Curable resin composition, fuel cell, and sealing method

Abstract

[Problem] The purpose of the present invention is to provide a curable resin composition which is suitable for application by means of screen printing, while maintaining the characteristics of a cured product including high strength and high elongation. [Solution] A curable resin composition which contains the components (A) to (C) described below. Component (A): a polyisobutylene resin which comprises one or more (meth)acryloyl groups and –(CH2C(CH3)2)- unit Component (B): a radical polymerization initiator Component (C): an antifoaming agent which does not contain an organic solvent, while containing a silicone compound that does not have any one of a methoxysilyl group, an ethoxysilyl group and a (meth)acryloyl group.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a fuel cell, and a sealing method. [Background technology]

[0002] In recent years, fuel cells have been attracting attention as a new energy system for automobiles and homes. A fuel cell is a power generation device that generates electricity by chemically reacting hydrogen and oxygen. Furthermore, fuel cells are highly energy efficient when generating electricity, and are a clean, next-generation power generation device because water is produced by the reaction between hydrogen and oxygen. There are four types of fuel cells: polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells. Among these, polymer electrolyte fuel cells have high power generation efficiency despite their relatively low operating temperature (around 80°C), making them promising for use as a power source for automobiles, home power generation devices, small power sources for electronic devices such as mobile phones, and emergency power sources.

[0003] As shown in FIG. 1, a cell 1 of a polymer electrolyte fuel cell is a structure comprising a membrane electrode assembly (MEA) 5 in which a polymer electrolyte membrane 4 is sandwiched between an air electrode (cathode electrode) 3a and a fuel electrode (anode electrode) 3b, a frame 6 that supports the MEA, and a separator 2 in which a gas flow path is formed.

[0004] To start a polymer electrolyte fuel cell, a fuel gas containing hydrogen must be supplied to the anode electrode, and an oxidizing gas containing oxygen must be supplied to the cathode electrode, while keeping them separate. If the separation is insufficient and one gas mixes with the other, this can result in a decrease in power generation efficiency. For this reason, sealants are often used to prevent leakage of fuel gas and oxidizing gas. Specifically, sealants are used between adjacent separators, between the separator and the frame, and between the frame and the electrolyte membrane or MEA.

[0005] As a sealant for a polymer electrolyte fuel cell, a polymer composition using a polyisobutylene polymer is used because it is a rubber elastic material that has excellent gas permeability resistance, low moisture permeability, heat resistance, and acid resistance. Specifically, Patent Document 1 discloses a polymer composition that contains a telechelic polyisobutylene polymer having a terminal acrylate group and a reactive diluent, and that has excellent cured product properties such as high strength and high elongation. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-88614 Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, manufacturing sites have been demanding further reductions in takt time in the application and curing processes of sealants. Specifically, from the perspective of productivity, this has led to compatibility with screen printing (see JP 2009-117314 A). However, the polymer composition of Patent Document 1 uses a high-molecular-weight polymer to improve the properties of the cured product, such as high strength and elongation. Therefore, the polymer composition suffers from repelling from the adherend during application by screen printing, and it is difficult to eliminate bubbles generated during screen printing, making it unsuitable for screen printing.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable resin composition that can be applied by screen printing while maintaining the cured product properties of high strength and high elongation. [Means for solving the problem]

[0009] The gist of the present invention will now be described.

[0010] [1] A curable resin composition containing the following components (A) to (C): Component (A): a polyisobutylene resin containing one or more (meth)acryloyl groups and a —[CH2C(CH3)2]— unit. Component (B): Radical polymerization initiator Component (C): A defoaming agent containing a silicone compound that has no methoxysilyl group, no ethoxysilyl group, and no (meth)acryloyl group, and that does not contain any organic solvent.

[0011] [2] The curable resin composition according to [1], wherein the component (A) is a polyisobutylene resin represented by general formula (1):

[0012] [ka]

[0013] (In formula (1), R 1 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group which may have an aromatic ring; PIB represents a polyisobutylene skeleton containing the -[CHC(CH)]- unit; R 4 represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom, and R 2 and R 3 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; R 5 represents a hydrogen atom, a methyl group or an ethyl group, and n is an integer of 1 to 6.

[0014] [3] The curable resin composition according to [1] or [2], characterized in that it contains 0.1 to 10 parts by mass of the component (C) per 100 parts by mass of the component (A).

[0015] [4] The curable resin composition according to any one of [1] to [3], further comprising a monofunctional monomer as component (D).

[0016] [5] The curable resin composition according to any one of [1] to [4], which does not contain an organic solvent.

[0017] [6] The curable resin composition according to any one of [1] to [5], wherein the silicone compound of the component (C) is a compound having a structure of dimethylsiloxane, methylphenylsiloxane, or diphenylsiloxane.

[0018] [7] The curable resin composition according to any one of [4] to [6], wherein the component (C) is contained in an amount of 0.1 to 9 parts by mass per 100 parts by mass of the total amount of the components (A) and (D).

[0019] [8] The curable resin composition according to any one of [1] to [7], wherein the component (B) is a photoradical polymerization initiator or an organic peroxide.

[0020] [9] A curable sealant for a fuel cell, comprising the curable resin composition according to any one of [1] to [8].

[0021]

[10] The curable sealant for fuel cells described in [9], wherein the curable sealant for fuel cells is used for any component selected from the group consisting of a separator, a frame, an electrolyte membrane, a fuel electrode, an air electrode, and an electrolyte membrane electrode assembly, which are components of a fuel cell.

[0022]

[11] A cured product of the curable resin composition according to any one of [1] to [8].

[0023]

[12] A fuel cell including any seal selected from the group consisting of a seal between adjacent separators in the fuel cell and a seal between the frame of the fuel cell and an electrolyte membrane or an electrolyte membrane electrode assembly, wherein any of the seals is the cured product according to

[11] .

[0024]

[13] A sealing method for sealing at least a portion of the gap between at least two flanges of a sealed part having at least two flanges, wherein at least one of the flanges is permeable to active energy rays, the sealing method comprising the steps of: applying the curable resin composition according to any one of [1] to [8] to a surface of at least one of the flanges; bonding one flange coated with the curable resin composition to the other flange via the curable resin composition; and irradiating the active energy rays through the flange permeable to active energy rays to cure the curable resin composition, thereby sealing at least a portion of the gap between the at least two flanges.

[0025]

[14] A sealing method for sealing at least a portion of the gap between at least two flanges of a sealed part having the at least two flanges, the sealing method comprising the steps of: applying the curable resin composition according to any one of [1] to [8] to at least one of the flanges; irradiating the applied curable resin composition with active energy rays to cure the curable resin composition and form a gasket made of a cured product of the curable resin composition; and placing the other flange on the gasket and crimping the one flange coated with the curable resin composition and the other flange via the gasket to seal at least a portion of the gap between the at least two flanges.

[0026]

[15] A sealing method for sealing at least a portion of the gap between at least two flanges of a sealed part having at least two flanges, the sealing method comprising the steps of: placing a gasket-forming mold on at least one of the flanges; injecting the curable resin composition according to any one of [1] to [8] into at least a portion of the gap between the gasket-forming mold and the one flange on which the mold is placed; irradiating the curable resin composition with the active energy ray to cure the curable resin composition and form a gasket made of a cured product of the curable resin composition; removing the mold from the one flange; and placing the other flange on the gasket and crimping the one flange and the other flange together via the gasket, thereby sealing at least a portion of the gap between the at least two flanges. [Effects of the Invention]

[0027] The present invention provides a curable resin composition that can be applied by screen printing while maintaining high strength and high elongation properties of the cured product. [Brief explanation of the drawings]

[0028] [Figure 1] FIG. 1 is a schematic cross-sectional view of a single cell of a fuel cell. [Figure 2] FIG. 1 is a schematic diagram showing an entire fuel cell. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention will be described in detail below. In this specification, "X to Y" is used to mean "at least X and at most Y," with the numerical values ​​(X and Y) before and after it being included as the lower and upper limits, respectively. In addition, in the present invention, "(meth)acrylate" means both acrylate and methacrylate.

