WO2015046199A1 - Thermal curing-type magnetizable adhesive composition and adhesive sheet - Google Patents

Thermal curing-type magnetizable adhesive composition and adhesive sheet Download PDF

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Publication number
WO2015046199A1
WO2015046199A1 PCT/JP2014/075187 JP2014075187W WO2015046199A1 WO 2015046199 A1 WO2015046199 A1 WO 2015046199A1 JP 2014075187 W JP2014075187 W JP 2014075187W WO 2015046199 A1 WO2015046199 A1 WO 2015046199A1
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WO
WIPO (PCT)
Prior art keywords
heat
adhesive composition
magnetic adhesive
curable magnetic
epoxy resin
Prior art date
Application number
PCT/JP2014/075187
Other languages
French (fr)
Japanese (ja)
Inventor
悟 須藤
小野　義友
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201480052657.0A priority Critical patent/CN105579544B/en
Priority to KR1020167010475A priority patent/KR20160063354A/en
Priority to JP2015539232A priority patent/JPWO2015046199A1/en
Publication of WO2015046199A1 publication Critical patent/WO2015046199A1/en

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    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic 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
    • 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
    • C09J2301/304—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 the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the present invention relates to a heat-curable magnetic adhesive composition and a heat-curable magnetic adhesive sheet suitable for joining two or more adherends of which at least one is a ferromagnetic material, and a joined body using them. It relates to the manufacturing method of
  • an adhesive sheet is used to join a member such as a reinforcing material to a steel plate such as a door of an automobile, for example. If the adhesive sheet has a large adhesive strength at the initial stage of bonding, the adhesive sheet is difficult to reattach or the adhesive sheet can be reattached when the position of the member with respect to the steel plate is shifted. There is a problem that the adhesive of the above remains on the surface of the steel plate. Therefore, in the initial stage of bonding, there is a demand for an adhesive sheet having good workability which can be temporarily fixed without adhesive force and can be firmly bonded thereafter.
  • the adhesive sheet which consists of an adhesive composition containing acrylic rubber and magnetic powder may be used.
  • the adhesive sheet using acrylic rubber in this way has a low shear force, and there is a problem that the adhered members are shifted with time.
  • Patent Document 1 proposes an adhesive sheet using an adhesive composition containing a hot melt adhesive and a ferromagnetic material.
  • the adhesive sheet is interposed between one member made of a ferromagnetic material and another member made of a ferromagnetic material, and both members are temporarily fixed and then heated. Bond the two parts together.
  • the shear force is maintained high by using a hot melt adhesive.
  • the hot melt adhesive softens again and loses its adhesive strength, which causes a problem of low heat resistance.
  • An object of the present invention is to provide an adhesive composition, a heat-curable magnetic adhesive sheet, and a method for producing a joined body using them.
  • the present invention is heat-cured containing an acrylic polymer (A), an epoxy resin (B), a curing agent (C) and a ferromagnetic material (D).
  • Type magnetic adhesive composition wherein the epoxy resin (B) contains at least one selected from the group consisting of cresol novolac type epoxy resin, phenol novolac type epoxy resin and bisphenol type epoxy resin
  • the heat-curable magnetic adhesive composition is provided (Invention 1).
  • the magnetic force by the ferromagnetic material (D), and in some cases, the acrylic polymer (A) in the initial stage (before heat-curing) The adhesive strength (preferably fine adhesive strength) of the epoxy resin (B) before curing and before curing shows a good temporary fixing power to the ferromagnetic material. After the heat curing, the cured epoxy resin (B) has high adhesion and shear force. Further, the adhesive obtained by heat-hardening the above-mentioned heat-curable magnetic adhesive composition is excellent in heat resistance because it does not soften or melt even when it is reheated, particularly by the hardened epoxy resin (B).
  • the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is preferably 5 to 60% by volume (Invention 2).
  • the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is 100 parts by mass of the acrylic polymer (A) in terms of solid content. Preferably, it is 10 to 5000 parts by mass with respect to (Invention 3).
  • the content of the epoxy resin (B) in the heat-curable magnetic adhesive composition is 100 parts by mass of the acrylic polymer (A) in terms of solid content. On the other hand, it is preferably 5 to 3000 parts by mass (invention 4).
  • the curing agent (C) is preferably an amine curing agent (Invention 5).
  • the present invention provides a heat-curable magnetic adhesive sheet in which the heat-curable magnetic adhesive composition (inventions 1 to 5) is formed into a sheet (invention 6).
  • the thickness is preferably 0.1 to 5 mm (Invention 7).
  • a third aspect of the present invention is a method for producing a joined body obtained by joining two or more adherends of which at least one is a ferromagnetic material, wherein the heat-curable magnetic adhesive composition (invention 1) ⁇ 5) or the heat-curable magnetic adhesive sheet (inventions 6 and 7), the two or more adherends are temporarily fixed, and after the temporary fixing, the heat-curable magnetic adhesive
  • the present invention provides a method for producing a joined body, comprising heating the composition or the heat-curable magnetic adhesive sheet and bonding the two or more adherends (Invention 8).
  • the heat-curable magnetic adhesive composition and the heat-curable magnetic adhesive sheet according to the present invention show temporary fixing power by magnetic force in the initial stage, and also have high shear force after heat-hardening and heat resistance. Excellent. Moreover, according to the method of manufacturing a joined body according to the present invention, bonding work can be performed with excellent workability, and a joined body having high shear force and excellent heat resistance can be obtained.
  • the heat-curable magnetic adhesive composition according to the present embodiment (hereinafter sometimes simply referred to as "adhesive composition") comprises an acrylic polymer (A), an epoxy resin (B), and a cured product. It contains an agent (C) and a ferromagnetic substance (D).
  • the epoxy resin (B) contains at least one selected from the group consisting of cresol novolac epoxy resin, phenol novolac epoxy resin and bisphenol epoxy resin.
  • the heat-curable magnetic adhesive composition containing the above components has a magnetic force due to the ferromagnetic material (D), and in some cases, an acrylic polymer (A) and before curing.
  • the adhesive force (preferably minute adhesive force) of the epoxy resin (B) of the present invention shows a good temporary fixing force to the ferromagnetic material.
  • the cured epoxy resin (B) has high adhesion and shear force.
  • an adhesive obtained by heat-curing a heat-curable magnetic adhesive composition containing the above components, particularly an epoxy resin (B) is excellent in heat resistance because it does not soften or melt even if it is reheated. . Furthermore, by not melting, it is hard to produce thickness change by a line of magnetic force.
  • Acrylic polymer (A) An acrylic polymer (A) is a polymer which has (meth) acrylic acid ester as a main component as a monomer unit which comprises the said polymer.
  • (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester.
  • Other similar terms are also the same.
  • the acrylic polymer (A) contained in the heat-curable magnetic adhesive composition according to the present embodiment is preferably acrylic rubber.
  • “acrylic rubber” in the present specification means a homopolymer consisting of a constituent unit derived from (meth) acrylic acid ester, a copolymer consisting of a constituent unit derived from (meth) acrylic acid ester, A polymer selected from the group consisting of one or more selected from the group consisting of a copolymer of a constituent unit derived from (meth) acrylic acid ester and a constituent unit derived from a polymerizable monomer other than (meth) acrylic acid ester; Alternatively, it means a material containing a cross-linked reaction product of the polymer and a cross-linking agent (preferably a curing agent (C)) and having mechanical properties as a rubbery elastomer.
  • the heat-curable magnetic adhesive composition according to the present embodiment contains an acrylic rubber as the acrylic polymer (A), the heat-curable magnetic adhesive composition exhibits good flexibility.
  • the (meth) acrylic acid ester having an acrylic polymer (A) as a main component as a monomer unit constituting the polymer is a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group Is preferred.
  • a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group Is preferred By containing such (meth) acrylic acid alkyl ester, desired elasticity and / or tackiness (slight tackiness) can be expressed.
  • Examples of the (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n- (meth) acrylate.
  • (meth) acrylic acid ester having 1 to 8 carbon atoms, particularly 2 to 4 carbon atoms in the alkyl group is preferable, and ethyl (meth) acrylate and (meth) acrylate Particularly preferred is n-butyl acrylate. These may be used alone or in combination of two or more.
  • the acrylic polymer (A) preferably contains 50 to 100% by mass of (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer, particularly 75 It is preferable to contain up to 99% by mass, and more preferable to contain 92 to 98% by mass.
  • the acrylic polymer (A) contains a monomer having a functional group as a monomer unit constituting the polymer so as to impart desired properties to the adhesive composition to be obtained or the adhesive after curing.
  • the resulting acrylic polymer (A) is crosslinked by the crosslinking agent (curing agent (C)) (usually at the time of heat-forming of the adhesive composition), and has good elasticity. Demonstrate.
  • an acrylic polymer (A) having a crosslinked structure (three-dimensional network structure) formed thereon is bonded to the epoxy resin (B) via the curing agent (C) to be entangled with each other. It is estimated to be.
  • the cured adhesive exhibits excellent heat resistance.
  • a carboxyl group, a hydroxyl group, an epoxy group, halogen etc. are mentioned, for example.
  • the crosslinking agent preferably the curing agent (C)
  • a carboxyl group having high reactivity with an amine is preferred.
  • Examples of the monomer having a carboxyl group include, for example, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like, among which acrylic acid or methacrylic Acids are preferred and acrylic acid is particularly preferred. These may be used alone or in combination of two or more.
  • the acrylic polymer (A) preferably contains 0.1 to 10% by mass of a carboxyl group-containing monomer as a monomer unit constituting the polymer, In particular, the content is preferably 1 to 5% by mass, and more preferably 2 to 4% by mass.
  • crosslinking is favorably acquired as content of a carboxyl group-containing monomer is 0.1 mass% or more. Further, when the content of the carboxyl group-containing monomer is 10% by mass or less, the flexibility of the heat-curable magnetic adhesive composition can be well maintained even after crosslinking.
  • the acrylic polymer (A) is, as a monomer unit constituting the polymer, other monomers, for example, (meth) acrylic acid alkoxy alkyl ester such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like , Non-crosslinkable acrylamide such as acrylamide and methacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and other non-crosslinkable tertiary amino groups (Meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring such as cyclohexyl (meth) acrylate, etc. (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate, vinyl acetate, It may contain styrene or the like.
  • the polymerization mode of the acrylic polymer (A) may be a random copolymer or a block copolymer.
  • the mass average molecular weight (Mw) of the acrylic polymer (A) is preferably 500,000 to 2,500,000, particularly preferably 800,000 to 2,000,000, and still more preferably 1,000,000 to 1,500,000.
  • the mass mean molecular weight in this specification is a value of standard polystyrene conversion measured by gel permeation chromatography (GPC) method.
  • the mass average molecular weight of the acrylic polymer (A) is 500,000 or more, the tackiness of the obtained adhesive composition before curing is suppressed, and when the mass average molecular weight is 2,500,000 or less, the obtained curing is achieved.
  • the tack of the previous adhesive composition is such that it can be easily peeled off by hand. Therefore, the adhesive force suitable for temporary fixation can be acquired because the mass mean molecular weight of acrylic polymer (A) exists in said range.
  • the (acrylic polymer (A) may be used alone or in combination of two or more. .
  • Epoxy resin (B) The epoxy resin (B) contained in the heat-curable magnetic adhesive composition according to this embodiment contains at least one selected from the group consisting of cresol novolac epoxy resin, phenol novolac epoxy resin, and bisphenol epoxy resin. contains. Thereby, the adhesive after curing the adhesive composition exhibits desired adhesive strength, shear force and heat resistance.
