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  • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
  • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/40—Redox systems
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
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  • 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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09J109/02—Copolymers with acrylonitrile
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  • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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  • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
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  • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
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  • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/53—Core-shell polymer
• • 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
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2409/00—Presence of diene rubber
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  • 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
  • C09J2433/00—Presence of (meth)acrylic polymer
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2451/00—Presence of graft polymer

Definitions

• the present invention relates to compositions, adhesives and joined bodies.
• Room-temperature fast-curing adhesives include two-component fast-curing epoxy adhesives, instant adhesives, anaerobic adhesives, non-anaerobic acrylic adhesives, and the like.
• the two-component fast-curing epoxy adhesive is used by weighing and mixing the main agent and curing agent, and there was a risk of a significant decrease in strength if the weighing and mixing were not carried out sufficiently. Moreover, even if the weighing and mixing are sufficiently performed, there is a problem that the peel strength and the impact strength are low.
• anaerobic adhesives are adhesives that harden when the materials to be glued are pressed against each other and the air is cut off, so naturally the parts that come into contact with the air, such as the protruding parts, do not harden. Therefore, when the adherend is porous or the adherend is not well-balanced, there is a problem that the adhesive is not sufficiently cured, resulting in poor adhesion.
• non-anaerobic acrylic adhesives generally called second-generation acrylic adhesives (SGA)
• SGA second-generation acrylic adhesives
• nitrile-butadiene rubber component by controlling the content of acrylonitrile monomer units in 100 parts by mass of the nitrile-butadiene rubber component to 5 to 30 parts by mass, durability is improved and a metal such as copper is adhered. It is reported in Patent Document 1 that it is possible to prevent corrosion reactions such as oxidation of the adherend when it is used as an object, and to achieve even higher adhesiveness.
• Patent document 2 reports that moisture resistance can be improved by controlling the content to 10 to 30 parts by mass.
• adhesive strength can be improved by using at least one type of oligomer having two or more (meth)acrylic groups in the molecule in a one-component acrylic adhesive.
• Document 3 reports a (meth)acrylate-modified liquid rubber as an example of the oligomer.
• An object of the present invention is to provide a composition that can be used as an adhesive with excellent fast-curing properties and heat cycle resistance.
• the first component contains an elastomer (A), a first acrylic component (B), a second acrylic component (C), and polymerization initiation agent (D), the second agent contains a condensate (E) of an amine and an aldehyde, a third acrylic component (F), and a reducing agent (G), and the first acrylic
• the system component (B) contains two or more hydroxyl groups bonded to carbon atoms in one molecule, or has an amide group, a cyclic amide group, a sulfoxide group, a ketone group, an aldehyde group, a sulfo group, or a sulfino group in one molecule.
• the second acrylic component (C) is a (meth)acrylate or (meth)acrylic acid other than the first acrylic component (B)
• the third acrylic component (F) is a (meth)acrylate or (meth)acrylic acid.
• the present invention (1) It consists of a first agent and a second agent, and the first agent comprises an elastomer (A), a first acrylic component (B), a second acrylic component (C), and a polymerization initiator (D ), the second agent contains a condensate (E) of an amine and an aldehyde, a third acrylic component (F), and a reducing agent (G), and the first acrylic component ( B) contains two or more hydroxyl groups bonded to carbon atoms in one molecule, or amide group, cyclic amide group, sulfoxide group, ketone group, aldehyde group, sulfo group, sulfino group, phosphonic group in one molecule a (meth)acrylate or (meth)acrylic acid containing one or more functional groups selected from the group consisting of a group consisting of a sulfobetaine group, a carbobetaine group, and a phosphobetaine group;
• the content of the first acrylic component (B) is 10 to 40 parts by mass when the total of the first acrylic component (B) and the second acrylic component (C) is 100 parts by mass.
• the content of monofunctional (meth)acrylate or (meth)acrylic acid in the first acrylic component (B) and the second acrylic component (C) is equal to the content of the first acrylic component (B) and the second acrylic component (C) is 70 to 100 parts by mass when the total is 100 parts by mass
• the content of the elastomer (A) is 30 to 70 parts by mass when the total of the first acrylic component (B) and the second acrylic component (C) is 100 parts by mass
• the composition according to any one of (5), (7) According to any one of (1) to (6), wherein one or more of the elastomer components contained in the elastomer (A) is a liquid elastomer (A1) that is liquid at 23°C.
• composition of (8) The composition according to any one of (1) to (7), wherein said elastomer (A) contains one or more NBRs; (9) The composition according to (8), wherein the one or more NBRs contain two or more NBRs with different nitrile contents; (10) According to any one of (1) to (9), wherein the content of nitrile in the elastomer (A) is 0.001 to 0.300 parts by mass per 100 parts by mass of the elastomer (A).
• the elastomer (A) contains a core-shell type graft copolymer (A2), and the content of the core-shell type graft copolymer (A2) is less than or equal to the first acrylic component (B ) and the second acrylic component (C) is 0 to 10 parts by mass when the total is 100 parts by mass, the composition according to any one of (1) to (10), (12) The composition according to any one of (1) to (11), wherein the elastomer (A) contains a (meth)acryloyl-modified elastomer (A3), (13) The composition according to any one of (1) to (12), wherein the first agent has a viscosity at 25° C.