[0030] The curable resin composition of the present invention comprises: (A) component: a polyisobutylene resin containing one or more (meth)acryloyl groups and a -[CHC(CH)]- unit; (B) component: a radical polymerization initiator; and (C) component: an organic solvent-free defoaming agent containing a silicone compound having no methoxysilyl groups, no ethoxysilyl groups, and no (meth)acryloyl groups. The present invention provides a curable resin composition that has high strength and elongation and is suitable for screen printing. "Suitable for screen printing" means, for example, that the composition does not repel water from the adherend during application by screen printing, and does not generate bubbles during screen printing.

[0031] <Component (A)> The component (A) used in the present invention is not particularly limited as long as it is a polymer having a polyisobutylene skeleton containing one or more (meth)acryloyl groups and -[CHC(CH)]- units. The component (A) may, for example, contain -[CHC(CH)]- units (polyisobutylene skeleton), or may be a polymer further containing "structural units other than -[CHC(CH)]- units." The component (A) suitably contains -[CHC(CH)]- units in an amount of, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, based on the total amount of structural units. The component (A) also suitably contains -[CHC(CH)]- units in an amount of, for example, 100% by mass or less, in another embodiment 95% by mass or less, and in another embodiment 90% by mass or less. Component (A) preferably has 1 to 12 (meth)acryloyl groups, more preferably 2 to 8, even more preferably 2 to 4, and particularly preferably 2. In the present invention, a polymer can be defined, without being bound by theory, as a compound having a structure in which a monomer repeating unit is attached to the polymer main chain and consisting of 100 or more repeating units. The (meth)acryloyl groups may be present in the side chain and / or at the terminals of the molecule, but from the viewpoint of rubber elasticity, they are preferably present at the terminals of the molecule.

[0032] As component (A), a polymer having a polyisobutylene skeleton represented by general formula (1) is preferred, from the viewpoint of obtaining a curable resin composition having excellent cured product properties such as high strength and high elongation. Specific examples of component (A) include polyisobutylene having a (meth)acryloyloxyalkoxyphenyl group. While the main skeleton of component (A) in the present invention is a polyisobutylene skeleton, other monomers may be copolymerized in addition to isobutylene as the main monomer constituting this polyisobutylene skeleton, as long as the effects of the present invention are not impaired. It is preferable that component (A) be liquid at room temperature (25°C), since this will result in a curable resin composition that is more suitable for application by screen printing.

[0033] [ka]

[0034] In formula (1), R 1represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group which may have an aromatic ring. The monovalent or polyvalent aromatic hydrocarbon group is preferably an aryl group having 6 to 18 carbon atoms or an arylene group having 6 to 18 carbon atoms. Specific examples of the monovalent or polyvalent aromatic hydrocarbon group include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a biphenyl group, a tolyl group, a tolylene group, a xylyl group, and a xylylene group. The monovalent or polyvalent aliphatic hydrocarbon group which may have an aromatic ring is an alkyl group having 6 to 18 carbon atoms, an alkylene group having 6 to 18 carbon atoms, an arylalkyl group having 6 to 18 carbon atoms, or an alkylenearylenealkylene group having 6 to 18 carbon atoms. Specific examples of monovalent or polyvalent aliphatic hydrocarbon groups which may have an aromatic ring include groups represented by -C(CH3)2CH2C(CH3)2CH3, -C(CH3)2CH2C(CH3)2CH2C(CH3)2-, and -C(CH3)2-CH4-C(CH3)2- (dicumyl group). Among these, polyvalent aromatic hydrocarbon groups or aliphatic hydrocarbon groups which may have an aromatic ring are preferred, and divalent groups such as phenylene and dicumyl groups (more preferably p-dicumyl groups) are particularly preferred.

[0035] PIB denotes a polyisobutylene backbone containing -[CH2C(CH3)2]- units.

[0036] R 4 represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom, and is preferably a divalent hydrocarbon group having 2 or 3 carbon atoms. Preferred examples of the divalent saturated hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom include -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2-O-CH2CH2-, and -CH2CH(OH)CH2-. Of these, -CH2CH2- is preferred.

[0037] R 2 and R 3R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and is preferably a hydrogen atom. 5 represents a hydrogen atom, a methyl group, or an ethyl group, and is preferably a hydrogen atom or a methyl group. n is an integer of 1 to 6, and particularly preferably an integer of 2 to 4.

[0038] The molecular weight of component (A) in the present invention is not particularly limited, but in order to be compatible with application by screen printing and to have excellent sealing properties, the number average molecular weight measured by chromatography is, for example, preferably 200 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 3,000 to 50,000. exclusion Calculation was performed using standard polystyrene conversion method using chromatography (SEC).

[0039] The viscosity of component (A) at 25°C in the present invention is not particularly limited, but from the standpoint of workability and the like, it is, for example, 5 Pa·s or more, preferably 50 Pa·s or more, more preferably 100 Pa·s or more, even more preferably 500 Pa·s or more, and particularly preferably 1000 Pa·s or more, and for example, 3000 Pa·s or less, preferably 2500 Pa·s or less, more preferably 2000 Pa·s or less. A particularly preferred viscosity is 1800 Pa·s or less. Unless otherwise specified, viscosity was measured at 25°C using a cone-plate viscometer.

[0040] The method for producing component (A) is not particularly limited, and known techniques can be used. Examples include the method disclosed in Polymer Bulletin, Vol. 6, pp. 135-141 (1981), T.P. Liao and J.P. Kennedy, and Polymer Bulletin, Vol. 20, pp. 253-260 (1988), Puskas et al., in which hydroxyl-terminated polyisobutylene is reacted with acryloyl chloride or methacryloyl chloride. Other methods for producing component (A) include reacting hydroxyl-terminated polyisobutylene with a compound having (meth)acryloyl groups and isocyanate groups, reacting hydroxyl-terminated polyisobutylene with a compound having isocyanate groups and a compound having (meth)acryloyl groups and hydroxyl groups, and reacting hydroxyl-terminated polyisobutylene with (meth)acrylic acid or a lower (meth)acrylic acid ester using a dehydration esterification method or an ester exchange method.

[0041] The method for producing polyisobutylene represented by general formula (1) is not particularly limited, but preferably includes the method disclosed in JP 2013-216782 A in which halogen-terminated polyisobutylene is reacted with a compound having a (meth)acryloyl group and a phenoxy group, such as that represented by general formula (2). Halogen-terminated polyisobutylene can be obtained by known methods, such as cationic polymerization, and more preferably living cationic polymerization.

[0042] [ka]

[0043] In general formula (2), R 2、 R 3 , R 4 , and R 5 may be as defined in the general formula (1). 4 represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom. 2 and R 3R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. 5 represents a hydrogen atom, a methyl group, or an ethyl group. Examples of the compound represented by the general formula (2) include phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, and phenoxypentyl (meth)acrylate, and preferred are phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, and phenoxypentyl (meth)acrylate.

[0044] <(B) component> The component (B) that can be used in the present invention is a radical polymerization initiator. Examples of such a component (B) include a photoradical polymerization initiator and an organic peroxide (thermal radical polymerization initiator). The curing form of the radical curable resin composition of the present invention can be selected to be photocuring, heat curing, or redox curing by selecting the component (B) of the present invention. For example, if one wishes to impart "photocurability" to the radical curable resin composition, one should select a photoradical polymerization initiator, and if one wishes to impart "thermal curing or curing by redox reaction," one should select an organic peroxide.