  • cresol novolac epoxy resin for example, those represented by the following formula can be used. (Wherein n is an integer of 1 to 60)
  • the mass average molecular weight of the cresol novolac epoxy resin is preferably 1,000 to 10,000, and particularly preferably 1,500 to 5,000.
  • the epoxy equivalent is preferably 100 to 300 g / eq, and more preferably 200 to 230 g / eq.
  • those having a softening point of 30 to 150 ° C. are preferable, and those having a softening point of 50 to 100 ° C. are particularly preferable.
  • phenol novolac epoxy resin for example, those represented by the following formula can be used. (Wherein n is an integer of 1 to 60)
  • the phenol novolac epoxy resin preferably has a weight average molecular weight of 500 to 10,000, and more preferably 1,000 to 3,000.
  • the epoxy equivalent is preferably 100 to 300 g / eq, and more preferably 170 to 210 g / eq. Furthermore, those which are semisolid at normal temperature are preferable.
  • bisphenol-type epoxy resin examples include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin. Among them, bisphenol A-type epoxy resin is preferable.
  • n is an integer of 1 to 80
  • the bisphenol type epoxy resin preferably has a mass average molecular weight of 1,000 to 20,000, and particularly preferably 3,000 to 8,000.
  • the epoxy equivalent is preferably 400 to 1300 g / eq, and particularly preferably 700 to 1000 g / eq.
  • those having a softening point of 50 to 150 ° C. are preferable, and those having a softening point of 80 to 100 ° C. are particularly preferable.
  • cresol novolac epoxy resins and phenol novolac epoxy resins are preferable, and phenol novolac epoxy resins are particularly preferable.
  • the adhesive after curing exerts excellent adhesion and shear force, and the adhesive composition before curing is good Demonstrate flexibility.
  • the phenol novolac epoxy resin is semisolid at normal temperature, the effect of flexibility is remarkable.
  • the acrylic polymer (A) is an acrylic rubber, in particular, the combination with the acrylic rubber makes the adhesive composition more excellent in flexibility.
  • the sheet-like adhesive composition can be made to follow the three-dimensional curved surface well.
  • a bisphenol-type epoxy resin preferably, bisphenol A-type epoxy resin
  • the flexibility of the adhesive composition is secured by adjusting the amount to be small. can do.
  • said epoxy resin (B) can be used individually by 1 type or in combination of 2 or more types, in order to balance the tack force before hardening, and the shearing force after hardening, 2 or more types are used. It is particularly preferable to contain both an epoxy resin which is solid at normal temperature and an epoxy resin which is semi-solid at normal temperature.
  • the content of the epoxy resin (B) in the heat-curable magnetic adhesive composition according to the present embodiment is 5 to 3000 parts by mass relative to 100 parts by mass of the acrylic polymer (A) in terms of solid content. It is preferably 10 to 2000 parts by mass, and more preferably 30 to 500 parts by mass.
  • the said effect by the said epoxy resin (B) is exhibited favorably as content of an epoxy resin (B) is 5 mass parts or more. Moreover, it is suppressed that the elasticity by an acrylic polymer (A) is inhibited as content of an epoxy resin (B) is 3000 mass parts or less.
  • Hardening agent (C) The curing agent (C) contained in the heat-curable magnetic adhesive composition according to this embodiment can cure the epoxy resin (B) by heating.
  • the acrylic polymer (A) has a functional group that reacts with the curing agent (C)
  • the acrylic polymer (A) is crosslinked.
  • a compound having two or more functional groups capable of reacting with an epoxy group in one molecule is preferably used.
  • the functional group include phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, acid anhydride and the like. Among them, amino group and phenolic hydroxyl group are preferable, and amino group is particularly preferable. That is, as a curing agent (C), an amine curing agent and a phenol curing agent are preferable, and an amine curing agent is particularly preferable.
  • the amine curing agent has high reactivity with the epoxy resin (B), and also has high reactivity with the acrylic polymer (A) when the acrylic polymer (A) has a carboxyl group. Furthermore, the acrylic polymer (A) crosslinked by the amine curing agent is particularly excellent in heat resistance.
  • amine curing agents examples include dicyandiamide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylsulfone, aromatic amines such as m-phenylenediamine, m-xylylenediamine, etc. Dicyandiamide is preferred.
  • curing agent a phenol novolak resin, bisphenol A novolak resin, a triazine modified
  • curing agent (C) can be used individually by 1 type or in combination of 2 or more types.
  • the content of the curing agent (C) in the heat-curable magnetic adhesive composition according to the present embodiment is 0.02 to 15 parts by mass with respect to 100 parts by mass of the epoxy resin (B) in terms of solid content. And particularly preferably 0.1 to 10 parts by mass, and further preferably 0.3 to 4 parts by mass. Curing of the epoxy resin (B) (and crosslinking of the acrylic polymer (A)) is favorably achieved when the content of the curing agent (C) is 0.02 parts by mass or more. On the other hand, if the content of the curing agent (C) is too large, it may be unnecessarily left in the adhesive, which may be economically disadvantageous.
  • the heat-curable magnetic adhesive composition according to the present embodiment preferably contains a curing catalyst that accelerates or adjusts the reaction between the epoxy resin (B) and the curing agent (C). .
  • tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol
  • 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole
  • Organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine, etc.
  • Tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate and triphenyl phosphine tetraphenyl borate, etc. are mentioned.
  • imidazoles are preferable, and 2-phenyl-4,5-dihydroxymethylimidazole is particularly preferably used. These can be used singly or in combination of two or more.
  • the content of the curing catalyst in the heat-curable magnetic adhesive composition according to the present embodiment is 0 based on 100 parts by mass of the total amount of the epoxy resin (B) and the curing agent (C) in terms of solid content.
  • the content is preferably from 0.01 to 7 parts by mass, particularly preferably from 0.05 to 5 parts by mass, and further preferably from 0.15 to 2 parts by mass.
  • the ferromagnetic material (D) used for the heat-curable magnetic adhesive composition according to the present embodiment is a substance capable of having spontaneous magnetization without an external magnetic field, and also includes a ferrimagnetic material.
  • the ferromagnetic substance (D) include metals such as iron, nickel and cobalt, alloys thereof (for example, stainless steel) or oxides, strontium ferrite, barium ferrite, manganese zinc ferrite, nickel zinc ferrite, Magnetic materials such as ferrites such as copper-zinc ferrites, alnicos such as aluminum-nickel-cobalt alloys, and rare earths such as rare earths-transition metals (eg SmCo, SmFeN and NbFeB) may be mentioned.
  • ferrites are preferable, and strontium ferrite and barium ferrite are more preferable among them.
  • the ferromagnetic material (D) is preferably a powder (hereinafter referred to as "magnetic powder").
  • the average particle diameter of the magnetic powder is preferably 0.5 to 20 ⁇ m, particularly preferably 0.5 to 15 ⁇ m, and further preferably 1 to 5 ⁇ m.
  • the average particle size of the magnetic powder can be measured, for example, by the Coulter counter method.
  • the content of the ferromagnetic material (D) (magnetic powder) in the heat-curable magnetic adhesive composition according to the present embodiment is preferably 5 to 60% by volume, particularly 10 to 50% by volume It is preferably 20 to 40% by volume.
  • the content of the ferromagnetic material (D) is 5% by volume or more, the temporary fixing force to the ferromagnetic material is exerted by the magnetic force of the ferromagnetic material (D) in the initial stage (before heat curing).
  • the content of the ferromagnetic substance (D) is 60% by volume or less, inhibition of the action and effect by the other components, in particular, the flexibility and the shear force is suppressed.
  • the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition according to the present embodiment is 10 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer (A) in terms of solid content.
  • the amount is preferably 5000 parts by mass, particularly preferably 50 to 2000 parts by mass, and still more preferably 150 to 700 parts by mass.
  • the content of the ferromagnetic material (D) is 10 parts by mass or more, the temporary fixing force to the ferromagnetic material is exerted by the magnetic force of the ferromagnetic material (D) in the initial stage (before heat curing).
  • the content of the ferromagnetic material (D) is 5000 parts by mass or less, the flexibility is good without the hardness being too high, and a sufficient shearing force can be maintained.
  • the heat-curable magnetic adhesive composition according to the present embodiment is, for example, one of a crosslinking agent, a tackifier, an antioxidant, a filler, and a dispersing agent, in addition to the above components. You may contain the above suitably.
  • the curing agent (C), the ferromagnetic material (D), preferably the curing catalyst, and, if desired, other components may be blended and mixed. At this time, the components are well dispersed by heating the mixture at about 20 to 120.degree.
  • the ferromagnetic material (D) mixed with the heat-curable magnetic adhesive composition as described above may be in a magnetized state or may not be in a magnetized state. Good. In the latter case, after mixing, after the adhesive composition is obtained, it may be magnetized (magnetized).
  • the magnetization can be performed by a known method, for example, using a commercially available magnetization / demagnetization power supply or the like.
  • the heat-curable magnetic adhesive composition according to the present embodiment has a magnetic force at an initial stage (before heat-curing). And, in some cases, adhesion (preferably, fine adhesion), exhibit excellent temporary fixation to ferromagnetic materials. And the adhesive agent formed by heat-hardening the heat-hardenable-type magnetically sensitive adhesive composition which concerns on this embodiment shows high shear force. In addition, the adhesive does not soften or melt even if it is reheated, so it is excellent in heat resistance, and furthermore, the thickness change due to the magnetic lines of force does not occur.
  • the heat-curable magnetic adhesive composition according to the present embodiment contains an acrylic rubber as the acrylic polymer (A) and a semi-solid one at room temperature as the epoxy resin (B), it forms a sheet. When you do, you can make it follow a three-dimensional curved surface.
  • the heat-curable magnetic adhesive composition according to the present embodiment is used to join two or more members (adhered members) at least one of which is a ferromagnetic material.
  • a member made of a material exhibiting ferromagnetism a member made of a material containing iron, cobalt, nickel or the like can be mentioned.
  • the heat-curable magnetic adhesive composition according to the present embodiment is suitably used for a part that is at a high temperature, because the heat resistance after curing is high.
  • automotive parts such as automobile door and body steel plates, hole sealing plates of steel plates, reinforcing parts of car bodies, particularly in the vicinity of heat generating parts such as engines and exhaust pipes; in structures such as buildings It is suitably used for steel parts; metal parts for precision instruments, electronic instruments, etc., particularly in the vicinity of heat-generating parts in those instruments.
  • the heat-curable magnetic adhesive composition according to the present embodiment can be formed into a predetermined shape required to join the members as described above.
  • the shape include various shapes such as triangles, quadrilaterals, polygons such as pentagons, hexagons and octagons, circles such as circles and ovals, and ring-like shapes from which the central part of these shapes is removed.
  • sheet-like bodies of a shape corresponding to the heat-curable magnetic adhesive sheet of the present invention
  • plate-like bodies block-like bodies, columnar bodies, rod-like bodies and the like.
  • the acrylic polymer (A) of the heat-curable magnetic adhesive composition according to the present embodiment has a functional group that reacts with the cross-linking agent (hardening agent (C)), the heat-curable type When the magnetic adhesive composition is thermoformed, the acrylic polymer (A) is crosslinked.
  • the heating temperature at this time is preferably 20 to 120 ° C., particularly preferably 40 to 80 ° C.
  • the heating temperature when bonding the adherend with the heat-curable magnetic adhesive composition according to the present embodiment is preferably 70 to 250 ° C., particularly preferably 130 to 200 ° C. By heating at such a temperature, the heat-curable magnetic adhesive composition according to the present embodiment is cured to exhibit high adhesive strength, thereby firmly bonding the adherend.
