TW202140726A - Resin composition for electrolyte membrane adhesion, resin film for electrolyte membrane adhesion, method for producing resin film for electrolyte membrane adhesion - Google Patents

Abstract

The present invention provides a resin composition for an electrolyte membrane adhesion, a resin film for an electrolyte membrane adhesion, and a method for producing a resin film for an electrolyte membrane adhesion, which can adhere in a short time and are not easily degraded by water. More specifically, the present invention is a resin composition for an electrolyte membrane adhesion for adhering an electrolyte membrane, which contains an acid-modified polyolefin resin (A) and a resin compound (B) as essential components. The resin compound (B) has in one molecule two or more functional groups that react with the functional group of the electrolyte membrane, and in one molecule four or more functional groups that react with the acid functional group of the acid-modified polyolefin resin (A). The resin compound (B) has an epoxy group and a hydroxy group, or only an epoxy group.

Description

Resin composition for bonding electrolyte membrane, resin film for bonding electrolyte membrane, and manufacturing method of resin film for bonding electrolyte membrane

The present invention relates to a method for producing a resin composition for adhering an electrolyte membrane, a resin film for adhering an electrolyte membrane, and a resin film for adhering an electrolyte membrane.

Patent Document 1 describes that the reinforcing sheet in contact with the electrolyte membrane-catalyst layer of the fuel cell is composed of an adhesive layer and an elastic layer. As the adhesive layer, selected from epoxy resin, acrylic resin, urethane resin, silicone resin, And at least one of the group consisting of solid polymer electrolyte ion polymer resin. In the reinforcing sheet described in Patent Document 1, in order to follow the expansion and contraction of the electrolyte membrane and suppress the breakage of the electrolyte membrane, an elastic layer formed of a specific type of rubber is laminated. The adhesive layer described in Patent Document 1 is a solid electrolyte Nafion (registered trademark) ionic polymer, epoxy resin, acrylic resin and other adhesives dispersed in organic solvents, water and other solvents, and the adhesive solution is coated Film is formed by machine coating and drying solvent. Prior art literature Patent literature

Patent Document 1: Japanese Patent No. 5720810

The problem to be solved by the invention

The electrolyte membrane is deformed by the differential pressure between the anode and the cathode of the gas supplied to the fuel cell during power generation. In order to prevent deformation and cracking of the electrolyte membrane, a frame-shaped reinforcing material may be used for the electrolyte membrane, and the reinforcing material must be adhered to the electrolyte membrane. As described in Patent Document 1, when a liquid adhesive is applied in a frame shape and cured by thermal drying and fixed to the electrolyte membrane, the flow of application and curing of the adhesive is long, resulting in productivity The problem. Furthermore, there is a problem of deterioration of the adhesive and gas leakage due to heat and water generated during power generation.

The present invention was made in view of the above matters, and its subject is to provide a resin composition for adhering an electrolyte membrane, a resin film for adhering an electrolyte membrane, and a resin for adhering an electrolyte membrane that can be adhered in a short time and are not easily deteriorated by water Film manufacturing method. Technical methods used to solve the problem

In order to solve the above-mentioned problems, the present invention provides a resin composition for adhering an electrolyte membrane, which is a resin composition for adhering an electrolyte membrane, which is characterized by containing an acid-modified polyolefin resin (A) and a resin The compound (B) is an essential component, and the resin compound (B) has two or more functional groups that react with the functional groups of the electrolyte membrane in one molecule, and four or more functional groups that react with the acid-modified polyolefin in one molecule. The functional group to which the acid functional group of the resin (A) reacts, and the said resin type compound (B) has an epoxy group and a hydroxyl group, or only an epoxy group is a functional group.

The resin composition for the electrolyte membrane adhesive may also contain a graft copolymer (G ). The solid content of the resin composition for adhering an electrolyte membrane may be contained within a range of 1 to 25 parts by weight of the resin compound (B) in 100 parts by weight. The aforementioned resin compound (B) may be an epoxy resin or a phenoxy resin. In 100 parts by weight of the solid content of the resin composition for adhering an electrolyte membrane, the thermoplastic elastomer resin (C) may be contained in the range of 1 to 15 parts by weight.

Furthermore, the present invention provides a resin membrane for adhering an electrolyte membrane, which is characterized in that the aforementioned resin composition for adhering an electrolyte membrane is formed into a film. Furthermore, the present invention provides a resin film for adhering an electrolyte membrane, characterized in that an adhesive layer formed from the aforementioned resin composition for adhering an electrolyte membrane is laminated on at least one side of a base layer.

