JP7275875B2 - METHOD FOR MANUFACTURING LAMINATE HAVING CATALYST LAYER - Google Patents

Description

The present invention relates to a method for producing a laminate having a catalyst layer, and furthermore, a laminate obtained from a substrate having a polymer electrolyte can be preferably used as a fuel cell, an electrochemical hydrogen pump, various sensors, and the like. , belong to these technical fields.

2. Description of the Related Art Due to growing interest in environmental problems and energy problems, there is a growing movement to widely spread fuel cells as power sources for automobiles and households.
As a fuel cell, polymer electrolyte fuel cells have advantages such as light weight and low operating temperature, and are expected to spread widely.
A polymer electrolyte fuel cell has a power generating part that has catalyst layers (anode and cathode) on both sides of a polymer electrolyte membrane, and separates the gas to be supplied to the anode and the gas to be supplied to the cathode, or forms a flow path. is a laminate composed of a resin frame, a separator, and the like (for example, Patent Document 1).

The structure of the laminate varies in detail, but in many cases there is a portion where two or more members constituting the laminate are adhered. In some cases, a sealing member is formed on a member and is brought into contact with the other member via the sealing member to separate two types of fluid (gas or refrigerant) (for example, Patent Document 2). Thus, polymer electrolyte fuel cells usually require adhesives and/or sealants.
When a polymer electrolyte fuel cell is to be put into practical use, it is usually necessary to stack a large number of cells, so it is necessary to manufacture one cell in a short period of time. For this reason, short-time adhesion and short-time curing are required, and hot-melt adhesives (thermoplastic resins) are often used. 5). Advantages of a photocurable adhesive over a hot-melt adhesive include that it is easy to apply because it is liquid, and that deformation of the adherend due to heat can be avoided. In addition, as a sealing material, it has the advantage that the curing time is extremely short and the storage stability of the liquid is excellent as compared with the thermosetting sealing material.
Here, there is also a form in which the adhesive or sealing material is arranged in contact with the catalyst layer (for example, Patent Documents 1 and 3).
In addition, various research and development efforts have been made to enhance the activity of the catalyst layer (for example, Patent Document 6).
Note that the product form of the laminate having the catalyst layer is not limited to the fuel cell, and includes, for example, an electrochemical hydrogen pump (eg, Patent Document 7).

JP 2017-168364 A JP 2009-158481 A JP 2014-99409 A JP 2009-245797 A International Publication No. 2018/190415 Pamphlet International Publication No. 2015/019953 pamphlet JP 2017-226911 A

However, when a photocurable composition is applied onto a highly active catalyst layer and then cured by light irradiation, adhesion may deteriorate.
An object of the present invention is to provide a method for producing a laminate in which a cured product layer of an adhesive or sealing material made of a photocurable composition is formed with good adhesion on a substrate having a highly active catalyst layer. That is.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the cause of the deterioration in adhesion between a substrate having a catalyst layer and other substrates is the low molecular weight contained in the photocurable composition ( We found that the cause was the decomposition of a monomer such as meth)acrylate, and conducted intensive studies based on the idea that the above problem could be solved if we could provide a means for suppressing the decomposition of the monomer. rice field.
As a result, after coating the photocurable composition on the substrate having the catalyst layer, it is rapidly pre-cured with a relatively small irradiation dose using a light-emitting diode (hereinafter referred to as "LED"), After that, the pre-cured composition is irradiated with light in an environment of low oxygen concentration to be completely cured, thereby finding that the above-described problem of deterioration of adhesion does not occur, and completed the present invention.

The present invention relates to a method for manufacturing a laminate having a catalyst layer, including steps 1 to 3 below.
Step 1: Step of applying a photocurable composition containing (meth)acrylate to the catalyst layer side of the substrate having the catalyst layer Step 2: Within 1 minute after Step 1, in an air atmosphere, light emission Pre-curing step of irradiating with an LED having a peak wavelength of 350 to 420 nm at a dose of 20 to 1,000 mJ/cm ² at the peak wavelength Step 3: For the photocurable composition precured in step 2 , In an atmosphere with an oxygen concentration of 5% or less, a main curing step in which light is irradiated at a peak wavelength of 50 mJ/cm ² or more with an LED or other ultraviolet irradiation device having a peak emission wavelength of 350 to 420 nm. 3: For the photocurable composition precured in step 2, in an atmosphere with an oxygen concentration of 5% or less, with an LED or other ultraviolet irradiation device other than an LED having a peak emission wavelength of 350 to 420 nm, at the peak wavelength. Main curing step of light irradiation at an irradiation dose of 50 mJ/cm ² or more

According to the method for producing a laminate of the present invention, a laminate is produced without reducing the adhesion of a cured product of an adhesive or sealing material made of a photocurable composition onto a substrate having a catalyst layer. way can be.

The present invention relates to a method for manufacturing a laminate having a catalyst layer, including steps 1 to 3 below.
Step 1: Step of applying a photocurable composition to the catalyst layer side of a substrate having a catalyst layer Step 2: Within 1 minute after Step 1, in an air atmosphere, the emission peak wavelength is 350 to 420 nm. A pre-curing step of irradiating with an LED having a peak wavelength of 20 to 1,000 mJ/cm ² at a dose of 20 to 1,000 mJ/cm 2 Step 3: With respect to the photocurable composition pre-cured in step 2, the oxygen concentration is 5% or less. In an atmosphere of , the main curing step of irradiating with an irradiation amount of 50 mJ / cm ² or more at the peak wavelength by an LED or an ultraviolet irradiation device other than an LED having a peak emission wavelength of 350 to 420 nm Below, a substrate having a catalyst layer The material, the photocurable composition, and steps 1 to 3 will be described.
In the present specification, acrylate and/or methacrylate are represented as (meth)acrylate, acryloyl group and/or methacryloyl group as (meth)acryloyl group, and acrylic acid and/or methacrylic acid as (meth)acrylic acid. , and a compound having one (meth)acryloyl group is represented as a monofunctional (meth)acrylate, and a compound having two or more (meth)acryloyl groups is represented as a polyfunctional (meth)acrylate.

1. Substrate Having Catalyst Layer A substrate having a catalyst layer will be described.
Base materials for forming the catalyst layer include polymeric materials, carbon, metal oxides, sulfides, and the like.
Polymeric materials include hydrophilic polymeric films and hydrophobic polymeric films.
Specific examples of hydrophilic polymer films include polyvinyl alcohol films and cellulose ester films.
An ion exchange resin (polymer electrolyte membrane) can also be used as the hydrophilic polymer film. Examples of ion exchange groups in the ion exchange resin include cation (cation) exchange groups such as sulfonic acid group, carboxylic acid group, and phosphonic acid group. Anion (anion) exchange groups include amino groups, quaternary ammonium groups, pyridyl groups, imidazole groups, quaternary pyridinium groups, and quaternary imidazolium groups.
Specific examples of ion-exchange resins include polymers obtained by polymerizing aromatic vinyl compounds such as styrene, vinylpyridine, and vinylimidazole; poly(meth)acrylic acid; Nafion (registered trademark)] and the like.