• the description “A to B” means A or more and B or less.
• the description “(meth)acrylate or (meth)acrylic acid” includes (meth)acrylate only, (meth)acrylic acid only, and (meth)acrylate and ( It includes the case of containing meth)acrylic acid.
• the term "acrylic component” includes cases in which only acrylic components are contained, cases in which only methacrylic components are contained, and cases in which acrylic components and methacrylic components are contained.
• the two-component composition according to this embodiment consists of a first agent and a second agent, and the first agent comprises an elastomer (A), a first acrylic component (B), and a second acrylic component ( C) and a polymerization initiator (D), and the second agent contains a condensate (E) of an amine and an aldehyde, a third acrylic component (F), and a reducing agent (G).
• the first acrylic component (B) contains two or more hydroxyl groups bonded to carbon atoms in one molecule, or contains an amide group, a cyclic amide group, a sulfoxide group, a ketone group, or an aldehyde group in one molecule.
• a sulfo group a sulfino group, a phosphonic group (phosphonic acid group), a sulfobetaine group, a carbobetaine group, and one or more functional groups selected from the group consisting of a phosphobetaine group, containing one or more (meta) acrylate or (meth)acrylic acid, the second acrylic component (C) is a (meth)acrylate or (meth)acrylic acid other than the first acrylic component (B), and the third acrylic component ( F) is (meth)acrylate or (meth)acrylic acid.
• the first agent and the second agent will be described below.
• the two-component composition according to this embodiment contains the elastomer (A) in the first component.
• the elastomer (A) include various rubbers such as nitrile butadiene rubber (NBR), butadiene rubber, acrylic rubber, urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer (butadiene/MMA/ST copolymer), Examples thereof include graft copolymers such as (meth)acrylate-butadiene-(meth)acrylonitrile-styrene copolymers and acrylonitrile-butadiene-styrene graft copolymers.
• these elastomers may be used alone or in combination of two or more.
• the content of the elastomer (A) is the total of the first acrylic component (B) and the second acrylic component (C) is preferably 30 to 70 parts by mass, more preferably 30 to 50 parts by mass, when the is 100 parts by mass.
• the content of the elastomer (A) is, for example, 30, 35, 40, 45, 50, 55, 60, 65, or 70 parts by mass. may be within the range of When the elastomer (A) is used together, the content of the elastomer (A) means the total amount of the elastomer (A) used together.
• Liquid elastomer (A1) In the two-component composition according to the present embodiment, from the viewpoint of improving heat cycle resistance while considering workability (applicability of adhesive), at least one type of elastomer (A) is a liquid elastomer ( A1) is preferably contained.
• the term "liquid” in the present invention means exhibiting a liquid state at room temperature (23°C). Solid” test is determined to be a liquid.
• the liquid elastomer (A1) preferably has a viscosity of 100,000 to 400,000 mPa s, more preferably 200,000 to 300,000 mPa s, measured at 27°C using a BH viscometer. is more preferred. Specifically, for example, 100,000, 150,000, 200,000, 250,000, 300,000, 350,000, or 400,000 mPa s. It may be in the range between.
• liquid elastomer (A1) examples include liquid nitrile-butadiene rubber (NBR) and liquid butadiene rubber (BR). From the viewpoint of toughness, liquid nitrile-butadiene rubber (NBR) is preferred.
• a (meth)acryloyl-modified elastomer (A3) may be used as the liquid elastomer (A1) according to the present embodiment.
• these liquid elastomers may be used alone or in combination of two or more.
• liquid elastomer (A1) for example, "HYPRO (registered trademark) 1300X33LC VTBNX” manufactured by HUNTSMAN can be mentioned as a commercially available product.
• the content of the liquid elastomer (A1) is the same as that of the first acrylic component (B) and the second acrylic component (C).
• the total is 100 parts by mass, it is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass.
• the content of the liquid elastomer (A1) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, or 50 parts by mass. It may be in a range between the two.
• the content of the liquid elastomer (A1) means the total amount of the liquid elastomer (A1) used together.
• the content of liquid nitrile-butadiene rubber (NBR) is preferably 80 parts by mass or less in 100 parts by mass of the elastomer (A), and is 30 to 65 parts by mass. It is even more preferable to have
• Nitrile-butadiene rubber is a polymer having (meth)acrylonitrile and 1,3-butadiene as structural units and having rubber-like elasticity at room temperature. Obtainable. By containing nitrile-butadiene rubber (NBR) in combination with other components, toughness can be expected. Examples of NBR include solid NBR and liquid NBR. The “solid NBR” referred to here is NBR that does not correspond to the aforementioned “liquid NBR”.
• the two-component composition according to the present embodiment contains two or more NBRs with different nitrile contents from the viewpoint of improving heat cycle resistance while considering workability (applicability of adhesive). is preferred.
• the nitrile content of NBR is the content (parts by mass) of (meth)acrylonitrile monomer units in 100 parts by mass of NBR.
