Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/66—Mercaptans
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/14—Polysulfides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/02—Ingredients treated with inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/18—Homopolymers or copolymers of nitriles
  • C08L33/20—Homopolymers or copolymers of acrylonitrile
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/04—Polysulfides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
  • C09K2200/0647—Polyepoxides

Definitions

• the present invention relates to a curable resin composition that can be cured at room temperature and is capable of withstanding high compression.
• the CIPG (cured-in-place gasket) method has been known as a sealing method using a sealant.
• the CIPG method is a method in which a bead of a curable resin composition as a sealant is applied to the flange of the sealed part, cured to form a gasket, and then laminated to the other flange and compressed.
• FIPG formed-in-place gasket
• the CIPG method has the advantages of being less affected by outgassing during curing because the curable resin composition is cured before lamination, and being removable, making it possible to reuse the parts.
• JP 2019-156965 A discloses an epoxy resin composition that cures at a temperature of 80°C for 5 hours.
• curable resin compositions require energy such as heating or ultraviolet light irradiation when applying CIPG to components, and there have been concerns about the effects of heat and ultraviolet light on components.
• the cured product of the curable resin composition when used as a gasket, it may be used under high compression conditions. If the cured product cannot withstand the high compression pressure and is crushed or deformed, it will not be able to exhibit its sealing performance. To avoid this problem, the cured product of the curable resin composition is required to have a certain degree of flexibility, but on the other hand, if the flexibility of the cured product is increased too much, the surface of the cured product will not cure properly, and will be transferred to the bonding material after curing, causing another problem that the material cannot be reused.
• the present inventors have made this invention in consideration of the above circumstances, and it is an object of the present invention to provide a curable resin composition that does not require heat or a light source, can be cured at room temperature, the cured product can withstand high compression conditions, and the components can be reused. Another object of the present invention is to provide a cured product of the above curable resin composition.
• the inventors discovered that the curable resin composition described in detail below does not require heat or a light source, can be cured at room temperature, the cured product can withstand high compression conditions, and the components can be reused, which led to the completion of the present invention.
• a curable resin composition comprising the following components (A) to (D): Component (A): a compound having two or more epoxy groups; Component (B): a thiol curing agent; Component (C): resin hollow particles; Component (D): a curing accelerator.
• X to Y is used to mean that the numerical values (X and Y) written before and after it are included as the lower and upper limits, respectively, and means “X or more and Y or less.” Furthermore, unless otherwise specified, operations and measurements of physical properties are performed under the conditions of room temperature (20 to 25°C) and relative humidity of 40 to 55% RH. Furthermore, “A and/or B” means that A and B are each included, and a combination of these.
• a curable resin composition according to one embodiment of the present invention contains the following components (A) to (D): Component (A): a compound having two or more epoxy groups; Component (B): a thiol curing agent; Component (C): resin hollow particles; Component (D): a curing accelerator.
• the component (A) used in the present invention is a compound having two or more epoxy groups in one molecule.
• the component (A) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, but examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, dicyclopentadiene type epoxy resin, orthocresol novolac type epoxy resin, and alicyclic epoxy resin, but are not limited thereto.
• the components (A) from the viewpoint of high compression resistance, it is preferable to include a bisphenol type epoxy resin and/or a hydrogenated bisphenol type epoxy resin, more preferably to include a hydrogenated bisphenol type epoxy resin, and most preferably to consist of only a hydrogenated bisphenol A type epoxy resin. These may be used alone or in a mixture of two or more types.
• the epoxy equivalent of the (A) component is preferably 50 g/eq or more and less than 400 g/eq, and more preferably 100 g/eq or more and less than 300 g/eq.
• the viscosity of the (A) component at 25°C is preferably 0.1 Pa ⁇ s to 300 Pa ⁇ s, more preferably 0.1 Pa ⁇ s to less than 100 Pa ⁇ s, and most preferably 0.1 Pa ⁇ s to 10 Pa ⁇ s.
• jER828, 1001, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Mitsubishi Chemical Corporation
• Epicron 830, EXA-830LVP, EXA-850CRP, EXA-835LV, HP4032D, HP4700, HP820 manufactured by DIC Corporation
• EP-4100, EP-4100G, EP-4100E, and EP-4100T EP-4100T.