Furthermore, the present invention provides a method for producing a resin film for electrolyte membrane bonding, which is characterized in that the aforementioned resin composition for electrolyte membrane bonding is melt-kneaded and extrusion-molded to form a film into a film. Furthermore, the present invention provides a method for producing a resin film for adhering an electrolyte membrane, characterized in that the resin composition for adhering an electrolyte membrane is dissolved in a solvent and applied. Invention effect

According to the present invention, it is possible to provide a resin composition for adhering an electrolyte membrane, a resin film for adhering an electrolyte membrane, and a method for producing a resin film for adhering an electrolyte membrane, which can be adhered in a short time and are not easily deteriorated by water.

Hereinafter, the present invention will be described based on a preferred embodiment. The adhesive resin composition according to the embodiment of the present invention contains an acid-modified polyolefin resin (A) and a resin-based compound (B) as essential components, and the resin-based compound (B) has two or more in one molecule and The functional group of the electrolyte membrane is a functional group that reacts, and there are 4 or more functional groups that react with the acid functional group of the acid-modified polyolefin resin (A) in one molecule. Furthermore, the adhesive resin composition according to the embodiment of the present invention can be used for the adhesive of an electrolyte membrane.

〔Acid modified polyolefin resin (A)〕 The acid-modified polyolefin resin (A) used in the aforementioned adhesive resin composition is a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof, and the polyolefin-based resin has a carboxyl group and a carboxylic anhydride group. Preferably, the polyolefin resin is modified with an unsaturated carboxylic acid or a derivative thereof. In acid-modified polyolefin resins, as an acid-modified method, there can be cited the presence of organic peroxides, aliphatic azo compounds, and other radical polymerization initiators, combining acid functional group-containing monomers with polyolefin resins. Grafting modification such as melt kneading, copolymerization of acid-functional monomers and olefins, etc.

Examples of the aforementioned polyolefins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers of propylene and ethylene or α-olefin, block copolymers of propylene and ethylene or α-olefin, and the like. Among them, polypropylene resins such as homopolypropylene (homoPP (homoPP), propylene homopolymer), propylene-ethylene block copolymer (block PP), propylene-ethylene random copolymer (random PP), etc. Better. Especially random PP is better. Examples of the aforementioned olefins in the copolymerization include olefin monomers such as ethylene, propylene, 1-butene, isobutene, 1-hexene, and α-olefin.

As the aforementioned acid functional group monomer is a compound having an ethylenic double bond and a carboxylic acid group or carboxylic anhydride group in the same molecule, and is composed of various unsaturated monocarboxylic, dicarboxylic, or anhydrides of dicarboxylic acids . As the acid functional group-containing monomer having a carboxylic acid group (carboxylic acid group-containing monomer), acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, and Conic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid) ) And other α,β-unsaturated carboxylic acid monomers. As the acid functional group-containing monomer having a carboxylic anhydride group (carboxylic acid anhydride group-containing monomer), maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, endic anhydride can be cited anhydride) and other unsaturated dicarboxylic anhydride monomers. In the acid-modified polyolefin resin (A), one type of these acid-functional group-containing monomers may be used, or two or more types may be used in combination.

Among the aforementioned acid functional group-containing monomers, carboxylic acid anhydride group-containing monomers are more preferred, and maleic anhydride is more preferred. When a part of the acid functional group-containing monomer used for acid modification is not reacted, in order to suppress the adverse effect on the adhesive force, the acid-containing functional group monomer that has been removed from the unreacted is used as the acid-modified polyolefin Resin (A) is preferred.

Regarding the propylene component in the acid-modified polyolefin resin (A), from the viewpoint of the heat resistance of the resin, the amount of the propylene unit is preferably more than half. The "over half amount" here means that the acid-modified polyolefin resin (A) has a propylene content of 50% by weight or more. Therefore, as the acid-modified polyolefin resin (A), an acid-modified polypropylene resin having more than half of the propylene unit is preferred.

