Classifications

• • 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
  • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
• • 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
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
  • C08G59/4253—Rubbers
• • 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
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
  • C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
• • 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
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
• • 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
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
  • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
  • C08G59/623—Aminophenols
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to a two-component adhesive useful for structurally adhering various members and parts to manufacture an article.
• a method of using a structural adhesive when manufacturing a structure by joining various parts / members made of different materials is known.
• the conventional structural adhesive has excellent adhesive strength (storage elastic modulus) after curing, the cured adhesive is hard and is not satisfactory in terms of extensibility.
• the structure is subjected to a thermal itinerary in which the structure is placed in a cold or high temperature state, there is a possibility that peeling may occur due to a difference in the coefficient of linear expansion between the parts and the members.
• Patent Document 1 describes an agent A containing (A) a polyoxyalkylene polymer containing a reactive silicon group, (C) an epoxy resin curing agent, and (D) a silane coupling agent, and (E) an epoxy resin. It is described that a two-component curable composition comprising (F) a condensation catalyst and (G) a water-containing agent B is used as an adhesive. This two-component curable composition is said to have improved storage stability and good internal curability, but its properties and usefulness as a structural adhesive are not described.
• Patent Document 2 describes an epoxy resin composition comprising an epoxy resin, a core-shell type rubber particle, and a hollow polymer.
• Patent Document 3 describes a thermosetting resin composition containing an epoxy resin, rubber particles having a core-shell structure, an epoxysilane coupling agent, and polybutadiene having an alkoxysilyl group at both ends.
• This thermosetting resin composition is said to be useful as a structural adhesive because the decrease in adhesive strength (storage elastic modulus) after curing is small even when it is placed under high temperature and high humidity conditions after being applied.
• the elongation rate and the elastic modulus are sufficient.
• An object of the present invention is to obtain an adhesive having excellent adhesive strength (storage elastic modulus) after curing, excellent elongation after curing, and less likely to peel off due to thermal itinerary.
• Agent A containing epoxy resin and B agent containing a polymer having a crosslinkable silicon group and an epoxy resin curing agent, and It is a two-component adhesive having A two-component adhesive containing core-shell type rubber particles in Agent A and / or Agent B, and a crosslinkable silicon group condensation catalyst in Agent A and / or Agent B.
• the two-component adhesive according to [1] which contains a (meth) acrylic polymer in the agent B.
• Epoxy resin, core-shell type rubber particles, a polymer having a crosslinkable silicon group, an epoxy resin curing agent, and a condensation catalyst of a crosslinkable silicon group are included.
• the breaking strength (tensile strength at cutting) of the adhesive cured product measured according to JIS K 6251 after 7 days curing in a 23 ° C 50% RH environment is 5 MPa or more, and the fracture breaks.
• Time elongation (elongation at cutting) is 30% or more
• an adhesive having excellent adhesive strength (storage elastic modulus) after curing, excellent elongation after curing, and less likely to peel off due to thermal itinerary.
• the first adhesive according to the present invention is a two-component adhesive having an agent A containing an epoxy resin, an agent B containing a polymer having a crosslinkable silicon group, and an epoxy resin curing agent.
• This is a two-component adhesive containing core-shell type rubber particles in the agent A and / or the agent B, and a crosslinkable silicon group condensation catalyst in the agent A and / or the agent B.
• the agent B may contain a (meth) acrylic polymer.
• the epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule.
• Examples of such an epoxy resin include biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type.
• Epoxy resin bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopropylidene) ) Bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexidiene bisphenol type epoxy resin), bisphenol type epoxy resin hydrogenated with these, bisphenol obtained by halogenating (brominating, chlorinating) these Bisphenol type epoxy resin such as type epoxy resin; Stilben type epoxy resin; phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, cresol novolak type epoxy resin, novolak type epoxy resin having condensed ring aromatic hydrocarbon structure, etc.
• Novorak type epoxy resin Polyfunctional epoxy resin such as trihydroxyphenylmethane type epoxy resin, alkyl-modified trihydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin; phenylene skeleton-containing phenol aralkyl type epoxy resin, biphenylene skeleton-containing phenol Biphenolal kill type epoxy resin such as aralkyl type epoxy resin; bifunctional to tetrafunctional naphthalene 2 obtained by glycidyl etherification of dimers of dihydroxynaphthalene type epoxy resin, naphthalenediol type epoxy resin, hydroxynaphthalene and / or dihydroxynaphthalene.
• Polyfunctional epoxy resin such as trihydroxyphenylmethane type epoxy resin, alkyl-modified trihydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin
• Epoxy resin having a naphthalene skeleton such as weight type epoxy resin, naphthylene ether type epoxy resin, binaphthyl type epoxy resin, naphthol aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene modified phenol type epoxy resin, etc.
• a modified epoxy resin having a siloxane bond which is obtained by modifying these epoxy resins with alkoxysilane, silsesquioxane, or the like, can also be used.
• the modified epoxy resin having a siloxane bond include an epoxy resin composition modified with an alkoxysilane disclosed in Japanese Patent Application Laid-Open No. 2010-275411, and a silsesquioxane-modified epoxy resin disclosed in Japanese Patent No. 5569703. can give.
• Examples of commercially available products include one or more selected from the group consisting of the composelan E series manufactured by Arakawa Chemical Industry Co., Ltd., the composelan SQ series, and the like.
• bisphenol type epoxy resin novolak type epoxy resin, epoxy resin having a naphthalene skeleton, rubber-modified epoxy from the viewpoints of curability, adhesiveness, water resistance, durability, workability, availability, versatility, etc. It is preferable to use one or more selected from the group consisting of resins and the like. In the present invention, it is more preferable to use a bisphenol type epoxy resin.
• the epoxy resin one type may be used alone or two or more types of epoxy resins may be used in combination.
• the epoxy resin can be blended in an amount of 20 to 80 parts by mass, preferably 25 to 70 parts by mass, and more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the agent A. Further, it can be blended in an amount of 10 to 60 parts by mass, preferably 15 to 50 parts by mass, and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the total of the agent A and the agent B.
• the blending amount of the epoxy resin is less than 10 parts by mass with respect to 100 parts by mass in total of the agents A and B, the curability of the adhesive is lowered, and the breaking strength (tensile strength at cutting) and the storage elastic modulus are lowered. There is a risk of Further, when the compounding amount of the epoxy resin exceeds 60 parts by mass with respect to 100 parts by mass in total of the agents A and B, the compounding amount of the polymer having a crosslinkable silicon group relatively decreases, and the breaking strength (break strength ( Tensile strength at the time of cutting) and storage elastic modulus may decrease.
• the core-shell type rubber particles are included in the agent A and / or the agent B.
• the core-shell type rubber particles include a core that is a rubber particle formed of a polymer containing an elastomer or a rubber-like polymer, and a polymer shell layer that covers at least a part of the core surface, and the core and shell are required. It is a particle which may have an intermediate layer between the layers.
• the core, intermediate layer and shell layer can be composed of a single layer or multiple layers, respectively. When any of the layers has a multi-layer structure, each layer may be composed of different components.
• the core and / or shell layer may be crosslinked by ionic bonds, covalent bonds, or the like, if necessary.
• the shell layer may be formed by graft polymerization on the core.
• the shell layer may have a reactive functional group such as an epoxy group or a carboxyl group.
• the volume average particle diameter of the core-shell type rubber particles is not particularly limited. By setting the volume average particle diameter to 30 ⁇ m or less, the stress relaxation characteristics can be significantly improved.
• the volume average particle diameter of the core-shell type rubber particles is, for example, 0.01 ⁇ m or more, preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less. More preferably, it is 2 ⁇ m or less.
• the core constituting the core-shell type rubber particles is a diene-based rubber obtained from a monomer component containing a conjugated diene-based monomer as a main component and, if necessary, a copolymerizable monomer, from the viewpoint of improving the toughness of the cured adhesive.
• a diene-based rubber obtained from a monomer component containing a conjugated diene-based monomer as a main component and, if necessary, a copolymerizable monomer, from the viewpoint of improving the toughness of the cured adhesive.
• natural rubber organosiloxane rubber
• (meth) acrylic acid alkyl ester as the main component, if necessary. It is composed of one kind selected from the group consisting of acrylic rubber and the like obtained from a mono
• Examples of the conjugated diene-based monomer include one or more selected from the group consisting of butadiene, isoprene, chloroprene and the like. Butadiene is preferred in the present invention.
• Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• One or more types selected from the group consisting of. Butyl (meth) acrylates are preferred in the present invention.
• Examples of the monomer copolymerizable with these include aromatic vinyl such as styrene, vinyltoluene and ⁇ -methylstyrene, vinyl cyanide such as aromatic vinylidene, acrylonitrile and methacrylonitrile, vinylidene cyanide, methylmethacrylate and butyl.
• Examples thereof include alkyl methacrylate such as methacrylate, benzyl acrylate, phenoxyethyl acrylate, and aromatic (meth) acrylate such as benzyl methacrylate.
• a monomer having a functional group such as an epoxy group, a carboxyl group, a hydroxyl group and an amino group can be copolymerized.
• one or more selected from the group consisting of glycidyl (meth) acrylate, methacrylic acid, acrylic acid, maleic acid, itaconic acid, 2-hydroxymethacrylate, 2-hydroxyacrylate and the like can be mentioned.
• the glass transition temperature (Tg) of the polymer constituting the core is 0 ° C. or lower, preferably -20 ° C. or lower, more preferably -30 ° C. or lower, in order to increase the toughness of the cured adhesive and enhance the stress relaxation characteristics. More preferably, it is ⁇ 60 ° C. or lower, and ⁇ 200 ° C. or higher.
• the glass transition temperature of at least one layer is preferably 0 ° C. or lower.
• the core-shell type rubber particles may have an intermediate layer between the core and the shell layer.
• the components forming the intermediate layer are not particularly limited.
• conjugated diene, the (meth) acrylic acid alkyl ester, and the monomer copolymerizable with these one or more kinds selected from the group consisting of those used in the formation of the core can be mentioned.
• the glass transition temperature of the intermediate layer is 0 ° C. or lower, preferably ⁇ 30 ° C. or lower.
• the shell layer constituting the core-shell type rubber particles contains (meth) acrylic acid alkyl ester as a main component in consideration of compatibility with the adhesive constituents and dispersibility in the adhesive, and is copolymerized as necessary. It is composed of monomer components containing possible monomers.
• Examples of the (meth) acrylic acid alkyl ester forming the shell layer and the monomer copolymerizable therewith include one or more selected from the group consisting of those used in the formation of the core.
• the shell layer may contain an epoxy group, a hydroxy group, an oxetane group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, or a benz as a monomer component forming the shell layer, if necessary.
• a monomer containing at least one selected from the group consisting of an oxadin group and a cyanate ester group even if it has a group having a reactivity or an affinity with other adhesive constituents. good.
• the amount of (meth) acrylic acid alkyl ester in the monomer component forming the shell layer is 10 to 95% by mass, preferably 30 to 92% by mass, more preferably 30% by mass, based on 100% by mass of the total amount of the monomers for forming the shell layer. It is 50 to 90% by mass.
• the glass transition temperature of the polymer constituting the shell layer is 40 ° C. or higher, preferably 50 ° C. or higher.
• composition of each layer of core-shell type rubber particles there is no limitation on the composition ratio of the core, the intermediate layer and the shell layer.
• the core is 20 to 95% by mass, preferably 50 to 95% by mass, and more preferably 60 to 90% by mass with respect to 100% by mass of the entire core-shell type rubber particles.
• the intermediate layer is 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 20% by mass with respect to 100% by mass of the entire core-shell type rubber particles.
• the shell layer is 5 to 80% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40% by mass with respect to 100% by mass of the entire core-shell type rubber particles.
• the method for producing the core-shell type rubber particles is not particularly limited, and can be produced by a method known in the art such as emulsion polymerization, suspension polymerization, and microsuspension polymerization.
• the core can be formed by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like using the monomer component forming the core.
• the intermediate layer can be formed by polymerizing by a known radical polymerization (emulsion polymerization or the like) using a monomer forming the intermediate layer.
• the shell layer can be formed by polymerizing by a known radical polymerization (emulsion polymerization) using a monomer forming the shell layer.
• the shell layer is preferably formed by graft-polymerizing a monomer forming the shell layer on the core and / or the intermediate layer. Further, the polymerization of the monomers forming each layer may be carried out in one stage or in two or more stages.
• the core-shell type rubber particles can be blended with the liquid A and / or the liquid B by using, for example, powdery ones. Further, for example, an epoxy resin composition in the form of being dispersed in an epoxy resin in advance may be used and blended in the liquid A.
• the blending amount of the core-shell type rubber particles in the epoxy resin composition is not particularly limited.
• the total amount of the epoxy resin and the core-shell type rubber particles is 1 to 80% by mass, preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 50% by mass with respect to 100% by mass. be.
• core-shell type rubber particles various commercially available ones may be used. These commercially available core-shell type rubber particles may be used alone or in combination of two or more. For example, one or more types selected from the following groups can be mentioned, but the present invention is not limited thereto.
• Stafyroid series, Zefiac series, Ganzpearl series, etc. manufactured by Aica Kogyo Co., Ltd. for example, F351, IM-101, IM-203, IM-301, IM-401, IM-601, AC-3355, AC -3364, AC-3816, AC-3832, AC-4030, etc.).
• C GENIOPERL series manufactured by Wacker Chemie (for example, P22, P23, P52, P53, etc.).
• various epoxy resin-core-shell type rubber particle compositions commercially available in the form of being dispersed in the epoxy resin in advance may be used. These various commercially available epoxy resin-core-shell type rubber particle compositions may be used alone or in combination of two or more. For example, one or more types selected from the following groups can be mentioned, but the present invention is not limited thereto.
• G Kaneka series manufactured by Kaneka Corporation (for example, MX120, MX125, MX130, MX136, MX154, MX551, MX960, etc.).
• H GENIOPERL series manufactured by Wacker Chemie (for example, M23A, etc.).
• the core-shell type rubber particles As the core-shell type rubber particles, one type may be used alone, or two or more types of core-shell type rubber particles may be used in combination.
• the core-shell type rubber particles are blended in an amount of 3 to 35 parts by mass, preferably 5 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to a total of 100 parts by mass of the agents A and B. Can be done.
• the amount is 5 to 50 parts by mass, preferably 10 to 45 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the agent A. Can be blended.
• the blending amount of the core-shell type rubber particles is less than 3 parts by mass with respect to 100 parts by mass in total of the agents A and B, the toughness of the obtained cured adhesive is lowered, and the breaking strength (tensile strength at cutting), Elongation at break (elongation at cutting) and storage elastic modulus may decrease. Further, when the blending amount of the core-shell type rubber particles exceeds 35 parts by mass with respect to 100 parts by mass in total of the agents A and B, the curing reactivity of the adhesive is lowered and the breaking strength (tensile strength at the time of cutting). And the storage elastic modulus may decrease. When the core-shell type rubber particles dispersed in the epoxy resin are used, the content of the core-shell type rubber particles and the content of the epoxy resin are obtained, respectively, and the blending amount of each component is used.
• the crosslinkable silicon group condensation catalyst is contained in the agent A and / or the agent B.
• the crosslinkable silicon group condensation catalyst is contained in the liquid B, it is preferable to store the liquid B in a container capable of shielding moisture and moisture.
• the condensation catalyst of the crosslinkable silicon group the crosslinkable silicon group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond is hydrated in the presence of water. Any compound that exerts a catalytic action when it is decomposed and cured can be used without limitation.
• the crosslinkable silicon group is, for example, a group represented by the following formula (1); -SiR 1 3-a X a ... (1)
• R 1 represents an organic group.
• X is a hydroxyl group or a hydrolyzable group.
• A is either an integer of 1, 2 or 3). Can be given.
• crosslinkable silicon group condensation catalyst examples include organic metal compounds (organic tin compounds, organic iron compounds, organic aluminum compounds, organic titanium compounds, etc.), amines, fatty acids (organic acid bismuth, etc.), and organic acidic phosphoric acid.
• examples thereof include one or more selected from the group consisting of an ester compound, a silicon compound having a Si—F bond, and the like.
• R4 represents a divalent alkylene group having 1 to 6 carbon atoms, and may be the same or different from each other when there are two or more in one molecule.
• R 5 represents an alkyl group having 1 to 10 carbon atoms, and when there are two or more in one molecule, they may be the same or different from each other.
• One or more selected from the group consisting of an organic tin-based compound or an organic iron-based compound represented by is used.