• the component (B) of the present invention is a thiol curing agent.
• the thiol curing agent is not particularly limited as long as it has a thiol group (SH group), but from the viewpoint of compression resistance and room temperature curing ability, a compound having two or more thiol groups is preferable.
• the mercaptobutyryloxyethyl (oxy)butane 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(
• (B) components from the viewpoint of realizing sealing properties at high compression, it is preferable to include (B-1) a thiol curing agent having a polyether skeleton and no disulfide bond in the main chain and/or (B-2) a thiol curing agent having a disulfide bond in the main chain, and it is more preferable to include both (B-1) a thiol curing agent having a polyether skeleton and no disulfide bond in the main chain and (B-2) a thiol curing agent having a disulfide bond in the main chain.
• the (B-1) thiol curing agent having a polyether skeleton and no disulfide bond in the main chain is preferably a polymer having a polyether skeleton and no disulfide bond in the main chain, and having three or more thiol groups in one molecule.
• the (B-2) thiol curing agent having a disulfide bond in the main chain is preferably a polymer having a disulfide bond and a polyether skeleton in the main chain and having a thiol group at the end.
• the component (B) more preferably includes a polymer having a polyether skeleton but no disulfide bonds in its main chain and having three or more thiol groups in one molecule and/or a polymer having a disulfide bond and a polyether skeleton in its main chain and having thiol groups at its terminals, and most preferably includes both a polymer having a polyether skeleton but no disulfide bonds in its main chain and having three or more thiol groups in one molecule, and a polymer having a disulfide bond in its main chain and having thiol groups at its terminals.
• component (B) Commercially available products of component (B) include, but are not limited to, TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (manufactured by SC Organic Chemicals Co., Ltd.), Karenz MTPE1, BD1, NR1, and TPMB (manufactured by Showa Denko K.K.), Thiokol LP, FLEP, and Polythiol QE-340M (manufactured by Toray Fine Chemicals Co., Ltd.).
• the average molecular weight is preferably 500 to 4000, more preferably 600 to 3000, and most preferably 800 to 2000, from the viewpoint of compression resistance.
• the ratio of (B-1):(B-2) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and most preferably 40:60 to 60:40.
• the (B) component is preferably contained in an amount of 20 to 200 parts by mass, more preferably 50 to 150 parts by mass, and most preferably 70 to 120 parts by mass, per 100 parts by mass of the (A) component. If it is 20 parts by mass or more, the cured product is flexible and can exhibit sealing properties, and if it is 200 parts by mass or less, there is no risk of the surface curing property decreasing, and the member can be reused.
• the (C) component used in the present invention is a resin hollow particle.
• the resin hollow particle is a hollow body having a hollow portion, and refers to a particle formed by a resin.
• the reaction force refers to a force that repels compression, and if the reaction force is large during high compression, there is a risk that the member will be distorted.
• the shape of the (C) component is not particularly limited and may be any shape, such as spherical, needle-like, fibrous, or plate-like, but a spherical shape is preferred from the viewpoints of dispersibility in the (A) and (B) components and sealing properties at high compression.
• spherical means that the aspect ratio is 1.0 to 2.0, preferably 1.0 to 1.5, and does not necessarily mean that the shape is a perfect sphere.
• the aspect ratio in the case of a sphere is determined by the ratio of the major axis to the minor axis.
• the average particle size of the (C) component is not particularly limited, but is, for example, 5 to 200 ⁇ m, preferably 10 to 200 ⁇ m, more preferably 40 to 170 ⁇ m, even more preferably 50 to 150 ⁇ m, and most preferably 100 to 150 ⁇ m.
• the average particle size means the particle size (D50) at a cumulative volume ratio of 50% in the particle size distribution determined by the laser diffraction scattering method.
• the resin constituting the (C) component is not particularly limited, but is preferably a thermoplastic resin, and more preferably a polymer (homopolymer) of one or more monomers selected from the group consisting of vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic acid esters, and methacrylic acid esters, or a copolymer of two or more monomers.
• a copolymer is preferred, more preferably a copolymer containing acrylonitrile as a constituent unit, and most preferably an acrylonitrile-methacrylonitrile-methyl methacrylate copolymer.