[0045] The blending amount of component (B) of the present invention is not particularly limited, but is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 0.3 to 18 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 1.5 to 10 parts by mass, relative to 100 parts by mass of component (A). A blending amount within the above range is preferred because it allows for the cured product to have high strength and high elongation properties.

[0046] The photoradical polymerization initiator, which is one of the components (B) that can be used in the present invention, is not limited as long as it is a compound that generates radicals upon irradiation with light (active energy rays). Here, active energy rays include all light in the broad sense, such as radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams (EB), ultraviolet rays with wavelengths of approximately 100 to 400 nm, and visible light with wavelengths of approximately 400 to 800 nm, with ultraviolet rays being preferred. Examples of photoradical polymerization initiators for component (B) include acetophenone-based photoradical polymerization initiators, benzoin-based photoradical polymerization initiators, benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and titanocene-based photoradical polymerization initiators. Among these, acetophenone-based photoradical polymerization initiators and acylphosphine oxide-based photoradical polymerization initiators are preferred from the viewpoint of obtaining cured products with high strength and elongation. These may be used alone or in combination of two or more.

[0047] Examples of acetophenone-based photoradical polymerization initiators include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. Commercially available acetophenone-based photoradical polymerization initiators include Omnirad (registered trademark, the same applies hereinafter) 184, Omnirad 1173, Omnirad 2959, Omnirad 127, and ESACURE (registered trademark) KIP-150 (manufactured by IGM Resins BV).

[0048] Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available acylphosphine oxide-based photoradical polymerization initiators include Omnirad TPO, Omnirad 819, and Omnirad 819DW (manufactured by IGM Resins BV).

[0049] The organic peroxide, which is one of the components (B) that can be used in the present invention, is a compound that generates radical species upon heating or a redox reaction. Here, heating is suitably performed at a temperature of, for example, 50°C or higher, preferably 80°C or higher, and more preferably 100°C or higher. Compounds that generate radical species upon heating are also called thermal radical polymerization initiators. A redox reaction, also known as an oxidation-reduction reaction, is a phenomenon in which an oxidation-reduction reaction occurs due to radical species released from an organic peroxide. Using a redox reaction is preferred because radical species can be generated at room temperature. The organic peroxide as component (B) is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; peroxides such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; Hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;Diacyl peroxides such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate peroxydicarbonates such as di-n-propyl peroxydicarbonate, bis-(4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, and diallyl peroxydicarbonate; t-butyl peroxyacetate, t-butyl peroxydicarbonate, Peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxy Examples of organic peroxides include peroxyesters such as cymaleic acid, t-butyl peroxyisopropyl carbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, and cumyl peroxyneohexanoate; and acetylcyclohexylsulfonyl peroxide and t-butyl peroxyallyl carbonate. These organic peroxides may be used alone or in combination. Of these, cumene hydroperoxide is preferred from the viewpoint of high strength and high elongation of the cured product.

[0050] When an organic peroxide is used as component (B), a curing accelerator can be added to accelerate the redox reaction. Such curing accelerators are not particularly limited, but preferred examples include saccharin (o-benzoix sulfimide), hydrazine compounds, amine compounds, mercaptan compounds, and transition metal-containing compounds.

[0051] Examples of hydrazine compounds include 1-acetyl-2-phenylhydrazine, 1-acetyl-2(p-tolyl)hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1',1',1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2-(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethyl carbazate, p-nitrophenylhydrazine, and p-trisulfonylhydrazide.

[0052] Examples of the amine compound include heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, and 1,2,3,4-tetrahydroquinaldine; heterocyclic tertiary amines such as quinoline, methylquinoline, quinaldine, and quinoxalinephenazine; aromatic tertiary amines such as N,N-dimethyl-p-toluidine, N,N-dimethyl-anisidine, and N,N-dimethylaniline; and azole compounds such as 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotriazole.

[0053] Examples of mercaptan compounds include n-dodecyl mercaptan, ethyl mercaptan, butyl mercaptan, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthioglycolate.

[0054] The transition metal-containing compound is preferably a metal chelate complex salt, such as iron pentadione, cobalt pentadione, copper pentadione, propylenediamine copper, ethylenediamine copper, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octate, iron hexoate, iron propionate, or vanadium acetylacetonate.

[0055] The above-mentioned curing accelerators may be used alone or in combination. Among them, a mixture of saccharin, a hydrazine compound, an amine compound, and a transition metal-containing compound is more preferred because it exhibits a good curing acceleration effect.

[0056] <(C) component> The component (C) of the present invention is a defoaming agent that contains a silicone compound that does not contain a methoxysilyl group, an ethoxysilyl group, or a (meth)acryloyl group, and does not contain an organic solvent. That is, the defoaming agent does not contain an organic solvent and contains a silicone compound that does not contain a methoxysilyl group, an ethoxysilyl group, or a (meth)acryloyl group. By selecting the component (C) of the present invention from among the many available defoaming agents and combining it with the other components of the present invention, the present invention has the remarkable effect of providing a curable resin composition that can be applied by screen printing while maintaining high strength and high elongation properties of the cured product. The silicone compound includes a compound containing a -Si-O-Si- (siloxane bond), and more specifically, compounds having a structure such as dimethylsiloxane, methylphenylsiloxane, or diphenylsiloxane. Furthermore, the silicone compound of component (C) does not have any of methoxysilyl groups, ethoxysilyl groups, or (meth)acryloyl groups at the terminals or side chains of the silicone compound molecule, from the viewpoint of maintaining the tensile strength of the cured product while minimizing repelling when the curable resin composition is applied to an adherend by screen printing. Preferably, the silicone compound is a compound in which at least one of the terminals is blocked with a trimethylsilyl group. Furthermore, component (C) is characterized by the absence of an organic solvent, from the viewpoint of maintaining the tensile strength of the cured product while minimizing repelling when the curable resin composition is applied to an adherend by screen printing. Herein, the term "organic solvent" refers to an organic compound that is liquid at 25°C other than the silicone compound, components (B), and (D), such as propylene glycol or diisobutyl ketone. Furthermore, as described below, the curable resin composition of the present invention preferably does not contain an organic solvent. For this reason, component (C) does not contain an organic solvent.

[0057] The silicone compound contained in component (C) preferably contains a dimethylpolysiloxane structure having a siloxane bond (Si-O-Si) and a methyl group. By containing a dimethylpolysiloxane structure in the silicone compound contained in component (C), the desired effects of the present invention can be more effectively achieved, and a curable resin composition suitable for screen printing can be obtained.

[0058] The silicone compound contained in component (C) is preferably silicone oil, which is a type of silicone compound, and therefore component (C) is preferably an oil-type defoaming agent.

[0059] The silicone compound contained in component (C) has a viscosity of 1 to 500 mm at 25°C. 2 / s, and 10 to 350 mm 2 / s. When the viscosity of the silicone compound at 25°C is in the above range, it can exhibit its antifoaming effect. Furthermore, from the viewpoint of exhibiting its antifoaming effect, the viscosity of component (C) at 25°C is also preferably in the range of 1 to 500 mm 2 / s, and 10 to 350 mm 2 It is more preferable that the range is / s.

[0060] In component (C), the silicone compound is preferably contained as the main component. In this specification, "main component" means that it accounts for 75% by mass or more of the total mass of component (C). The upper limit of the silicone compound content in component (C) is 100% by mass, based on the total mass of component (C). The content of the silicone compound in component (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the antifoaming agent.