• R 2 one kind selected from the group consisting of, for example, -CH 3 , -C 2 H 5 , -C 4 H 9 , -C 8 H 17 , -C 17 H 35 , a naphthyl group and the like.
• R 3 include one or more selected from the group consisting of -CH 3 , -C 2 H 5 , -C 4 H 9 , -C 8 H 17 , -C 17 H 35 , and the like. Be done.
• R 4 include one or more selected from the group consisting of -CH 2- , -C 2 H 4- , -C 3 H 6- , -C 4 H 8- , and the like.
• R 5 include one or more selected from the group consisting of -CH 3 , -C 2 H 5 , -C 4 H 9 , and -C 8 H 17 .
• organic tin-based compound or the organic iron-based compound include Sn (OCOC 7 H 15 ) 2 , Sn (OCOC 17 H 35 ) 2 , (C 4 H 9 ) 2 Sn (OCOCCH 3 ) 2 , (C).
• the silicon compound having a Si—F bond various compounds including a silicon group having a Si—F bond (hereinafter, may be referred to as a fluorosilyl group) can be used. Both an inorganic compound and an organic compound can be used as the silicon compound having a Si—F bond.
• a silicon compound having a Si—F bond an organic compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more suitable because of its high safety. Further, a small molecule organosilicon compound having a fluorosilyl group is preferable because the composition has a low viscosity.
• Examples of the silicon compound having a Si—F bond include, for example, fluorosilane, a compound having a fluorosilyl group, an organic polymer having a fluorosilyl group, and the like described in International Publication No. 2015/088021.
• fluorosilane a compound having a fluorosilyl group
• organic polymer having a fluorosilyl group an organic polymer having a fluorosilyl group
• the crosslinkable silicon group condensation catalyst may be used alone or in combination of two or more.
• the condensation catalyst of the crosslinkable silicon group is, for example, 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 0 parts by mass with respect to 100 parts by mass of the polymer having a crosslinkable silicon group. It can be blended in an amount of 3 parts by mass. If the blending amount of the crosslinkable silicon group condensation catalyst is less than 0.05 parts by mass with respect to 100 parts by mass of the polymer having a crosslinkable silicon group, the polymer having a crosslinkable silicon group is insufficiently cured and the curability becomes poor. There is a risk that the breaking strength (tensile strength at the time of cutting) and the storage elasticity will decrease.
• the crosslinkable silicon group condensation catalyst exceeds 10 parts by mass with respect to 100 parts by mass of the polymer having a crosslinkable silicon group
• the crosslinkable silicon is affected by the influence of the excessive crosslinkable silicon group condensation catalyst.
• the reactivity of the polymer having a group or the epoxy resin may decrease, and the breaking strength (tensile strength at the time of cutting) and the storage elasticity may decrease.
• ⁇ Polymer having a crosslinkable silicon group As the polymer having a crosslinkable silicon group contained in the agent B, a crosslinkable silicon group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond is used.
• the polymer is not particularly limited as long as it is a polymer having a terminal and / or a side chain.
• Crosslinkable silicon group As the crosslinkable silicon group, as described above, for example, the group represented by the following formula (1); -SiR 1 3-a X a ... (1) (In the formula (1), R 1 represents an organic group. When two or more R 1s are present, a plurality of R 1s may be the same or different. X is a hydroxyl group or a hydrolyzable group. When two or more Xs are present, the plurality of Xs may be the same or different. A is either an integer of 1, 2 or 3). Can be given.
• the organic group of R 1 in the formula (1) is not particularly limited as long as it is a group that does not exhibit hydrolyzability.
• a hydrocarbon group which may have a substituent having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms can be mentioned.
• the hydrolyzable group of X in the formula (1) is not particularly limited as long as it is a group other than a hydroxyl group that is hydrolyzed by water.
• a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, a mercapto group, an aminooxy group, an alkenyloxy group and the like can be mentioned.
• an alkoxy group is preferable from the viewpoint of mild hydrolysis and easy handling, an alkoxy group having 1 to 6 carbon atoms having high reactivity is preferable, and a methoxy group, an ethoxy group and a butoxy group are particularly preferable.
• the a in the formula (1) is preferably 2 or more, and more preferably 3. When a is 2 or more, an adhesive having sufficient flexibility can be obtained.
• the crosslinkable silicon group is, for example, one or more selected from the group consisting of a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group, and a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Can be given.
• the crosslinkable silicon group contained in the polymer may be one kind or two or more kinds.
• the crosslinkable silicon group may be attached to the terminal and / or side chain of the polymer. From the viewpoint of excellent physical properties of the cured product such as the tensile properties of the cured product of the adhesive, it is preferable that the crosslinkable silicon group is present at the end of the molecular chain.
• the number of crosslinkable silicon groups is 1.0 to 5.0, preferably 1.1 to 3.0 on average in one molecule of the polymer. If the number of crosslinkable silicon groups contained in one molecule of the polymer is less than one, the curability becomes insufficient, and if it is too large, the network structure becomes too dense and good mechanical properties are not exhibited.
• polymer main clavicle examples of the main chain skeleton of the polymer having a crosslinkable silicon group include a polyoxyalkylene polymer, a (meth) acrylic polymer, an isobutylene polymer, a butadiene polymer, an olefin polymer, and a styrene weight.
• a polyoxyalkylene polymer a (meth) acrylic polymer, an isobutylene polymer, a butadiene polymer, an olefin polymer, and a styrene weight.
• a coalescence a vinyl halide polymer, a vinyl acetate polymer, a vinyl alcohol polymer, a vinyl acetal polymer, a copolymer thereof, and the like can be mentioned.
• a polyoxyalkylene polymer having a crosslinkable silicon group a (meth) acrylic polymer having a crosslinkable silicon group
• an isobutylene polymer having a crosslinkable silicon group is particularly preferable.
• the main chain skeleton of the polyoxyalkylene polymer having a crosslinkable silicon group is the following formula (2); -R 6 -O -... (2) (In the formula, R 6 is a divalent organic group having 1 to 20 carbon atoms.) It is a polymer having a repeating unit represented by.
• R 6 in the formula (2) is, for example, a linear or branched alkylene group having 2 to 20 carbon atoms, preferably a linear or branched alkylene group having 2 to 14 carbon atoms, and more preferably 2 carbon atoms.
• the repeating units represented by the equation (2) include -CH 2 CH 2 O-, -CH (CH 3 ) CH 2 O-, -CH 2 CH (CH 3 ) O-, and -CH 2 CH (C 2 ).
• the main clavicle of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
• the main chain skeleton of the polyoxyalkylene polymer having a crosslinkable silicon group is a polyoxyethylene polymer, a polyoxypropylene polymer, a polyoxytetramethylene polymer, or a polyoxyethylene-polyoxypropylene co-weight.
• One or more selected from the group consisting of coalescing is preferable, and a (co) polymer containing a polyoxypropylene repeating unit as a main component is particularly preferable.
• the main chain skeleton may have a branched structure.
• the polyoxyalkylene polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
• the molecular weight of the polyoxyalkylene polymer having a crosslinkable silicon group is not particularly limited. From the viewpoint of workability when the adhesive is formed, the number average molecular weight is 500 or more, preferably 1,000 or more, and the number average molecular weight is 100,000 or less, preferably 70,000 or less. From the viewpoint of imparting an appropriate viscosity to the adhesive, it is preferable to contain a polymer having a number average molecular weight of 20,000 or more.
• the number average molecular weight of the present invention is a polystyrene-equivalent molecular weight obtained by gel permeation chromatography.
• a polyoxyalkylene polymer having a crosslinkable silicon group becomes a more flexible cured product at the initial stage because the crosslink density in the cured product decreases when the content of the crosslinkable silicon group is appropriately lowered, and the modulus property becomes modular. As the value becomes smaller, the elongation at break (elongation at cutting) characteristics can be increased.
• the number of crosslinkable silicon groups present in one molecule of the polymer is 1.0 to 5.0 on average, preferably 1.2 to 2.8. The number is more preferably 1.3 to 2.6, still more preferably 1.4 to 2.4.
• the main chain skeleton of the polyoxyalkylene polymer can be synthesized, for example, by ring-opening polymerization of a monoepoxide in the presence of an initiator and a catalyst.
• the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydride bisphenol A, neopentyl glycol, polybutadienediol, diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol.
• dihydric alcohols such as polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, polyhydric alcohols, and various oligomers having hydroxyl groups. Can be given.