  • the heat-curable magnetic adhesive sheet according to the present embodiment is a sheet of the heat-curable magnetic adhesive composition.
  • the thickness of the heat-curable magnetic adhesive sheet is preferably 0.1 to 5 mm, particularly 0.2 to 3 mm, and more preferably 0. It is preferably 3 to 2 mm.
  • the method for producing the heat-curable magnetic adhesive sheet according to the present embodiment is not particularly limited, but can be preferably produced by hot pressing the heat-curable magnetic adhesive composition.
  • the temperature of the hot press is preferably 20 to 120 ° C., particularly preferably 40 to 80 ° C.
  • the acrylic polymer (A) of the heat-curable magnetic adhesive composition according to the present embodiment has a functional group that reacts with the crosslinking agent (curing agent (C))
  • the above-mentioned hot is crosslinked by pressing.
  • the release sheet is laminated on both sides of the heat-curable magnetic adhesive sheet obtained when hot pressing as described above, the heat-curable magnetic adhesive composition is sandwiched between two release sheets. It is preferable to do.
  • the release sheet may be a release sheet subjected to double-sided release treatment, or may be a release sheet subjected to single-side release treatment. The release sheet is used such that the release treated surface is on the side of the heat-curable magnetic adhesive sheet.
  • the above-mentioned release sheet is, for example, a polyester resin film such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, a plastic film such as polyolefin resin film such as polypropylene resin or polyethylene resin, glassine paper, coated paper, What apply
  • coats release agents, such as a silicone resin, etc. is used for the lamination paper etc. which laminated thermoplastic resins, such as polyethylene, on paper base materials, such as a high quality paper.
  • the thickness of the release sheet is not particularly limited, but is preferably 20 to 200 ⁇ m in general.
  • the heat-curable magnetic adhesive sheet according to the present embodiment has high adhesion after heat-hardening, and does not soften / melt even after reheating, so it is excellent in heat resistance. Furthermore, by not melting after heat curing, the thickness change due to the magnetic lines of force does not occur.
  • the shear force after heat bonding of the heat-curable magnetic adhesive sheet according to the present embodiment is preferably 80 N / cm 2 or more, particularly preferably 120 N / cm 2 or more, and further preferably 200 N / cm. It is preferable that it is two or more.
  • one surface of the heat-curable magnetic adhesive sheet is attached to a stainless steel plate (0.5 mm in thickness), and the other surface is another stainless steel plate. After sticking to (thickness 0.5 mm) and heating at 150 ° C. for 40 minutes, it is returned to normal temperature and refers to a shear force measured according to JIS K 6850 (testing speed 50 mm / min).
  • the heat-curable magnetic adhesive sheet according to the present embodiment can achieve high shear force as described above when the heat-curable magnetic adhesive composition contains the epoxy resin (B). . According to the heat-curable magnetic adhesive sheet having such a shearing force, it is possible to effectively suppress that the adhered members are shifted with time or the like.
  • the heat-curable magnetic adhesive sheet according to the present embodiment preferably has a surface magnetic force of 1 mT or more at normal temperature, particularly preferably 3 to 100 mT, and more preferably 5 to 50 mT.
  • the surface magnetic force in the present specification refers to the surface magnetic force measured by a gauss meter at a distance of 1 cm from the surface of the heat-curable magnetic adhesive sheet having a thickness of 1 mm. If the surface magnetic force is 1 mT or more, temporary fixing can be performed sufficiently on a member made of a ferromagnetic material. Further, if the surface magnetic force is 100 mT or less, repositioning can be easily performed even if the temporarily fixed position is deviated from the predetermined position.
  • the heat-curable magnetic adhesive sheet according to this embodiment preferably has a bending resistance of 10 to 2,000 mN, particularly preferably 50 to 1,500 mN, and further preferably 100 to 800 mN.
  • the bending resistance in the present specification refers to JIS L 1096 (1999) 8.20., Using a bending resistance tester, for a heat-curable magnetic adhesive sheet having a length of 38 mm and a width of 25 mm. It refers to the bending resistance measured according to the Gurley method of 1.
  • the heat-curable magnetic adhesive composition contains the acrylic rubber as the acrylic polymer (A) to obtain the above-mentioned hardness and hardness. Can be achieved.
  • the heat-curable magnetic adhesive sheet having such a bending resistance exhibits excellent flexibility, and even if the adherend has a three-dimensional curved surface, it adheres to the adherend and adheres reliably. can do.
  • the heat-curable magnetic adhesive sheet according to the present embodiment can also be used for the same application as the above-described heat-curable magnetic adhesive composition.
  • the method for producing a joined body according to the present embodiment is a method for producing a joined body by joining two or more adherends of which at least one is made of a ferromagnetic material. First, two or more adherends are temporarily fixed using the above-mentioned heat-curable magnetic adhesive composition or heat-curable magnetic adhesive sheet, and then the above-mentioned heat-curable magnetic adhesive The composition or the heat-curable magnetic adhesive sheet is heated to bond the two or more adherends. More specifically, the following method is exemplified.
  • a method of bonding a first member made of a ferromagnetic material and a second member made of a ferromagnetic material, with the above-mentioned heat-curable magnetic adhesive sheet interposed between the bonding surfaces thereof Will be explained.
  • a heat-curable magnetically attachable adhesive sheet having the shape of the joint surface between the first member and the second member is prepared.
  • the heat-curable magnetic adhesive sheet is held between the joining surfaces of two members, and the first member and the second member are separated by the magnetic force (and adhesive force) of the heat-curable magnetic adhesive sheet. Temporarily fix. This improves the workability.
  • the heat-curable magnetic adhesive sheet is heated and then cooled to firmly bond the first member and the second member to obtain a joined body.
  • the shapes of the first member and the second member are not particularly limited.
  • a method of bonding a first member and a second member made of a ferromagnetic material with a heat-curable magnetic adhesive composition interposed therebetween on a bonding surface thereof will be described.
  • an adhesive portion made of a heat-curable magnetic adhesive composition is formed on a first member.
  • a heat-curable magnetic adhesive composition may be applied to the first member, or the first member with respect to the heat-curable magnetic adhesive composition. May be stacked.
  • the first member may or may not be ferromagnetic.
  • the adhesive portion formed on the first member is adsorbed to the second member by the magnetic force (and adhesive force) of the adhesive portion, and the first member and the second member are temporarily fixed. . This improves the workability. Then, the heat-curable magnetic adhesive composition is heated and then cooled to strongly bond the first member and the second member to obtain a joined body.
  • the adhesive in the joined body obtained as described above has high adhesion and shear force, and does not soften / melt even after reheating, so it is also excellent in heat resistance. Furthermore, since the adhesive does not melt, no thickness change occurs due to magnetic lines of force.
  • Example 1 As acrylic polymer (A), ethyl acrylate (EA), n-butyl (meth) acrylate (BA), and acrylic acid (AA) are copolymerized at a mass ratio of 37: 60: 3. An acrylic rubber having a mass average molecular weight of 1,300,000 and a molecular weight distribution of 2.70 was prepared.
  • release sheet two release sheets (made by Lintec Co., Ltd., product name “SP-PET 381130, thickness: 38 ⁇ m) were prepared in which one side of a polyethylene terephthalate film was release-treated with a silicone release agent.
  • the heat-curable magnetic adhesive composition obtained above is sandwiched between the two release sheets, and the release-treated surface of the release sheet is in contact with the heat-curable magnetic adhesive composition.
  • Examples 2-28, Comparative Examples 1-2 The same procedure as in Example 1 was carried out except that the types and blending amounts of the components constituting the heat-curable magnetic adhesive composition and the thickness of the heat-curable magnetic adhesive sheet were changed as shown in Table 1. A heat-curable magnetic adhesive sheet was produced.
  • two types of epoxy resins (B) epoxy resin (B) -1 and epoxy resin (B) -2) were used.
  • Test Example 2 (Surface Magnetic Force Measurement) A gauss meter (Toyo Technica Co., Ltd.) at a distance of 1 cm from the surface of the heat-curable magnetic adhesive sheet obtained by peeling one release sheet from the heat-curable magnetic adhesive sheet obtained in Examples and Comparative Examples. The surface magnetic force (mT) at room temperature was measured by a product name “5080 Handy Gauss Meter”. The results are shown in Table 1.
  • the heat-curable magnetic adhesive sheet obtained in the examples had a good surface magnetic force and exhibited high shear force after heat-hardening.
  • the heat-curable magnetic adhesive sheet obtained in Examples 1 to 23 and 25 to 28 had a low bending resistance and was excellent in flexibility.
  • the present invention can be suitably used to bond a member and a member made of a ferromagnetic material, or to bond members made of a ferromagnetic material to each other.

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  • Organic Chemistry (AREA)
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Abstract

　Provided is a thermal curing-type magnetizable adhesive composition containing an acrylic polymer (A), an epoxy resin (B), a curing agent (C), and a ferromagnetic body (D), the epoxy resin (B) including at least one type selected from the group consisting of cresol novolac epoxy resins, phenol novolac epoxy resins, and bisphenol novolac epoxy resins. In the initial stage, this thermal curing-type magnetizable adhesive composition exhibits temporary fixing power due to magnetic attraction, and after being thermally cured, has high shear force, and exceptional heat resistance as well.

Description

加熱硬化型磁着性接着剤組成物および接着シートHeat-curable magnetic adhesive composition and adhesive sheet
　本発明は、少なくとも一つが強磁性材料からなる２以上の被接着体の接合に適した加熱硬化型磁着性接着剤組成物および加熱硬化型磁着性接着シート、ならびにそれらを使用した接合体の製造方法に関するものである。 The present invention relates to a heat-curable magnetic adhesive composition and a heat-curable magnetic adhesive sheet suitable for joining two or more adherends of which at least one is a ferromagnetic material, and a joined body using them. It relates to the manufacturing method of
　従来より、例えば自動車のドア等の鋼板に、補強材等の部材を接合するのに、接着シートが使用されている。この接着シートが貼合の初期段階において大きな接着力を有していると、鋼板に対する部材の位置合わせがずれた場合に、貼り直しが困難であったり、貼り直しができたとしても、接着シートの接着剤が鋼板の表面に残ったりする問題がある。したがって、貼合の初期段階において、接着力によることなく仮固定することができ、その後、強固に接着することのできる、作業性の良好な接着シートが求められている。 Conventionally, an adhesive sheet is used to join a member such as a reinforcing material to a steel plate such as a door of an automobile, for example. If the adhesive sheet has a large adhesive strength at the initial stage of bonding, the adhesive sheet is difficult to reattach or the adhesive sheet can be reattached when the position of the member with respect to the steel plate is shifted. There is a problem that the adhesive of the above remains on the surface of the steel plate. Therefore, in the initial stage of bonding, there is a demand for an adhesive sheet having good workability which can be temporarily fixed without adhesive force and can be firmly bonded thereafter.
　そこで、アクリルゴムと磁性粉とを含有する接着剤組成物からなる接着シートが用いられることがある。しかしながら、このようにアクリルゴムを使用した接着シートは、せん断力が低く、経時により、接着した部材同士がずれてきてしまうという問題が生じる。 Then, the adhesive sheet which consists of an adhesive composition containing acrylic rubber and magnetic powder may be used. However, the adhesive sheet using acrylic rubber in this way has a low shear force, and there is a problem that the adhered members are shifted with time.