[0061] Component (C) may contain additives to the extent that the properties of the defoaming agent are not impaired. Examples of additives include waxes such as polyethylene wax, hydrophobic silica, etc. For example, the content of additives in component (C) is 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content of additives in component (C) is 0% by mass, based on the total mass of component (C).

[0062] Commercially available products of the component (C) of the present invention include, for example, BYK-1799 (manufactured by BYK-Chemie) and KF-96 series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0063] The amount of (C) added is not particularly limited, but for example, the content of component (C) is in the range of 0.1 to 10 parts by mass, preferably 0.15 to 5 parts by mass, more preferably 0.15 to 4.5 parts by mass, even more preferably 0.2 to 4 parts by mass, particularly preferably 0.2 to 3 parts by mass, and even more preferably 0.5 to 2.5 parts by mass, per 100 parts by mass of the combined amount of component (A) and component (D), described below, the content of component (C) is preferably in the range of 0.1 to 9 parts by mass, more preferably 0.2 to 7 parts by mass, even more preferably 0.3 to 5 parts by mass, particularly preferably 0.3 to 3 parts by mass, and most preferably 0.3 to 1.5 parts by mass. By keeping the content within the above ranges, it is possible to obtain a curable resin composition that can be applied by screen printing while maintaining the cured product properties of high strength and high elongation.

[0064] <(D) component> Furthermore, the curable resin composition of the present invention can further contain a monofunctional monomer as component (D). When combined with the other components of the present invention (components (A) to (C)), component (D) can be more easily applied by screen printing and can maintain the properties of the cured product. Examples of component (D) include a (meth)acrylate monomer having an alkyl group of 5 to 30 carbon atoms or a (meth)acrylate monomer having an alicyclic hydrocarbon group of 5 to 30 carbon atoms. Of these, it is particularly preferable to use a combination of a (meth)acrylate monomer having an alkyl group of 5 to 30 carbon atoms and a (meth)acrylate monomer having an alicyclic hydrocarbon group of 5 to 30 carbon atoms, from the viewpoint of being more easily applied by screen printing and maintaining the properties of the cured product.

[0065] Examples of (meth)acrylate monomers having an alkyl group having 5 to 30 carbon atoms include 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, n-octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecane (meth)acrylate, isostearyl (meth)acrylate, and stearyl (meth)acrylate. Of these, preferred are 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isooctadecyl (meth)acrylate, isostearyl (meth)acrylate, and stearyl (meth)acrylate. Of the (meth)acrylate monomers having an alkyl group having 5 to 30 carbon atoms, (meth)acrylate monomers having an alkyl group having 6 to 20 carbon atoms are preferred, and (meth)acrylate monomers having an alkyl group having 8 to 20 carbon atoms are preferred. Component (D) can be used alone or as a mixture of two or more. Commercially available (meth)acrylate monomers having an alkyl group having 5 to 30 carbon atoms are not particularly limited, but examples include SR335, SR395, SR440, SR489D, SR313, SR324, and SR493D (manufactured by Sartomer Corporation), and S-1800A (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0066] Examples of (meth)acrylate monomers having an alicyclic hydrocarbon group having 5 to 30 carbon atoms include cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and dicyclopentenyl di(meth)acrylate. Among these, trimethylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, and isobornyl (meth)acrylate are preferred. These can be used alone or in combination. Of the (meth)acrylate monomers having an alicyclic hydrocarbon group having 5 to 30 carbon atoms, (meth)acrylate monomers having an alicyclic hydrocarbon group having 6 to 20 carbon atoms are preferred, and (meth)acrylate monomers having an alicyclic hydrocarbon group having 8 to 20 carbon atoms are preferred. Commercially available (meth)acrylate monomers having an alicyclic hydrocarbon group having 5 to 30 carbon atoms are not particularly limited, but examples include SR506 and SR423 (all manufactured by Sartomer), IBX and IBX-A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT and FA-513M (all manufactured by Showa Denko Materials K.K.).

[0067] The amount of component (D) blended is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, even more preferably 12 to 200 parts by mass, particularly preferably 30 to 150 parts by mass, and most preferably 40 to 100 parts by mass, per 100 parts by mass of component (A). By keeping the amount within the above range, it is possible to provide a curable resin composition that is more suitable for application by screen printing and can be photocured in a short period of time. When two or more types of component (D) are combined, the total amount is taken as the content of component (D). Furthermore, when a (meth)acrylate monomer having an alkyl group having 5 to 30 carbon atoms and a (meth)acrylate monomer having an alicyclic hydrocarbon group having 5 to 30 carbon atoms are used in combination, the mass ratio (x:y) of the (meth)acrylate monomer (x) having an alkyl group having 5 to 30 carbon atoms to the (meth)acrylate monomer (y) having an alicyclic hydrocarbon group having 5 to 30 carbon atoms is, for example, in the range of 1:99 to 99:1, preferably 10:90 to 90:10, and particularly preferably 15:85 to 85:15.

[0068] <Optional ingredients> Additives such as an oligomer or polymer having a (meth)acryloyl group (excluding the component (A) of the present invention), an inorganic filler, a curing accelerator, a storage stabilizer, an antioxidant, a light stabilizer, a plasticizer, a pigment, a flame retardant, and a surfactant can be added to the curable resin composition of the present invention, as long as the object of the present invention is not impaired.

[0069] The oligomer or polymer having a (meth)acryloyl group (not including the component (A) of the present invention) is not particularly limited, and examples thereof include urethane (meth)acrylates having a polybutadiene skeleton, urethane (meth)acrylates having a hydrogenated polybutadiene skeleton, urethane (meth)acrylates having a polycarbonate skeleton, urethane (meth)acrylates having a polyether skeleton, urethane (meth)acrylates having a polyester skeleton, urethane (meth)acrylates having a castor oil skeleton, isoprene-based (meth)acrylates, hydrogenated isoprene-based (meth)acrylates, epoxy (meth)acrylates, and (meth)acrylic group-containing acrylic polymers. Among these, urethane (meth)acrylates having a polybutadiene skeleton, urethane (meth)acrylates having a hydrogenated polybutadiene skeleton, urethane (meth)acrylates having a castor oil skeleton, isoprene-based (meth)acrylates, and hydrogenated isoprene-based (meth)acrylates are preferred because of their excellent compatibility with the components (A) and (B) of the present invention. In the present invention, an oligomer refers to a compound having a structure with repeating units of a monomer in the main chain, and consisting of 2 to 100 repeating units. These may be used alone or in combination of two or more kinds.

[0070] To improve the elastic modulus, flowability, etc. of the cured product, an inorganic filler may be added to the curable resin composition of the present invention to an extent that does not impair storage stability. Specific examples include inorganic powders and metallic powders. Examples of inorganic powder fillers include glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth. The amount of inorganic powder added is preferably about 0.1 to 100 parts by mass per 100 parts by mass of component (A).

[0071] Fumed silica can be blended to adjust the viscosity of the curable resin composition or to improve the mechanical strength of the cured product. Preferably, silica that has been hydrophobized with organochlorosilanes, polyorganosiloxane, hexamethyldisilazane, or the like can be used. Specific examples of fumed silica include commercially available products such as Aerosil (registered trademark) R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, and R202 manufactured by Nippon Aerosil.

[0072] An antioxidant may be added to the curable resin composition of the present invention. Examples of the antioxidant include quinone compounds such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, and tert-butylcatechol. Chole, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol) ), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(Mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethyl bis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, reaction products of N-phenylbenzenamine with 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5 -triazin-2-ylamino)phenol, picric acid, citric acid and other phenolic compounds; tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl] phosphorus compounds such as tetrakis(2,4-di-tert-butylphenyl)[1,1-bisphenyl]-4,4'-diylbisphosphonate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphene; dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,Examples of suitable compounds include sulfur compounds such as 3'-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), and 2-mercaptobenzimidazole; amine compounds such as phenothiazine; lactone compounds; and vitamin E compounds. Among these, phenolic compounds are preferred.