[Resin compound (B)] The resin compound (B) used in the aforementioned adhesive resin composition has two or more functional groups that react with the functional groups of the electrolyte membrane in one molecule, and four or more functional groups that react with the aforementioned acid-modified polyolefin in one molecule. The acid functional group of the resin (A) reacts with the functional group. The resin compound (B) has an epoxy group and a hydroxyl group, or only an epoxy group as a functional group. As the resin compound (B), an epoxy resin or a phenoxy resin can be mentioned, for example. Furthermore, as a resin having epoxy groups and hydroxyl groups or only epoxy groups in the functional group of the side chain, a polymer obtained by polymerizing a monomer having an epoxy group, an epoxy group-containing monomer and an epoxy group-containing resin can be used. Copolymers of hydroxyl monomers, etc.

As the resin compound (B), a polymer having plural hydroxyl groups such as polyhydroxy polyether, polyhydroxy polyester, polyhydroxy polycarbonate, polyhydroxy polyamide, etc., is glycidylated. Obtained by epoxidation, a compound having two or more epoxy groups in one molecule. Specific examples thereof include epoxy resins or phenoxy resins synthesized by reacting bisphenols with epichlorohydrin, and resin compounds having epoxy groups at both ends represented by the following general formula (1).

R ¹ -O-[R ² -O-CH ₂ CH(OH)CH ₂ -O] _p -R ² -OR ¹ . . . (1)

In the general formula (1), R ¹ represents glycidyl (that is, 2,3-epoxypropyl). Further, R ² is a bisphenol to _{HO-C 6 H 4 -C (} R 3) (R 4) -C ₆ H ₄ -OH when expressed, is equivalent to -C ₆ H ₄ -C (R ³ ) (R ⁴ ) -C ₆ H ₄ -is the divalent group. As the substituents R ³ and R ^{4 of the} bisphenols, an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, or the like can be exemplified.

Furthermore, in the general formula (1), the integer p is equal to the number of hydroxyl groups (the number of hydroxyl groups) contained in one molecule of the aforementioned compound. In this case, the functional groups that can react with the acid functional groups of the acid-modified polyolefin resin (A) are p hydroxyl groups and 2 epoxy groups at both ends. In order to have 4 or more functional groups that react with acid functional groups in one molecule, p+2≧4 is preferred.

As the aforementioned phenoxy resin, bisphenol A (BPA) type phenoxy resin in which ^{the substituents R 3} and R ⁴ of the bisphenols in the general formula (1) are both CH ₃ ^{, R 3} and R ⁴ Bisphenol F (BPF) type phenoxy resin which is the same as H, BPA/BPF copolymerization type phenoxy resin in which bisphenol A and bisphenol F are copolymerized, one of R ³ or R ⁴ is CH ₃ , bisphenol B type phenoxy resin with H on the other side, etc. In addition, since the bisphenol-type epoxy resin can be represented by the above-mentioned general formula (1) in the same manner as the phenoxy resin, it is possible to select and use a relatively high molecular weight and a larger number of hydroxyl groups p.

The weight average molecular weight (Mw) of the aforementioned phenoxy resin or epoxy resin is preferably about 3,000 (in the case of bisphenol A type, the number of hydroxyl groups p is about 10) or more, for example, about 15,000 (in the case of bisphenol A type) , The number of hydroxyl groups p is about 50), about 20,000 (in the case of bisphenol A type, the number of hydroxyl groups p is about 70), higher molecular weight can be used. The upper limit of the average molecular weight of the phenoxy resin or epoxy resin is not particularly limited, but it is preferably about 80,000 (in the case of the bisphenol A type, the number of hydroxyl groups p is about 280). In addition, in the case of obtaining the average molecular weight of phenoxy resin or epoxy resin by GPC, for example, tetrahydrofuran (THF) can be used as the cleaning solution (elute) of GPC, and TSKgel G4000H and TSKgel G3000H (both Tosoh Corporation) can be used. Company system, product name) linker is obtained as a pipe string.

As a specific example of the aforementioned phenoxy resin, a trade name manufactured by NIPPON STEEL Chemical & Material Co., Ltd.: YP-50 (Mw is 60,000 to 80,000, BPA type, hydroxyl number p is about 210 to 280), YP-50S (Mw is 50,000~70,000, BPA type, hydroxyl number p is about 175~245), YP-55U (Mw is 40,000~45,000, BPA type, hydroxyl number p is about 140~160), YP-70 (Mw is 50,000 ~60,000, BPA/BPF copolymerization type), ZX-1356-2 (Mw is 60,000~80,000, BPA/BPF copolymerization type), FX-316 (Mw is 40,000~60,000, BPF type), etc.; Mitsubishi Chemical Corporation The phenoxy type model (Grade) 1256 (molecular weight about 50,000, BPA type), the same 4250 (molecular weight about 60,000, BPA/BPF copolymerization type), the same 4275 (molecular weight about 60,000, BPA/BPF copolymerization type) , 1255HX30, YX8100BH30, YX6954BH30, etc.; Pakistan Industrial Joint Stock Company PKHB, PKHC, PKHH, PKHJ, etc.