• the (C) component has an inorganic filler attached to its surface, and more preferably that it has calcium carbonate attached.
• the true specific gravity of the (C) component is preferably 0.001 to 0.3, more preferably 0.01 to 0.2, and most preferably 0.01 to 0.15, from the viewpoint of dispersibility in the (A) and (B) components.
• the true specific gravity of the (B) component is determined by a method in accordance with JIS Z8807:2012.
• the (C) component is preferably contained in an amount of 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and most preferably 15 to 50 parts by mass, per 100 parts by mass of the (A) component. If the amount is 5 to 70 parts by mass, the cured product has a low reaction force and can achieve high sealing properties even under high compression conditions.
• the curing accelerator is further included as component (D).
• the curing accelerator is not particularly limited as long as it can accelerate the effect of component (B). From the viewpoint of realizing room temperature curing, it is preferable to include one or more compounds selected from the group consisting of imidazole compounds, amine compounds, and polyol compounds, more preferably amine compounds and/or polyol compounds, and most preferably tertiary amine compounds and/or polyol compounds.
• tertiary amine compounds include, for example, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,6-diaminohexane, N,N-dimethylbenzylamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, (dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tripropylamine, diazabicycloundecene, and diazabicyclononene.
• polyol compound examples include aliphatic polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonanediol, neopentyl glycol, tricyclodecane dimethylol, cyclohexane dimethylol, trimethylolpropane, glycerin, hydrogenated polybutadiene polyol, and hydrogenated dimer diol; (poly)ether polyols having one or more ether bonds such as ditrimethylolpropane; polyester polyol compounds; polycaprolactone polyol compounds; polyol compounds having a phenolic hydroxyl group; and polycarbonate polyols such as polycarbonate diol.
• aliphatic polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonan
• component (B) it is preferable to contain both an amine compound that is liquid at 25° C. and a polyol compound that is solid at 25° C., and it is preferable to combine 2,4,6-tris(dimethylaminomethyl)phenol and trimethylolpropane.
• the viscosity at 25°C is preferably 1 to 10,000 mPa ⁇ s, more preferably 10 to 5,000 mPa ⁇ s, and most preferably 100 to 1,000 mPa ⁇ s.
• component (D) is a solid at 25°C, it preferably has a melting point of 30 to 80°C, more preferably 40 to 75°C, and most preferably 50 to 70°C.
• the amount of the (D) component is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the (B) component. If it is 0.1 to 20 parts by mass, room temperature curing can be achieved without reducing storage stability.
• the mass ratio of the amine compound:polyol compound is preferably 9:1 to 5:5, more preferably 8:2 to 5:5, and most preferably 7:3 to 5:5. If it is 9:1 to 5:5, excellent room temperature curing can be achieved by combining it with the (B) component.
• additives such as inorganic fillers, organic fillers other than component (C), pigments, dyes, silane coupling agents, leveling agents, rheology control agents, and storage stabilizers may be further contained in appropriate amounts.
• the inorganic filler may be, but is not limited to, alumina powder, calcium carbonate powder, talc powder, silica powder, fumed silica powder, silver powder, nickel powder, palladium powder, carbon powder, tungsten powder, plating powder, etc.
• the preferred range of the amount of inorganic filler to be blended is 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of component (A).
• the organic filler other than the component (C) may be an organic solid body composed of rubber, elastomer, plastic, polymer (or copolymer), etc. Also, it may be an organic filler having a multi-layer structure such as a core-shell type.
• the average particle size of the organic filler is preferably in the range of 0.05 to 50 ⁇ m. From the viewpoint of improving the characteristics in the durability test, it is preferable to include a filler composed of a polymer or copolymer of an acrylic acid ester and/or a (meth)acrylic acid ester, or a filler composed of a polymer or copolymer of a styrene compound.
• the suitable amount of the organic filler is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of (A).