• the nitrile content of NBR is preferably 1 to 70 parts by mass, more preferably 15 to 60 parts by mass per 100 parts by mass of NBR, from the viewpoint of improving heat cycle resistance. Specifically, for example, 1, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 parts by mass. It may be in the range between any two.
• the nitrile content of the NBR with the higher nitrile content is NBR 100 mass from the viewpoint of toughness. It is preferably 20 to 40 parts by mass, more preferably 30 to 35 parts by mass.
• the nitrile content of the NBR having a lower nitrile content is preferably 1 to 39 parts by mass, preferably 15 to 34 parts by mass, based on 100 parts by mass of the NBR from the viewpoint of improving heat cycle resistance. is more preferred.
• the nitrile content of the NBR with the higher nitrile content and the NBR with the lower nitrile content is preferably 0.1 to 25 parts by mass in 100 parts by mass of NBR. , more preferably 10 to 20 parts by mass.
• the nitrile content in the elastomer (A) is such that the elastomer ( A) It is preferably 0.001 to 0.300 parts by mass, more preferably 0.003 to 0.275 parts by mass per 100 parts by mass. Specifically, for example, 0.001, 0.010, 0.100, 0.200, 0.210, 0.220, 0.230, 0.240, 0.250, 0.260, 0.270 , 0.280, 0.290, or 0.300 parts by weight, and may be within a range between any two of the numerical values exemplified herein.
• the nitrile content in the elastomer (A) as used herein means acrylonitrile monomer units contained in the elastomer (A).
• the acrylonitrile monomer unit is contained, for example, in the NBR or MBAS resin in the elastomer (A).
• the nitrile content in the elastomer (A) can be measured according to JISK6451-2.
• the nitrile content can be controlled by adjusting the blending amounts of acrylonitrile and 1,3-butadiene, which are structural units in the production of the NBR used.
• the two-component composition according to the present embodiment preferably contains a core-shell graft copolymer (A2).
• a core-shell type graft copolymer means a graft copolymer in which a polymer serving as a shell component is grafted to a crosslinked rubber serving as a core component.
• the main components of the crosslinked rubber that serves as the core component include butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene-diene rubber, isobutylene polymer rubber, ethylene-vinyl acetate copolymer rubber, isoprene rubber, chloroprene rubber, and nitrile rubber. etc.
• a crosslinked rubber containing butadiene as a main component and/or a crosslinked rubber containing styrene-butadiene as a main component are preferred from the viewpoint of flexibility.
• a known butadiene rubber can be used as the crosslinked rubber containing butadiene as a main component.
• a known styrene-butadiene rubber can be used as the crosslinked rubber containing styrene-butadiene as a main component. These rubbers may be used alone or in combination of two or more.
• the core component may contain other optional components as long as the effects of the present invention are not impaired.
• the content of the optional component is preferably 70 parts by mass or less, preferably less than 70 parts by mass, more preferably 50 parts by mass or less, and less than 50 parts by mass per 100 parts by mass of the core component. is more preferred.
• the shell component is a homopolymer or copolymer grafted with one or more monomers selected from the group consisting of (meth)acrylate monomers, (meth)acrylonitrile, and vinyl monomers having a double bond. is preferably the main component.
• Examples of (meth)acrylate monomers used in the shell component include monofunctional (meth)acrylates. Among these monofunctional (meth)acrylates, alkyl (meth)acrylates are preferred, and methyl (meth)acrylate is more preferred.
• Examples of vinyl-based monomers having double bonds used in the shell component include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene, divinylbenzene and the like. These can be used individually or in combination of 2 or more types. Among these vinylic monomers having double bonds, styrene is preferred.
• (meth)acrylate monomers are preferred from the viewpoint of swelling degree.
• the core-shell type graft copolymer (A2) is obtained by graft copolymerizing (meth)acrylate and, if necessary, styrene as a shell component on a core component that is a butadiene crosslinked rubber and/or a styrene-butadiene crosslinked rubber.
• MBS resin (Meth)acrylate-butadiene-styrene copolymer obtained by the above-described process, a butadiene crosslinked rubber and/or a styrene-butadiene crosslinked rubber as a core component, and a (meth)acrylate as a shell component and (Meth)acrylate-butadiene-(meth)acrylonitrile-styrene copolymer obtained by graft copolymerizing styrene and (meth)acrylonitrile as necessary (hereinafter referred to as MBAS resin), butadiene crosslinked rubber and/or styrene Acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS resin) obtained by graft copolymerizing acrylonitrile and styrene as a shell component to a core component that is a butadiene crosslinked rubber.
• ABS resin butadiene crosslinked rubber and
• MBAS resin is preferable from the viewpoint of toughness and curability.
• these core-shell graft copolymers (A2) may be used alone or in combination of two or more.
• MBS resins include the Kane Ace B series (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), the BTA series (manufactured by Rohm and Haas), and the Metabrene series (manufactured by Mitsubishi Rayon).
• MBAS resins include Denka BL-20 (manufactured by Denka).
• ABS resins include Denka ABS (manufactured by Denka Co., Ltd.).