[0073] A light stabilizer may be added to the curable resin composition of the present invention. Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6, 6-Tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, Decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, N,N',N' ',N' ' '-Tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, polycondensate of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)butylamine] N-acetyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5·1·11·2]heneicosan-21-one, β-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-Tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanediol acid, [(4-methoxyphenyl)-methylene]-bis(1,2,2 ,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, hindered amine compounds such as N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl); benzophenone compounds such as octabenzone; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methyl 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)benzotriazole Examples of suitable benzotriazole compounds include reaction products of benzotriazole-based benzoates with polyethylene glycol, benzotriazole compounds such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol. Hindered amine compounds are particularly preferred.

[0074] An adhesion promoter may be added to the curable resin composition of the present invention. Examples of the adhesion promoter include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-chloropropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glucan. Examples of such silanes include ricidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, hydroxyethyl methacrylate phosphate ester, methacryloxyoxyethyl acid phosphate, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylic acid phosphate, etc. Among these, hydroxyethyl methacrylate phosphate ester, methacryloxyoxyethyl acid phosphate, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylic acid phosphate, etc. are preferred. The content of the adhesion promoter is preferably 0.05 to 30 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the component (A).

[0075] The curable resin composition of the present invention preferably does not contain an organic solvent, from the viewpoint of maintaining the tensile strength of the cured product while minimizing repelling when the curable resin composition is applied to an adherend by screen printing. The organic solvent refers to an organic compound that is liquid at 25°C other than the silicone compound, component (B), component (C), and component (D), and examples thereof include propylene glycol and diisobutyl ketone.

[0076] The viscosity of the curable resin composition of the present invention at 25°C is not particularly limited, but from the viewpoint of workability and the like, it is, for example, 0.1 Pa·s or more, preferably 0.2 Pa·s or more, more preferably 0.5 Pa·s or more, even more preferably 1 Pa·s or more, particularly preferably 2 Pa·s or more, and for example, 100 Pa·s or less, preferably 50 Pa·s or less, more preferably 20 Pa·s or less. A particularly preferred viscosity is 10 Pa·s or less. Unless otherwise specified, the viscosity was measured at 25°C using a cone-plate viscometer.

[0077] The curable resin composition of the present invention can be produced by a conventionally known method. For example, it can be produced by blending the predetermined amounts of components (A) to (C) and mixing them using a mixing means such as a mixer at a temperature of preferably 10 to 70°C for preferably 0.1 to 5 hours. It is also preferable to produce it in a light-shielded environment.

[0078] <Application method> The curable resin composition of the present invention can be applied to an adherend by, for example, dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, spin coating, etc. Among these, the curable resin composition of the present invention is most suitable for screen printing because it has the effect of defoaming bubbles generated during screen printing. From the viewpoint of coatability, the curable resin composition of the present invention is preferably liquid at 25°C.

[0079] <Curing method> The light source used when curing the curable resin composition of the present invention by irradiating it with ultraviolet light, visible light, or the like is not particularly limited, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, an electron beam irradiation device, etc. The exposure dose of light irradiation is set to 3 kJ / m from the viewpoint of the properties of the cured product. 2 It is preferable that the concentration is equal to or higher than 5 kJ / m2 From the viewpoint of the takt time of the curing process, 2 It is preferably equal to or less than 80 kJ / m 2 or less, and particularly preferably 60 kJ / m 2 The following is the result.

[0080] <Cured product> The cured product of the present invention is obtained by curing the curable resin composition of the present invention by irradiating it with ultraviolet light using the above-mentioned curing method. The cured product of the present invention can be obtained by any curing method as long as it is obtained by curing the curable resin composition of the present invention.

[0081] <Applications and sealants> The curable resin composition of the present invention or its cured product is preferably used as a curable sealant. In the present invention, the sealant also includes applications such as adhesives, coating agents, casting agents, and potting agents. When used in such applications, the curable resin composition of the present invention is preferably liquid at 25°C.

[0082] The curable resin composition of the present invention or a cured product thereof is a rubbery elastic body that has excellent properties such as low gas permeability (gas barrier properties), low moisture permeability, heat resistance, acid resistance, and flexibility, and therefore specific applications of the sealant include fuel cells, solar cells, dye-sensitized solar cells, lithium ion batteries, electrolytic capacitors, liquid crystal displays, organic EL displays, electronic paper, LEDs, hard disk drives, photodiodes, optical communications and circuits, electric wires, cables, and optical fibers, optical isolators, laminates such as IC cards, sensors, substrates, pharmaceutical and medical instruments and devices, etc. The curable resin composition of the present invention cures rapidly upon irradiation with active energy rays such as ultraviolet rays and has excellent gas barrier properties, and therefore, among these applications, fuel cell application is particularly preferred.

[0083] <Fuel cell> Fuel cells are power generation devices that generate electricity by chemically reacting hydrogen and oxygen. There are four types of fuel cells: polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells. Among them, polymer electrolyte fuel cells have high power generation efficiency despite their relatively low operating temperature (around 80°C), so they are used as power sources for automobiles, home power generators, small power sources for electronic devices such as mobile phones, and emergency power sources.

[0084] As shown in Figure 1, a typical solid polymer fuel cell cell 1 comprises a membrane electrode assembly 5 (MEA) in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and an anode 3b, a frame 6 that supports the MEA, and a separator 2 in which gas channels are formed. When the solid polymer fuel cell is started, fuel gas (hydrogen gas) and oxidizing gas (oxygen gas) are supplied through oxidizing gas channel 8a and fuel gas channel 8b, respectively. Cooling water flows through channel 9 to reduce heat generation during power generation. Several hundred such cells are stacked and packaged together to form a cell stack 10, as shown in Figure 2.

[0085] When fuel gas (hydrogen gas) is supplied to the fuel electrode and oxidizing gas (oxygen gas) is supplied to the oxygen electrode (air electrode), the following reactions occur at each electrode, with the overall reaction producing water (H2+1 / 2O2→H2O). In more detail, protons (H+) produced at the fuel electrode diffuse through the solid polymer membrane and move to the oxygen electrode side, and the water (H2O) produced by reacting with oxygen is discharged from the oxygen electrode side. Fuel electrode (anode electrode): H2 → 2H+ + 2e - Oxygen electrode (cathode electrode): 1 / 2O2 + 2H + +2e - →H2O To start a polymer electrolyte fuel cell, a fuel gas containing hydrogen must be supplied to the anode electrode, and an oxidizing gas containing oxygen must be supplied to the cathode electrode, while keeping them separate. If the separation is insufficient and one gas mixes with the other, this can result in a decrease in power generation efficiency. For this reason, sealants are often used to prevent leakage of fuel gas and oxygen gas. Specifically, sealants are used between adjacent separators, between the separator and the frame, and between the frame and the electrolyte membrane or MEA.

[0086] The polymer electrolyte membrane may be a cation exchange membrane having ion conductivity, preferably a fluorine-based polymer having sulfonic acid groups, because it is chemically stable and resistant to high-temperature operation. Commercially available products include Nafion (registered trademark) from DuPont, Flemion (registered trademark) from AGC Corporation, and Aciplex (registered trademark) from Asahi Kasei Corporation. Polymer electrolyte membranes are usually made of materials that are difficult to bond, but they can be bonded by using the curable resin composition of the present invention.