Specific examples of hydrophobic polymer films include polycarbonate films, polyethylene terephthalate films, polyethylene naphthalate films, acrylic films, acrylic/styrene films, aliphatic polyamide (nylon) films, and aromatic polyamide films. , polyarylate-based film, polyethersulfone-based film, polysulfone-based film, polyphenylsulfone-based film, polyetheretherketone-based film, polyphenylene oxide-based film, polyurethane-based film, polyimide-based film, ethylene-vinyl acetate copolymer system films, polyvinyl chloride films, polyvinylidene chloride films, polyethylene films, polypropylene films, polycycloolefin films, polystyrene films, ABS films, chlorinated polypropylene films, and the like.

Examples of carbon include carbon fibers, graphite, carbon nanotubes, fullerenes, etc., which are heat-treated or compounded with fluorine-based resins, etc., and made into sheets.

Metal oxides include silicon, aluminum, germanium, gallium, titanium, zirconium, vanadium, niobium, manganese, iron, cobalt, nickel, molybdenum, indium, tin, zinc, yttrium, tungsten, lanthanum, cerium, lithium, and sodium. and oxides of these metals, and composite oxides of these metals.

Sulfides include sulfides such as lithium, sodium, phosphorus, selenium, germanium, iron, zinc, and copper, and composites thereof.

Metals, metal oxides, metal complexes, and the like can be used as the catalyst layer formed on the substrate.
Examples of metals include platinum, palladium, ruthenium, rhodium, cobalt, and the like.
These catalysts may be carried on a carrier such as carbon fine particles.
Further, a polymer binder is preferably used for immobilizing the catalyst or the catalyst-carrying carrier on a base material such as a polymer film. As a polymer binder, perfluoro

As the substrate having a catalyst layer in the present invention, it is preferable to apply a catalyst layer formed on a polymer electrolyte (ion exchange resin) used in the manufacture of fuel cells, electrochemical hydrogen pumps, various sensors, etc. can be done.
A specific example of the polymer electrolyte in this case is a perfluorocarbon material having a sulfonic acid group. Commercially available polymer electrolytes include Nafion (registered trademark) manufactured by DuPont, Flemion FLEMION (registered trademark) manufactured by Asahi Glass Co., Ltd., Aciplex (registered trademark) manufactured by Asahi Kasei Corporation, and Gore Japan Co., Ltd. and GORE-SELECT Gore-Select (registered trademark) membrane manufactured by Sanyo Denki.
The polymer electrolyte may have a coating film formed on its surface, or may be a membrane/electrode assembly (MEA) for a fuel cell in which a polymer electrolyte membrane and electrodes are integrated. .

2. Photocurable Composition As the photocurable composition used in the present invention, various compositions can be used as long as they contain (A) a photocurable compound and (B) a polymerization initiator.

2-1. Component (A) In the present invention, the photocurable compound of component (A) preferably contains component (AR): a photoradical polymerizable compound.
Furthermore, as the (A) component, the (AR) component and the (AC) component (photo-cationically polymerizable compound) may be used together to form a so-called hybrid composition.
Hereinafter, the (AR) component and the (AC) component will be described.

2-1-1. (AR) Component The (AR) component is a radical polymerizable compound.
The (AR) component includes a compound having an ethylenically unsaturated group.
Specific examples of the compound having ethylenic unsaturation as the (AR) component include compounds having a (meth)acryloyl group, compounds having a vinyl group, and the like, and compounds having a (meth)acryloyl group are preferred.
Furthermore, examples of compounds having a (meth)acryloyl group include (AR1) component: a compound having one (meth)acryloyl group, and (AR2) component: a compound having two or more (meth)acryloyl groups. can be mentioned.

2-1-1-1. (AR1) component The (AR1) component is a compound having one (meth)acryloyl group.
Preferred compounds for the (AR1) component include alkyl (meth)acrylates, monofunctional (meth)acrylates having an alicyclic ring, and monofunctional (meth)acrylates having a hydroxyl group.

Alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl ( meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. is mentioned.
Among these compounds, alkyl (meth)acrylates having an alkyl group with 8 or more carbon atoms are preferable because they can increase the flexibility of the cured product of the composition and increase the peel strength against various materials.

A monofunctional (meth)acrylate having a hydroxyl group is preferable because the cured product of the composition has excellent adhesion to the polymer electrolyte.

Specific examples of monofunctional (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate acrylate, polytetramethylene glycol mono(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

A monofunctional (meth)acrylate having a ring structure enhances toughness and heat resistance of the cured product of the composition, enhances adhesion to polymer electrolytes and various materials, and enhances resistance to hot water immersion. It is preferable because it can
Examples of ring structures in monofunctional (meth)acrylates having ring structures include alicyclic rings, aromatic rings and heterocyclic rings.

Monofunctional (meth)acrylates having an alicyclic ring include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl ( meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate and the like.
Examples of monofunctional (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylates of phenol alkylene oxide adducts, (meth)acrylates of nonylphenol alkylene oxide adducts, Examples include (meth)acrylates of phenoxyphenol alkylene oxide adducts, (meth)acrylates of p-cumylphenol alkylene oxide adducts, and (meth)acrylates of o-phenylphenol alkylene oxide adducts.
Monofunctional (meth)acrylates having a heterocyclic ring include tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 3-ethyl-3-oxetanyl (meth)acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, N-(meth)acryloyloxyethylhexahydrophthalimide, and and N-(meth)acryloyloxyethyltetrahydrophthalimide.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide.

Compounds other than those described above can be used as the (AR1) component.
Specific examples include n-butoxyethyl (meth)acrylate, ethylcarbitol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, 2,2,3,3-tetrafluoropropyl (Meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl acid phosphate, acrylamide, N , N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, (meth)acryloylmorpholine, N,N-dimethylaminopropyl ( meth)acrylamide, (3-(meth)acryloyloxypropyl)trimethoxysilane, and the like.