Furthermore, as a specific example of the aforementioned epoxy resin, a product name manufactured by NIPPON STEEL Chemical & Material Co., Ltd.: YD-020G (epoxy equivalent 3500~4500, BPA type), etc.; model number manufactured by Mitsubishi Chemical Co., Ltd. ( Grade) 1010 (average molecular weight 5500, BPA type, epoxy equivalent 3000~5000), same as 1009 (average molecular weight 3800, BPA type, epoxy equivalent 2400~3300), etc.

In addition, as the aforementioned resin compound (B), the functional group that reacts with the acid functional group is only an epoxy group, and a compound having 4 or more epoxy groups in one molecule can be cited. As a specific example of such a compound, a phenolic novolak epoxy resin synthesized by reacting phenolic novolak with epichlorohydrin can be cited, and O-cresol novolak can be reacted with epichlorohydrin. On the other hand, synthetic cresol phenol resins and other resin compounds having 4 or more epoxy groups in the molecular chain. In addition, as commercial products of this type of epoxy resin, for example, a bisphenol A type novolac epoxy resin manufactured by Mitsubishi Chemical Corporation: jER157S70, DIC Corporation's product name: EPICLON N-865, N-885, the trade name of DIC Co., Ltd. as the cresol novolac epoxy resin: EPICLON N-670, N-673, N-680, N-690, N-695, as the DIC share of the phenol novolac epoxy resin The company's trade names: N-770, N-775, etc.

Furthermore, as the aforementioned resin-based compound (B), in addition to a resin-based compound having 4 or more epoxy groups that react with the acid functional group of the acid-modified polyolefin resin (A) in one molecule, it may be more Contains two or more epoxy groups in one molecule, and four or more functional groups in one molecule that react with the acid functional group of the acid-modified polyolefin resin (A), the functional group being an epoxy group and a hydroxyl group Resin compound.

The aforementioned adhesive resin composition exerts an adhesive functional group to the adherend through the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the resin compound (B) The function, and has excellent adhesion to the substrate with electrolyte membrane. Furthermore, since the acid functional groups of the acid-modified polyolefin resin (A) and the functional groups (epoxy groups, hydroxyl groups) of the resin compound (B) are easily reacted by heating, there is no need to prepare other groups capable of reacting with these Hardeners that react with functional groups, etc.

In 100 parts by weight of the solid content of the aforementioned adhesive resin composition, the resin-based compound (B) is preferably contained within a range of 1 to 25 parts by weight. The affinity of the polyolefin part of the acid-modified polyolefin resin (A) to plastics with low polarity and the affinity of the adhesive functional group to heterogeneous materials like electrolyte membranes have a suitable balance. In addition to bonding with dissimilar materials like electrolyte membranes, it also has excellent adhesion when bonding with low-polarity plastics such as polyolefins. Specific examples of the ratio of the resin compound (B) relative to 100 parts by weight of the aforementioned solid content include, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, etc., or this The nearby or intermediate value.

〔Graft Copolymer (G)〕 The aforementioned adhesive resin composition preferably contains a graft copolymer (G). The graft copolymer (G) is composed of the acid functional groups of the acid-modified polyolefin resin (A) and the resin compound (B). The functional group (epoxy group, hydroxyl group) possessed is obtained by graft polymerization. According to the graft copolymer (G), the acid-modified polyolefin resin (A) and the resin compound (B) are graft-polymerized to prevent the separation of the two. The acid functional group and the functional group ( The addition effect of epoxy group and hydroxyl group can have excellent adhesive force.

The graft copolymer (G) preferably has an epoxy group derived from the resin compound (B). In this case, as the graft copolymer (G), it is possible to obtain the effect of improving the adhesive force through the epoxy group in common with the acid functional group and the functional group (epoxy group, hydroxyl group). The graft copolymer (G) is obtained by blending the acid-modified polyolefin resin (A) at a ratio of 75 to 99% by mass to the resin compound (B) at a ratio of 1 to 25% by mass, and performing graft polymerization Better.