• Examples of monoepoxides include alkylene oxides such as ethylene oxide, propylene oxide, ⁇ -butylene oxide, ⁇ -butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide and ⁇ -methylstyrene oxide, and methylglycidyl ether and ethylglycidyl.
• alkylene oxides such as ethylene oxide, propylene oxide, ⁇ -butylene oxide, ⁇ -butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide and ⁇ -methylstyrene oxide, and methylglycidyl ether and ethylglycidyl.
• Examples thereof include one or more selected from the group consisting of alkyl glycidyl ethers such as ether, isopropyl glycidyl ether and butyl glycidyl ether, and allyl gly
• the catalyst includes, for example, an alkaline catalyst such as KOH and NaOH, an acidic catalyst such as trifluoroboran-etherate, and a complex metal cyanide complex catalyst such as an aluminoporphyllin metal complex and a cyanide cobalt zinc-glime complex catalyst.
• an alkaline catalyst such as KOH and NaOH
• an acidic catalyst such as trifluoroboran-etherate
• a complex metal cyanide complex catalyst such as an aluminoporphyllin metal complex and a cyanide cobalt zinc-glime complex catalyst.
• a complex metal cyanide complex catalyst such as an aluminoporphyllin metal complex and a cyanide cobalt zinc-glime complex catalyst.
• the polyoxyalkylene polymer can be obtained by, for example, an alkali-catalyzed polymerization method such as KOH, for example, a composite metal cyanide complex-catalyzed polymerization method, but is not particularly limited.
• an alkali-catalyzed polymerization method such as KOH
• a composite metal cyanide complex-catalyzed polymerization method but is not particularly limited.
• the number average molecular weight is 6,000 or more
• Mw weight average molecular weight
• Mn number average molecular weight
• the main chain skeleton of the polyoxyalkylene polymer is a hydroxyl group-terminated polyoxyalkylene polymer in the presence of a basic compound such as KOH, NaOH, KOCH 3 , NaOCH 3 , etc., and a bifunctional or higher functional alkyl halide such as CH. It can also be obtained by chain extension with 2 Cl 2 , CH 2 Br 2 , etc. Further, the hydroxyl group-terminated polyoxyalkylene polymer can be chain-extended with a bifunctional or trifunctional isocyanate compound.
• the method for introducing the crosslinkable silicon group into the polyoxyalkylene polymer is not particularly limited, and various methods can be used.
• a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule, and a compound having a functional group reactive with this functional group and a crosslinkable silicon group.
• a method of reacting the contained compound with the group VIII transition metal catalyst is preferable.
• R 7 is a divalent organic group having 1 to 20 carbon atoms
• R 8 is a hydrocarbon group having 10 or less carbon atoms.
• R 9 and R 10 are represented by the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R') 3 SiO-.
• R 9 or R 10 indicates a triorganosyloxy group and there are two or more R 9 or R 10 , they may be the same or different.
• R' is a monovalent hydrocarbon group with 1 to 20 carbon atoms. The three R's may be the same or different.
• X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different.
• a indicates 0, 1, 2 or 3
• b indicates 0, 1, or 2, respectively, and a + ⁇ b ⁇ 2. is satisfied.
• M- [Si (R 9 ) 2-b (X) b -O "- B in the group may be the same or different.
• M indicates an integer from 0 to 19.)
• crosslinkable silicon group-containing isocyanate compound to hydroxyl group-terminated polyoxyalkylene polymer
• a reaction with a crosslinkable silicon group-containing mercaptan compound or the like can also be used.
• the polyoxyalkylene polymer may contain other skeletons such as a polyurethane skeleton.
• the polyurethane skeleton includes, for example, one or more selected from the group consisting of aromatic polyisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; polyisocyanates such as aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, and hydroxyl groups. It can be formed by reacting with a polyoxyalkylene polymer having.
• the method for producing a polyoxyalkylene polymer having an unsaturated group represented by the formula (3) or the formula (4) at the terminal is, for example, a functional group having a hydroxyl group reactivity with the hydroxyl group-terminated polyoxyalkylene polymer.
• a method of introducing an unsaturated group into a polyoxyalkylene polymer via an ether bond, an ester bond, a urethane bond, or a carbonate bond by reacting a compound having an unsaturated group with an unsaturated group can be mentioned.
• One or more types selected from the group consisting of CH 2 Br and the like can be mentioned.
• Group VIII transition metal catalyst examples include one or more types of metal complex catalysts selected from the group consisting of Group VIII transition metal elements such as platinum, rhodium, cobalt, palladium, and nickel.
• Group VIII transition metal elements such as platinum, rhodium, cobalt, palladium, and nickel.
• RhCl (PPh 3 ) 3 platinum-vinylsiloxane complex
• platinum-olefin complex platinum-olefin complex
• Pt metal RhCl (PPh 3 ) 3 , RhCl 3 , Rh / Al 2
• the main chain skeleton of the (meth) acrylic polymer having a crosslinkable silicon group is the following formula (8). -CH 2 -C (R 11 ) (COOR 12 ) -... (8) (In the formula, R 11 is an H or methyl group, and R 12 is a divalent organic group having 1 to 30 carbon atoms.) It is a polymer having a repeating unit represented by.
• the main chain structure of the (meth) acrylic polymer may be composed of only one kind of repeating unit, or may be composed of two or more kinds of repeating units.
• any of a random polymer, a block polymer, and a graft polymer may be used, but a random polymer is preferable.
• (meth) acrylic means acrylic type and / or methacrylic type.
• the (meth) acrylic polymer constituting the main chain skeleton of the (meth) acrylic polymer having a crosslinkable silicon group has a glass transition temperature (Tg) of 0 ° C. or higher, preferably 20 ° C. or higher, more preferably 40 ° C. or higher. ° C. or higher, 120 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. If the glass transition temperature is less than 0 ° C., the adhesive strength (storage elastic modulus) immediately after adhesion tends to be inferior. When the glass transition temperature exceeds 120 ° C., the viscosity becomes high, and it tends to be difficult to apply the adhesive to the adherend.
• Tg glass transition temperature
• the glass transition temperature (Tg) is a value obtained by converting the glass transition temperature Tga at the absolute temperature obtained by the following formula (a) into the temperature in degrees Celsius.
• 1 / Tg a ⁇ ( Wi / Tg i ) ⁇ ⁇ ⁇ (a)
• Tga is the glass transition temperature (unit is absolute temperature) of the polymer composed of only the monofunctional (meth) acrylic monomer (C1). Wi is each (meth) acrylic monomer i . It is the mass ratio in the (meth) acrylic polymer.
• Tg i is the glass transition temperature (unit is absolute temperature) of the homopolymer formed only from each (meth) acrylic monomer i.)
• the formula (a) is a formula called a Fox formula, and for each monomer constituting the polymer, the glass transition temperature Tg of the polymer is based on the glass transition temperature Tg i of the homopolymer of the monomer. It is an equation for calculating a . Details can be found in the Bulletin of the American Physical Society, Series 2, Volume 1, Issue 3, page 123 (1956). .. Further, the glass transition temperature (Tgi) of homopolymers of various monomers for calculation by the Fox formula is described in, for example, paints and paints (Paints Publishing Co., Ltd., 10 (No. 358), 1982). It is possible to adopt the numerical value etc.
• the weight average molecular weight of the (meth) acrylic polymer constituting the main chain skeleton of the (meth) acrylic polymer having a crosslinkable silicon group is 1,000 or more, preferably 2,000 or more, more preferably 3,. It is 000 or more, and the weight average molecular weight is 20,000 or less, preferably 10,000 or less, and more preferably 6,000 or less. If the weight average molecular weight is less than 1,000, the initial adhesive strength (storage elastic modulus) after coating is low, and if it exceeds 20,000, the viscosity during coating work becomes too high and workability deteriorates.
• the weight average molecular weight of the present invention is a polystyrene-equivalent molecular weight obtained by gel permeation chromatography. Further, the (meth) acrylic polymer is preferably solid at room temperature (20 ° C.) or has a ring-ball method softening point of 80 ° C. or higher.
• the number of crosslinkable silicon groups is 1.0 to 5.0, preferably 1.1 to 3.0 on average in one molecule of the polymer.
• the number is more preferably 1.3 to 2.6, still more preferably 1.4 to 2.4.
• the main chain structure of the (meth) acrylic polymer can be synthesized by radical polymerization of the monomer components containing the (meth) acrylic monomer.