2-1-1-2. (AR2) Component The (AR2) component is a compound having two or more (meth)acryloyl groups.
Specific examples of compounds having two (meth)acryloyl groups in the (AR2) component include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propane Di(meth)acrylates of aliphatic diols such as diol di(meth)acrylates and 1,9-nonanediol di(meth)acrylates;
Di(meth)acrylates of alicyclic diols such as cyclohexanedimethylol di(meth)acrylate and tricyclodecanedimethylol di(meth)acrylate;
Polyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate;
esterification reaction product of neopentyl glycol, hydroxypivalic acid and (meth)acrylic acid;
Fluorene-based di(meth)acrylates such as 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene;
Di(meth)acrylates of alkylene oxide adducts of bisphenol compounds such as di(meth)acrylates of bisphenol A alkylene oxide adducts;
Di(meth)acrylates of hydrogenated bisphenol compounds such as di(meth)acrylates of hydrogenated bisphenol A;
Bisphenol A type epoxy resin and (meth)acrylic acid adduct, 1,9-nonanediol diglycidyl ether and (meth)acrylic acid adduct, having two (meth)acryloyl groups in one molecule epoxy (meth)acrylate;
Polyester (meth)acrylates having two (meth)acryloyl groups in one molecule, such as esters of phthalic acid, ethylene glycol and (meth)acrylic acid; and isophorone diisocyanate and 2-hydroxyethyl (meth)acrylate Urethane reaction product, urethane reaction product of tolylene diisocyanate, polyether diol and 2-hydroxypropyl (meth)acrylate, urethane reaction product of hexamethylene diisocyanate, polyester diol and 2-hydroxybutyl (meth) acrylate and urethane (meth)acrylates having two (meth)acryloyl groups in one molecule, such as urethanized reaction products of isophorone diisocyanate, polycarbonate diol and 4-hydroxybutyl (meth)acrylate.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide.

Specific examples of compounds having three or more (meth)acryloyl groups in the component (AR2) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di, tri or tetra(meth) ) Polyol poly(meth)acrylate such as acrylate, dipentaerythritol penta or hexa(meth)acrylate, tri(meth)acrylate of isocyanurate ethylene oxide 3-mol adduct, glycerin tri(meth)acrylate, polyglycerin poly(meth)acrylate acrylate;
tri(meth)acrylate of trimethylolpropane alkylene oxide adduct, tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, tri or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly(meth)acrylates of polyol alkylene oxide adducts such as penta or hexa(meth)acrylates of glycerin alkylene oxide adducts, tri(meth)acrylates of glycerin alkylene oxide adducts, and poly(meth)acrylates of polyglycerin alkylene oxide adducts;
Epoxy (meth) having three or more (meth)acryloyl groups in one molecule, such as an adduct of phenol novolac type epoxy resin and (meth)acrylic acid, an adduct of cresol novolac type epoxy resin and (meth)acrylic acid, etc. ) acrylates;
3 or more molecules in one molecule, such as a urethanized reaction product of isophorone diisocyanate and pentaerythritol tri(meth)acrylate, a urethanized reaction product of an isocyanurate-type trimer of hexamethylene diisocyanate and 4-hydroxybutyl acrylate, etc. Urethane (meth)acrylate having a (meth)acryloyl group;
Polyester (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule, such as an ester of phthalic acid, trimethylolpropane and (meth)acrylic acid, or a dendrimer-type poly(meth)acrylate; and ( Polymers obtained by adding glycidyl (meth)acrylate to carboxylic acid of (meth)acrylic polymers containing meth)acrylic acid as structural units, and epoxy groups of (meth)acrylic polymers containing glycidyl (meth)acrylate as structural units. Polymers having (meth)acryloyl groups, such as polymers obtained by adding (meth)acrylic acid to, and the like.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide.

Furthermore, as the (AR2) component, at least one skeleton selected from the group consisting of (AR2-1) polybutadiene, polyisoprene, hydrogenated polybutadiene, and hydrogenated polyisoprene (hereinafter referred to as "polydiene skeleton"). , and compounds having two or more (meth)acryloyl groups are preferred from the viewpoint of excellent adhesion to various materials.

In the component (AR2-1), the molecular weight of the polydiene-based skeleton, that is, the molecular weight of the compound having the polydiene-based skeleton, which is the raw material compound of the component (AR2-1), has excellent solubility in the composition. The number average molecular weight (hereinafter referred to as "Mn") is preferably 500 to 5,000, preferably 500 to 4,000, in terms of the cured product having excellent adhesive strength and hot water immersion resistance. is more preferred, and 700 to 3,000 is even more preferred.
Examples of the compound having a polydiene skeleton include a compound having a polydiene skeleton and one or more hydroxyl groups [hereinafter referred to as "polydiene alcohol"], a compound having a polydiene skeleton and an epoxy group, a polydiene skeleton and a carboxyl group. and a compound having a polydiene skeleton and a carboxylic acid anhydride.
In the present invention, Mn (number average molecular weight) means a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") into polystyrene.
The molecular weight of the (AR2-1) component is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, still more preferably 5,000 to 60,000 in terms of Mn. When the Mn of the (AR2-1) component is 1,000 or more, the resulting cured product of the composition has excellent adhesive strength and resistance to hot water immersion. It can be excellent in solubility.
When the composition is used as a photocurable composition, the (meth)acryloyl group is preferably an acryloyl group because the composition is excellent in curability.

Examples of the (AR2-1) component include the following (AR2-1-1) to (AR2-1-6) components.
• (AR2-1-1) component: Polydiene-based alcohol, polyisocyanate, and urethanized reaction product of (meth)acrylate having a hydroxyl group.
• (AR2-1-2) component: an addition reaction product of a compound having an isocyanate group and a (meth)acryloyl group to a polydiene alcohol.
• (AR2-1-3) component: (meth)acrylate of polydiene alcohol.
• (AR2-1-4) component: an addition product of (meth)acrylic acid to a compound having a polydiene skeleton and an epoxy group.
• (AR2-1-5) component: an adduct of (meth)acrylate having an epoxy group to a compound having a polydiene skeleton and a carboxyl group.
• (AR2-1-6) component: an adduct of a (meth)acrylate having a hydroxyl group to a compound having a polydiene skeleton and a carboxylic anhydride.

(AR2-1-3) component can be produced by dehydration esterification reaction of polydiene alcohol and (meth)acrylic acid under an acid catalyst, and esterification of polydiene alcohol and low molecular weight (meth)acrylate. and the like.

The (AR2-1) component preferably contains a compound having a urethane bond in the molecule (hereinafter referred to as "polydiene-based urethane (meth)acrylate") from the viewpoint of excellent adhesion to various substrates.
As the polydiene-based urethane (meth)acrylate, the (AR2-1-1) component described above is preferable.
Furthermore, among the (AR2-1-1) components, urethane (meth)acrylate obtained by urethanization reaction of polydiene-based diol, diisocyanate, and compounds containing hydroxyl groups and (meth)acryloyl groups has excellent compatibility with various base materials. It is particularly preferred because of its excellent adhesive strength.
Polydiene diols, diisocyanates, and compounds containing hydroxyl groups and (meth)acryloyl groups, which are preferred starting compounds for component (AR2-1-1), are described below.

Polydiene diols include polybutadiene diol, polyisoprene diol, diol of butadiene-styrene copolymer, and the like. Hydrogenated polydiene diols include hydrogenated polybutadiene diols, hydrogenated polyisoprene diols, and hydrogenated diols of butadiene-styrene copolymers.
The Mn of the polydiene diol is preferably from 500 to 5,000, more preferably from 1,000 to 4,000. As described above, the polydiene diol that satisfies the Mn has excellent solubility in the composition, and the resulting cured product of the composition has excellent adhesion and hot water immersion resistance.

Diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate, and tolylene diisocyanate, diphenylmethane diisocyanate, and tolidine diisocyanate. , naphthalene diisocyanate, and xylylene diisocyanate.

Compounds containing a hydroxyl group and a (meth)acryloyl group include caprolactone of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. Examples include modified products and glycidol di(meth)acrylates.
Among these compounds, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred.

A preferred method for producing component (AR2-1-1) is to produce a urethane prepolymer having an isocyanate group by reacting a polydiene-based diol and a diisocyanate, and reacting the prepolymer with a compound containing a hydroxyl group and a (meth)acryloyl group. (hereinafter referred to as "process 1"), and a method of reacting a polydiene-based diol, diisocyanate and a compound containing a hydroxyl group and a (meth)acryloyl group (hereinafter referred to as "process 2").
In the present invention, the polydiene-based urethane (meth)acrylate obtained by production method 1 is easy to control the molecular weight, the obtained polydiene-based urethane (meth)acrylate has excellent solubility in other components, and the resulting composition is preferable in terms of excellent adhesive strength.

The molar ratio of the polydiene-based diol and the diisocyanate in the production of the preferred (AR2-1-1) component is preferably 1:2.2 to 1:1.05, preferably 1:2 to 1:1.1. and more preferably 1:1.8 to 1:1.1. The (AR2-1-1) component reacted at this ratio has excellent solubility with other (meth)acrylates, and the cured product of the resulting composition has adhesive strength. It will be excellent for

The content of the (AR2-1) component is preferably 20 to 100% by weight based on the entire (AR) component in that the cured product of the composition has excellent adhesiveness and hot water immersion resistance. It is preferably 20 to 94% by weight, more preferably 30 to 80% by weight.

2-1-1-3. As other (AR) components, compounds having unsaturated groups other than (meth)acryloyl groups can be used.
Examples include N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactone, acryloylmorpholine and the like.
In addition, when the composition of the present invention is used for gas sensors, fuel cells, etc., the volatile components of the composition are adsorbed to metals such as platinum catalysts present on the surface of the polymer electrolyte, resulting in deterioration of performance. Sometimes. In order to solve this problem, the (AR) component preferably does not contain volatile (meth)acrylates in an amount of 5% by weight or more based on the total composition.
Volatile (meth)acrylates include (meth)acrylates having a molecular weight of 250 or less that do not have a hydrogen-bonding group and (meth)acrylates that have a hydrogen-bonding group and have a molecular weight of 200 or less. Here, specific examples of the hydrogen-bonding group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an imide group, an amide group and the like.

2-1-2. (AC) Component The (AC) component is a photo-cationically polymerizable compound.
Specific examples of the (AC) component include epoxy compounds, oxetanes, vinyl ethers, and the like.
These compounds are described below.

2-1-2-1. Epoxy compound The epoxy compound is not particularly limited as long as it has at least one epoxy group in the molecule, and various commonly known curable epoxy compounds can be used. .
Preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (hereinafter referred to as "aromatic epoxy compounds") and compounds having at least two epoxy groups in the molecule. and at least one of which is formed between two adjacent carbon atoms forming an alicyclic ring (hereinafter referred to as "alicyclic epoxy compound").

Examples of aromatic epoxy compounds include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of brominated bisphenol A; phenol novolak-type epoxy resins, and cresol novolak-type epoxy resins. Novolac type epoxy resins such as; other biphenyl type epoxy resins, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, epoxidized styrene-butadiene copolymer, styrene-isoprene copolymer Examples include epoxidized polymers, addition reaction products of carboxylic acid-terminated polybutadiene and bisphenol A type epoxy resin, and the like.

Here, the term "epoxy resin" refers to a compound or polymer that has one or more epoxy groups in its molecule and is cured by reaction. According to the practice in this field, in this specification, even a monomer having one or more curable epoxy groups in the molecule is sometimes referred to as an epoxy resin.

Alicyclic epoxy compounds include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, and bis(3,4-epoxycyclohexyl and compounds having at least one epoxidized cyclohexyl group such as methyl)adipate.

In addition to the above, aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and polytetramethylene glycol diglycidyl ether; epoxy compounds in which the aromatic ring is hydrogenated, such as glycidyl ether; compounds in which both ends of polybutadiene having hydroxyl groups at both ends are glycidyl etherified;
Internal epoxidized products of polybutadiene, compounds in which the double bonds of styrene-butadiene copolymers are partially epoxidized [eg, "Epofriend" manufactured by Daicel Chemical Industries, Ltd.], and ethylene-butylene copolymers and poly Examples thereof include polymer-based epoxy compounds such as compounds in which isoprene units of isoprene block copolymers are partially epoxidized.

As the epoxy compound, it is preferable to use a compound having a polydiene skeleton and an epoxy group [hereinafter referred to as "(AC-1) component"].
The number of epoxy groups contained in one molecule is preferably two or more.

The content of component (AC-1) is 1 to 40% by weight, preferably 1 to 30% by weight, still more preferably 1 to 25% by weight, based on the total composition. By setting the blending amount of the component (B) to 1 to 40% by weight, the cured product of the composition becomes excellent in adhesion to the polymer electrolyte and resistance to hot water immersion.

Specific examples of the (AC-1) component include the following (AC-1-1) to (AC-1-4) components.
• (AC-1-1) component: a compound obtained by epoxidizing the double bond of polybutadiene or polyisoprene.
• (AC-1-2) component: a compound obtained by epoxidizing the double bonds of polybutadiene or polyisoprene and adding hydrogen to the remaining double bonds.
• (AC-1-3) component: an epoxy compound obtained by glycidyl-etherifying the hydroxyl groups of a high molecular weight polymer having a polydiene skeleton and having hydroxyl groups at both ends with epichlorohydrin or the like.
- Component (AC-1-4): A compound obtained by adding a compound having two or more epoxy groups in one molecule to the carboxyl groups of a high molecular weight polymer having a polydiene skeleton and having carboxyl groups at both ends.
A more specific example of the component (AC-1-4) is a compound obtained by adding a bisphenol A type epoxy resin to polybutadiene modified with carboxyl groups on both ends.
As the (AC-1) component, among these compounds, the (AC-1-1) component is preferable because the cured product of the composition has excellent hot water immersion resistance.

As the (AC-1) component, one type can be used alone, or two or more types can be used in combination.
The molecular weight of component (AC-1) is preferably 500 to 5,000, more preferably 500 to 3,000 in terms of Mn. By setting the Mn of the component (B) to 500 or more, the adhesive strength with the polymer electrolyte can be enhanced, and by setting the Mn to 5,000 or less, the solubility in the composition can be improved. .
The proportion of epoxy groups contained in component (AC-1) is preferably 1 to 20%, more preferably 3 to 15%, in terms of oxirane oxygen concentration. By setting the oxirane oxygen concentration of the component (B) within the range of 1 to 20%, the hot water immersion resistance of the adherent to the polymer electrolyte can be improved.
In the present invention, the oxirane oxygen concentration means a value measured according to ASTM D1652 (HBr titration).