The graft copolymer (G) preferably involves melt graft polymerization of the acid-modified polyolefin resin (A) and the resin compound (B). In this melt graft polymerization, the resin composition for subsequent use containing the acid-modified polyolefin resin (A) and the resin compound (B) is melt-kneaded to perform graft polymerization in an apparatus. As a melt-kneading device, a single-shaft extruder, a multi-shaft extruder, a closed kneader, a PLASTOMILL mixer, a heated roll kneader, etc. can be used.

During the aforementioned melt graft polymerization, in order to suppress the decomposition of epoxy groups in the graft copolymer (G), it is desirable to remove and discharge volatile components capable of reacting with epoxy groups, such as moisture, to the outside of the device. In addition, when volatile components are generated during melt kneading, it is desirable to discharge them from the device at any time by degassing or the like. Thereby, the foaming at the time of forming an adhesive layer into a film using the said adhesive resin composition can be suppressed.

When the acid-modified polyolefin resin (A) has an acid anhydride group as the acid functional group, it has high reactivity with the functional group (epoxy group, hydroxyl group) of the resin compound (B) and can be used under milder conditions. Graft polymerization is therefore preferred.

The heating temperature (kneading temperature) during the melting and kneading is 130~ It is better to choose within the range of 300°C. When the aforementioned acid-modified polyolefin resin (A) is an acid-modified polypropylene resin, it is preferably 180 to 300°C, and in order to further improve the dispersibility, 240 to 300°C is preferred. In addition, the kneading temperature can be measured by a method in which the adhesive resin composition in a molten state is brought into contact with a thermocouple or the like immediately after being extruded from a melt-kneading device.

〔Thermoplastic elastomer resin (C)〕 The aforementioned adhesive resin composition can contain a thermoplastic elastomer resin (C) as an optional component. As the thermoplastic elastomer resin (C), styrene elastomer, styrene butadiene copolymer, epoxy modified styrene butadiene copolymer, olefin elastomer, polyester elastomer, styrene butadiene Ethylene styrene block copolymer, styrene ethylene propylene styrene block copolymer, styrene isoprene butadiene styrene block copolymer, styrene isoprene styrene block copolymer, etc. When the thermoplastic elastomer resin (C) is added, the solid content of the adhesive resin composition is preferably within a range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition.

The thermoplastic elastomer resin (C) is a product that does not react with the acid-modified polyolefin resin (A) or the resin compound (B) under the conditions of the melt-kneading of the resin composition. Can be blended before melt kneading. In this case, when a mixture containing the acid-modified polyolefin resin (A), the resin compound (B), and the thermoplastic elastomer resin (C) is melt-kneaded, the acid-modified polyolefin is The resin (A) and the resin compound (B) are selectively reacted to obtain an adhesive resin composition containing the graft copolymer (G).

〔Resin composition for subsequent use〕 The aforementioned resin composition for subsequent use contains the aforementioned acid-modified polyolefin resin (A) and the aforementioned resin compound (B) as essential components, and the aforementioned subsequent resin composition is melt-kneaded and extruded by a method (1 step ), can manufacture adhesive layer. If the adhesive layer is shaped into a single-layer film, a single-layer adhesive film can be obtained. If the adhesive layer is laminated on the substrate layer, a multilayer adhesive film can be obtained.

Furthermore, the adhesive layer can be manufactured by a method of dissolving the aforementioned adhesive resin composition in a solvent and applying it. The method of applying the aforementioned adhesive resin composition is not particularly limited, and it can be applied by a usual method using a well-known coating device such as a roll coater, a die coater, and a gravure coater. The object to be subsequently coated with the resin composition includes an adherend, a release material (a release film, etc.) capable of peeling the adhesive layer after coating, and the substrate layer of the adhesive resin laminate described later.

The organic solvent used for coating is preferably a compound that is difficult to react with the resin component constituting the aforementioned resin composition for adhesive, for example, hydrocarbon solvents such as toluene, ether solvents such as ethylene glycol dimethyl ether, and methyl Ketone solvents such as ethyl ketone, and ester solvents such as ethyl acetate. The drying conditions may be appropriately set according to the organic solvent used. For example, at least a part of the organic solvent can be volatilized by heating at a temperature of 40 to 150° C. for 5 to 600 seconds.

The adhesive resin composition has the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the resin compound (B), thereby obtaining excellent adhesive force. In particular, even in a relatively low temperature region close to the melting point (Tm) of the acid-modified polyolefin resin (A) of the base resin, excellent adhesion can be obtained and low-temperature adhesion can be improved.