• a usual solution polymerization method or bulk polymerization method using a peroxide such as benzoyl peroxide or a thermal polymerization initiator such as an azo compound such as azobisisobutyronitrile can be used.
• a known polymerization method such as a method of irradiating light or radiation to polymerize using a photopolymerization initiator and a living radical polymerization method is used.
• radical polymerization method using a thermal polymerization initiator is preferable because a polymer of a (meth) acrylic acid ester polymer can be easily obtained.
• a chain transfer agent such as lauryl mercaptan or ⁇ -mercaptopropyltrimethoxysilane may be used to adjust the molecular weight.
• R 13 is an H or methyl group
• R 14 is a divalent organic group having 1 to 30 carbon atoms.
• the (meth) acrylic monomer represented by the formula (9) is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms, and the alkyl group having a substituent having 1 to 30 carbon atoms. No (meth) acrylic acid alkyl esters are particularly preferred.
• Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth).
• One or more types selected from the group consisting of acrylates and the like can be mentioned.
• methyl methacrylate as an essential monomer component.
• alkyl (meth) acrylate having an ester group having 8 or more carbon atoms such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. It is preferable to contain at least one selected from the group consisting of esters.
• n-butyl acrylate -55 ° C
• Tg glass transition temperature
• the hydrocarbon group such as the alkyl group of the (meth) acrylic acid ester may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom or an epoxy group.
• a substituent such as a hydroxyl group, an alkoxy group, a halogen atom or an epoxy group.
• examples of such compounds include (meth) acrylic acid ester having a hydroxyl group such as hydroxyethyl (meth) acrylate, (meth) acrylic acid ester having an alkoxy group such as methoxyethyl (meth) acrylate, and glycidyl (meth).
• One or more selected from the group consisting of a (meth) acrylic acid ester having an epoxy group such as acrylate and a (meth) acrylic acid ester having an amino group such as diethylaminoethyl (meth) acrylate can be mentioned.
• an unsaturated compound (macromonomer or macromer) having a polymer chain such as an acrylic acid ester having a polystyrene chain can also be used.
• the monomer component constituting the main chain structure of the (meth) acrylic polymer may contain a monomer copolymerizable with the (meth) acrylic monomer represented by the formula (9).
• unsaturated carboxylic acids such as (meth) acrylic acid; (meth) acrylamide compounds such as (meth) acrylamide, vinyl ether compounds such as alkyl vinyl ethers; aromatics such as (meth) acrylonitrile compounds, styrene, ⁇ -methylstyrene and the like.
• group vinyl compounds, vinyl halide compounds such as vinyl chloride
• carboxylic acid vinyl ester compounds such as vinyl acetate
• the content of methyl methacrylate with respect to a total of 100 parts by mass of the monomer components constituting the main chain structure of the (meth) acrylic polymer is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass. It is preferably parts by mass or more, and is preferably 90 parts by mass or less, preferably 80 parts by mass or less.
• the content of the monomer copolymerizable with the (meth) acrylic monomer represented by the formula (9) is 20 with respect to a total of 100 parts by mass of the monomer components constituting the main chain structure of the (meth) acrylic polymer. It is not less than parts by mass, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
• a total of 100 parts by mass of the monomer components constituting the main chain structure of the (meth) acrylic polymer is used.
• the content of the macromonomer with respect to the above is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.
• the method for introducing the crosslinkable silicon group into the (meth) acrylic polymer is not particularly limited, and various methods can be used. For example, the following methods, (1) copolymerize an unsaturated compound having a crosslinkable silicon group, (2) polymerize using an initiator or a chain transfer agent having a crosslinkable silicon group, (3) in a molecule.
• a crosslinkable silicon group can be introduced into the (meth) acrylic polymer.
• a (meth) acrylic acid ester having a crosslinkable silicon group and an unsaturated olefin compound having a crosslinkable silicon group are preferable.
• an unsaturated olefin compound having a crosslinkable silicon group such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
• the initiator and chain transfer agent having a crosslinkable silicon group include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
• a (meth) acrylic polymer having a crosslinkable silicon group can be obtained by a method according to Synthesis Example 4 of International Publication No. 2015/08821 using a polymerization terminator).
• the method (3) when the method (3) is used, it can be the same method as the method for introducing a crosslinkable silicon group into the polyoxyalkylene polymer.
• a (meth) acrylic polymer having an unsaturated group represented by the above formula (3) and / or the above formula (4) at the end and a crosslinkable silicon group-containing compound represented by the above formula (5) are used.
• a method of reacting in the presence of a Group VIII transition metal catalyst is preferred.
• modified silicone resins / modified silicone resins may be used as the polymer having a crosslinkable silicon group contained in the agent B.
• modified silicone resin / modified silicone resin may be used alone or in combination of two or more.
• one or more types selected from the following groups can be mentioned, but the present invention is not limited thereto.
• SAX530 SAX575, SAX580, SAX710, SAX720, SAX725, SAX770, S203, S303, S203H, S303H, S943S, S903, S911S, MA430, MA440, MA447, MA451, MA903, MA903M, MA904, S943 EP100S, EP103S, EP303S, EP505S, FCS-1, FCS-2, FCS-5, FCS-7, FCS-8, FCSA-1, FCSA-2, SA100S, SA310S, SA410S, SB802S, OR100S, etc.).
• AGC Exester series for example, ES-S3620, ES-S3430, ES-S2420, ES-S2410).
• C Actflow series manufactured by Soken Chemical Co., Ltd., STP E-30 manufactured by Wacker Chemie, etc.
• the polymer having a crosslinkable silicon group may be blended in an amount of 70 to 98 parts by mass, preferably 75 to 95 parts by mass, and more preferably 80 to 95 parts by mass with respect to 100 parts by mass of the B agent. can. Further, it can be blended in an amount of 30 to 65 parts by mass, preferably 30 to 60 parts by mass, and more preferably 35 to 60 parts by mass with respect to 100 parts by mass of the total of the agent A and the agent B.
• the blending amount of the polymer having a crosslinkable silicon group is less than 30 parts by mass with respect to 100 parts by mass in total of the agents A and B, the curability of the adhesive is lowered and the breaking strength (tensile strength at cutting). And the storage elastic modulus may decrease.
• the blending amount of the polymer having a crosslinkable silicon group exceeds 65 parts by mass with respect to the total of 100 parts by mass of the agents A and B, the blending amount of the epoxy resin is relatively lowered, and the breaking strength (break strength ( Tensile strength at the time of cutting) and storage elastic modulus may decrease.
• the epoxy resin curing agent contained in the agent B is not particularly limited as long as it is a compound that acts as a curing agent for the epoxy resin.
• aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine; mensendiamine, isophoronediamine, Norbornan diamine, piperidine, N, N'-dimethylpiperazine, N-aminoethyl piperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, polycyclohexyl Alicyclic amines such as polyamines, 1,
• Aromatic amines such as m-xylylene diamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-Aminopropyl) -2,4,8,10-Tetraoxaspiro [5,5] Undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine, etc.
• Amines having an ether bond hydroxyl group-containing amines such as diethanolamine and triethanolamine; acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydroanophthalic acid, methylnadic acid anhydride, hexahydrophthalic anhydride, and succinic acid anhydride.
• Polyamides obtained by the reaction of dimer acid and polyamines polyamide amines obtained by the reaction of polycarboxylic acids and polyamines; imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamides; phenols; polyamines and epoxys.
• Epoxy-modified amines obtained by reaction with compounds, modified amines such as Mannig-modified amines, Michael-added-modified amines, and ketimines obtained by reacting polyamines with aldehydes and phenolic compounds; 2,4,6-tris (dimethyl).
• Aminomethyl One or more selected from the group consisting of amine salts such as 2-ethylhexanoate of phenol, amidins and the like can be mentioned.
• tertiary amine compounds and amines having an ether bond are preferable from the viewpoint of curability and physical property balance.
• a tertiary amine compound examples include alicyclic amines such as N, N'-dimethylpiperazine; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2,4,6-tris (dimethylaminomethyl) phenol.
• Fat aromatic amines such as; amines having ether bonds such as morpholin and N-methylmorpholin; hydroxyl group-containing amines such as triethanolamine; epoxy-modified amines and amines obtained by reacting amines with an epoxy compound.
• Modified amines such as Mannig-modified amines, Michael-added modified amines, and ketimines obtained by reacting formalin and phenols with amines; amines such as 2-ethylhexanate of 2,4,6-tris (dimethylaminomethyl) phenol.