2-1-2-2. Oxetane compound The oxetane compound is not particularly limited as long as it has at least one oxetanyl group in the molecule, and various compounds having an oxetanyl group can be used.
As the oxetane compound, compounds having one oxetanyl group in the molecule (hereinafter referred to as "monofunctional oxetane") and compounds having two or more oxetanyl groups in the molecule (hereinafter referred to as "polyfunctional oxetane") are preferred. Examples include:

The monofunctional oxetane includes alkoxyalkyl group-containing monofunctional oxetane such as 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, aromatic group-containing monofunctional oxetane such as 3-ethyl-3-phenoxymethyloxetane, and hydroxyl group-containing monofunctional oxetanes such as 3-ethyl-3-hydroxymethyloxetane are preferred examples.

Examples of polyfunctional oxetanes include the following compounds.
3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane,
1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene,
1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
4,4′-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl,
2,2′-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl,
3,3′,5,5′-tetramethyl-4,4′-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl,
2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene,
bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]methane,
bis[2-{(3-ethyloxetan-3-yl)methoxy}phenyl]methane,
2,2-bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]propane,
3-chloromethyl-3-ethyloxetane etherified modification of novolac-type phenol-formaldehyde resin,
3(4),8(9)-bis[(3-ethyloxetan-3-yl)methoxymethyl]-tricyclo[5.2.1.0 ^2,6 ]decane,
2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane,
1,1,1-tris[(3-ethyloxetan-3-yl)methoxymethyl]propane,
1-butoxy-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]butane,
1,2-bis[{2-(3-ethyloxetan-3-yl)methoxy}ethylthio]ethane,
bis[{4-(3-ethyloxetan-3-yl)methylthio}phenyl]sulfide,
1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane,
a hydrolytic condensate of 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane,
condensates of tetrakis[(3-ethyloxetan-3-yl)methyl]silicate;

2-1-2-3. Vinyl ether Examples of vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether and 3-hydroxybutyl vinyl ether. , 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol divinyl ether, m- xylene glycol divinyl ether, o-xylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol divinyl ether, dipropylene glycol divinyl ether , tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol divinyl ether, polypropylene glycol divinyl ether, and derivatives thereof.

2-2. (B) Component (B) is a polymerization initiator, preferably a radical polymerization initiator.
Various radical generators can be used as the radical polymerization initiator.
The content of component (B) is 0.1 to 15% by weight, preferably 0.2 to 13% by weight, more preferably 0.5 to 10% by weight, based on the total composition. If the component (B) is less than 0.1% by weight, the curability of the composition will be insufficient, and if it exceeds 15% by weight, the cured product of the composition will have poor heat resistance and hot water immersion resistance.

As the component (B), a photoradical polymerization initiator that generates radicals by light (hereinafter referred to as "component (b1)"), a radical polymerization initiator other than component (b1) (hereinafter referred to as "component (b2)" ) are mentioned.
The composition used in the present invention is a photocurable composition containing component (b1), but component (b2) can also be used in combination.
The components (b1) and (b2) are described below in order.

2-2-1. (b1) Component (b1) is a photoradical polymerization initiator, and various compounds can be used.

Specific examples of component (b1) include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[ 4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopro pan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpho Acetophenone compounds such as lin-4-yl-phenyl)butan-1-one and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-octylcarbazole;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl ]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone and 4-methoxy-4′ - benzophenone compounds such as dimethylaminobenzophenone;
bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. Acylphosphine oxide compounds; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2 -yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and thioxanthone compounds such as fluorothioxanthone.
Compounds other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, methyl phenylglyoxylate, ethylanthraquinone, phenanthrenequinone, and camphorquinone.

Among these compounds, the component (b1) preferably contains an acylphosphine oxide compound from the viewpoint of excellent curability of the composition.

In addition, when it is necessary to increase the film thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, and when using an ultraviolet absorber or pigment in combination For the purpose of improving the curability of the composition, it is preferable to use a plurality of compounds selected from acylphosphine oxide compounds, thioxanthone compounds and α-aminoalkylphenone compounds in combination.
Preferred examples of the compound in this case include acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2, 4,6-trimethylbenzoyl)phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc., and thioxanthone compounds include 2,4-diethylthioxanthone , isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like, and α-aminoalkylphenone compounds include 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine- 4-yl-phenyl)-butan-1-one and the like.

As the component (b1), one type can be used alone, or two or more types can be used in combination.

The content of component (b1) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the entire component (B). By setting the proportion of the photoradical polymerization initiator to 0.1% by weight or more, the photocurability of the composition can be improved and adhesion can be improved. The internal curability of the product can be improved, and the adhesion to the substrate can be improved.

2-2-2. Component (b2) Component (b2) is a radical polymerization initiator other than component (b1), and thermal radical polymerization initiators such as peroxides and azo compounds can be used. A redox radical polymerization initiator can also be used.

Specific examples of organic peroxides include 1,1-bis(t-butylperoxy) 2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1 , 1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2 , 2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxy oxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2, 2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α, α '-Bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.
Specific examples of azo compounds include 1,1′-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile , azodi-t-octane, azodi-t-butane and the like.

(b2) component can be used individually by 1 type, and can also use 2 or more types together. Organic peroxides can also be used as redox initiators by combining them with reducing agents.

The content of the component (b2) is preferably 10% by weight or less, preferably 5% by weight or less, based on the entire component (B) for the purpose of improving the curability of the composition and enhancing the adhesion to the substrate. More preferred. On the other hand, considering the storage stability of the composition, it is preferable not to include it under conditions where light can sufficiently reach the composition.

2-2-3. Other (B) Components When the (AR) component and the (AC) component are used together as the (A) component of the present invention, a photocationic polymerization initiator can be used as the (B) component.
The photocationic polymerization initiator may be any compound that produces a cationic species or a Lewis acid upon irradiation with an active energy ray. -allene complex and the like.

2-3. Other Ingredients As the composition used in step 1, various compounds other than the above-mentioned components (A) and (B) can be blended as needed.
The composition used in step 1 contains the above components (A) and (B) as essential components, but may contain various other components depending on the purpose.

As other components, it is preferable to include fine particles (hereinafter referred to as "component (C)").
The component (C) and other components other than the component (C) are described below.

2-3-1. (C) Component (C) is fine particles.
Further, fine particles having a volume average primary particle diameter of 0.1 to 100 μm are preferable as the component (C). When the component (C) having such a particle size is blended, the thickness of the adhesive layer can be maintained at a certain level or more even when the polymer electrolyte and the other base material are laminated and pressure is applied. In addition, the suitability for screen printing is also improved.