　これに対し、特許文献１では、ホットメルト接着剤と強磁性体とを含有する接着剤組成物を使用した接着シートが提案されている。かかる接着シートを使用するには、強磁性材料からなる一の部材と、強磁性材料からなる他の部材との間に上記接着シートを介在させて、両部材を仮止めした後、加熱することにより、両部材を互いに接着する。 On the other hand, Patent Document 1 proposes an adhesive sheet using an adhesive composition containing a hot melt adhesive and a ferromagnetic material. In order to use such an adhesive sheet, the adhesive sheet is interposed between one member made of a ferromagnetic material and another member made of a ferromagnetic material, and both members are temporarily fixed and then heated. Bond the two parts together.
国際公開ＷＯ２００９／１１９８８５号公報International Publication WO2009 / 19885
　上記の接着シートでは、ホットメルト接着剤を使用することにより、せん断力は高く維持される。しかしながら、接着部材が高温下におかれると、ホットメルト接着剤は再度軟化して接着力を喪失してしまうため、耐熱性が低いという問題がある。 In the above adhesive sheet, the shear force is maintained high by using a hot melt adhesive. However, when the adhesive member is placed under high temperature, the hot melt adhesive softens again and loses its adhesive strength, which causes a problem of low heat resistance.
　本発明は、このような実状に鑑みてなされたものであり、初期段階では磁力により仮固定力を示すとともに、加熱硬化後にはせん断力が高く、耐熱性にも優れた加熱硬化型磁着性接着剤組成物および加熱硬化型磁着性接着シート、ならびにそれらを使用した接合体の製造方法を提供することを目的とする。 The present invention has been made in view of such a situation, and in the initial stage, a temporary fixing force is exhibited by a magnetic force, and a heat curing type magnetic attachment having high shear force after heat curing and excellent heat resistance. An object of the present invention is to provide an adhesive composition, a heat-curable magnetic adhesive sheet, and a method for producing a joined body using them.
　上記目的を達成するために、第１に本発明は、アクリル系重合体（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）と、強磁性体（Ｄ）とを含有する加熱硬化型磁着性接着剤組成物であって、前記エポキシ樹脂（Ｂ）が、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂およびビスフェノール型エポキシ樹脂からなる群から選ばれる少なくとも一種を含有することを特徴とする加熱硬化型磁着性接着剤組成物を提供する（発明１）。 In order to achieve the above object, firstly, the present invention is heat-cured containing an acrylic polymer (A), an epoxy resin (B), a curing agent (C) and a ferromagnetic material (D). Type magnetic adhesive composition, wherein the epoxy resin (B) contains at least one selected from the group consisting of cresol novolac type epoxy resin, phenol novolac type epoxy resin and bisphenol type epoxy resin The heat-curable magnetic adhesive composition is provided (Invention 1).
　上記発明（発明１）に係る加熱硬化型磁着性接着剤組成物によれば、初期段階（加熱硬化前）では、強磁性体（Ｄ）による磁力、ならびに場合によってはアクリル系重合体（Ａ）および硬化前のエポキシ樹脂（Ｂ）による粘着力（好ましくは微小な粘着力）により、強磁性材料に対して良好な仮固定力を示す。そして、加熱硬化後には、硬化したエポキシ樹脂（Ｂ）により、接着力およびせん断力が高いものとなる。また、上記加熱硬化型磁着性接着剤組成物を加熱硬化してなる接着剤は、特に硬化したエポキシ樹脂（Ｂ）により、再加熱しても軟化・溶融しないため、耐熱性に優れる。 According to the heat-curable magnetic adhesive composition according to the above invention (Invention 1), the magnetic force by the ferromagnetic material (D), and in some cases, the acrylic polymer (A) in the initial stage (before heat-curing) The adhesive strength (preferably fine adhesive strength) of the epoxy resin (B) before curing and before curing shows a good temporary fixing power to the ferromagnetic material. After the heat curing, the cured epoxy resin (B) has high adhesion and shear force. Further, the adhesive obtained by heat-hardening the above-mentioned heat-curable magnetic adhesive composition is excellent in heat resistance because it does not soften or melt even when it is reheated, particularly by the hardened epoxy resin (B).
　上記発明（発明１）において、前記加熱硬化型磁着性接着剤組成物中における前記強磁性体（Ｄ）の含有量は、５～６０体積％であることが好ましい（発明２）。 In the above invention (Invention 1), the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is preferably 5 to 60% by volume (Invention 2).
　上記発明（発明１，２）において、前記加熱硬化型磁着性接着剤組成物中における前記強磁性体（Ｄ）の含有量は、固形分換算で前記アクリル系重合体（Ａ）１００質量部に対して、１０～５０００質量部であることが好ましい（発明３）。 In the above inventions (Inventions 1 and 2), the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is 100 parts by mass of the acrylic polymer (A) in terms of solid content. Preferably, it is 10 to 5000 parts by mass with respect to (Invention 3).
　上記発明（発明１～３）において、前記加熱硬化型磁着性接着剤組成物中における前記エポキシ樹脂（Ｂ）の含有量は、固形分換算で前記アクリル系重合体（Ａ）１００質量部に対して、５～３０００質量部であることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the content of the epoxy resin (B) in the heat-curable magnetic adhesive composition is 100 parts by mass of the acrylic polymer (A) in terms of solid content. On the other hand, it is preferably 5 to 3000 parts by mass (invention 4).
　上記発明（発明１～４）において、前記硬化剤（Ｃ）は、アミン系硬化剤であることが好ましい（発明５）。 In the above inventions (Inventions 1 to 4), the curing agent (C) is preferably an amine curing agent (Invention 5).
　第２に本発明は、前記加熱硬化型磁着性接着剤組成物（発明１～５）をシート化した加熱硬化型磁着性接着シートを提供する（発明６）。 Second, the present invention provides a heat-curable magnetic adhesive sheet in which the heat-curable magnetic adhesive composition (inventions 1 to 5) is formed into a sheet (invention 6).
　上記発明（発明６）においては、厚さが０．１～５ｍｍであることが好ましい（発明７）。 In the above invention (Invention 6), the thickness is preferably 0.1 to 5 mm (Invention 7).
　第３に本発明は、少なくとも一つが強磁性材料からなる２以上の被接着体を接合して得られる接合体の製造方法であって、前記加熱硬化型磁着性接着剤組成物（発明１～５）または前記加熱硬化型磁着性接着シート（発明６，７）を使用して、前記２以上の被接着体を仮固定し、前記仮固定後に、前記加熱硬化型磁着性接着剤組成物または前記加熱硬化型磁着性接着シートを加熱し、前記２以上の被接着体を接合することを特徴とする接合体の製造方法を提供する（発明８）。 A third aspect of the present invention is a method for producing a joined body obtained by joining two or more adherends of which at least one is a ferromagnetic material, wherein the heat-curable magnetic adhesive composition (invention 1) ~ 5) or the heat-curable magnetic adhesive sheet (inventions 6 and 7), the two or more adherends are temporarily fixed, and after the temporary fixing, the heat-curable magnetic adhesive The present invention provides a method for producing a joined body, comprising heating the composition or the heat-curable magnetic adhesive sheet and bonding the two or more adherends (Invention 8).
　本発明に係る加熱硬化型磁着性接着剤組成物および加熱硬化型磁着性接着シートは、初期段階では磁力により仮固定力を示すとともに、加熱硬化後にはせん断力が高く、耐熱性にも優れる。また、本発明に係る接合体の製造方法によれば、優れた作業性で接着作業を行うことができるとともに、せん断力が高く、耐熱性に優れた接合体を得ることができる。 The heat-curable magnetic adhesive composition and the heat-curable magnetic adhesive sheet according to the present invention show temporary fixing power by magnetic force in the initial stage, and also have high shear force after heat-hardening and heat resistance. Excellent. Moreover, according to the method of manufacturing a joined body according to the present invention, bonding work can be performed with excellent workability, and a joined body having high shear force and excellent heat resistance can be obtained.
　以下、本発明の実施形態について説明する。
〔加熱硬化型磁着性接着剤組成物〕
　本実施形態に係る加熱硬化型磁着性接着剤組成物（以下、単に「接着剤組成物」という場合がある。）は、アクリル系重合体（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）と、強磁性体（Ｄ）とを含有する。そして、エポキシ樹脂（Ｂ）は、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂およびビスフェノール型エポキシ樹脂からなる群から選ばれる少なくとも一種を含有する。 Hereinafter, embodiments of the present invention will be described.
[Heat-curable magnetic adhesive composition]
The heat-curable magnetic adhesive composition according to the present embodiment (hereinafter sometimes simply referred to as "adhesive composition") comprises an acrylic polymer (A), an epoxy resin (B), and a cured product. It contains an agent (C) and a ferromagnetic substance (D). The epoxy resin (B) contains at least one selected from the group consisting of cresol novolac epoxy resin, phenol novolac epoxy resin and bisphenol epoxy resin.
　上記の成分を含有する加熱硬化型磁着性接着剤組成物は、初期段階（加熱硬化前）では、強磁性体（Ｄ）による磁力、ならびに場合によってはアクリル系重合体（Ａ）および硬化前のエポキシ樹脂（Ｂ）による粘着力（好ましくは微小な粘着力）により、強磁性材料に対して良好な仮固定力を示す。そして、加熱硬化後には、硬化したエポキシ樹脂（Ｂ）により、接着力およびせん断力が高いものとなる。また、上記の成分、特にエポキシ樹脂（Ｂ）を含有する加熱硬化型磁着性接着剤組成物を加熱硬化してなる接着剤は、再加熱しても軟化・溶融しないため、耐熱性に優れる。さらには、溶融しないことで、磁力線による肉厚変化が生じにくい。 In the initial stage (before heat curing), the heat-curable magnetic adhesive composition containing the above components has a magnetic force due to the ferromagnetic material (D), and in some cases, an acrylic polymer (A) and before curing. The adhesive force (preferably minute adhesive force) of the epoxy resin (B) of the present invention shows a good temporary fixing force to the ferromagnetic material. After the heat curing, the cured epoxy resin (B) has high adhesion and shear force. In addition, an adhesive obtained by heat-curing a heat-curable magnetic adhesive composition containing the above components, particularly an epoxy resin (B), is excellent in heat resistance because it does not soften or melt even if it is reheated. . Furthermore, by not melting, it is hard to produce thickness change by a line of magnetic force.
（１）アクリル系重合体（Ａ）
　アクリル系重合体（Ａ）は、当該重合体を構成するモノマー単位として、（メタ）アクリル酸エステルを主成分とする重合体である。なお、本明細書における「重合体」には「共重合体」の概念も含まれるものとする。また、本明細書において、（メタ）アクリル酸エステルとは、アクリル酸エステル及びメタクリル酸エステルの両方を意味する。他の類似用語も同様である。 (1) Acrylic polymer (A)
An acrylic polymer (A) is a polymer which has (meth) acrylic acid ester as a main component as a monomer unit which comprises the said polymer. In addition, the concept of a "copolymer" shall also be included in the "polymer" in this specification. Moreover, in this specification, (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. Other similar terms are also the same.