• Imidazoles such as salts, imidazoles and 2-ethyl-4-methylimidazoles; imidazolines such as 2-methylimidazolin and 2-phenylimidazolin; 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), Cyclic amidines such as 6- (dibutylamino) -1,8-diazabicyclo [5,4,0] undecene-7 (DBA-DBU), 1,5-diazabicyclo [4,3,0] nonen-5 (DBN) Kind: One or more selected from the group consisting of amidin salts such as DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, and DBU-phenol novolak resin salt.
• amidin salts such as DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, and DBU-phenol novolak resin salt.
• a tertiary amine compound having active hydrogen examples include 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol.
• the epoxy resin curing agent may be used alone or in combination of two or more.
• the epoxy resin curing agent can be blended in an amount of 0.5 to 100 parts by mass, preferably 1 to 70 parts by mass, more preferably 5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the epoxy resin. .. If the blending amount of the epoxy curing agent is less than 0.5 parts by mass with respect to 100 parts by mass of the epoxy resin, the curing of the epoxy resin may be insufficient, and the breaking strength (tensile strength at cutting) and the storage elastic modulus may decrease. be.
• the blending amount of the epoxy curing agent exceeds 100 parts by mass with respect to 100 parts by mass of the epoxy resin, the reactivity of the polymer having a crosslinkable silicon group is lowered due to the influence of the excess epoxy resin curing agent, and the breaking strength is reduced. (Tensile strength at cutting) and storage elastic modulus may decrease.
• the agent B may contain a (meth) acrylic polymer.
• the (meth) acrylic polymer may be the (meth) acrylic polymer having the crosslinkable silicon group.
• the polymer having a crosslinkable silicon group can be composed of a (meth) acrylic polymer having one or more kinds of crosslinkable silicon groups. Further, it can be composed of a (meth) acrylic polymer having one or more kinds of crosslinkable silicon groups and a polymer having one or more kinds of other crosslinkable silicon groups.
• the (meth) acrylic polymer may not have a crosslinkable silicon group.
• the crosslinkable silicon group is introduced into the (meth) acrylic polymer in the (meth) acrylic polymer having the crosslinkable silicon group. Some can be obtained by not using the method.
• the (meth) acrylic polymer may be used alone or in combination of two or more.
• the (meth) acrylic polymer can be blended in an amount of 0 to 98 parts by mass, preferably 0 to 60 parts by mass, and more preferably 0 to 45 parts by mass with respect to 100 parts by mass of the B agent, for example. ..
• the adhesive of the present invention includes water, a silane coupling agent, a tackifier, a filler, a plasticizer, an antioxidant, an antioxidant, and a pigment, as necessary, as long as the characteristics of the adhesive are not impaired.
• These "other components” can be added to the agent A and / or the agent B in consideration of the reactivity with the components constituting the agent A or the agent B.
• Water is necessary for the hydrolysis condensation reaction of a polymer having a crosslinkable silicon group. Water is preferably contained in the agent A from the viewpoints of improving the curability of the adhesive, improving the adhesive strength (storage elastic modulus) after curing, ensuring the thickness of the adhesive coating film, and storing stability.
• the water is not particularly limited, but general tap water, industrial water, pure water and the like can be used, and water vapor in the atmosphere can also be used.
• the blending amount of water is not particularly limited, but can be, for example, 0.01 to 5 parts by mass, preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of the agent A and the agent B.
• the silane coupling agent has various functions such as improvement of the curability of the adhesive, improvement of the adhesive strength (storage elastic modulus) after the curing of the adhesive, and a function as an auxiliary catalyst for the hydrolysis condensation reaction of the polymer having a crosslinkable silicon group. From the viewpoint of improving the wettability with respect to the adherend, it may be contained in any of the agents A and B.
• the silane coupling agent has active hydrogen such as aminosilane, it can also react with an epoxy resin, so that the curability of the adhesive is improved and the adhesive strength (storage elastic modulus) after curing of the adhesive is improved. It is useful for improvement, and is preferably contained in Agent B from the viewpoint of storage stability and the like.
• the silane coupling agent is not particularly limited, and for example, amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane and N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane; ⁇ -mercaptopropyl.
• Mercapto group-containing silanes such as trimethoxysilane; epoxy group-containing silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane; N- (1,3-) Ketimine-type silanes such as dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane and ⁇ -methacryloyloxypropyltrimethoxysilane; ⁇ - From chlorine atom-containing silanes such as chloropropyltrimethoxysilane; isocyanate-containing silanes such as ⁇ -isocyanatepropyltriethoxysilane; alkylsilanes such as decyltrimethoxysilane; phenyl group-containing silanes such as
• modified amino group-containing silanes obtained by reacting amino group-containing silanes with the above-mentioned silane-containing epoxy group-containing compound, isocyanate group-containing compound, and (meth) acryloyl group-containing compound to modify the amino group. You may use it.
• These silane coupling agents may be used alone or in combination of two or more.
• a silane coupling agent having active hydrogen is preferable, and amino group-containing silanes, mercapto group-containing silanes, and modified amino group-containing silanes are preferable.
• the blending amount of the silane coupling agent is not particularly limited, but for example, it may be 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total of the A agent and the B agent. can.
• tackifier examples include terpene resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin and the like. These tackifiers may be used alone or in combination of two or more.
• Fillers include reinforcing fillers such as fumed silica, settling silica, fused silica, silicic acid anhydride, and carbon black; calcium carbonate, magnesium carbonate, aluminum hydroxide, aluminum oxide, titanium oxide, silica soil, and calcined. Fillers such as clay, clay, talc, titanium oxide, bentnite, organic bentonite, ferric oxide, zinc oxide, active zinc flower, silas balloon, etc .; using fibrous fillers such as asbestos, glass fiber, and filament. Can be done. These fillers may be used alone or in combination of two or more.
• plasticizer examples include phthalates such as dioctylphthalate; aliphatic dibasic acid esters such as dioctyl adipate; glycol esters; aliphatic esters; phosphoric acid esters; polyester plasticizers; polypropylene glycol and Examples thereof include polyethers such as derivatives; hydrocarbon plasticizers; chlorinated paraffins; low molecular weight acrylic acid ester polymers and the like. These plasticizers may be used alone or in combination of two or more.
• sagging preventive agent As the sagging preventive agent, a known sagging preventive agent can be widely used, and there is no particular limitation.
• polyamide wax hydrogenated castor oil derivative
• metal soap such as calcium stearate, aluminum stearate, barium stearate, organic bentnite, silica, modified polyester polyol, inorganic shaker such as asbestos powder, fatty acid amide and the like.
• organic rocking agents and the like can be mentioned.
• antioxidant examples include compounds such as hindered phenols, butylhydroxytoluene, and butylhydroxyanisole. These antioxidants may be used alone or in combination of two or more.
• pigments examples include inorganic pigments such as carbon black, titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, and organic pigments such as azo pigments and copper phthalocyanine pigments. Pigments and the like can be mentioned. These pigments may be used alone or in combination of two or more.
• filler one or more kinds selected from the group consisting of a resin filler (resin fine powder), an inorganic filler, and a functional filler can be used.
• the filler may be surface-treated with a silane coupling agent, a titanium chelating agent, an aluminum coupling agent, a fatty acid, a fatty acid ester, rosin or the like.
• resin filler a particulate filler made of an organic resin or the like can be used.
• the resin filler is selected from the group consisting of organic fine particles such as polyacrylic acid ester resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, and styrene resin. More than one kind can be used.
• the adhesive of the present invention may also contain a diluent.
• a solvent having a flash point (open type) of 50 ° C. or higher is used as the diluent.
• a diluent By containing a diluent, physical properties such as viscosity can be adjusted.
• various diluents can be used as the diluent.
• the diluent include saturated hydrocarbon solvents such as normal paraffin and isoparaffin, ⁇ -olefin derivatives such as linearene dimer (trade name of Idemitsu Kosan Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents, and ester solvents. Examples thereof include one or more kinds of solvents selected from the group consisting of a solvent, a citrate ester solvent such as acetyltriethyl citrate, and a ketone solvent.
• the adhesive of the present invention may contain a porous additive.
• the porous additive include an inorganic compound having pores (mesopores) and a compound having oil absorption.
• the porous additive include an inorganic compound having pores (mesopores) and a compound having oil absorption.