• each component in the core-shell type graft copolymer (A2) is based on 100 parts by mass of the copolymer (preferably, a total of 100 parts by mass of (meth)acrylate, butadiene, and other vinyl monomers). middle), 5 to 30 parts by mass of (meth)acrylate, 40 to 80 parts by mass of butadiene, and 10 to 40 parts by mass of other vinyl-based monomers, 10 to 25 parts by mass of (meth)acrylate, and 40 to 75 parts by mass of butadiene 10 to 40 parts by mass of other vinyl monomers, more preferably 13 to 25 parts by mass of (meth)acrylate, 45 to 75 parts by mass of butadiene, and 0 to 30 parts by mass of other vinyl monomers. .
• vinyl-based monomers mean monomers other than (meth)acrylate and other than butadiene.
• Other vinyl monomers include (meth)acrylonitrile, styrene, divinylbenzene and the like. Among these, (meth)acrylonitrile and/or styrene are preferred. If the content ratio of each component in the core-shell type graft copolymer (A2) is within the range of the present invention, toughness can be expected.
• the method for producing the core-shell graft copolymer (A2) is not particularly limited, but known techniques such as emulsion polymerization using an aqueous dispersion medium and an emulsifier can be used.
• a radical monomer As a constituent of the core component, normal emulsion polymerization can be applied.
• a radical-poor monomer a method of emulsifying and dispersing a prepolymer obtained by ionic polymerization such as cationic polymerization, anionic polymerization, or coordination polymerization in an aqueous dispersion medium can be applied.
• a method in which each monomer component is uniformly mixed in advance and then emulsified and dispersed to carry out a reaction A method of additional polymerization (seed polymerization) of other components to seed (seed) particles made from The core component can be produced using methods such as enlarging. At this time, the form (phase structure) inside the obtained particles can be controlled by the production method, the ratio of each component, the order of reaction, and the like.
• a method of graft polymerizing the constituent components of the shell component a method of adding a monomer to the emulsified dispersion (latex) of the core component in one step or multiple steps and polymerizing it by a radical polymerization technique can be applied.
• the emulsified dispersion (latex) of the core-shell graft copolymer (A2) obtained by the above production method can be separated, recovered and used by salting out.
• the content of the core-shell type graft copolymer (A2) is 0 to 10 parts by mass when the total of the first acrylic component (B) and the second acrylic component (C) is 100 parts by mass. is preferred, more preferably 3 to 7 parts by mass.
• the content of the core-shell type graft copolymer (A2) is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by mass. may be within a range between any two of the numerical values exemplified in . Within this range, a decrease in heat cycle resistance can be suppressed, and thixotropy can be imparted.
• the content of the core-shell graft copolymer (A2) is the same as that of the core-shell graft copolymer (A2) used in combination. means total volume.
• the two-component composition according to the present embodiment preferably contains a (meth)acryloyl-modified elastomer (A3).
• (Meth)acryloyl-modified elastomer (A3) means an elastomer having (meth)acrylic acid monomer units. Examples of a mode of imparting (meth)acrylic acid monomer units include a mode having a (meth)acryloyl group at the terminal position of the elastomer molecule and a mode having a (meth)acryloyl group in the molecular chain of the elastomer molecule. .
• the (meth)acryloyl-modified elastomer has (meth)acryloyl groups at least at terminal positions of the elastomer molecule.
• the (meth)acryloyl-modified elastomer (A3) according to the present embodiment includes, for example, terminal (meth)acrylic-modified NBR, terminal (meth)acrylic-modified polybutadiene, urethane (meth)acrylate, terminal (meth)acrylic-modified silicone oil and the like. Terminal (meth)acryl-modified NBR is preferred from the viewpoint of toughness.
• HYPRO registered trademark 1300X33LC VTBNX
• HUNTSMAN HUNTSMAN
• these (meth)acryloyl-modified elastomers (A3) may be used alone or in combination of two or more.
• the content of the (meth)acryloyl-modified elastomer (A3) according to the present embodiment is 1 to 40 when the total of the first acrylic component (B) and the second acrylic component (C) is 100 parts by mass. It is preferably 10 to 30 parts by mass, more preferably 10 to 30 parts by mass. Specifically, it is, for example, 1, 5, 10, 15, 20, 25, or 30 parts by mass, and may be within a range between any two of the numerical values exemplified here. Within this range, toughness can be imparted.
• the content of the (meth)acryloyl-modified elastomer is the total amount of the (meth)acryloyl-modified elastomer (A3) used in combination. means.
• the two-component composition according to this embodiment contains the first acrylic component (B).
• the first acrylic component (B) contains two or more hydroxyl groups bonded to carbon atoms in one molecule, or an amide group, a cyclic amide group, a sulfoxide group, a ketone group, an aldehyde group, a sulfo (meth)acrylates or (meth)acryls containing one or more functional groups selected from the group consisting of groups, sulfino groups, phosphonic acid groups, sulfobetaine groups, carbobetaine groups, and phosphobetaine groups is an acid.
• the first acrylic component (B) preferably contains two or more hydroxyl groups bonded to carbon atoms in one molecule, or contains a ketone group, an aldehyde group, or a sulfoxide group.
• It is acrylic acid, more preferably (meth)acrylate or (meth)acrylic acid containing two or more hydroxyl groups bonded to carbon atoms in one molecule.