　本実施形態に係る加熱硬化型磁着性接着剤組成物が含有するアクリル系重合体（Ａ）は、アクリルゴムであることが好ましい。ここで、本明細書における「アクリルゴム」とは、（メタ）アクリル酸エステルに由来する構成単位からなる単独重合体、（メタ）アクリル酸エステルに由来する構成単位からなる共重合体、および（メタ）アクリル酸エステルに由来する構成単位と（メタ）アクリル酸エステル以外の重合性モノマーに由来する構成単位との共重合体からなる群から選ばれる１種または２種以上からなる重合体および／またはその重合体と架橋剤（好ましくは硬化剤（Ｃ））との架橋反応生成物を含有し、ゴム状弾性体としての機械的性質を有する材料を意味する。本実施形態に係る加熱硬化型磁着性接着剤組成物が、アクリル系重合体（Ａ）としてアクリルゴムを含有すると、当該加熱硬化型磁着性接着剤組成物は、良好な柔軟性を発揮し得る。なお、アクリルゴムは、通常粘着力は殆どないか、微小な粘着力を有する。 The acrylic polymer (A) contained in the heat-curable magnetic adhesive composition according to the present embodiment is preferably acrylic rubber. Here, “acrylic rubber” in the present specification means a homopolymer consisting of a constituent unit derived from (meth) acrylic acid ester, a copolymer consisting of a constituent unit derived from (meth) acrylic acid ester, A polymer selected from the group consisting of one or more selected from the group consisting of a copolymer of a constituent unit derived from (meth) acrylic acid ester and a constituent unit derived from a polymerizable monomer other than (meth) acrylic acid ester; Alternatively, it means a material containing a cross-linked reaction product of the polymer and a cross-linking agent (preferably a curing agent (C)) and having mechanical properties as a rubbery elastomer. When the heat-curable magnetic adhesive composition according to the present embodiment contains an acrylic rubber as the acrylic polymer (A), the heat-curable magnetic adhesive composition exhibits good flexibility. It can. Acrylic rubber usually has little or no adhesion.
　アクリル系重合体（Ａ）が、当該重合体を構成するモノマー単位として主成分とする（メタ）アクリル酸エステルは、アルキル基の炭素数が１～２０の（メタ）アクリル酸アルキルエステルであることが好ましい。かかる（メタ）アクリル酸アルキルエステルを含有することで、所望の弾性および／または粘着性（微粘着性）を発現することができる。 The (meth) acrylic acid ester having an acrylic polymer (A) as a main component as a monomer unit constituting the polymer is a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group Is preferred. By containing such (meth) acrylic acid alkyl ester, desired elasticity and / or tackiness (slight tackiness) can be expressed.
　アルキル基の炭素数が１～２０の（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、（メタ）アクリル酸ステアリル等が挙げられる。中でも、弾性および微粘着性をより望ましいものとするために、アルキル基の炭素数が１～８、特に２～４の（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸エチルおよび（メタ）アクリル酸ｎ－ブチルが特に好ましい。なお、これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n- (meth) acrylate. Butyl, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, (meth) acrylate Examples include n-dodecyl, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate and the like. Among them, in order to make elasticity and slight tackiness more desirable, (meth) acrylic acid ester having 1 to 8 carbon atoms, particularly 2 to 4 carbon atoms in the alkyl group is preferable, and ethyl (meth) acrylate and (meth) acrylate Particularly preferred is n-butyl acrylate. These may be used alone or in combination of two or more.
　アクリル系重合体（Ａ）は、当該重合体を構成するモノマー単位として、アルキル基の炭素数が１～２０の（メタ）アクリル酸アルキルエステルを５０～１００質量％含有することが好ましく、特に７５～９９質量％含有することが好ましく、さらには９２～９８質量％含有することが好ましい。 The acrylic polymer (A) preferably contains 50 to 100% by mass of (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer, particularly 75 It is preferable to contain up to 99% by mass, and more preferable to contain 92 to 98% by mass.
　アクリル系重合体（Ａ）は、得られる接着剤組成物または硬化後の接着剤に所望の物性が付与されるように、当該重合体を構成するモノマー単位として、官能基を有するモノマーを含有してもよく、特に、架橋剤（好ましくは硬化剤（Ｃ））と反応する官能基を有するモノマー（官能基含有モノマー）を含有することが好ましい。かかる官能基含有モノマーを含有することにより、得られるアクリル系重合体（Ａ）は、架橋剤（硬化剤（Ｃ））によって架橋され（通常は接着剤組成物の加熱成形時）、良好な弾性を発揮する。また、硬化後の接着剤においては、架橋構造（三次元網目構造）を形成したアクリル系重合体（Ａ）が、硬化剤（Ｃ）を介してエポキシ樹脂（Ｂ）と結合し、絡まり合うものと推定される。かかる構造により、硬化後の接着剤は、優れた耐熱性を発揮する。 The acrylic polymer (A) contains a monomer having a functional group as a monomer unit constituting the polymer so as to impart desired properties to the adhesive composition to be obtained or the adhesive after curing. In particular, it is preferable to contain a monomer (functional group-containing monomer) having a functional group that reacts with the crosslinking agent (preferably, the curing agent (C)). By containing such a functional group-containing monomer, the resulting acrylic polymer (A) is crosslinked by the crosslinking agent (curing agent (C)) (usually at the time of heat-forming of the adhesive composition), and has good elasticity. Demonstrate. In addition, in the adhesive after curing, an acrylic polymer (A) having a crosslinked structure (three-dimensional network structure) formed thereon is bonded to the epoxy resin (B) via the curing agent (C) to be entangled with each other. It is estimated to be. By this structure, the cured adhesive exhibits excellent heat resistance.
　上記官能基含有モノマーの官能基の種類としては、例えば、カルボキシル基、水酸基、エポキシ基、ハロゲン等が挙げられる。特に、架橋剤（好ましくは硬化剤（Ｃ））がアミン系硬化剤の場合には、アミンと反応性の高いカルボキシル基が好ましい。 As a kind of functional group of the said functional group containing monomer, a carboxyl group, a hydroxyl group, an epoxy group, halogen etc. are mentioned, for example. In particular, when the crosslinking agent (preferably the curing agent (C)) is an amine curing agent, a carboxyl group having high reactivity with an amine is preferred.
　カルボキシル基を有するモノマー（カルボキシル基含有モノマー）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸等のエチレン性不飽和カルボン酸が挙げられ、中でもアクリル酸またはメタクリル酸が好ましく、アクリル酸が特に好ましい。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the monomer having a carboxyl group (carboxyl group-containing monomer) include, for example, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like, among which acrylic acid or methacrylic Acids are preferred and acrylic acid is particularly preferred. These may be used alone or in combination of two or more.
　硬化剤（Ｃ）がアミン系硬化剤の場合、アクリル系重合体（Ａ）は、当該重合体を構成するモノマー単位として、カルボキシル基含有モノマーを０．１～１０質量％含有することが好ましく、特に１～５質量％含有することが好ましく、さらには２～４質量％含有することが好ましい。カルボキシル基含有モノマーの含有量が０．１質量％以上であると、架橋による上記効果が良好に得られる。また、カルボキシル基含有モノマーの含有量が１０質量％以下であると、架橋後にも加熱硬化型磁着性接着剤組成物の柔軟性が良好に維持され得る。 When the curing agent (C) is an amine curing agent, the acrylic polymer (A) preferably contains 0.1 to 10% by mass of a carboxyl group-containing monomer as a monomer unit constituting the polymer, In particular, the content is preferably 1 to 5% by mass, and more preferably 2 to 4% by mass. The said effect by bridge | crosslinking is favorably acquired as content of a carboxyl group-containing monomer is 0.1 mass% or more. Further, when the content of the carboxyl group-containing monomer is 10% by mass or less, the flexibility of the heat-curable magnetic adhesive composition can be well maintained even after crosslinking.
　アクリル系重合体（Ａ）は、当該重合体を構成するモノマー単位として、その他のモノマー、例えば、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル等の（メタ）アクリル酸アルコキシアルキルエステル、アクリルアミド、メタクリルアミド等の非架橋性のアクリルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノプロピル等の非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル、（メタ）アクリル酸シクロヘキシル等の脂肪族環を有する（メタ）アクリル酸エステル、（メタ）アクリル酸フェニル等の芳香族環を有する（メタ）アクリル酸エステル、酢酸ビニル、スチレンなどを含有してもよい。 The acrylic polymer (A) is, as a monomer unit constituting the polymer, other monomers, for example, (meth) acrylic acid alkoxy alkyl ester such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like , Non-crosslinkable acrylamide such as acrylamide and methacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and other non-crosslinkable tertiary amino groups (Meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring such as cyclohexyl (meth) acrylate, etc. (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate, vinyl acetate, It may contain styrene or the like.
　アクリル系重合体（Ａ）の重合態様は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。 The polymerization mode of the acrylic polymer (A) may be a random copolymer or a block copolymer.
　アクリル系重合体（Ａ）の質量平均分子量（Ｍｗ）は５０万～２５０万であることが好ましく、特に８０万～２００万であることが好ましく、さらには１００万～１５０万であることが好ましい。なお、本明細書における質量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した標準ポリスチレン換算の値である。 The mass average molecular weight (Mw) of the acrylic polymer (A) is preferably 500,000 to 2,500,000, particularly preferably 800,000 to 2,000,000, and still more preferably 1,000,000 to 1,500,000. . In addition, the mass mean molecular weight in this specification is a value of standard polystyrene conversion measured by gel permeation chromatography (GPC) method.
　アクリル系重合体（Ａ）の質量平均分子量が５０万以上であると、得られる硬化前の接着剤組成物のタックが抑えられ、また、質量平均分子量が２５０万以下であると、得られる硬化前の接着剤組成物のタックが手で簡単に剥がせる程度となる。したがって、アクリル系重合体（Ａ）の質量平均分子量が上記の範囲内にあることで、仮固定に好適な粘着力を得ることができる。 When the mass average molecular weight of the acrylic polymer (A) is 500,000 or more, the tackiness of the obtained adhesive composition before curing is suppressed, and when the mass average molecular weight is 2,500,000 or less, the obtained curing is achieved. The tack of the previous adhesive composition is such that it can be easily peeled off by hand. Therefore, the adhesive force suitable for temporary fixation can be acquired because the mass mean molecular weight of acrylic polymer (A) exists in said range.
　なお、本実施形態に係る加熱硬化型磁着性接着剤組成物において、（アクリル系重合体（Ａ）は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In the heat-curable magnetic adhesive composition according to the present embodiment, the (acrylic polymer (A) may be used alone or in combination of two or more. .
（２）エポキシ樹脂（Ｂ）
　本実施形態に係る加熱硬化型磁着性接着剤組成物が含有するエポキシ樹脂（Ｂ）は、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂およびビスフェノール型エポキシ樹脂からなる群から選ばれる少なくとも一種を含有する。これにより、当該接着剤組成物を硬化した後の接着剤が、所望の接着力、せん断力および耐熱性を発揮することとなる。 (2) Epoxy resin (B)
The epoxy resin (B) contained in the heat-curable magnetic adhesive composition according to this embodiment contains at least one selected from the group consisting of cresol novolac epoxy resin, phenol novolac epoxy resin, and bisphenol epoxy resin. contains. Thereby, the adhesive after curing the adhesive composition exhibits desired adhesive strength, shear force and heat resistance.
　クレゾールノボラック型エポキシ樹脂としては、例えば、以下の式で示されるものが使用できる。
Figure JPOXMLDOC01-appb-C000001
（式中のｎは、１～６０の整数である。） As the cresol novolac epoxy resin, for example, those represented by the following formula can be used.