In addition, when the resin composition is melt-kneaded for the next step, when the acid-modified polyolefin resin (A) and the resin compound (B) are graft-polymerized, there is no need to separately provide a graft copolymer ( G) The preparation process is excellent in productivity and can suppress damage to the resin component. The aforementioned adhesive resin composition has an excellent adhesive force to a substrate having an electrolyte membrane, is formed of a simple composition, and can easily produce an adhesive layer. Furthermore, the main chain of the acid-modified polyolefin resin (A) used for the subsequent resin composition is composed of the addition polymerization of vinyl groups like polyolefin resins. Since it is not easily hydrolyzed, it has a high temperature environment. Water resistance.

The aforementioned resin composition for adhesive may be suitably added with fillers, colorants, antioxidants, defoamers, leveling agents, light absorbers, etc., as other additives. In addition to the acid-modified polyolefin resin (A) and the resin compound (B) or graft copolymer (G), which are essential components, the aforementioned resin composition for subsequent use, and the optional thermoplastic elastomer resin (C), It can be constituted without containing a resin component or a polymer component. In addition to the essential components of acid-modified polyolefin resin (A) and resin compounds (B) or graft copolymers (G), and optional components of thermoplastic elastomer resin (C) other solid content The ratio, based on 100 parts by weight of the total solid content, may be 10 parts by weight or less, 5 parts by weight or less, 1 part by weight, etc.

〔Instrumented〕 As the electrolyte membrane to be adhered, a solid polymer electrolyte membrane known or commercially available in applications such as fuel cells can be used. Examples include hydrogen ion conductive polymer electrolyte membranes, perfluorosulfonic acid-based fluoride ion exchange resins, and anion conductive solid polymer electrolyte membranes. Perfluorocarbonsulfonic acid (PFS-based polymer), due to the introduction of highly electronegative fluorine atoms into the polymer, is very chemically stable and has a high degree of dissociation of sulfonic acid groups, which can achieve high ion conductivity. Therefore it is better. The thickness of the electrolyte membrane can be, for example, 20 to 250 μm, preferably about 20 to 80 μm.

The surface of the electrolyte membrane can also be laminated with a catalyst layer of platinum, platinum alloy, platinum compound, etc. as a cathode catalyst or an anode catalyst. Furthermore, the electrolyte membrane of the body may have a reinforcing material or the like. Reinforcing materials and the like may be composed of polyolefin resins, olefin elastomers, and the like. When the aforementioned adhesive resin composition is used for an application for bonding two or more adherends, at least one adherend may have an electrolyte membrane. A part of the aforementioned adhesive resin composition may be attached by contacting a catalyst layer, a reinforcing material, or the like.

When the aforementioned resin compound (B) has two or more functional groups (epoxy groups, hydroxyl groups) that react with the functional groups of the electrolyte membrane in one molecule, the aforementioned resin composition for bonding is bonded so as to contact the electrolyte membrane , It forms a chemical bond between functional groups at the interface, and exhibits excellent water-resistant adhesiveness. As the functional group of the electrolyte membrane, for example, a sulfonic acid group, a carboxylic acid group, etc. can be cited.

〔Resin molded body for subsequent use〕 The adhesive resin molded body of the embodiment is formed of the aforementioned adhesive resin composition, and a molded body having a shape such as a film or a sheet can be used as a single-layer adhesive film or the like. The aforementioned resin molded body for adhesive is formed into a film shape by melt-kneading and extrusion molding the aforementioned resin composition for subsequent use containing the acid-modified polyolefin resin (A) and the aforementioned resin compound (B) as essential components. It can be manufactured by the method (1 step) of sheet shape and other shapes. Furthermore, by dissolving the adhesive resin composition in a solvent, and applying it to the adherend or the release material, the adhesive resin molded body can be manufactured. For example, as shown in FIG. 1, at least one side of the single-layer adhesive film 10 can be bonded to the object 21.

The aforementioned resin molded body for bonding can be bonded to the bulk layer by heating, preferably by heating and pressurizing, to various substrates by the methods listed in (1) to (4) below, for example. . (1) A method in which a resin molded body is laminated and bonded on one side of the body to be adhered. (2) A method of laminating separate resin moldings for bonding on both sides of the body to be adhered. (3) A method in which separate adherends are laminated on both sides of the resin molded body for bonding and then bonded. (4) A method of alternately laminating plural resin molded bodies for bonding and plural adherends and bonding them.