Component (C) is preferably one that does not dissolve in components (A) to (C).
Specific examples of component (C) include inorganic fine particles and polymer fine particles.
Examples of inorganic fine particles include alumina, silica, and zirconia.
Examples of polymer fine particles include chemically crosslinked polymer fine particles and non-crosslinked polymer fine particles that do not dissolve in components (A) to (C). Examples of non-crosslinked polymer fine particles include polyolefins, fluorinated polyolefins, and cellulosic resins.

(C) As a component, it can also be used individually by 1 type, and can also use 2 or more types together.

Among these, component (C) preferably contains polymer fine particles, more preferably chemically crosslinked polymer fine particles, in terms of excellent dispersibility and stability. preferable.

Specific examples of chemically crosslinked polymer microparticles include acrylic microparticles containing polymerized units of (meth)acrylate monomers such as methyl methacrylate, and polyurethane microparticles.
As a method for crosslinking the acrylic fine particles, a method of copolymerizing a monomer mixture containing a monofunctional (meth)acrylate monomer and a difunctional (meth)acrylate monomer, a method of copolymerizing a monofunctional (meth)acrylate monomer and an alkoxysilyl For example, a method of copolymerizing a monomer mixture containing a (meth)acrylate monomer having a group, hydrolyzing and condensing the alkoxysilyl group, and crosslinking.

The volume average primary particle size of component (C) is preferably 0.1 to 100 μm, more preferably 0.2 to 70 μm, still more preferably 0.5 to 50 μm, and particularly preferably 0.5 to 30 μm.
The volume average primary particle size of component (C) means a value measured by a laser diffraction scattering particle size distribution analyzer (wet method).

When the component (C) is added to the composition of the present invention, the content is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, based on the total composition. .

2-3-2. Other components other than component (C) Other components other than component (C) include particles in a particle size range not included in component (C) (for example, an average primary particle size of less than 0.1 μm, from several tens of nm to several nm). fine particles), polymers other than components (A) and (C) (hereinafter referred to as “other polymers”), tackifiers, plasticizers, antifoaming agents, leveling agents, polymerization inhibitors, stabilizers, organic solvents, etc. mentioned.

Fine particles not included in the component (C) having a particle size range include fine particles (fume Silica, etc.), and particles with a particle diameter of several 100 μm to several mm, which can be used for the purpose of considerably increasing the thickness of the cured product and reducing the curing shrinkage rate.

Specific examples of other polymers include polymers that are uncrosslinked and have solubility in the composition.
Examples of such polymers include (meth)acrylic resins, polystyrene, styrene-acrylonitrile copolymers, polybutadiene, polyisoprene, polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene, maleated polybutadiene, maleated polyisoprene, maleated Polypropylene, chlorinated polypropylene, petroleum resin, hydrogenated petroleum resin, xylene resin, polytetramethylene glycol, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-acrylic copolymer, polyester, polyamide, polyurethane, polycarbonate, etc. is mentioned.
These may act as adhesion imparting components, and may act as tackifiers or plasticizers, which will be described later.

Specific examples of tackifiers include rosin esters and petroleum resins.
Specific examples of plasticizers include dioctyl phthalate and the like.
Antifoaming agents include hydrocarbon-based, silicone-based, fluorosilicone-based, fluorine-based, and mineral spirits-based antifoaming agents, and known antifoaming agents can be used.
Examples of the leveling agent include hydrocarbon-based, silicone-based, fluorine-based, and the like, and known ones can be used.

Examples of the polymerization inhibitor include hydroquinone and methoxyhydroquinone, and known ones can be used.
Stabilizers include hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, and ultraviolet absorbers, and known stabilizers can be used.

Any known organic solvent can be used as long as it dissolves the components (A) and (B). However, considering that the solvent drying step lowers production efficiency and concerns about residual solvent, it is preferable not to blend the organic solvent.

2-4. Method for producing the composition The composition used in the present invention contains the components (A) and (B) described above, and the method for producing the composition may follow a conventional method, and the above (A) and (B) It can be produced by mixing the components, optionally mixing other components, and stirring in a conventional manner.
In this case, it can be heated as needed.

The viscosity of the composition used in the present invention can be appropriately set by those skilled in the art according to the coating method in order to obtain a coated surface with excellent coating properties that can be used in the manufacturing process of the laminate, that is, smoothness. can be done.

3. Process 1
Step 1 relates to a step of applying a photocurable composition to the catalyst layer side of a substrate having a catalyst layer.
The substrate having a catalyst layer and the photocurable composition are as described in detail above.
The coating method will be described below.

3-1. In the coating method step 1, the photocurable composition is coated on the catalyst layer side of the substrate having the catalyst layer.
The coating method may be appropriately set according to the composition to be used and the purpose. For example, various coating methods such as dispenser, screen printing, roll coater, inkjet, spray, and electrostatic attraction coating are employed. be able to.

In this case, the film thickness of the coated composition may be appropriately set according to the substrate having the catalyst layer to be used and the application, and is preferably 10 to 500 μm, more preferably 20 to 100 μm.

3-2. Other Steps In the present invention, after coating the composition, a light-transmitting member may be attached to the coated surface. In this case, this light-transmitting member is adhered in a subsequent curing step and integrated with the substrate having the catalyst layer.

4. Process 2
In step 2, within 1 minute after step 1, an LED having an emission peak wavelength of 350 to 420 nm is irradiated with light at a peak wavelength of 20 to 1,000 mJ/cm ² in an air atmosphere. This is a pre-curing step.

As the LED light source, as long as it has an emission peak wavelength of 350 to 420 nm, one type may be used alone, or two or more types may be used in combination.
For example, a 365 nm LED and a 405 nm LED may be combined. In this case, the sum of the doses of the respective wavelengths is adjusted so as to be within the target range.
Although the irradiation dose varies depending on the thickness of the coating film, the illuminance, etc., it may be appropriately set according to the emission wavelength of the LED light source and the compounding composition.

After the coating in step 1, the time until light irradiation shall be within 1 minute.
Furthermore, it is preferably within 1 minute and 50 seconds after coating, more preferably within 30 seconds, and particularly preferably within 10 seconds.
By shortening this time, even if the catalyst decomposes the low-molecular-weight (meth)acrylate at a very high rate, the amount of decomposition can be minimized.

In step 1, when a dispenser is employed as the coating method, it is preferable to have a structure in which the LED light source tracks immediately behind the nozzle portion of the dispenser. As a result, the time from coating to pre-curing can be shortened to within 1 second.

In step 2, light irradiation is performed at the peak wavelength of the LED at an irradiation amount of 20 to 1,000 mJ/cm ² . If the thickness is out of this range, the effect of the present invention that exhibits good adhesion even on a highly active catalyst layer is reduced, which is not preferable.
Specifically, if it is less than 20 mJ/cm ² , the effect of pre-curing is almost lost and the adhesion is lowered ^. Since the active species of the component (B) are almost lost in the main curing in the step 3, the curing does not progress.