Figure JPOXMLDOC01-appb-C000001
(Wherein n is an integer of 1 to 60)
　クレゾールノボラック型エポキシ樹脂は、質量平均分子量が１０００～１００００のものが好ましく、特に１５００～５０００のものが好ましい。また、エポキシ当量が、１００～３００ｇ／ｅｑのものが好ましく、特に２００～２３０ｇ／ｅｑのものが好ましい。さらには、軟化点が、３０～１５０℃のものが好ましく、特に５０～１００℃のものが好ましい。 The mass average molecular weight of the cresol novolac epoxy resin is preferably 1,000 to 10,000, and particularly preferably 1,500 to 5,000. The epoxy equivalent is preferably 100 to 300 g / eq, and more preferably 200 to 230 g / eq. Furthermore, those having a softening point of 30 to 150 ° C. are preferable, and those having a softening point of 50 to 100 ° C. are particularly preferable.
　フェノールノボラック型エポキシ樹脂としては、例えば、以下の式で示されるものが使用できる。
Figure JPOXMLDOC01-appb-C000002
（式中のｎは、１～６０の整数である。） As the phenol novolac epoxy resin, for example, those represented by the following formula can be used.
Figure JPOXMLDOC01-appb-C000002
(Wherein n is an integer of 1 to 60)
　フェノールノボラック型エポキシ樹脂は、質量平均分子量が５００～１００００のものが好ましく、特に１０００～３０００のものが好ましい。また、エポキシ当量が、１００～３００ｇ／ｅｑのものが好ましく、特に１７０～２１０ｇ／ｅｑのものが好ましい。さらには、常温で半固形のものが好ましい。 The phenol novolac epoxy resin preferably has a weight average molecular weight of 500 to 10,000, and more preferably 1,000 to 3,000. The epoxy equivalent is preferably 100 to 300 g / eq, and more preferably 170 to 210 g / eq. Furthermore, those which are semisolid at normal temperature are preferable.
　ビスフェノール型エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂等が挙げられ、中でもビスフェノールＡ型エポキシ樹脂が好ましい。 Examples of the bisphenol-type epoxy resin include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin. Among them, bisphenol A-type epoxy resin is preferable.
　ビスフェノールＡ型エポキシ樹脂としては、例えば、以下の式で示されるものが使用できる。
Figure JPOXMLDOC01-appb-C000003
（式中のｎは、１～８０の整数である。） As a bisphenol A-type epoxy resin, what is shown by the following formula can be used, for example.
Figure JPOXMLDOC01-appb-C000003
(Wherein n is an integer of 1 to 80)
　ビスフェノール型エポキシ樹脂は、質量平均分子量が１０００～２００００のものが好ましく、特に３０００～８０００のものが好ましい。また、エポキシ当量が、４００～１３００ｇ／ｅｑのものが好ましく、特に７００～１０００ｇ／ｅｑのものが好ましい。さらには、軟化点が、５０～１５０℃のものが好ましく、特に８０～１００℃のものが好ましい。 The bisphenol type epoxy resin preferably has a mass average molecular weight of 1,000 to 20,000, and particularly preferably 3,000 to 8,000. The epoxy equivalent is preferably 400 to 1300 g / eq, and particularly preferably 700 to 1000 g / eq. Furthermore, those having a softening point of 50 to 150 ° C. are preferable, and those having a softening point of 80 to 100 ° C. are particularly preferable.
　上記の中でも、クレゾールノボラック型エポキシ樹脂およびフェノールノボラック型エポキシ樹脂が好ましく、フェノールノボラック型エポキシ樹脂が特に好ましい。クレゾールノボラック型エポキシ樹脂およびフェノールノボラック型エポキシ樹脂、特にフェノールノボラック型エポキシ樹脂によれば、硬化後の接着剤が優れた接着力およびせん断力を発揮するとともに、硬化前の接着剤組成物が良好な柔軟性を示す。特にフェノールノボラック型エポキシ樹脂は、常温で半固形であるため、柔軟性の効果が顕著である。また、特にアクリル系重合体（Ａ）がアクリルゴムである場合、当該アクリルゴムとの組み合わせにより、接着剤組成物は柔軟性により優れたものとなる。これにより、例えば、本実施形態に係る加熱硬化型磁着性接着剤組成物をシート状に成形した場合に、当該シート状接着剤組成物を三次元曲面にも良好に追従させることができる。なお、エポキシ樹脂（Ｂ）として、ビスフェノール型エポキシ樹脂（好ましくはビスフェノールＡ型エポキシ樹脂）を使用した場合であっても、配合量を少なめに調整することにより、接着剤組成物の柔軟性を確保することができる。 Among the above, cresol novolac epoxy resins and phenol novolac epoxy resins are preferable, and phenol novolac epoxy resins are particularly preferable. According to cresol novolac epoxy resin and phenol novolac epoxy resin, particularly phenol novolac epoxy resin, the adhesive after curing exerts excellent adhesion and shear force, and the adhesive composition before curing is good Demonstrate flexibility. In particular, since the phenol novolac epoxy resin is semisolid at normal temperature, the effect of flexibility is remarkable. In addition, when the acrylic polymer (A) is an acrylic rubber, in particular, the combination with the acrylic rubber makes the adhesive composition more excellent in flexibility. Thereby, for example, when the heat-curable magnetic adhesive composition according to the present embodiment is formed into a sheet, the sheet-like adhesive composition can be made to follow the three-dimensional curved surface well. Even when a bisphenol-type epoxy resin (preferably, bisphenol A-type epoxy resin) is used as the epoxy resin (B), the flexibility of the adhesive composition is secured by adjusting the amount to be small. can do.
　なお、上記のエポキシ樹脂（Ｂ）は、１種を単独で、または２種以上を組み合わせて用いることができるが、硬化前のタックと硬化後の剪断力のバランスを取るために、２種以上を含有することが好ましく、常温で固体のエポキシ樹脂と常温で半固形のエポキシ樹脂との両方を含有することが特に好ましい。 In addition, although said epoxy resin (B) can be used individually by 1 type or in combination of 2 or more types, in order to balance the tack force before hardening, and the shearing force after hardening, 2 or more types are used. It is particularly preferable to contain both an epoxy resin which is solid at normal temperature and an epoxy resin which is semi-solid at normal temperature.
　本実施形態に係る加熱硬化型磁着性接着剤組成物中におけるエポキシ樹脂（Ｂ）の含有量は、固形分換算でアクリル系重合体（Ａ）１００質量部に対して、５～３０００質量部であることが好ましく、特に１０～２０００質量部であることが好ましく、さらには３０～５００質量部であることが好ましい。エポキシ樹脂（Ｂ）の含有量が５質量部以上であると、当該エポキシ樹脂（Ｂ）による上記効果が良好に発揮される。また、エポキシ樹脂（Ｂ）の含有量が３０００質量部以下であると、アクリル系重合体（Ａ）による弾性が阻害されることが抑制される。 The content of the epoxy resin (B) in the heat-curable magnetic adhesive composition according to the present embodiment is 5 to 3000 parts by mass relative to 100 parts by mass of the acrylic polymer (A) in terms of solid content. It is preferably 10 to 2000 parts by mass, and more preferably 30 to 500 parts by mass. The said effect by the said epoxy resin (B) is exhibited favorably as content of an epoxy resin (B) is 5 mass parts or more. Moreover, it is suppressed that the elasticity by an acrylic polymer (A) is inhibited as content of an epoxy resin (B) is 3000 mass parts or less.
（３）硬化剤（Ｃ）
　本実施形態に係る加熱硬化型磁着性接着剤組成物が含有する硬化剤（Ｃ）は、加熱により上記エポキシ樹脂（Ｂ）を硬化させることができるものである。また、アクリル系重合体（Ａ）が、硬化剤（Ｃ）と反応する官能基を有する場合には、アクリル系重合体（Ａ）を架橋する。 (3) Hardening agent (C)
The curing agent (C) contained in the heat-curable magnetic adhesive composition according to this embodiment can cure the epoxy resin (B) by heating. When the acrylic polymer (A) has a functional group that reacts with the curing agent (C), the acrylic polymer (A) is crosslinked.
　かかる硬化剤（Ｃ）としては、エポキシ基と反応し得る官能基を１分子中に２個以上有する化合物が好ましく用いられる。当該官能基としてはフェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシル基、酸無水物等が挙げられ、中でもアミノ基およびフェノール性水酸基が好ましく、特にアミノ基が好ましい。すなわち、硬化剤（Ｃ）としては、アミン系硬化剤およびフェノール系硬化剤が好ましく、特にアミン系硬化剤が好ましい。アミン系硬化剤は、エポキシ樹脂（Ｂ）との反応性が高く、また、アクリル系重合体（Ａ）がカルボキシル基を有する場合には、アクリル系重合体（Ａ）との反応性も高い。さらに、アミン系硬化剤によって架橋されたアクリル系重合体（Ａ）は、特に耐熱性に優れたものとなる。 As such a curing agent (C), a compound having two or more functional groups capable of reacting with an epoxy group in one molecule is preferably used. Examples of the functional group include phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, acid anhydride and the like. Among them, amino group and phenolic hydroxyl group are preferable, and amino group is particularly preferable. That is, as a curing agent (C), an amine curing agent and a phenol curing agent are preferable, and an amine curing agent is particularly preferable. The amine curing agent has high reactivity with the epoxy resin (B), and also has high reactivity with the acrylic polymer (A) when the acrylic polymer (A) has a carboxyl group. Furthermore, the acrylic polymer (A) crosslinked by the amine curing agent is particularly excellent in heat resistance.
　アミン系硬化剤としては、例えば、ジシアンジアミドや、４,４'－ジアミノジフェニルアミン、４,４'－ジアミノジフェニルスルホン、ｍ－フェニレンジアミン、ｍ－キシリレンジアミン等の芳香族アミンなどが挙げられ、中でもジシアンジアミドが好ましい。また、フェノール系硬化剤としては、例えば、フェノールノボラック樹脂、ビスフェノールＡ型ノボラック樹脂、トリアジン変性フェノールノボラック樹脂等が挙げられる。 Examples of amine curing agents include dicyandiamide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylsulfone, aromatic amines such as m-phenylenediamine, m-xylylenediamine, etc. Dicyandiamide is preferred. Moreover, as a phenol-type hardening | curing agent, a phenol novolak resin, bisphenol A novolak resin, a triazine modified | denatured phenol novolak resin etc. are mentioned, for example.
　なお、上記の硬化剤（Ｃ）は、１種を単独で、または２種以上を組み合わせて用いることができる。 In addition, said hardening | curing agent (C) can be used individually by 1 type or in combination of 2 or more types.
　本実施形態に係る加熱硬化型磁着性接着剤組成物中における硬化剤（Ｃ）の含有量は、固形分換算でエポキシ樹脂（Ｂ）１００質量部に対して、０．０２～１５質量部であることが好ましく、特に０．１～１０質量部であることが好ましく、さらには０．３～４質量部であることが好ましい。硬化剤（Ｃ）の含有量が０．０２質量部以上であると、エポキシ樹脂（Ｂ）の硬化（およびアクリル系重合体（Ａ）の架橋）が良好に達成される。一方、硬化剤（Ｃ）の含有量が多過ぎると、不要に接着剤中に残存し、経済的にも不利益となるおそれがある。 The content of the curing agent (C) in the heat-curable magnetic adhesive composition according to the present embodiment is 0.02 to 15 parts by mass with respect to 100 parts by mass of the epoxy resin (B) in terms of solid content. And particularly preferably 0.1 to 10 parts by mass, and further preferably 0.3 to 4 parts by mass. Curing of the epoxy resin (B) (and crosslinking of the acrylic polymer (A)) is favorably achieved when the content of the curing agent (C) is 0.02 parts by mass or more. On the other hand, if the content of the curing agent (C) is too large, it may be unnecessarily left in the adhesive, which may be economically disadvantageous.