[0087] [ka]

[0088] The fuel electrode is called a hydrogen electrode or anode, and a known material is used. For example, a carbon supported catalyst such as platinum, nickel, or ruthenium is used. The air electrode is called an oxygen electrode or cathode, and a known material is used. For example, a carbon supported catalyst such as platinum or an alloy is used. The surface of each electrode may be provided with a gas diffusion layer that diffuses gas and keeps the electrolyte moist. Known gas diffusion layers are used, and examples thereof include carbon paper, carbon cloth, and carbon fiber.

[0089] The separator 2 has fine, uneven channels through which fuel gas and oxidizing gas pass and are supplied to the electrodes, as shown in Figure 1. The separator is made of aluminum, stainless steel, titanium, graphite, carbon, etc.

[0090] The frame supports and reinforces the thin electrolyte membrane or MEA to prevent it from breaking. Examples of the material for the frame include thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate, polyethylene terephthalate, polypropylene, and polycarbonate. In addition, in order to bond members using the curable resin composition of the present invention or its cured product, the frame is preferably made of a light-transmitting material.

[0091] The fuel cell of the present invention is characterized by being sealed with the curable resin composition of the present invention or a cured product thereof. Components that require sealing in a fuel cell include separators, frames, electrolyte membranes, fuel electrodes, air electrodes, and MEAs. More specific sealing locations include between adjacent separators, between separators and frames, and between frames and electrolyte membranes or MEAs. The primary purpose of sealing between separators and frames or between polymer electrolyte membranes or MEAs and frames is to prevent gas mixing and leakage. The purpose of sealing between adjacent separators is to prevent gas leakage and to prevent cooling water from leaking from the cooling water channels to the outside. Because acid generated by the electrolyte membrane creates a strongly acidic atmosphere, the sealing agent must be acid-resistant.

[0092] <Sealing method> The sealing method using the curable resin composition of the present invention is not particularly limited, but representative examples include FIPG (form-in-place gasket), CIPG (cure-in-place gasket), MIPG (mold-in-place gasket), and liquid injection molding.

[0093] FIPG is a technique in which the curable resin composition of the present invention is applied to a flange of a sealed part using an automatic application device or the like, and then, in a state in which the flange is laminated to another flange, active energy rays such as ultraviolet rays are irradiated from the light-transmitting flange side to cure the curable resin composition and provide an adhesive seal. More specifically, this is a method for sealing at least a portion of the space between at least two flanges of a sealed part having at least two flanges, at least one of which is active energy ray-transmitting, and the sealing method includes the steps of: applying the above-described curable resin composition to a surface of at least one of the flanges; laminating one flange (coated surface) coated with the curable resin composition to the other flange via the curable resin composition; and irradiating active energy rays through the active energy ray-transmitting flange to cure the curable resin composition and seal at least a portion of the space between the at least two flanges.

[0094] CIPG is a technique in which the curable resin composition of the present invention is bead-coated onto a flange of a sealed part using a screen printing applicator, an automatic applicator, or the like, and then irradiated with active energy rays such as ultraviolet light to cure the curable resin composition to form a gasket, which is then attached to the other flange for compression sealing. More specifically, this sealing method is a method for sealing at least a portion of the gap between at least two flanges of a sealed part having at least two flanges, and includes the steps of: applying the curable resin composition to at least one flange; irradiating the applied curable resin composition with active energy rays to cure the curable resin composition and form a gasket made of the cured product of the curable resin composition; and placing the other flange on the gasket and crimping the one flange coated with the curable resin composition to the other flange via the gasket to seal at least a portion of the gap between the at least two flanges.

[0095] MIPG is a technique in which a mold is first pressed against the flange of the part to be sealed, a curable resin composition is injected into the cavity formed between the mold made of a light-transmitting material and the flange, and then the composition is photocured by irradiating it with active energy rays such as ultraviolet light to form a gasket, which is then bonded to the other flange and compression sealed. The mold is preferably made of a light-transmitting material, specific examples of which include glass, polymethyl methacrylate (PMMA), polycarbonate, cycloolefin polymer, and olefin. Furthermore, to facilitate removal of the gasket from the mold after formation, it is preferable to coat the mold with a release agent such as a fluorine-based or silicone-based release agent. More specifically, the method is a method for sealing at least a portion of the gap between at least two flanges of a sealed part having the at least two flanges, comprising the steps of: placing a gasket-forming mold on at least one of the flanges; injecting the above-mentioned curable resin composition into at least a portion of the gap between the gasket-forming mold and the one flange on which the mold is placed; irradiating the curable resin composition with the active energy rays to cure the curable resin composition and form a gasket made of a cured product of the curable resin composition; removing the mold from the one flange; placing the other flange on the gasket and crimping the one flange and the other flange together via the gasket, thereby sealing at least a portion of the gap between the at least two flanges.

[0096] Liquid injection molding is a technique in which the curable resin composition of the present invention is poured into a mold made of a light-transmitting material under a specific pressure, and then photocured by irradiating it with active energy rays such as ultraviolet light to form a gasket. The resulting composition is then bonded to the other flange and compression sealed. The mold is preferably made of a light-transmitting material, specifically glass, PMMA, polycarbonate, cycloolefin polymer, olefin, etc. Furthermore, to facilitate removal of the gasket from the mold after formation, it is preferable to coat the mold with a release agent such as a fluorine-based or silicone-based release agent. [Example]

[0097] Examples are given below to explain the present invention in more detail, but the present invention is not limited to these examples.

[0098] <Production of a1> Production of polyisobutylene (a1) having an acryloyloxyethoxyphenyl group After purging the inside of a 5 L separable flask with nitrogen, 200 mL of n-hexane and 2000 mL of butyl chloride were added, and the mixture was cooled to -70 °C while stirring under a nitrogen atmosphere. Next, 840 mL (9 mol) of isobutylene, 12 g (0.05 mol) of p-dicumyl chloride, and 1.1 g (0.012 mol) of 2-methylpyridine were added. After the reaction mixture was cooled to -70 °C, 5.0 mL (0.05 mol) of titanium tetrachloride was added to initiate polymerization. Three hours after the start of polymerization, 40 g of phenoxyethyl acrylate (Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd.) and 110 mL of titanium tetrachloride were added. Thereafter, stirring was continued at -70 °C for 4 hours, and then 1000 mL of methanol was added to stop the reaction.

[0099] The supernatant was separated from the reaction solution, and after distilling off the solvent and the like, the product was dissolved in 3000 mL of n-hexane, washed three times with 3000 mL of pure water, reprecipitated from methanol, and then the solvent was distilled off under reduced pressure. The obtained polymer was vacuum dried at 80 °C for 24 hours to obtain polyisobutylene (a1) having an acryloyloxyethoxyphenyl group.

[0100] The above a1 contains -[CH2C(CH3)2]- units and contains two acryloyl groups. More specifically, in general formula (1), R 1 represents a dicumyl group, PIB represents a polyisobutylene skeleton, and R 4 represents a hydrocarbon group having 2 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom, and R 5is a polymer in which the atoms are hydrogen. The number average molecular weight of the a1 component (chromatographic method, polystyrene equivalent) was 11,100, and the viscosity of the a1 component (25°C) was 1550 Pa·s.