• the shape of the porous additive is not particularly limited, and may be, for example, a spherical shape, a crushed shape, a disk shape, a rod shape, a fibrous shape, or the like.
• the surface of the porous additive may be physically or chemically hydrophilized or hydrophobized.
• the surface is hydrophobized, it is preferably a chemically hydrophobized compound having an oil absorption amount (specified amount according to JIS K 5101) of 50 ml / 100 g or more.
• an oil absorption amount obtained amount according to JIS K 5101
• the adhesiveness to the polymer having a crosslinkable silicon group and / or the epoxy resin is increased, and the mechanical strength and other properties of the cured product are improved.
• a porous additive having a surface hydrophobized with an oil absorption amount of 50 ml / 100 g or more the adhesiveness with the epoxy resin can be improved and coloring at the time of thermosetting can be suppressed.
• the porous additive for example, porous silica can be preferably used.
• the apparent density of the porous additive is not particularly limited, but is 0.4 g / cm 3 or more, preferably 0.4 g / cm 3 to 2.0 g / cm 3 , from the viewpoint of ensuring the mechanical strength of the porous additive.
• the apparent density refers to the density in consideration of the density occupied by the raw material of the porous additive and the space occupied by the micropores (that is, the pore volume).
• the average particle size of the porous additive is not particularly limited, but is preferably 0.1 to 100 ⁇ m from the viewpoint of maintaining good fluidity of the adhesive.
• the specific surface area of the porous additive is 100 m 2 / g to 1000 m 2 / g, preferably 300 m 2 / g to 700 m 2 / g. If it is less than 100 m 2 / g, it becomes difficult to maintain an appropriate amount of lubrication of the porous additive, and if it exceeds 1000 m 2 / g, it becomes difficult to maintain good fluidity of the porous additive. ..
• the porous additive may be blended with either agent A or agent B.
• the blending amount of the porous additive is not particularly limited, but for example, the amount of the porous additive is preferably 1 part by mass or more with respect to 100 parts by mass of the polymer having a crosslinkable silicon group, and 2 parts by mass or more. It is more preferably 50 parts by mass or less, and more preferably 30 parts by mass or less from the viewpoint of workability.
• the second adhesive according to the present invention includes an epoxy resin, a core-shell type rubber particle, a polymer having a crosslinkable silicon group, an epoxy resin curing agent, and a condensation catalyst of the crosslinkable silicon group.
• the breaking strength (tensile strength at cutting) of the adhesive cured product measured according to JIS K 6251 after 7 days curing in a 23 ° C 50% RH environment is 5 MPa or more, and the fracture breaks.
• Time elongation (elongation at cutting) is 30% or more
• the epoxy resin, the core-shell type rubber particles, the polymer having a crosslinkable silicon group, the epoxy resin curing agent, and the condensation catalyst of the crosslinkable silicon group contained in the second adhesive according to the present invention are the first of the present invention.
• the same adhesive contained in Agent A or Agent B of 1 can be used.
• the second adhesive according to the present invention may contain any one or more of "other components" which may be contained in the first adhesive according to the present invention.
• the blending amount of each component contained in the second adhesive according to the present invention is the blending amount of each component with respect to the total amount of the A agent and the B agent specified in the first adhesive of the present invention, or a specific blending amount. It is the same as the blending amount of each component with respect to the component.
• the breaking strength (tensile strength at the time of cutting) of the cured adhesive of the second adhesive according to the present invention can be obtained by the following method. After mixing and stirring at least an epoxy resin, a core-shell type rubber particle, a polymer having a crosslinkable silicon group, an epoxy resin curing agent, and a condensation catalyst of the crosslinkable silicon group to prepare an adhesive, the depth is 2 mm. The mold is uniformly filled, heat-cured at 80 ° C. for 30 minutes, and then cured in a 23 ° C. and 50% RH environment for 7 days to prepare an adhesive cured product sheet.
• a dumbbell-shaped No. 3 test piece specified in JIS K6251 is die-cut and collected.
• the tensile speed was set to 10 mm / min, and the breaking strength (tensile strength at cutting) (MPa) and the breaking time when the test piece was applied with force until the test piece broke. It can be obtained by measuring the elongation (elongation at the time of cutting) (%).
• the second adhesive according to the present invention has a breaking strength of an adhesive cured product measured according to JIS K 6251 after being heat-cured at 80 ° C. for 30 minutes and then cured at 23 ° C. for 50% RH for 7 days.
• the tensile strength at the time of cutting is 5 MPa or more. It is preferably 5 to 30 MPa, more preferably 7 to 25 MPa, and even more preferably 10 to 20 MPa. If the breaking strength (tensile strength at the time of cutting) is less than 5 MPa, the adhesive strength (storage elastic modulus) after curing may be insufficient and it may be difficult to use it as a structural adhesive.
• the second adhesive according to the present invention is the elongation at break of the cured adhesive, which is measured according to JIS K 6251 after being heat-cured at 80 ° C. for 30 minutes and then cured at 23 ° C. for 50% RH for 7 days.
• (Elongation at the time of cutting) is 30% or more. It is preferably 50% or more, more preferably 50 to 400%, still more preferably 55 to 300%. If the elongation at break (elongation at cutting) is less than 30%, the cured adhesive may become brittle, and the adhesive strength (storage elastic modulus) after curing may be insufficient, making it difficult to use as a structural adhesive.
• the second adhesive according to the present invention was heat-cured at 80 ° C. for 30 minutes and then cured at 23 ° C. for 50% RH for 7 days.
• the cured adhesive product was replaced with JIS K 7198 (abolished and replaced with JIS K 7244-4).
• the tensile mode measured in accordance with (1) and the storage elastic coefficient (20 ° C. and 80 ° C.) at 1 Hz can be obtained by the following method. After mixing and stirring at least an epoxy resin, a core-shell type rubber particle, a polymer having a crosslinkable silicon group, an epoxy resin curing agent, and a condensation catalyst of the crosslinkable silicon group to prepare an adhesive, the depth is 2 mm.
• the mold is uniformly filled, heat-cured at 80 ° C. for 30 minutes, and then cured in a 23 ° C. and 50% RH environment for 7 days to prepare an adhesive cured product sheet.
• a 10 mm ⁇ 40 mm test piece is collected from the obtained cured adhesive sheet.
• the stored elastic modulus (E'(MPa)) of the obtained test piece is measured under the following conditions using a dynamic viscoelasticity measuring (DMA) device (DMS6100 manufactured by Seiko Instruments Inc.). (Conditions for DMA measurement) Measurement frequency: 1Hz, measurement mode: tension, temperature rise rate: 5 ° C / min, measurement temperature: -100 ° C to 200 ° C
• the second adhesive according to the present invention was JIS K 7198 (discontinued and replaced with JIS K 7244-4) after being heat-cured at 80 ° C. for 30 minutes and then cured at 23 ° C. for 50% RH for 7 days.
• the storage elastic modulus at 1 Hz in the tensile mode measured in accordance with the above is 100 to 1000 MPa at 20 ° C. It is preferably 100 to 700 MPa, more preferably 100 to 650 MPa, and even more preferably 100 to 600 MPa. If the storage elastic modulus at 20 ° C. is less than 100 MPa, the adhesive strength (storage elastic modulus) after curing may be insufficient, making it difficult to use as a structural adhesive. If the storage elastic modulus at 20 ° C. exceeds 1000 MPa, the material constituting the adhesive may become expensive, and the elongation at break (elongation at cutting) of the cured adhesive may decrease. ..
• the second adhesive according to the present invention was JIS K 7198 (discontinued and replaced with JIS K 7244-4) after being heat-cured at 80 ° C. for 30 minutes and then cured at 23 ° C. for 50% RH for 7 days.
• the storage elastic modulus at 1 Hz in the tensile mode measured in accordance with the above is 50 to 1000 MPa at 80 ° C. It is preferably 50 to 700 MPa, more preferably 50 to 200 MPa, and even more preferably 45 to 180 MPa. If the storage elastic modulus at 80 ° C. is less than 50 MPa, the adhesive strength (storage elastic modulus) after curing may be insufficient, making it difficult to use as a structural adhesive. If the storage elastic modulus at 80 ° C. exceeds 1000 MPa, the material constituting the adhesive may become expensive, and the elongation at break (elongation at cutting) of the cured adhesive may decrease. ..
• Agent A containing an epoxy resin, a core-shell type rubber particle, and a condensation catalyst of a crosslinkable silicon group, which are the first adhesives according to the present invention, a polymer having a crosslinkable silicon group, and epoxy resin curing.