（４）硬化触媒
　本実施形態に係る加熱硬化型磁着性接着剤組成物は、上記エポキシ樹脂（Ｂ）と硬化剤（Ｃ）との反応を促進または調整する硬化触媒を含有することが好ましい。 (4) Curing Catalyst The heat-curable magnetic adhesive composition according to the present embodiment preferably contains a curing catalyst that accelerates or adjusts the reaction between the epoxy resin (B) and the curing agent (C). .
　硬化触媒としては、例えば、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の３級アミン類；２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール類；トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩などが挙げられる。これらの中でもイミダゾール類が好ましく、特に２－フェニル－４，５－ジヒドロキシメチルイミダゾールが好ましく用いられる。これらは１種を単独で、または２種以上を混合して使用することができる。 As a curing catalyst, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine, etc. Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and triphenyl phosphine tetraphenyl borate, etc. are mentioned. Among these, imidazoles are preferable, and 2-phenyl-4,5-dihydroxymethylimidazole is particularly preferably used. These can be used singly or in combination of two or more.
　本実施形態に係る加熱硬化型磁着性接着剤組成物中における硬化触媒の含有量は、固形分換算でエポキシ樹脂（Ｂ）および硬化剤（Ｃ）の合計量１００質量部に対して、０．０１～７質量部であることが好ましく、特に０．０５～５質量部であることが好ましく、さらには０．１５～２質量部であることが好ましい。 The content of the curing catalyst in the heat-curable magnetic adhesive composition according to the present embodiment is 0 based on 100 parts by mass of the total amount of the epoxy resin (B) and the curing agent (C) in terms of solid content. The content is preferably from 0.01 to 7 parts by mass, particularly preferably from 0.05 to 5 parts by mass, and further preferably from 0.15 to 2 parts by mass.
（５）強磁性体（Ｄ）
　本実施形態に係る加熱硬化型磁着性接着剤組成物に用いられる強磁性体（Ｄ）は、外部磁場がなくても自発磁化を持つことができる物質であり、フェリ磁性体も含まれる。強磁性体（Ｄ）としては、具体的には、鉄、ニッケル、コバルト等の金属やそれらの合金（例えばステンレススチール）または酸化物、あるいはストロンチウムフェライト、バリウムフェライト、マンガン亜鉛フェライト、ニッケル亜鉛フェライト、銅亜鉛フェライト等のフェライト系、アルミニウム－ニッケル－コバルト合金のようなアルニコ系、希土類－遷移金属系（例：ＳｍＣｏ系，ＳｍＦｅＮ系，ＮｂＦｅＢ系）等の希土類系などの磁性体が挙げられる。これらの中でも、初期磁性を細かくコントロールすることが容易という観点から、フェライト系が好ましく、中でもストロンチウムフェライトおよびバリウムフェライトがより好ましい。 (5) Ferromagnet (D)
The ferromagnetic material (D) used for the heat-curable magnetic adhesive composition according to the present embodiment is a substance capable of having spontaneous magnetization without an external magnetic field, and also includes a ferrimagnetic material. Specific examples of the ferromagnetic substance (D) include metals such as iron, nickel and cobalt, alloys thereof (for example, stainless steel) or oxides, strontium ferrite, barium ferrite, manganese zinc ferrite, nickel zinc ferrite, Magnetic materials such as ferrites such as copper-zinc ferrites, alnicos such as aluminum-nickel-cobalt alloys, and rare earths such as rare earths-transition metals (eg SmCo, SmFeN and NbFeB) may be mentioned. Among these, from the viewpoint of facilitating fine control of the initial magnetism, ferrites are preferable, and strontium ferrite and barium ferrite are more preferable among them.
　強磁性体（Ｄ）は、粉体（以下「磁性粉体」という。）であることが好ましい。磁性粉体の平均粒径は、０．５～２０μｍであることが好ましく、特に０．５～１５μｍであることが好ましく、さらには１～５μｍであることが好ましい。なお、磁性粉体の平均粒径は、例えばコールターカウンター法により測定することができる。 The ferromagnetic material (D) is preferably a powder (hereinafter referred to as "magnetic powder"). The average particle diameter of the magnetic powder is preferably 0.5 to 20 μm, particularly preferably 0.5 to 15 μm, and further preferably 1 to 5 μm. The average particle size of the magnetic powder can be measured, for example, by the Coulter counter method.
　本実施形態に係る加熱硬化型磁着性接着剤組成物中における強磁性体（Ｄ）（磁性粉体）の含有量は、５～６０体積％であることが好ましく、特に１０～５０体積％であることが好ましく、さらには２０～４０体積％であることが好ましい。強磁性体（Ｄ）の含有量が５体積％以上であると、初期段階（加熱硬化前）において、強磁性体（Ｄ）による磁力により、強磁性材料に対する仮固定力が発揮される。一方、強磁性体（Ｄ）の含有量が６０体積％以下であると、他の成分による作用効果、特に柔軟性およびせん断力を阻害することが抑制される。 The content of the ferromagnetic material (D) (magnetic powder) in the heat-curable magnetic adhesive composition according to the present embodiment is preferably 5 to 60% by volume, particularly 10 to 50% by volume It is preferably 20 to 40% by volume. When the content of the ferromagnetic material (D) is 5% by volume or more, the temporary fixing force to the ferromagnetic material is exerted by the magnetic force of the ferromagnetic material (D) in the initial stage (before heat curing). On the other hand, when the content of the ferromagnetic substance (D) is 60% by volume or less, inhibition of the action and effect by the other components, in particular, the flexibility and the shear force is suppressed.
　また、本実施形態に係る加熱硬化型磁着性接着剤組成物中における強磁性体（Ｄ）の含有量は、固形分換算でアクリル系重合体（Ａ）１００質量部に対して、１０～５０００質量部であることが好ましく、特に５０～２０００質量部であることが好ましく、さらには１５０～７００質量部であることが好ましい。強磁性体（Ｄ）の含有量が１０質量部以上であると、初期段階（加熱硬化前）において、強磁性体（Ｄ）による磁力により、強磁性材料に対する仮固定力が発揮される。一方、強磁性体（Ｄ）の含有量が５０００質量部以下であると、剛軟度が高すぎることなく柔軟性が良好となり、また十分なせん断力を維持することができる。 In addition, the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition according to the present embodiment is 10 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer (A) in terms of solid content. The amount is preferably 5000 parts by mass, particularly preferably 50 to 2000 parts by mass, and still more preferably 150 to 700 parts by mass. When the content of the ferromagnetic material (D) is 10 parts by mass or more, the temporary fixing force to the ferromagnetic material is exerted by the magnetic force of the ferromagnetic material (D) in the initial stage (before heat curing). On the other hand, when the content of the ferromagnetic material (D) is 5000 parts by mass or less, the flexibility is good without the hardness being too high, and a sufficient shearing force can be maintained.
（６）その他の成分
　本実施形態に係る加熱硬化型磁着性接着剤組成物は、上記成分の他、例えば、架橋剤、粘着付与剤、酸化防止剤、充填剤、分散剤等の１種以上を適宜含有してもよい。 (6) Other Components The heat-curable magnetic adhesive composition according to the present embodiment is, for example, one of a crosslinking agent, a tackifier, an antioxidant, a filler, and a dispersing agent, in addition to the above components. You may contain the above suitably.
（７）加熱硬化型磁着性接着剤組成物の製造方法
　本実施形態に係る加熱硬化型磁着性接着剤組成物を製造するには、アクリル系重合体（Ａ）、エポキシ樹脂（Ｂ）、硬化剤（Ｃ）、強磁性体（Ｄ）、好ましくは硬化触媒、および所望により他の成分を配合し、混合すればよい。このとき、混合物を２０～１２０℃程度で加熱することにより、各成分は良好に分散する。 (7) Method of producing heat-curable magnetic adhesive composition To produce the heat-curable magnetic adhesive composition according to this embodiment, an acrylic polymer (A), an epoxy resin (B) The curing agent (C), the ferromagnetic material (D), preferably the curing catalyst, and, if desired, other components may be blended and mixed. At this time, the components are well dispersed by heating the mixture at about 20 to 120.degree.
　上記のように加熱硬化型磁着性接着剤組成物に混合する強磁性体（Ｄ）は、磁化された状態のものであってもよいし、未だ磁化されていない状態のものであってもよい。後者の場合は、混合後、接着剤組成物が得られてから、磁化（着磁）すればよい。着磁は、周知の方法で行うことができ、例えば、市販の着磁・脱磁電源装置等を使用して行うことができる。 The ferromagnetic material (D) mixed with the heat-curable magnetic adhesive composition as described above may be in a magnetized state or may not be in a magnetized state. Good. In the latter case, after mixing, after the adhesive composition is obtained, it may be magnetized (magnetized). The magnetization can be performed by a known method, for example, using a commercially available magnetization / demagnetization power supply or the like.
（８）加熱硬化型磁着性接着剤組成物の効果・用途
　以上説明したように、本実施形態に係る加熱硬化型磁着性接着剤組成物は、初期段階（加熱硬化前）では、磁力、および場合によっては粘着力（好ましくは微小な粘着力）により、強磁性材料に対して優れた仮固定力を示す。そして、本実施形態に係る加熱硬化型磁着性接着剤組成物を加熱硬化してなる接着剤は、高いせん断力を示す。また、当該接着剤は、再加熱しても軟化・溶融しないため、耐熱性に優れ、さらには、磁力線による肉厚変化が生じない。また、特に、本実施形態に係る加熱硬化型磁着性接着剤組成物がアクリル系重合体（Ａ）としてアクリルゴムおよびエポキシ樹脂（Ｂ）として常温で半固形のものを含有すると、シート状にしたときに、三次元曲面に追従させることができる。 (8) Effects and Applications of Heat-Curable Magnetic Adhesive Composition As described above, the heat-curable magnetic adhesive composition according to the present embodiment has a magnetic force at an initial stage (before heat-curing). And, in some cases, adhesion (preferably, fine adhesion), exhibit excellent temporary fixation to ferromagnetic materials. And the adhesive agent formed by heat-hardening the heat-hardenable-type magnetically sensitive adhesive composition which concerns on this embodiment shows high shear force. In addition, the adhesive does not soften or melt even if it is reheated, so it is excellent in heat resistance, and furthermore, the thickness change due to the magnetic lines of force does not occur. In particular, when the heat-curable magnetic adhesive composition according to the present embodiment contains an acrylic rubber as the acrylic polymer (A) and a semi-solid one at room temperature as the epoxy resin (B), it forms a sheet. When you do, you can make it follow a three-dimensional curved surface.
　本実施形態に係る加熱硬化型磁着性接着剤組成物は、少なくとも一つが強磁性材料からなる２以上の部材（被接着体）を接合するのに用いられる。強磁性を示す材料からなる部材としては、鉄、コバルト、ニッケルなどを含む材料からなる部材が挙げられる。また、本実施形態に係る加熱硬化型磁着性接着剤組成物は、硬化後の耐熱性が高いため、高温になる部分に好適に用いられる。具体的には、自動車用のドアやボディの鋼板、その鋼板の穴塞ぎ板、車体の補強部品などの自動車用部品、特にエンジンや排気管等の発熱部分の近傍；建築物等の構造物における鉄骨部分；精密機器、電子機器等の金属部分、特にそれら機器における発熱部分の近傍などに好適に用いられる。 The heat-curable magnetic adhesive composition according to the present embodiment is used to join two or more members (adhered members) at least one of which is a ferromagnetic material. As a member made of a material exhibiting ferromagnetism, a member made of a material containing iron, cobalt, nickel or the like can be mentioned. In addition, the heat-curable magnetic adhesive composition according to the present embodiment is suitably used for a part that is at a high temperature, because the heat resistance after curing is high. Specifically, automotive parts such as automobile door and body steel plates, hole sealing plates of steel plates, reinforcing parts of car bodies, particularly in the vicinity of heat generating parts such as engines and exhaust pipes; in structures such as buildings It is suitably used for steel parts; metal parts for precision instruments, electronic instruments, etc., particularly in the vicinity of heat-generating parts in those instruments.