5. Step 3
In step 3, the photocurable composition precured in step 2 is irradiated with an LED or other ultraviolet irradiation device other than an LED having an emission peak wavelength of 350 to 420 nm in an atmosphere with an oxygen concentration of 5% or less. This is the main curing step in which light is irradiated at a wavelength of 50 mJ/cm ² or more.

In step 3, light irradiation is performed in an atmosphere with an oxygen concentration of 5% or less.
If the oxygen concentration is more than 5%, the amount of residual monomers increases, and the residual monomers may be decomposed by a catalyst after the heat resistance test, resulting in a decrease in adhesion. The oxygen concentration is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.
Although the lower limit of the oxygen concentration is not particularly specified from the viewpoint of the performance of the laminate to be obtained, it is preferably 0.001% or more from the viewpoint of production cost.

As a method for reducing the oxygen concentration to 5% or less, it is preferable to use an inert gas having an oxygen concentration of less than 5%. Examples of inert gases include nitrogen, carbon dioxide, water vapor, argon, etc. Nitrogen is preferred.
In the case of using nitrogen gas, from the viewpoint of economy, nitrogen gas with a purity of about 96 to 99% obtained by membrane separation of air can be used, and for the purpose of reducing the oxygen concentration in a short time , nitrogen gas with a purity of 99% or more can also be used.

As a method for reducing the oxygen concentration around the photocurable composition precured in step 2 to 5% or less, the entire member is covered and an inert gas is flowed into it. Examples include a method of transferring to a space by a conveyor or the like, and a method of spraying an inert gas having an oxygen concentration of less than 5% onto the precured photocurable composition.

An LED light source having an emission peak wavelength of 350 to 420 nm should be appropriately selected according to the usage conditions. For example, when light-transmitting members are pasted together and the members absorb ultraviolet rays, it is preferable to select, for example, a 405 nm LED. In that case, it is necessary to use a photocurable resin that is sensitive to light of 405 nm. On the other hand, when bonding a member that transmits light with a wavelength of 350 nm or more, or when using a photocurable resin like a sealing material or adhesive (when exposed to a direct light source), it is widely used as UV-LED curing. The 365 nm or 385 nm UV-LEDs in use can be preferably used.

In the main curing step, UV irradiation devices other than LEDs, such as high-pressure mercury lamps and metal halide lamps, can be used, but LEDs are preferred in terms of reducing damage to the catalyst layer.

In step 3, light irradiation is performed at the peak wavelength of the light source at an irradiation dose of 50 mJ/cm ² or more. If it is less than 50 mJ/cm ² , even if the oxygen concentration is reduced, the residual monomer may not be sufficiently reduced, and the adhesion to the catalyst layer may deteriorate.

6. Uses of Laminate The laminate obtained by the present invention can be used for various purposes.
A preferred laminate is a laminate containing a polymer electrolyte as a substrate having a catalyst layer. The structure of the laminate is a laminate composed of a base material, a cured product formed from the composition described above, and the other base material, wherein both or one of the base material and the other base material , is a polyelectrolyte.
As the polymer electrolyte, a perfluorocarbon material having a sulfonic acid group is preferable from the viewpoint of chemical stability.

Applications of the resulting laminate include polymer electrolyte fuel cells, electrochemical hydrogen pumps, actuators for medical use, and various sensors such as medical sensors and gas sensors.

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below. However, the present invention is not limited by these examples.
In the following description, "parts" means parts by weight, and numerical values indicating blending ratios in the tables mean % by weight.

1. Manufacturing example
1) Preparation of electrolyte membrane-catalyst layer laminate
(1) Sulfonation of the catalyst 30 ml of concentrated sulfuric acid with a purity of 96 wt% and 30 ml of fuming sulfuric acid with an _SO3 content of 25 vol% were mixed with 3 g of carbon supporting a platinum catalyst (46 wt% of platinum supported, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E). was immersed and stirred at a liquid temperature of 40° C. for 8 hours for sulfonation. This was filtered, immersed in 4 L of deionized water at 70° C., stirred for 30 minutes, and filtered again to remove unreacted sulfuric acid and fuming sulfuric acid. This washing process was repeated until the washing water became neutral. After washing, the product was dried overnight in the air at 60° C. and ground in a mortar to obtain a sulfonated catalyst.

(2) Preparation of Transfer Sheet for Catalyst Layer Formation To 2 g of the sulfonated catalyst described above, 10 g of 1-butanol, 10 g of 3-butanol, and 5 g of an ionomer dispersion [Nafion (registered trademark) D2020, manufactured by DuPont, polymer content: 20 wt %]. and 21 g of water were added and stirred and mixed with a disperser to prepare a paste composition for forming a catalyst layer. Next, this composition was coated on a PET film so that the weight of platinum after drying the catalyst layer was 0.4 mg/cm ² and dried to prepare a transfer sheet for forming a catalyst layer.

(3) Preparation of electrolyte membrane-catalyst layer laminate Cut the transfer sheet for forming the catalyst layer described above into a size of 70 mm × 30 mm, prepare two sheets, and cut the polymer electrolyte membrane (Nafion (Nafion) (registered trademark) NRE-212, manufactured by DuPont, thickness 0.002 inch) was placed on each side so that the catalyst layer faced the electrolyte membrane side, and hot-pressed at 135° C., 5.0 MPa, and 150 seconds. After that, the PET film was peeled off to produce an electrolyte membrane-catalyst layer laminate. This is hereinafter referred to as "catalyst layer substrate A".

2) Preparation of photocurable composition
(1) Synthesis of urethane acrylate In a 2 L four-necked separable flask, GI-1000 (hydroxyl value 68.7 mg KOH / g, Mn about 1, 500) 900 g (1.1 mol as hydroxyl group), 0.65 g of 2,6-di-t-butyl-p-cresol, and 244 g of isophorone diisocyanate (2.2 mol as isocyanate group) were charged, and a stirrer was attached to stir and mix. and dissolved. A thermometer, a gas introduction tube, a dropping funnel, and a cooling tube were attached to the flask, and a mixed gas of oxygen and nitrogen (5% oxygen) was passed through. After adding 0.013 g of Nasem ferric iron as a catalyst to this solution and dissolving it, the liquid temperature was raised to 80° C. and reacted for 5 hours. ) was charged and reacted for 5 hours to synthesize urethane acrylate. This is hereinafter referred to as "UA-1".

(2) Preparation of photocurable composition 50 g of the above UA-1, 50 g of an acrylate adduct of 1 mol of nonylphenol EO [Aronix M-111 manufactured by Toagosei Co., Ltd.], and a photoradical polymerization initiator, Speed Cure TPO. 2 g of [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by Rambuson Co., Ltd.] and 0.1 g of BYK-1790 [Bik-Chemie Japan Co., Ltd.] as an antifoaming agent were blended and heated at 60 ° C. Stir to dissolve.
Next, 50 g of acrylic crosslinked fine particles [MX-500 manufactured by Soken Kagaku Co., Ltd.] having an average particle diameter of 5 μm were added and dispersed by a planetary stirrer to prepare a photocurable composition.
This is hereinafter referred to as "photocurable composition A".