• the silane coupling agent may, for example, be 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, 3-glycidoxypropyldimethylmonomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2-(3,4-epoxycyclohexyl)ethyl glycidyl group-containing silane coupling agents such as glycidyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris( ⁇ -me
• silane coupling agents include (meth)acrylic group-containing silane coupling agents such as dimethyl silane, 3-methacryloxypropyl dimethyl monoethoxysilane, 3-acryloxypropyl methyl dipropyloxysilane, 3-acryloxypropyl methyl dimethoxysilane, 3-acryloxypropyl methyl diethoxysilane, 3-acryloxypropyl methyl dipropyloxysilane, 3-acryloxypropyl dimethyl monopropyloxysilane, 3-acryloxypropyl dimethyl monomethoxysilane, 3-acryloxypropyl dimethyl monoethoxysilane, 3-acryloxypropyl dimethyl monopropyloxysilane, and ⁇ -methacryloxypropyl trimethoxysilane; amino group-containing silane coupling agents such as N- ⁇ -(aminoethyl)- ⁇ -aminopropyl trimethoxysilane, ⁇ -aminopropyl triethoxysilane; amino
• glycidyl group-containing silane coupling agents are more preferred from the viewpoint of excellent adhesive strength. These may be used alone or in combination of two or more.
• the preferred range of the amount of silane coupling agent to be blended is 0.1 to 20 parts by mass per 100 parts by mass of component (A) of the present invention.
• the storage stabilizer may be boric acid ester, phosphoric acid, alkyl phosphate ester, or p-toluenesulfonic acid.
• boric acid ester include, but are not limited to, tributyl borate, trimethoxyboroxine, and ethyl borate.
• alkyl phosphate ester include, but are not limited to, trimethyl phosphate and tributyl phosphate.
• the storage stabilizer may be used alone or in combination.
• the suitable amount of storage stabilizer is 0.1 to 10 parts by mass per 100 parts by mass of component (A) of the present invention.
• the curable resin composition of the present invention can be applied to an adherend by a known method for applying a sealant or adhesive, such as dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, spin coating, or the like.
• CIPG The curable resin composition of the present invention forms a cured product that can withstand high compression, and therefore can be suitably used for CIPG applications.
• CIPG is a technique in which a curable resin composition is bead-coated on a flange of a sealed part using an automatic coating device or the like, the curable resin composition is cured under any curing conditions to form a gasket, and then the gasket is compressed and sealed with the other flange.
• the method is a method for sealing at least a portion between at least two flanges of a sealed part having at least two flanges, and includes a step of coating at least one of the flanges with the above-mentioned curable resin composition, a step of curing the coated curable resin composition to form a gasket made of a cured product of the curable resin composition, and a step of placing the other flange on the gasket, and pressing 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.
• the curable resin composition of the present invention can be cured at room temperature.
• room temperature means a temperature of 20° C. or more and less than 30° C.
• the curing time is not particularly limited, but in the case of room temperature, it is preferably 1 minute or more and less than 24 hours, and more preferably 1 hour or more and less than 2 hours.
• the curable resin composition of the present invention preferably comprises two liquids.
• the two-part curable resin composition of the present invention comprises a first liquid (the main agent) and a second liquid (a curing agent). It is preferable that the first liquid contains the components (A) and (C), and the second liquid contains the components (B), (C), and (D).
• the mixing ratio is set to 1:1. It is preferable to mix the first liquid with the second liquid in a ratio of 40:60 to 60:40 by weight.
• the curable resin composition of the present invention can be used in various applications. Specific examples include adhesion, sealing, casting, coating, etc. of automotive switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, front hoods, fenders, body panels such as doors, windows, etc.; adhesion, sealing, casting, coating, etc. of flat panel displays (liquid crystal displays, organic EL displays, light-emitting diode display devices, field emission displays), video discs, CDs, DVDs, MDs, pickup lenses, hard disks, etc. in the electronic materials field; adhesion, sealing, casting, coating, etc. of lithium batteries, lithium ion batteries, manganese batteries, alkaline batteries, fuel cells, silicon-based batteries, etc.
• These materials can be used for bonding, sealing, coating, etc. for solar cells, dye-sensitized cells, organic solar cells, etc.; in the optical components field, for bonding, sealing, coating, etc. for optical fiber materials around optical switches and optical connectors, optical passive components, optical circuit components, and optoelectronic integrated circuits, etc.; in the optical equipment field, for bonding, sealing, coating, etc. for camera modules, lens materials, viewfinder prisms, target prisms, viewfinder covers, light receiving sensors, photographic lenses, our company's lenses for projection TVs, etc.; in the infrastructure field, they can be used as bonding, lining materials, seals, coating materials, etc. for gas pipes, water pipes, etc., but due to their excellent compression resistance, they are ideal for sealing applications.