[Adhesive resin laminate] The adhesive resin laminate according to the embodiment of the present invention is a laminate having an adhesive layer composed of the aforementioned adhesive resin composition on at least one surface of a base material layer. As shown in FIG. 2, the multilayer adhesive film 10A has an adhesive layer 11 on one side of the base layer 12, and the adhesive layer 11 can be used to adhere to the object 21. As the base layer, the base layer itself does not need to have adhesiveness, and it is preferably one that can be connected to the adhesive layer. Furthermore, the base layer preferably has flexibility that can follow the expansion and contraction of the electrolyte membrane, heat resistance, chemical resistance, etc. depending on the usage conditions of the electrolyte membrane.

As a specific example of the said base material layer, polyolefin resin, such as a polyethylene resin and a polypropylene resin, can be mentioned, for example. By using a thin base material layer such as a resin film, the aforementioned resin laminate for adhesive can be used as a resin film for adhesive, a resin sheet for adhesive, or the like. When the base material layer pursues water resistance in a high-temperature environment, a polyolefin resin is preferred.

The adhesive resin laminate is formed into an adhesive layer by melt-kneading and extrusion molding an adhesive resin composition containing the acid-modified polyolefin resin (A) and the resin compound (B) as essential components The method (1 step) can be manufactured. When the base material layer is made of a thermoplastic resin, it can be performed by a co-extrusion method by extrusion molding with the resin composition for subsequent use. In addition, the subsequent extrusion molding of the resin composition can also be performed by the extrusion lamination method. Furthermore, it is also possible to manufacture the adhesive resin laminate by the method of dissolving the said adhesive resin composition in a solvent, and apply|coating to a base material layer.

When the aforementioned adhesive resin laminate has the aforementioned adhesive layer resin layer on only one side of the aforementioned base material layer, for example, by the method mentioned in (1) or (2) above, and the bulk layer It can be bonded to various objects by heating, preferably by heating and pressurizing. In addition, when the adhesive layer resin laminate has the adhesive layer resin layer on both sides of the base material layer, for example, the method listed in (1) to (4) above may be used with the bulk layer. By heating, preferably by heating and pressurizing, it can be bonded to various objects.

The above description is based on the preferred embodiment of the present invention, but the present invention is not limited to the above embodiment, and various changes can be made within the scope not departing from the gist of the present invention. Example

Hereinafter, the present invention will be described in detail based on examples.

(Following film) Adhesive resin compositions of compositions 1 to 9 shown in Table 1 were blended to produce an adhesive film having a layer structure shown in Table 2. When there is no substrate layer (compositions 1 to 4, 6, 8, 9), the acid-modified polyolefin resin (A), resin compound (B), and thermoplastic elastomer resin (C) are modified to 240 After being melt-kneaded for 2 minutes at °C, it was molded into 150 μm by extrusion molding to produce an adhesive film composed of a single-layer adhesive layer.

In the case of a substrate layer (compositions 5 and 7), dissolve the acid-modified polyolefin resin (A) and the resin compound (B) in a mixed solvent of toluene and methyl ethyl ketone (MEK), and then prepare the After applying the coating liquid of the resin composition, on the corona-treated surface of a polypropylene (PP) film with a thickness of 140 μm, the coating liquid is dried by a roll coater to become a thickness of 10 μm. It was dried at 110°C for 2 minutes to produce a two-layer adhesive film composed of a base layer and an adhesive layer.

[Table 1]

The meanings of the abbreviations used in Table 1 are as follows. "(A)-1": Maleic acid modified polypropylene (acid addition 0.1% by mass, melting point 140°C) "(A)-2": Maleic acid modified polyolefin (acid addition 1.1% by mass, melting point 80°C) "(B)-1": Bisphenol A epoxy (weight average molecular weight 900, 2 hydroxyl groups in a molecule, 2 epoxy groups) "(B)-2": Bisphenol A type novolac epoxy (weight average molecular weight 900, 2 hydroxyl groups in a molecule, 2 epoxy groups) "(B)-3": Bisphenol A epoxy (weight average molecular weight 370, 0 hydroxyl groups per molecule, 2 epoxy groups) "(C)-1": Propylene-α-olefin copolymer elastomer (softening point 70°C)