[0101] <Preparation of Curable Resin Composition> Example 1 The present invention comprises 100 parts by mass of polyisobutylene (a1) having an acryloyloxyethoxyphenyl group as component (A), 7.8 parts by mass of bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (Omnirad 819, manufactured by IGM Resins BV) as component (b1) of component (B), and a defoaming agent (BYK-1799, manufactured by BYK-Chemie, kinematic viscosity (25°C): 158 mm) containing a silicone compound and a hydrophobic solid, which does not contain an organic solvent and has no methoxysilyl group, ethoxysilyl group, or (meth)acryloyl group as component (c1) of component (C). 2 0.9 parts by mass of acrylate (Isobornyl acrylate / s) as component (d1), 65 parts by mass of isobornyl acrylate (IBX-A manufactured by Kyoeisha Chemical Co., Ltd.) as component (D1), and 22 parts by mass of lauryl acrylate (LA manufactured by Kyoeisha Chemical Co., Ltd.) as component (d2) were added to the resulting mixture, and the mixture was mixed with a planetary mixer for 60 minutes at room temperature (25°C) in the dark to obtain Example 1, a curable resin composition containing no organic solvent.

[0102] Example 2 Example 2, which did not contain any organic solvent, was prepared in the same manner as Example 1, except that the amount of component (c1) in Example 1 was changed from 0.9 parts by mass to 1.8 parts by mass.

[0103] Example 3 Example 3, which did not contain any organic solvent, was prepared in the same manner as Example 1, except that the amount of component (c1) in Example 1 was changed from 0.9 parts by mass to 3.6 parts by mass.

[0104] Example 4 In Example 1, instead of the component (c1), a dimethylpolysiloxane (KF-96-100 manufactured by Shin-Etsu Chemical Co., Ltd.) containing no organic solvent, having no methoxysilyl group, ethoxysilyl group, or (meth)acryloyl group, and having both ends capped with trimethylsilyl groups was used as the component (c2). cs , Kinematic viscosity (25℃): 100mm 2 Example 4 was prepared in the same manner as in Example 1 except that the organic solvent was changed to 0.01 / s.

[0105] Comparison Example 1 Comparative Example 1, which did not contain any organic solvent, was prepared in the same manner as in Example 1, except that (c1) was omitted.

[0106] Comparison Example 2 Comparative Example 2, which does not contain organic solvents, was prepared in the same manner as Example 1, except that in Example 1, component (c1) was replaced with component (c'1), which is an antifoaming agent (BYK-1790 manufactured by BYK-Chemie) containing an organic polymer that is not a silicone compound and does not contain organic solvents, to obtain Comparative Example 2, which does not contain organic solvents.

[0107] Comparative Example 3 Comparative Example 3 containing an organic solvent was prepared in the same manner as in Example 1, except that in Example 1, the component (c1) was replaced with an antifoaming agent (BYK-066N manufactured by BYK-Chemie) containing an organic solvent diisobutyl ketone as the component (c'2) and a silicone compound having no methoxysilyl group, ethoxysilyl group, or (meth)acryloyl group.

[0108] Comparative Example 4 Comparative Example 4 containing an organic solvent was prepared in the same manner as in Example 1, except that in Example 1, the component (c1) was replaced with an antifoaming agent (BYK-067A manufactured by BYK-Chemie) containing an organic solvent propylene glycol as the component (c'3) and a silicone compound having no methoxysilyl group, ethoxysilyl group, or (meth)acryloyl group.

[0109] Comparative Example 5 Comparative Example 5, which does not contain organic solvents, was prepared in the same manner as Example 1, except that in Example 1, instead of component (c1), a silicone oligomer (KR-513 manufactured by Shin-Etsu Chemical Co., Ltd.) having an acryloyl group and a methoxy group in the side chain and not containing an organic solvent was used as component (c'4).

[0110] The test methods used in the examples and comparative examples in Table 1 are as follows. In the table, "-" means that no measurement was performed.

[0111] (1) Evaluation of repelling properties during screen printing Each curable resin composition was applied by printing onto a polytetrafluoroethylene sheet using a SUS mesh screen printing plate with a mesh size of 110 μm and a manual squeegee in an environment of 25°C. Whether each curable resin composition was repelled by the polytetrafluoroethylene sheet was confirmed visually. The results are summarized in Table 1. For the evaluation, a sample that showed no cissing on the polytetrafluoroethylene sheet was rated as "pass," and a sample that showed clear cissing was rated as "fail." Note that polytetrafluoroethylene has a surface tension equivalent to that of the electrolyte membrane.

[0112] (2) Evaluation of defoaming during screen printing Each curable resin composition was applied by printing onto a polytetrafluoroethylene sheet using a SUS mesh screen printing plate with a mesh size of 110 μm and a manual squeegee in an environment of 25°C. Thereafter, the time until bubbles disappeared from the printed layer (50 μm thick) of the curable resin composition was visually confirmed and recorded as the defoaming time (seconds). Note that time measurement began immediately after the printing application. The results are summarized in Table 1. From the viewpoint of line tact, the defoaming time is preferably within 60 seconds, more preferably within 50 seconds, and particularly preferably within 40 seconds.

[0113] (3) Hardness measurement The thickness of each curable resin composition was set to 1 mm, and the cumulative light dose was 45 kJ / m 2The sample is cured by irradiating it with ultraviolet light to produce a sheet-like cured product. The pressure surface of an A-type durometer (hardness tester) is pressed with a force of 10 N while being kept parallel to the test piece (six sheets of cured product stacked together, set to a thickness of 6 mm), and the pressure surface is pressed against the sample to bring them into close contact. The maximum value is read during measurement and this is taken as the "hardness." Details follow JIS K 6253 (2012). A hardness of 15 or more is preferable, and 20 or more is even more preferable.

[0114] (4) Method for measuring the elongation of the cured product The thickness of each curable resin composition was set to 1 mm, and the cumulative light dose was 45 kJ / m 2 The resin is cured by irradiating it with ultraviolet light to produce a sheet-like cured product. Test pieces are made by punching out with a No. 3 dumbbell, and benchmark lines are drawn on the test pieces at 20 mm intervals.

[0115] The test piece is fixed to the chuck in the same manner as for measuring tensile strength, and pulled at a pulling speed of 500 mm / min until it breaks. During measurement, the test piece stretches and the spacing between the gauge lines widens, so the spacing between the gauge lines is measured with a vernier caliper until the test piece breaks. The percentage of elongation based on the initial spacing between the gauge lines is taken as the "elongation rate (%)." Evaluation is based on the following criteria, and the results are shown in Table 1. From the perspective of high elongation, the elongation rate is preferably 300% or more, and more preferably 410% or more.

[0116] (5) Tensile strength measurement The thickness of the curable resin composition was set to 1 mm, and the cumulative light intensity was 45 kJ / m 2 The sample is cured by irradiating it with ultraviolet light to produce a sheet-like cured product. A test piece is prepared by punching it out with a No. 3 dumbbell. Both ends of the test piece are fixed to the chuck so that the long axis of the test piece and the center of the chuck are aligned. The test piece is pulled at a pulling rate of 500 mm / min and the maximum load is measured. The strength at this maximum load is taken as the "tensile strength (MPa)." Details follow JIS K 6251 (2010). The tensile strength is preferably 3.9 MPa or more, and more preferably 4.2 MPa or more.

[0117] [Table 1]

[0118] According to Examples 1 to 4 in Table 1, it can be seen that the present invention provides a curable resin composition that can be applied by screen printing while maintaining the cured product properties of high strength and high elongation.

[0119] Comparative Example 1 in Table 1 is a curable resin composition of the present invention that does not contain (c1) of the (C) component, but it experienced cissing from the adherend when applied by screen printing and had poor defoaming properties. Comparative Example 2 is a curable resin composition of the present invention that uses (c'1) instead of (c1) of the (C) component, but it experienced cissing from the adherend when applied by screen printing and had poor defoaming properties. Comparative Examples 3 and 4 are curable resin compositions of the present invention that use "solvent-containing defoamers (c'2) or (c'3)" instead of (c1) of the (C) component, but it experienced cissing from the adherend when applied by screen printing and had poor tensile strength of the cured product. Comparative Example 5 is a curable resin composition of the present invention that uses (c'4) instead of (c1) of the (C) component, but it experienced cissing from the adherend when applied by screen printing and had poor tensile strength and elongation of the cured product.