• D-1) 2,4,6-tris(dimethylaminomethyl)phenol
• Ancamine K54 Viscosity (25°C): 200 mPa ⁇ s
• D-2) Trimethylolpropane (reagent) Melting point: 58°C
• the (A) and (C) components were weighed in a stirring vessel and stirred with a mixer for 30 minutes to obtain a first liquid.
• the (C) and (D) components were added to the (B) component, and stirred with a mixer for 10 minutes to obtain a second liquid.
• the liquid (D) component was heated to 80°C to dissolve the solid (D) component, and then returned to room temperature and mixed into the second liquid as the (D) component.
• the detailed preparation amounts are shown in Table 1, and all values are expressed in parts by mass. All tests were performed at 25°C.
• the curable resin composition refers to a state in which the first liquid and the second liquid are mixed.
• the first and second liquids in Table 1 are mixed at 49 g:51 g, formed into a sheet using a spacer with a thickness of 2 mm, and cured at 25 ° C for 120 hours to obtain a sheet-like cured product, which is then stacked in three pieces to form a test piece.
• the pressure surface of an A-type durometer (hardness tester) is pressed with a force of 10 N while keeping it parallel to the test piece, and the pressure surface and the sample are brought into close contact with each other.
• the maximum value is read during measurement, and the maximum value is taken as the "hardness”. Details are in accordance with JIS K 6253 (2012).
• the lower limit is not particularly limited, but A30 or more is preferable, and A40 or more is more preferable.
• reaction force (at 50% compression) 100°C x 1 hour change rate The cured product for the reaction force test was left to stand at 100° C. for 1 hour, and then left to stand at 25° C. for 1 hour, and the test was performed using the cured product.
• the measurement method was the same as for the initial stage. Even when heat is applied to the member, if the reaction force is high, it may cause deformation of the member during compression, so the reaction force after heating is preferably 10 MPa or less, more preferably 8 MPa or less, and most preferably 3 MPa or less.
• reaction force change rate Furthermore, the rate of change was calculated from the initial value and the cured product after 1 hour at 100° C. according to the following formula.
• Rate of change (%) (reaction force of cured product after heating at 100°C for 1 hour) - (initial reaction force) / (initial reaction force)
• the rate of change in reaction force is preferably 50% or less, and more preferably 40% or less.
• Each first liquid and each second liquid in Table 1 were mixed at 49 g:51 g, and the mixed curable resin composition was applied in a sheet shape using a spacer with a thickness of 2 mm, and cured at 25 ° C. for 120 hours to obtain a cured product.
• a 2 mm thick, 20 mm square was cut out from the cured product to prepare a test piece for evaluating permanent compression set.
• the test piece was compressed at a compression rate of 50% using a jig and spacer specified in JIS-K-6262, and placed in a thermostatic chamber at 25 ° C., and taken out after 240 hours, the jig was removed, and the thickness of each test piece was measured after another 24 hours.
• Permanent compression set [%] (measured film thickness before test - measured film thickness after 24 hours) / (measured film thickness before test - spacer thickness) x 100 (%)
• Examples 1 to 3 were able to cure at room temperature, and showed good results in terms of repulsion and permanent compression set.
• the curable resin composition of Example 1 showed low repulsion and excellent results, even though the permanent compression set was equivalent to Examples 2 and 3.
• Comparative Example 4 which did not use component (B), did not cure even after 24 hours at 25°C, and curing was confirmed by applying heat at 100°C for 1 hour. From the above, by combining components (A) to (D), it is possible to form a cured product that can cure at room temperature and can withstand stress during high compression.
• the curable resin composition of the present invention does not require a heat source or light source, can be cured at room temperature, and the cured product has low repulsion even when highly compressed, has high compression resistance, and has excellent sealing properties, making it useful in a variety of fields as an adhesive, coating agent, and potting agent that can be used with the CIPG method.

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