• first acrylic component (B) examples include glycerin mono(meth)acrylate, maleic anhydride, and the like. From the viewpoint of storage stability, glycerin mono(meth)acrylate is preferred. As the first acrylic component (B) according to this embodiment, these first acrylic components (B) may be used alone or in combination of two or more.
• the content of the first acrylic component (B) is It is preferably 10 to 40 parts by mass, more preferably 15 to 30 parts by mass. Specifically, it is, for example, 10, 15, 20, 25, 30, 35, or 40 parts by mass, and may be within a range between any two of the numerical values exemplified here.
• the content of the first acrylic component (B) means the total amount of the first acrylic component (B) used together.
• the two-component composition according to this embodiment contains the second acrylic component (C).
• the second acrylic component (C) in the present embodiment means a second acrylic component (C) that does not correspond to the first acrylic component (B) described above.
• the second acrylic component (C) for example, (meth)acrylate or (meth)acrylic acid (C1) containing one hydroxyl group, (meth)acrylate or (meth) Acrylic acid (C2), (meth)acrylate or (meth)acrylic acid (C3) having an alkylene oxide or siloxane unit, acyclic polyfunctional (meth)acrylate or (meth)acrylic acid (C4), (meth ) a phosphate ester compound (C5) having an acryl group, and the like.
• (meth)acrylate or (meth)acrylic acid (C1) containing one hydroxyl group for example, (meth)acrylate or (meth) Acrylic acid (C2), (meth)acrylate or (meth)acrylic acid (C3) having an alkylene oxide or siloxane unit, acyclic polyfunctional (meth)acrylate or (meth)acrylic acid (C4), (meth ) a phosphate ester compound (C5) having an acryl group,
• the second acrylic component (C) according to the present embodiment may be used alone or in combination of two or more of these second acrylic components (C).
• Examples of the (meth)acrylate or (meth)acrylic acid (C1) containing one hydroxyl group according to the present embodiment include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy Butyl (meth)acrylate and the like can be mentioned. From the viewpoint of metal adhesion, 2-hydroxyethyl (meth)acrylate is preferred.
• the (meth)acrylate or (meth)acrylic acid (C1) according to the present embodiment may be used alone or in combination of two or more. may
• ⁇ Phenyl group-containing (meth)acrylate or (meth)acrylic acid (C2) Examples of the (meth)acrylate or (meth)acrylic acid (C2) having a phenyl group according to the present embodiment include phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, neopentyl glycol-(meth)acrylic acid-benzoate (meth)acrylate, benzyl (meth)acrylate and the like.
• phenoxyethyl (meth)acrylate is preferred.
• the (meth)acrylate or (meth)acrylic acid (C2) according to the present embodiment may be used alone or in combination of two or more. may
• the (meth)acrylate or (meth)acrylic acid (C3) having an alkylene oxide or siloxane unit has 4 to 15 alkylene oxide or siloxane units in its molecule, It preferably has 6 to 13.
• the alkylene oxide or siloxane unit is contained separately at two or more locations in the molecule, the total number of alkylene oxide or siloxane units present at each location is 4 to 15, preferably 6 to 13 pieces.
• the (meth)acrylate or (meth)acrylic acid (C3) having an alkylene oxide or siloxane unit according to the present embodiment is more preferably polyfunctional from the viewpoint of toughness and curing speed.
• the (meth)acrylate (C3) having such an alkylene oxide or siloxane unit includes, for example, bisphenol A alkylene oxide-modified di(meth)acrylate, 2,2-bis(4-(meth)acryloxyphenyl)propane , 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxyphenyl) 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane and the like.
• Bisphenol A alkylene oxide-modified di(meth)acrylate is preferred from the viewpoint of curing speed.
• bisphenol A alkylene oxide-modified di(meth)acrylates bisphenol A EO (ethylene oxide)-modified di(meth)acrylate is preferred.
• bisphenol A alkylene oxide-modified di(meth)acrylates compounds of general formula (A) are preferred.
• R 1 and R 1 ' represent a hydrogen atom or a methyl group.
• R 1 and R 1 ' may be the same or different.
• R 2 and R 2 ' represent an alkylene group.
• the alkylene group may have one hydroxyl group,
• R 2 and R 2 ' may be the same or different, and
• R 3 and R 3 ' are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.
• R 3 and R 3 ′ may be the same or different p+q represents a number from 1 to 20. p and q may be the same or different.
• R 2 and R 2 ′ are preferably alkylene groups having no hydroxyl group from the viewpoint of storage stability. Among these, the following are preferable in terms of high resin strength.
• R 1 and R 1 ' are preferably methyl groups.
• R 2 and R 2 ' are preferably C 1-12 alkylene groups, more preferably ethylene groups. It is preferred that the alkylene group does not have a hydroxyl group.
• R 3 and R 3 ' are preferably methyl groups.
• p+q is a number of 1 to 20, preferably 5 to 15, more preferably 10, from the viewpoint of the resin properties and flame resistance of the cured product.
• the (meth)acrylate or (meth)acrylic acid (C3) according to the present embodiment may be used alone or in combination of two or more. may
• the (meth)acrylate or (meth)acrylic acid (C4) according to the present embodiment may be used alone or in combination of two or more. may
• Phosphate ester compound (C5) having (meth)acrylic group include phosphate ester compounds having a (meth)acryl group.