2. Example
1) Example 1 (Method for producing a laminate having a catalyst layer)
(1) Process 1
On the catalyst layer substrate A, the photocurable composition A was applied by screen printing to a width of 6 mm, a length of 60 mm, and a thickness of 0.05 mm.

(2) Process 2
Ten seconds after coating, pre-curing was performed by irradiating 250 mJ/cm ² ultraviolet rays using a 365 nm LED.
As the LED, a controller 8332A and a standard head 8361 manufactured by CCS Co., Ltd. were used, and a line lens AC8343 was attached to the tip of the head (the irradiation range was a rectangle of 5 mm×16 mm). This LED head is set above a movable stage whose speed can be adjusted so that the stage traverses the short side of the irradiation range, and the irradiation amount is set to 250 mJ/cm ² when the stage speed is 6 mm/sec. It was adjusted. At this time, the illuminance at the central portion of the irradiation range was 500 mW/cm ² . In this way, by performing screen printing right next to the previously adjusted LED and stage, the time from screen printing to pre-curing can be shortened to 10 seconds.

(3) Process 3
A cycloolefin polymer film [ZF14 manufactured by Nippon Zeon Co., Ltd.] having a width of 10 mm and a length of 60 mm, which had been corona-treated in advance, was placed on the pre-cured coating film on the pre-cured coating film with a width of 6 mm and a length of 60 mm. They were laminated so that 30 mm was adhered.
Next, this was placed in a stainless steel container equipped with quartz glass on the top, a gas inlet with a cock on the side, a gas outlet with a cock on the side, and an oxygen sensor, and nitrogen was substituted for 5 minutes to check the oxygen concentration in the container. After making it 0.1 vol%, the container was sealed, and a UV-LED irradiation device (365 nm) manufactured by Sentech Co., Ltd. equipped with a stage moving device was used to irradiate 1,000 mJ/cm ² ultraviolet rays for main curing. A laminate with layers was prepared (200 mW/cm ² peak illumination, 8 mm/sec stage speed, 2 passes at 500 mJ/cm ² per pass).

2) Example 2
A laminate was produced in the same manner as in Example 1, except that in the pre-curing step 2 of Example 1, the moving speed of the LED head was 15 mm/sec and the UV irradiation dose was 100 mJ/cm ² .

3) Example 3
A laminate was produced in the same manner as in Example 1, except that the pre-curing in step 2 of Example 1 was performed twice in succession, and the UV irradiation dose in the pre-curing was 500 mJ/cm ² .

4) Comparative Example 1
A laminate was produced in the same manner as in Example 1, except that the time from application to pre-curing was changed to 2 minutes.

5) Comparative example 2
A laminate was produced in the same manner as in Example 1, except that the pre-curing in step 2 was omitted.

6) Comparative Example 3
A laminate was produced in the same manner as in Example 1, except that in the pre-curing step 2 of Example 1, the moving speed of the LED head was changed to 150 mm/sec and the UV irradiation amount was changed to 10 mJ/cm ² .

7) Comparative Example 4
A laminate was produced in the same manner as in Example 1, except that the pre-curing in step 2 of Example 1 was performed eight times in succession, and the UV irradiation dose in the pre-curing was changed to 2,000 mJ/cm ^{2 .} .

8) Comparative Example 5
A laminate was produced in the same manner as in Example 1, except that the oxygen concentration during main curing was changed to 6%.

9) Comparative Example 6
A laminate was produced in the same manner as in Example 1, except that the main curing condition was changed to 1 pass at a conveyor speed of 160 mm/sec and the UV irradiation amount was changed to 25 mJ/cm ² .

10) Comparative Example 7
A laminate was produced in the same manner as in Example 1, except that the main curing was omitted.

3. After the laminate after the main curing in the adhesion evaluation step 3 of the photocurable composition layer on the catalyst layer was left at room temperature for 1 hour under air, it was placed in a drying oven at 120 ° C. for 10 minutes and then taken out to obtain a cured film. was visually observed. Based on the results, the adhesion was evaluated according to the following four levels.
The results are shown in Table 1 together with the experimental conditions.
○: No peeling part △: Slight peeling was observed at the edge of the cured product ×: The edge of the cured product was peeled off from the catalyst layer by about 1 mm XX: Most of the cured product was peeled off from the catalyst layer

4) Evaluation Results As is clear from the results of Examples 1 to 3, the laminate obtained by the production method of the present invention was excellent in adhesion.
On the other hand, the manufacturing method of Comparative Example 1 in which the time from step 1 to step 2 exceeds 1 minute, the manufacturing method of Comparative Example 2 in which the second step was not performed, and the lower limit of the irradiation dose in the second step was 20 mJ. In the production method of Comparative Example 3, where the thickness was less than /cm ² , the adhesion of the resulting laminate was insufficient, and slight peeling was observed at the edges of the cured product.
Further, the manufacturing method of Comparative Example 4 in which the upper limit of the irradiation dose in the second step exceeded 1,000 mJ/cm ² , the manufacturing method of Comparative Example 5 in which the upper limit of the oxygen concentration in the third step exceeded 5%, and the third step. In the production method of Comparative Example 6, in which the lower limit of the irradiation dose was not 50 mJ/cm ² , the adhesion of the obtained laminate was lowered, and peeling of about 1 mm from the catalyst layer at the edge of the cured product occurred. rice field.
Furthermore, in the manufacturing method of Comparative Example 7 in which the third step was not performed, the adhesion of the obtained laminate was greatly reduced, and most of the cured product was peeled off from the catalyst layer.

The manufacturing method of the present invention can be preferably applied to a method of manufacturing a laminate having a catalyst layer.
In particular, laminates obtained from substrates having a polymer electrolyte are preferably used as fuel cells, electrochemical hydrogen pumps, various sensors, and the like.

Claims (3)

A method for producing a laminate having a catalyst layer, including steps 1 to 3 below.
Step 1: Step of applying a photocurable composition containing (meth)acrylate to the catalyst layer side of the substrate having the catalyst layer Step 2: Within 1 minute after Step 1, in an air atmosphere, light emission A pre-curing step in which a light emitting diode (hereinafter referred to as “LED”) having a peak wavelength of 350 to 420 nm is irradiated with light at a peak wavelength of 20 to 1,000 mJ/cm ² Step 3: Pre-curing in step 2 The resulting photocurable composition is irradiated with an LED having a peak emission wavelength of 350 to 420 nm or an ultraviolet irradiation device other than an LED in an atmosphere with an oxygen concentration of 5% or less at a peak wavelength of 50 mJ/cm ² or more. The main curing process that irradiates light in the amount 2. The method for producing a laminate according to claim 1, wherein the step 1 includes a step of laminating a light-transmitting member on the coated photocurable composition. 2. The method for producing a laminate according to claim 1, further comprising a step of laminating a light-transmissive member on the pre-cured photocurable composition after performing the step 2.