• the method for producing a two-component adhesive having the agent B and the agent B is not particularly limited.
• the epoxy resin constituting the agent A, the core-shell type rubber particles, and the condensation catalyst of the crosslinkable silicon group are blended in a predetermined amount, and if necessary, other components are blended, and the agent A is degassed and stirred. To manufacture. At that time, the blending order of each component is not particularly limited.
• the polymer having a crosslinkable silicon group constituting the agent B and the epoxy resin curing agent are blended in a predetermined amount, and if necessary, other components are blended, and the agent B is degassed and stirred. To manufacture. At that time, the blending order of each component is not particularly limited. By combining the obtained A agent and B agent as a set, a two-component adhesive can be obtained.
• the second adhesive according to the present invention includes an epoxy resin, a core-shell type rubber particle, a polymer having a crosslinkable silicon group, an epoxy resin curing agent, and a condensation catalyst of the crosslinkable silicon group, and has a breaking strength (break strength).
• breaking strength break strength
• a two-component adhesive can be obtained in the same manner as the first adhesive according to the present invention.
• an epoxy resin, a core-shell type rubber particle, a crosslinkable silicon group condensation catalyst, a polymer having a crosslinkable silicon group, and an epoxy resin curing agent are blended in a predetermined amount, and other components are blended as necessary.
• the adhesive composition can be obtained by degassing and stirring. At that time, the blending order of each component is not particularly limited.
• an adhesive is applied to at least one of two adherends, and the adhesive is sandwiched between the two adherends.
• Examples thereof include a method in which the adhesive is bonded in such a manner, heat-treated as necessary, cooled as necessary, and the adhesive is cured and bonded.
• the adhesive When the adhesive is applied to the adherend, the adhesive may be applied to the entire adherend surface, partially, or a predetermined pattern. Further, for the two-component adhesive which is the first adhesive according to the present invention, the agent A is applied to one of the adherend surfaces of the adherend, and the agent B is applied to the adherend surface of the other adherend. Then, the method of pasting may be used. Further, after the agent A and the agent B are separately mixed, the mixture may be applied to the adherend.
• the second adhesive according to the present invention can also be applied to the adherend in the same manner as the first adhesive according to the present invention.
• the method of applying the adhesive is not particularly limited, and a conventionally known application method can be selected.
• a method of discharging an adhesive from a predetermined dispenser can be mentioned.
• the atmosphere, temperature, and humidity in the coating process are not particularly limited, and the adhesive can be applied in the atmosphere or at room temperature.
• the coating amount and coating thickness when applying the adhesive are not particularly limited.
• an adhesive layer having an arbitrary thickness (for example, 0.1 mm or more) is formed after bonding.
• an adhesive layer having an arbitrary thickness it is possible to more preferably follow the thermal strain.
• a method of forming an adhesive layer of an arbitrary thickness after bonding a method of adding a filler having a desired particle size to the adhesive, a method of using an adherend having a shape capable of maintaining the thickness, and the like are used. can give. Further, it is also possible to adjust the thickness of the adhesive layer between the adherends by applying pressure to the adherends after superimposing the adherends on each other.
• the heat treatment performed as needed can accelerate the curing of the adhesive.
• the heating temperature, heating time, heating atmosphere, heating pressure, and the like can be appropriately determined according to the curing temperature of the adhesive, the manufacturing process of the product, and the like.
• the heating temperature can be 50 ° C. or higher, preferably 80 ° C. or higher, 120 ° C. or lower, and preferably 100 ° C. or lower.
• the heating temperature is 120 ° C. or lower, preferably 100 ° C. or lower from the viewpoint of preventing foaming in the adhesive.
• the heating method is not particularly limited. Examples include a method using a heating furnace, a hot plate, a hot air generator, and the like.
• the cooling treatment performed as necessary is a treatment for cooling the adherend to room temperature after heating.
• the curing treatment can be performed by curing at room temperature.
• the adhesive according to the present invention exhibits sufficient adhesiveness and has flexibility. Therefore, when the adhesive is cooled after the heat treatment, the hardness (storage elastic modulus) of the adhesive is gradually increased, and the thermal strain generated between the adherends can be alleviated. Further, by curing in a room temperature environment, the adhesiveness can be maintained and improved, the strain can be alleviated, and the hardness can be improved.
• the first adhesive and the second adhesive according to the present invention can be used when two or more adherends are adhered to form a structure.
• the adherend include metal materials such as aluminum, iron, titanium and stainless steel, various resins, resin materials such as carbon fiber reinforced plastics, paper, cloth, wood, glass and various ceramics.
• the two or more adherends may be made of the same material or different materials.
• the shape of the two or more adherends is not particularly limited, and may be a shape corresponding to various parts such as electric / electronic parts, mechanical parts, and automobile parts.
• the first adhesive and the second adhesive according to the present invention can be suitably used for applications in which two or more adherends having different linear expansion coefficients are bonded to form a structure.
• the first adhesive according to the present invention is excellent in elongation, toughness, and adhesive strength (storage elastic modulus) after curing, and is caused by the difference in linear expansion coefficient of the adherend when subjected to cold heat treatment. It is possible to absorb the heat strain, warpage, etc. that occur as a result, and peeling between the adherends is unlikely to occur.
• the cured product according to the present invention is obtained by curing the first adhesive or the second adhesive according to the present invention.
• the cured product can be obtained by curing the adhesive by the method described in the above [How to use the adhesive].
• the article according to the present invention is obtained by being bonded with the first adhesive or the second adhesive according to the present invention.
• the various adherends described in the above [Use of Adhesive] are used in the first adhesive or the second adhesive according to the present invention, and the method described in the above [Adhesive Usage]. It is composed by adhering with.
• Examples of the article include electric / electronic devices, electric / electronic parts, mechanical parts, vehicle parts, vehicle interior members, and the like.
• DMA Dynamic Viscoelasticity
• each component in Tables 1 and 2 is "part by mass”.
• Each component of the adhesive (agent A and agent B) in Tables 1 and 2 is as follows.
• Epoxy resin 1 Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828)
• Epoxy resin 2 Carboxyl group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin (Huntsman, HyPox RA840)
• CTBN Carboxyl group-terminated butadiene nitrile rubber
• DOTL Dioctyl tin dilaurate-Core shell type rubber particles 1: Bisphenol A type epoxy resin and core shell type rubber particles whose core is butadiene rubber particles and shell layer is acrylic resin
• epoxy resin: core shell type rubber particles 6: Epoxy resin-core-shell type rubber particle composition contained in 4 (manufactured by Kaneka, MX154)
• -Core-shell type rubber particles 2 Core-shell type rubber particles whose core is butad
• the cured adhesives of Examples 1 to 10 have a large value (MPa) of breaking strength (tensile strength at cutting) and a value (%) of elongation at breaking (elongation at cutting), and further, at 20 ° C. Since the storage elastic modulus (MPa) and the storage elastic modulus at 80 ° C. (MPa) are also large, this adhesive has excellent adhesive strength (storage elastic modulus) after elongation and curing, and is peeled off due to thermal itinerary. It turns out that it is unlikely to occur. Since the cured adhesive of Comparative Example 1 containing no core-shell type rubber particles has a low storage elastic modulus value (MPa) at 20 ° C.
• the cured adhesive of Comparative Example 2 containing no epoxy resin has a breaking strength (tensile strength at cutting) value (MPa), a storage elastic modulus value at 20 ° C. (MPa), and a storage elastic modulus value at 80 ° C. Since (MPa) is small, it can be seen that this adhesive has a problem in adhesive strength (storage elastic modulus) after elongation and curing.
• the adhesive cured product of Comparative Example 3 using a carboxyl group-terminated butadiene nitrile rubber (CTBN) -modified epoxy resin and containing no core-shell type rubber particles had a breaking strength (tensile strength at cutting) value (MPa) of 20 ° C. Since both the storage elastic modulus value (MPa) and the storage elastic modulus value (MPa) at 80 ° C. are small, it can be seen that this adhesive has a problem in the adhesive strength (storage elastic modulus) after elongation and curing. .. Since the cured adhesive of Comparative Example 4 containing no polymer having a crosslinkable silicon group was hard and brittle, it was not possible to prepare a test piece having a predetermined shape.
• CBN carboxyl group-terminated butadiene nitrile rubber

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• 2021
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