• Phosphate esters having a meth) acrylic group include (2-hydroxyethyl) methacryl acid phosphate, (meth) acryloyloxyethyl acid phosphate, dibutyl 2-(meth) acryloyloxyethyl acid phosphate, dioctyl 2-( meth) acryloyloxyethyl phosphate, diphenyl 2-(meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate and (meth) acryloyloxyethyl acid phosphate monoethanolamine half salt, etc. be done. These 1 type(s) or 2 or more types can be used.
• the two-component composition according to this embodiment preferably contains a monofunctional (meth)acrylate or (meth)acrylic acid.
• Monofunctional (meth)acrylate or (meth)acrylic acid in the present embodiment means (meth)acrylate or (meth)acrylic acid containing one (meth)acrylate group or (meth)acrylic acid group in the molecule. means.
• the first acrylic component (B) may be contained as a monofunctional (meth)acrylate or (meth)acrylic acid
• the second acrylic component (C) may be a monofunctional (meth)acrylate or (meth)acrylic acid.
• first acrylic component (B) and the second acrylic component (C) may be contained as monofunctional (meth)acrylates or (meth)acrylic acid.
• first acrylic component (B) is contained as a monofunctional (meth)acrylate or (meth)acrylic acid.
• the monofunctional (meth)acrylate or (meth)acrylic acid for example, glycerin mono(meth)acrylate as the first acrylic component (B), etc., as the second acrylic component (C) 2-hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and the like.
• the monofunctional (meth)acrylate or (meth)acrylic acid according to the present embodiment may be used alone or in combination of two or more of these monofunctional (meth)acrylates or (meth)acrylic acids. good.
• the two-component composition according to the present embodiment has monofunctional (meth)acrylate or (meth)acrylic acid in the first acrylic component (B) and the second acrylic component (C).
• the content of is preferably 70 to 100 parts by mass when the total of the first acrylic component (B) and the second acrylic component (C) is 100 parts by mass, and is 75 to 90 parts by mass. is more preferred.
• the content of monofunctional (meth)acrylate or (meth)acrylic acid is specifically, for example, 70, 75, 80, 85, 90, 95, or 100 parts by mass, any of the numerical values illustrated here or within a range between the two.
• the content of the monofunctional (meth) acrylate or (meth) acrylic acid is the monofunctional (meth) acrylate or (meth) It means the total amount of acrylic acid.
• the two-component composition according to this embodiment contains a polymerization initiator (D).
• the polymerization initiator (D) according to this embodiment has a role of curing the two-component composition.
• Examples of the polymerization initiator (D) according to the present embodiment include cumene hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, t-butyloxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyphthalate and the like. Cumene hydroperoxide is preferred from the viewpoint of curability and storage stability.
• the polymerization initiator (D) according to this embodiment may be used alone or in combination of two or more of these polymerization initiators (D).
• the content of the polymerization initiator (D) is the first acrylic component (B) and the second acrylic component (C ) is preferably 1 to 10 parts by mass, more preferably 3 to 7 parts by mass, when the total of 100 parts by mass.
• the content of the polymerization initiator (D) is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts by mass. or within a range between the two.
• the content of a polymerization initiator (D) means the total amount of the polymerization initiator (D) used together.
• the two-component composition according to this embodiment contains a condensate (E) of an amine and an aldehyde.
• the condensate (E) of an amine and an aldehyde according to the present embodiment is a condensate of any amine (alkylamine and arylamine) and any aldehyde, not only having a single structure, but also as a result of condensation It may also include resulting mixtures or composites.
• a condensate of amine and aldehyde for example, at least 1 mol, preferably 1.5 to 3 mol of aldehyde per 1 mol of amine in the presence of a carboxylic acid or an inorganic acid is condensed at 40 to 70°C. Included are the resulting amine complex mixtures.
• carboxylic acids or inorganic acids include propionic acid, phosphoric acid, and acetic acid
• examples of amines and aldehydes include butylamine or aniline and butyraldehyde.
• Examples of the condensate (E) of amine and aldehyde according to the present embodiment include reaction condensate of butylamine or aniline and butyraldehyde, aldehyde aniline, and the like.
• the aldehyde aniline according to the present embodiment means a reaction condensate of aldehydes and anilines. More specific examples include n-butyraldehyde aniline and the like. From the viewpoint of curing speed, n-butyraldehyde aniline is preferred.
• these condensates (E) of amine and aldehyde may be used alone or in combination of two or more.
• the content of the condensate of amine and aldehyde (E) is the third acrylic component (F), the condensate of amine and aldehyde (E ) and the reducing agent (G) is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, when the total is 100 parts by mass.
• the content of the condensate (E) of amine and aldehyde is, for example, 5, 10, 15, 20, 25, 30, 35, or 40 parts by mass. It may be in a range between the two.
• the content of the condensate (E) of amine and aldehyde is for each of the condensates (E) of (E), not only those of a single structure, but also the total amount of mixtures or composites resulting from the condensation.
• the two-part composition according to this embodiment contains the third acrylic component (F) in the second part.
