 2, wherein the elastic water absorbing member is restored by an elastic member to absorb moisture.   6. The fuel cell system according to claim 1, wherein the fuel discharge mechanism and the fuel cell are accommodated in a casing.   The fuel cell system according to claim 1, wherein no liquid component is present in the initial fuel cartridge.   The fuel according to any one of claims 1 to 7, wherein the liquid fuel component is one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals. Battery system.   The fuel cell system according to any one of claims 1 to 8, wherein the fuel composition contains a molecular compound of a liquid fuel component and a counterpart compound.   The fuel cell system according to claim 9, wherein the molecular compound of the fuel composition is an inclusion compound formed from the fuel for a fuel cell and a host compound. The fuel cell system according to any one of claims 1 to 8, wherein the fuel composition contains a fatty acid ester of a polyhydric alcohol and a fuel for a fuel cell.

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