[0120] Furthermore, (6) viscosity measurement and (7) moisture permeability (water vapor barrier property) were evaluated as follows.

[0121] (6) Viscosity measurement The viscosity (Pa s) of the curable resin composition was measured under the following measurement conditions using a cone-plate viscometer (manufactured by Brookfield). Evaluation was based on the following criteria, and the results are shown in Table 2. The viscosity is preferably 100 Pa s or less, more preferably 0.1 to 50 Pa s, and particularly preferably in the range of 0.2 to 10 Pa s.

[0122] The results in Table 2 show that Examples 1 to 4 and Comparative Examples 1 and 3 to 5 have similar viscosities.

[0123] [Measurement conditions] Cone type CPE-52, shear rate 10 (1 / s), temperature 25℃.

[0124] [Table 2]

[0125] (7) Moisture permeability (water vapor barrier properties) The curable resin compositions of Examples 2 and 4 were poured into a 200 mm × 200 mm × 1.0 mm frame. Thereafter, an ultraviolet irradiator was used to irradiate the curable resin compositions with an integrated light dose of 45 kJ / m 2 The cured product was then irradiated with ultraviolet light for 20 seconds to a thickness of 1.0 mm, producing a sheet-like cured product. 5 g of calcium chloride (anhydrous) was placed in an aluminum cup with an opening of 30 mm in diameter, and the cup was set so as to cover the cured product. After measuring the "initial total weight" (g), the product was left in a thermo-hygrostat chamber maintained at an atmospheric temperature of 40°C and a relative humidity of 95% for 24 hours, and the "total weight after leaving" (g) was measured, and the moisture permeability (g / m 2 The moisture permeability (moisture permeability) was calculated and evaluated based on the following evaluation criteria. Both Examples 2 and 4 passed the test. The detailed test method was in accordance with JIS Z 0208-1976. When used as a curable sealant for fuel cells, the moisture permeability was 10 g / m 2 Preferably less than 24 hours.

[0126] [Evaluation criteria] Passed: Moisture permeability is 10g / m 2 Less than 24 hours Fail: Moisture permeability is 10g / m 2 24 hours or more.

[0127] This application is based on Japanese Patent Application No. 2020-146349, filed on August 31, 2020, the disclosure of which is incorporated herein by reference in its entirety. [Industrial Applicability]

[0128] The present invention has been made in view of the above circumstances, and provides a curable resin composition that can be applied by screen printing while maintaining high strength and elongation properties of the cured product, and can be used for various sealing applications. In particular, the curable resin composition is effective as a curable sealant for fuel cells, and is therefore industrially useful. [Explanation of symbols]

[0129] 1. Polymer electrolyte fuel cell cell 2 Separator 3a Air electrode (cathode) 3b Fuel electrode (anode) 4 Polymer electrolyte membrane 5 Electrolyte membrane electrode assembly (MEA) 6 frames 7. Adhesives or sealants 8a Oxidizing gas flow path 8b Fuel gas flow path 9 Cooling water flow path 10 Cell stack 11 Polymer electrolyte fuel cell

Claims

1. The following components (A) to (D): Component (A): 1 to 6 (meth)acryloyl groups and —[CH ２ C(CH ３ ) ２ ]- units, and the polyisobutylene resin contains 80 mass % or more of the --[CH 2 C(CH 3 ) 2 ]- units relative to the total amount of constituent units. Component (B): Radical polymerization initiator Component (C): a defoaming agent containing a silicone compound that has no methoxysilyl group, no ethoxysilyl group, and no (meth)acryloyl group and that does not contain an organic solvent Component (D): a (meth)acrylate monomer having an alkyl group having 5 to 30 carbon atoms or a (meth)acrylate monomer having an alicyclic hydrocarbon group having 5 to 30 carbon atoms Contains Contains no organic solvents The blending amount of the component (B) is 0.1 to 30 parts by mass per 100 parts by mass of the component (A), The blending amount of the component (C) is 0.1 to 10 parts by mass per 100 parts by mass of the component (A), The curable resin composition of the present invention, wherein the blending amount of the component (D) is in the range of 30 to 150 parts by mass per 100 parts by mass of the component (A).

2. The curable resin composition according to claim 1, wherein the component (A) is a polyisobutylene resin represented by general formula (1): 【Chemistry 1】 (In formula (1), R １ represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group which may have an aromatic ring, and PIB represents the —[CH ２ C(CH ３ ) ２ ]-units, and R ４ represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an oxygen atom, and R ２ and R ３ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ５ represents a hydrogen atom, a methyl group, or an ethyl group, and n is an integer of 1 to 6.

3. 3. The curable resin composition according to claim 1, wherein the silicone compound of component (C) is a compound having a structure of any one of dimethylsiloxane, methylphenylsiloxane, and diphenylsiloxane.

4. The curable resin composition according to any one of claims 1 to 3, wherein the component (C) is contained in an amount of 0.1 to 9 parts by mass per 100 parts by mass of the total amount of the components (A) and (D).

5. The curable resin composition according to any one of claims 1 to 4, wherein the component (B) is a photoradical polymerization initiator or an organic peroxide.

6. A curable sealant for a fuel cell, comprising the curable resin composition according to any one of claims 1 to 5.

7. The curable sealant for fuel cells according to claim 6, which is used for any component selected from the group consisting of a separator, a frame, an electrolyte membrane, a fuel electrode, an air electrode, and an electrolyte membrane electrode assembly, which are components of a fuel cell.

8. A cured product of the curable resin composition according to any one of claims 1 to 5.

9. A fuel cell comprising any seal selected from the group consisting of a seal between adjacent separators in a fuel cell and a seal between a frame of the fuel cell and an electrolyte membrane or an electrolyte membrane electrode assembly, wherein any of the seals is the cured product described in claim 8.

10. A sealing method for sealing at least a portion between at least two flanges of a sealed part having the at least two flanges, the method comprising: At least one of the flanges is transmissive to active energy rays, A step of applying the curable resin composition according to any one of claims 1 to 5 to at least one surface of the flange; a step of bonding one flange coated with the curable resin composition to the other flange via the curable resin composition; and a step of applying active energy rays through flanges that are permeable to the active energy rays to cure the curable resin composition and seal at least a portion of the gap between the at least two flanges; A sealing method comprising:

11. A sealing method for sealing at least a portion between at least two flanges of a sealed part having the at least two flanges, the method comprising: A step of applying the curable resin composition according to any one of claims 1 to 5 to at least one of the flanges; a step of irradiating the applied curable resin composition with active energy rays to cure the curable resin composition, thereby forming a gasket made of a cured product of the curable resin composition; and a step of placing the other flange on the gasket, and press-fitting the one flange coated with the curable resin composition and the other flange via the gasket to seal at least a portion between the at least two flanges; A sealing method comprising:

12. A sealing method for sealing at least a portion between at least two flanges of a sealed part having the at least two flanges, the method comprising: placing a gasket forming mold on at least one of the flanges; A step of injecting the curable resin composition according to any one of claims 1 to 5 into at least a part of a gap between the gasket-forming mold and one of the flanges on which the mold is disposed; a step of irradiating the curable resin composition with active energy rays to cure the curable resin composition, thereby forming a gasket made of a cured product of the curable resin composition; removing the mold from the one flange; and placing the other flange on the gasket and crimping the one flange and the other flange together via the gasket to seal at least a portion between the at least two flanges; A sealing method comprising:

Images