• the third acrylic component (F) according to this embodiment include those exemplified for the first acrylic component (B) and the second acrylic component (C) used in the first agent.
• the third acrylic component (F) according to this embodiment may be used alone or in combination of two or more. Moreover, it may be the same as or different from the first acrylic component (B) and the second acrylic component (C) used in the first agent.
• Phenoxyethyl (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, neopentylglycol from the viewpoint of low volatility and applicability At least one selected from the group consisting of (meth)acrylic acid-benzoic acid ester (meth)acrylate and benzyl (meth)acrylate is preferred.
• the third acrylic component (F) contains fluorine (meta- ) acrylate or fluorine-containing (meth)acrylic acid (F1).
• Fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid means (meth)acrylate or (meth)acrylic acid having one or more fluorine atoms in the molecule.
• a fluorine-containing (meth)acrylate containing a fluorinated alkyl group is preferable as the fluorine-containing (meth)acrylate (F1) according to the present embodiment.
• difluoromethylene (--CF 2 --).
• difluoromethylene (--CF 2 --).
• (Meth)acrylate and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decane di(meth)acrylate 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate is most preferable from the viewpoint of wettability to the adherend and storage stability.
• the fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid (F1) can be You may use it in combination of 2 or more types.
• the two-component composition according to the present embodiment is a fluorine-containing (meth)acrylate or a fluorine-containing
• the content of (meth)acrylic acid (F1) is preferably 0.001 to 3 parts by mass when the total of the third acrylic component (F) is 100 parts by mass, and 0.5 to 2 parts by mass. is more preferable.
• the content of fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid (F1) is, for example, 0.001, 0.5, 1.0, 1.5, 2.0, or 3.0 parts by mass, and may be within a range between any two of the numerical values exemplified here.
• fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid (F1) is used in combination, the content of fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid (F1) is It means the total amount of fluorine-containing (meth)acrylate or fluorine-containing (meth)acrylic acid (F1).
• the two-component polymerizable composition according to this embodiment contains a reducing agent (G).
• a reducing agent (G) examples include those capable of generating radicals by reacting with the polymerization initiator (D) used in the first agent.
• the reducing agent (G) includes those capable of generating radicals by reacting with the polymerization initiator (D) used in the first agent.
• D polymerization initiator
• at least one selected from the group consisting of tertiary amines, thiourea derivatives, and transition metal salts is more preferred.
• thiourea derivatives include acetylthiourea and ethylenethiourea.
• transition metal salts include cobalt naphthenate, cobalt octylate, copper naphthenate, copper neodecanoate and vanadyl acetylacetonate. Transition metal salts are preferred from the viewpoints of curing speed, toughness of the cured adhesive, and heat cycle resistance.
• the transition metal salt is preferably at least one selected from the group consisting of copper naphthenate and copper neodecanoate, more preferably copper neodecanoate.
• these reducing agents (G) may be used alone or in combination of two or more.
• the content of the reducing agent (G) is the third acrylic component (F), the condensate of amine and aldehyde (E), and the reducing agent
• the total amount of (D) is 100 parts by mass, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass.
• the content of the reducing agent (G) is, for example, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 2.0, 3 .0, 4.0, or 5.0 parts by weight, and may be within a range between any two of the numerical values exemplified herein.
• the content of the reducing agent (G) means the total amount of the reducing agent (G) used together.
• the two-component polymerizable composition according to the present embodiment preferably further contains a stabilizer (H) in the second component.
• a stabilizer (H) in the second agent By further containing the stabilizer (H) in the second agent, it is possible to prevent the viscosity of the second agent from increasing during storage. This is because the condensate (E) of amine and aldehyde accelerates the oxidation-reduction reaction between the reducing agent (D) and oxygen during storage, generating radicals and polymerizing the third acrylic component (F). This is probably because the stabilizer (H) prevents the viscosity from increasing.
• the content of the stabilizer (H) is the condensate (E) of amine and aldehyde, the third acrylic component (F ) and the reducing agent (G) is preferably 0.001 to 0.5 parts by mass when the total is 100 parts by mass.
• the content of the stabilizer (H) is more preferably 0.05 to 0.4 parts by mass, still more preferably 0.1 to 0.3 parts by mass, from the viewpoint of storage stability and curing speed.
• the content of the stabilizer (H) means the total amount of the stabilizer (H) used in combination.
• Stabilizer (H) is not particularly limited as long as it is a known stabilizer, polymerization inhibitor, or antioxidant, but methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tert-butylphenol ), quinones such as catechol, hydroquinone monomethyl ether, monotertiarybutylhydroquinone, 2,5-ditertiarybutylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone system stabilizer; azine-based stabilizer such as phenothiazine; citric acid, picric acid, tertiary butylcatechol, 4-methoxyphenol, 2-butyl-4-hydroxyanisole, 2,6-ditertiarybutyl-p-cresol, N- ammonium salt of nitroso-N-phenylhydroxylamine, te
• stable radical type compounds are preferable in terms of storage stability.
• Stable radical type compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl and 4-methacryloyloxy-2,2, At least one selected from the group consisting of 6,6-tetramethylpiperidine-1-oxyl is preferred.