(Method of measuring bonding strength) Nafion (registered trademark) NRE-212 (thickness 0.002 inch) was used as the object to be adhered and processed into a size of 50mm×50mm. The adhered object was superimposed on the adhesive film, and the test piece was made by heating and pressing from the side of the adhered object. The aforementioned adherend was peeled off at a stretching speed of 300 mm/min, a width of 15 mm, and 180°, and the adhesive strength of the adhesive film was measured. The conditions of the heating and pressing were a temperature of 170° C., a pressure of 0.1 MPa, and heating and pressing for 10 seconds. When the strength was 5N/15mm or more, it was evaluated as "○", when it was 3N/15mm or more and less than 5N/15mm, it was evaluated as "△", and when it was less than 3N/15mm, it was evaluated as "×".

(Evaluation method of water resistance) A test piece was produced in the same manner as the evaluation method of adhesive strength, and it was immersed in water with a water temperature of 90°C for 300 hours, and the adhesive strength was measured. When the adhesive strength after water immersion was 5N/15mm or more, it was evaluated as "○", when it was 3N/15mm or more and less than 5N/15mm, it was evaluated as "△", and when it was less than 3N/15mm, it was evaluated as "×".

[Table 2]

Table 2 shows the evaluation results of the adhesive film. The adhesive film of the adhesive resin composition using compositions 1 to 5 has sufficient adhesive strength not only before water immersion but also after water immersion. The adhesive film of the adhesive resin composition using compositions 6 to 7 does not have adhesiveness to the electrolyte membrane. The adhesive film of the adhesive resin composition using compositions 8 to 9 does not have adhesiveness to the electrolyte membrane after being immersed in water. Industrial availability

The present invention can provide a substrate with an electrolyte membrane that has excellent adhesive force. Since it is formed of a simple composition, it can easily produce a resin composition for electrolyte membrane bonding, a resin membrane for electrolyte membrane bonding, and a resin membrane for electrolyte membrane bonding. The manufacturing method of the resin film is therefore of great industrial use value.

10: Single layer adhesive film 10A: Multi-layer adhesive film 11: Next layer 12: Substrate layer 21: Being Embodied

[Fig. 1] A cross-sectional view showing an example of an adhesive film without a base material layer. [Fig. 2] A cross-sectional view showing an example of an adhesive film having a base layer.

Claims (9)

A resin composition for adhering an electrolyte membrane, which is a resin composition for adhering an electrolyte membrane to an electrolyte membrane, and is characterized in that: Contains acid-modified polyolefin resin (A) and resin-based compound (B) as essential components, wherein the resin-based compound (B) has two or more functional groups in one molecule that react with the functional groups of the aforementioned electrolyte membrane, and 1 There are 4 or more functional groups in the molecule that react with the acid functional groups of the acid-modified polyolefin resin (A), The aforementioned resin compound (B) has an epoxy group and a hydroxyl group, or only an epoxy group as a functional group. The resin composition for the next electrolyte membrane according to claim 1, which contains the acid functional group of the acid-modified polyolefin resin (A) and the functional group of the resin compound (B) for graft polymerization And the obtained graft copolymer (G). The resin composition for electrolyte membrane adhesion according to claim 1 or 2, wherein the solid content of the resin composition for electrolyte membrane adhesion contains 100 parts by weight of the resin compound (B) in the range of 1 to 25 parts by weight . The resin composition for adhering an electrolyte membrane according to any one of claims 1 to 3, wherein the resin compound (B) is an epoxy resin or a phenoxy resin. The resin composition for adhering an electrolyte membrane according to any one of claims 1 to 4, wherein the solid content of the resin composition for adhering to an electrolyte membrane contains 100 parts by weight of a thermoplastic elastomer resin (C) 1 to 15 Within the range of parts by weight. A resin membrane for adhering an electrolyte membrane, characterized by being formed into a film from the electrolyte membrane according to any one of claims 1 to 5, followed by a resin composition. A resin film for adhering an electrolyte membrane, characterized in that an adhering layer formed of the resin composition for adhering an electrolyte membrane according to any one of claims 1 to 5 is laminated on at least one side of a substrate layer. A method for producing a resin film for following an electrolyte membrane, characterized in that the electrolyte membrane according to any one of claims 1 to 5 is subsequently melt-kneaded with a resin composition, and then extruded to form a film into a film. . A method for producing a resin film for electrolyte membrane adhesion, characterized in that the electrolyte membrane resin composition according to any one of claims 1 to 5 is dissolved in a solvent and applied.

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