• a stable radical type compound having a nitroxide radical as a stable radical is more preferred.
• 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl is most preferred.
• the stabilizer (H) may be used alone or in combination of two or more.
• the first component preferably has a viscosity of 1,000 to 100,000 mPa s from the viewpoint of workability (applicability of the adhesive). More preferably, it is up to 50,000 mPa ⁇ s.
• the viscosity of the first agent here means the viscosity of the composition containing the elastomer (A), the first acrylic component (B), the second acrylic component (C), and the polymerization initiator (D). is.
• the viscosity of the first agent according to this embodiment is measured at 25°C in accordance with JISK7117-1.
• the second component preferably has a viscosity of 1 to 1000 mPa s, more preferably 5 to 100 mPa s, from the viewpoint of improving the applicability to the adherend. is more preferred.
• the viscosity of the second agent according to this embodiment is measured at 25°C in accordance with JISK7117-1.
• the two-part composition according to the present embodiment has the total amount of the elastomer (A) contained in the first part and the elastomer (A) contained in the second part
• the elastomer (A) contained in the first agent is preferably 55 to 100 parts by mass, more preferably 80 to 100 parts by mass, and preferably 95 to 100 parts by mass. More preferred. In one embodiment, it is preferred that substantially only the first agent contains the elastomer (A).
• Additives such as polymerization inhibitors, stabilizers, antioxidants, and UV absorbers can be added to the two-component composition according to the present embodiment to form an adhesive.
• a joined body can be obtained by applying the composition according to the present embodiment to an adherend and adhering the adherend.
• the joined body according to the present embodiment is produced by, for example, applying the first agent to one of the adherend surface or the adherend, applying the second agent to the other of the adherend surface or the adherend, and then applying these agents. It is obtained by joining two adherend surfaces or adherends together.
• the material of the adherend in the above embodiment is not limited to this, but examples thereof include iron and plated surfaces. Since the adhesive composition exhibits excellent adhesiveness particularly to iron and plated surfaces, it can be suitably used for ferrite magnets, plated products, and the like.
• the composition according to the present embodiment it is possible to bond adherends together in an extremely short period of time, thereby achieving rapid curability. Moreover, the composition according to the present embodiment is also excellent in heat cycle resistance. Therefore, the composition according to the present embodiment is required to be fast curing, and is an adhesive in the manufacture of products that are assumed to be used in environments including low to high temperatures such as -40 to 100 ° C. It is suitable as Examples of such products include speakers, motors, power transformers, and the like.
• Examples 1 to 20 and Comparative Examples 1 to 6> The elastomer (A), the first acrylic component (B), the second acrylic component (C), and the polymerization initiator (D) were mixed in the ratio shown in Table 1 to prepare the first agent.
• the condensate (E) of amine and aldehyde, the third acrylic component (F), the reducing agent (G), and the stabilizer (H) were mixed in the ratio shown in Table 1 to prepare the second agent.
• An adhesive composed of a first agent and a second agent was prepared. The first part and the second part were mixed at a mass ratio of 9:1.
• the fixing time of the adhesive obtained by using the adhesive composed of the first part and the second part to which the above additives are added and the impact resistance after heat cycle exposure of the cured product are measured by the following method. bottom.
• a ferrite magnet/iron plate was adhered as an adherend by the coating method described above to prepare a test piece for heat cycle exposure.
• a test piece for heat cycle exposure was repeatedly exposed 50 times to a heat cycle in which the temperature was raised from -40°C to 110°C at a rate of 2°C/min and cooled from 110°C to -40°C at a rate of 2°C/min. After the exposure, the test piece was dropped from a height of 1 m to conduct an impact resistance test.
• the impact resistance of the cured product after heat cycle exposure was evaluated according to the following evaluation criteria, and used as an index of heat cycle resistance.
• B The test piece peeled after 21 to 29 impact resistance tests were performed.
• C 11 to 20 impact resistance tests were performed.
• the test piece peeled off by D The test piece peeled off by performing the impact resistance test at 10 times or less
• ⁇ Viscosity of second agent> The viscosity of the second agent was measured under conditions of 25° C. according to JIS K7117-1.
• ⁇ Storage stability (second agent)> 10 g of the second agent was weighed into a 20 ml vial bottle (made of glass), exposed in an atmosphere of 60 ° C. for 14 days, and then the viscosity was measured under the conditions of 25 ° C. according to JIS K7117-1, and the following formula was used. A viscosity increase rate was calculated. Viscosity increase rate (%) (viscosity after exposure for 14 days/viscosity before exposure for 14 days) x 100
• the above results are shown in Tables 1 to 4.
• the nitrile content of NBR is the content (parts by mass) of (meth)acrylonitrile monomer units in 100 parts by mass of NBR.
• the content of B in A means the content of B contained in 100 parts by mass of A.
• Adhesives using the composition according to the present invention are excellent in rapid curing and heat cycle resistance.
• INDUSTRIAL APPLICABILITY The composition according to the present invention can be suitably used, for example, as an adhesive in the manufacture of products that are required to be fast-curing and are expected to be used in high-temperature environments, and has industrial applicability. .

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• 2022
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