　本実施形態に係る加熱硬化型磁着性接着剤組成物は、上記のような部材同士を接合するために必要な所定の形状に成形することができる。その形状の具体例としては、三角形、四角形、五角形、六角形、八角形等の多角形や、円形、楕円形などの円形類、これらの形状の中央部を取り除いたリング状形状などの種々の形状のシート状体（本発明の加熱硬化型磁着性接着シートに該当）、板状体、ブロック状体、柱状体、棒状体などが挙げられる。 The heat-curable magnetic adhesive composition according to the present embodiment can be formed into a predetermined shape required to join the members as described above. Specific examples of the shape include various shapes such as triangles, quadrilaterals, polygons such as pentagons, hexagons and octagons, circles such as circles and ovals, and ring-like shapes from which the central part of these shapes is removed. Examples include sheet-like bodies of a shape (corresponding to the heat-curable magnetic adhesive sheet of the present invention), plate-like bodies, block-like bodies, columnar bodies, rod-like bodies and the like.
　ここで、本実施形態に係る加熱硬化型磁着性接着剤組成物のアクリル系重合体（Ａ）が、架橋剤（硬化剤（Ｃ））と反応する官能基を有する場合、当該加熱硬化型磁着性接着剤組成物を加熱成形するときに、アクリル系重合体（Ａ）は架橋される。このときの加熱温度は、２０～１２０℃であることが好ましく、特に４０～８０℃であることが好ましい。 Here, when the acrylic polymer (A) of the heat-curable magnetic adhesive composition according to the present embodiment has a functional group that reacts with the cross-linking agent (hardening agent (C)), the heat-curable type When the magnetic adhesive composition is thermoformed, the acrylic polymer (A) is crosslinked. The heating temperature at this time is preferably 20 to 120 ° C., particularly preferably 40 to 80 ° C.
　本実施形態に係る加熱硬化型磁着性接着剤組成物により被接着体を接着するときの加熱温度は、７０～２５０℃であることが好ましく、特に１３０～２００℃であることが好ましい。かかる温度で加熱することにより、本実施形態に係る加熱硬化型磁着性接着剤組成物は硬化して高い接着力を発揮し、被接着体を強固に接着する。 The heating temperature when bonding the adherend with the heat-curable magnetic adhesive composition according to the present embodiment is preferably 70 to 250 ° C., particularly preferably 130 to 200 ° C. By heating at such a temperature, the heat-curable magnetic adhesive composition according to the present embodiment is cured to exhibit high adhesive strength, thereby firmly bonding the adherend.
〔加熱硬化型磁着性接着シート〕
　本実施形態に係る加熱硬化型磁着性接着シートは、上記加熱硬化型磁着性接着剤組成物をシート状に成形したものである。この加熱硬化型磁着性接着シートの厚さは、その用途にもよるが、通常は０．１～５ｍｍであることが好ましく、特に０．２～３ｍｍであることが好ましく、さらには０．３～２ｍｍであることが好ましい。 Heat-curable magnetic adhesive sheet
The heat-curable magnetic adhesive sheet according to the present embodiment is a sheet of the heat-curable magnetic adhesive composition. The thickness of the heat-curable magnetic adhesive sheet is preferably 0.1 to 5 mm, particularly 0.2 to 3 mm, and more preferably 0. It is preferably 3 to 2 mm.
　本実施形態に係る加熱硬化型磁着性接着シートの製造方法は、特に限定されないが、上記加熱硬化型磁着性接着剤組成物をホットプレスすることによって、好ましく製造することができる。ホットプレスの温度は、２０～１２０℃であることが好ましく、特に４０～８０℃であることが好ましい。なお、本実施形態に係る加熱硬化型磁着性接着剤組成物のアクリル系重合体（Ａ）が、架橋剤（硬化剤（Ｃ））と反応する官能基を有する場合には、上記のホットプレスにより、アクリル系重合体（Ａ）は架橋される。 The method for producing the heat-curable magnetic adhesive sheet according to the present embodiment is not particularly limited, but can be preferably produced by hot pressing the heat-curable magnetic adhesive composition. The temperature of the hot press is preferably 20 to 120 ° C., particularly preferably 40 to 80 ° C. In the case where the acrylic polymer (A) of the heat-curable magnetic adhesive composition according to the present embodiment has a functional group that reacts with the crosslinking agent (curing agent (C)), the above-mentioned hot The acrylic polymer (A) is crosslinked by pressing.
　上記のようにホットプレスするときに、得られる加熱硬化型磁着性接着シートの両面に剥離シートが積層されるように、２枚の剥離シートで加熱硬化型磁着性接着剤組成物をサンドイッチすることが好ましい。剥離シートは、両面剥離処理された剥離シートであってもよいし、片面剥離処理された剥離シートであってもよい。剥離シートは、その剥離処理面が加熱硬化型磁着性接着シート側となるように用いられる。 As the release sheet is laminated on both sides of the heat-curable magnetic adhesive sheet obtained when hot pressing as described above, the heat-curable magnetic adhesive composition is sandwiched between two release sheets. It is preferable to do. The release sheet may be a release sheet subjected to double-sided release treatment, or may be a release sheet subjected to single-side release treatment. The release sheet is used such that the release treated surface is on the side of the heat-curable magnetic adhesive sheet.
　上記の剥離シートとしては、例えば、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂等のポリエステル樹脂フィルム、ポリプロピレン樹脂、ポリエチレン樹脂等のポリオレフィン樹脂フィルムなどのプラスチックフィルム、あるいはグラシン紙、コート紙、上質紙等の紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙などに、シリコーン樹脂等の剥離剤を塗布したものなどが用いられる。この剥離シートの厚さは、特に制限はないが、通常２０～２００μｍであることが好ましい。 The above-mentioned release sheet is, for example, a polyester resin film such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, a plastic film such as polyolefin resin film such as polypropylene resin or polyethylene resin, glassine paper, coated paper, What apply | coats release agents, such as a silicone resin, etc. is used for the lamination paper etc. which laminated thermoplastic resins, such as polyethylene, on paper base materials, such as a high quality paper. The thickness of the release sheet is not particularly limited, but is preferably 20 to 200 μm in general.
　本実施形態に係る加熱硬化型磁着性接着シートは、加熱硬化後の接着力が高く、また、再加熱しても軟化・溶融しないため、耐熱性に優れる。さらに、加熱硬化後に溶融しないことにより、磁力線による肉厚変化が生じない。 The heat-curable magnetic adhesive sheet according to the present embodiment has high adhesion after heat-hardening, and does not soften / melt even after reheating, so it is excellent in heat resistance. Furthermore, by not melting after heat curing, the thickness change due to the magnetic lines of force does not occur.
　本実施形態に係る加熱硬化型磁着性接着シートの加熱接着後のせん断力は、８０Ｎ／ｃｍ２以上であることが好ましく、特に１２０Ｎ／ｃｍ２以上であることが好ましく、さらには２００Ｎ／ｃｍ２以上であることが好ましい。ここで、本明細書における加熱接着後のせん断力とは、加熱硬化型磁着性接着シートの一方の面をステンレス鋼板（厚さ０．５ｍｍ）に貼付し、他方の面を別のステンレス鋼板（厚さ０．５ｍｍ）に貼付し、１５０℃で４０分間加熱した後、常温に戻し、ＪＩＳ　Ｋ６８５０に従って測定（試験速度５０ｍｍ／ｍｉｎ）したせん断力をいう。 The shear force after heat bonding of the heat-curable magnetic adhesive sheet according to the present embodiment is preferably 80 N / cm 2 or more, particularly preferably 120 N / cm 2 or more, and further preferably 200 N / cm. It is preferable that it is two or more. Here, with the shear force after heat bonding in the present specification, one surface of the heat-curable magnetic adhesive sheet is attached to a stainless steel plate (0.5 mm in thickness), and the other surface is another stainless steel plate. After sticking to (thickness 0.5 mm) and heating at 150 ° C. for 40 minutes, it is returned to normal temperature and refers to a shear force measured according to JIS K 6850 (testing speed 50 mm / min).
　本実施形態に係る加熱硬化型磁着性接着シートは、加熱硬化型磁着性接着剤組成物がエポキシ樹脂（Ｂ）を含有することにより、上記のように高いせん断力を達成することができる。かかるせん断力を有する加熱硬化型磁着性接着シートによれば、接着した部材同士が経時等によりずれてきてしまうことを効果的に抑制することができる。 The heat-curable magnetic adhesive sheet according to the present embodiment can achieve high shear force as described above when the heat-curable magnetic adhesive composition contains the epoxy resin (B). . According to the heat-curable magnetic adhesive sheet having such a shearing force, it is possible to effectively suppress that the adhered members are shifted with time or the like.
　本実施形態に係る加熱硬化型磁着性接着シートは、常温での表面磁力が１ｍＴ以上であることが好ましく、特に３～１００ｍＴであることが好ましく、さらには５～５０ｍＴであることが好ましい。ここで、本明細書における表面磁力とは、厚さ１ｍｍの加熱硬化型磁着性接着シートの表面から１ｃｍ離れた距離でガウスメーターにより測定した表面磁力をいう。表面磁力が１ｍＴ以上であると、強磁性材料からなる部材に対し、十分に仮固定することができる。また、表面磁力が１００ｍＴ以下であると、仮固定の位置が所定の位置からずれていたとしても、容易に位置直しをすることができる。 The heat-curable magnetic adhesive sheet according to the present embodiment preferably has a surface magnetic force of 1 mT or more at normal temperature, particularly preferably 3 to 100 mT, and more preferably 5 to 50 mT. Here, the surface magnetic force in the present specification refers to the surface magnetic force measured by a gauss meter at a distance of 1 cm from the surface of the heat-curable magnetic adhesive sheet having a thickness of 1 mm. If the surface magnetic force is 1 mT or more, temporary fixing can be performed sufficiently on a member made of a ferromagnetic material. Further, if the surface magnetic force is 100 mT or less, repositioning can be easily performed even if the temporarily fixed position is deviated from the predetermined position.
　本実施形態に係る加熱硬化型磁着性接着シートは、剛軟度が１０～２０００ｍＮであることが好ましく、特に５０～１５００ｍＮであることが好ましく、さらには１００～８００ｍＮであることが好ましい。ここで、本明細書における剛軟度とは、長さ３８ｍｍ、幅２５ｍｍの加熱硬化型磁着性接着シートについて、剛軟度試験機を使用して、ＪＩＳ Ｌ １０９６（１９９９）８．２０．１のガーレ法に準じて測定した剛軟度をいう。 The heat-curable magnetic adhesive sheet according to this embodiment preferably has a bending resistance of 10 to 2,000 mN, particularly preferably 50 to 1,500 mN, and further preferably 100 to 800 mN. Here, the bending resistance in the present specification refers to JIS L 1096 (1999) 8.20., Using a bending resistance tester, for a heat-curable magnetic adhesive sheet having a length of 38 mm and a width of 25 mm. It refers to the bending resistance measured according to the Gurley method of 1.
　本実施形態に係る加熱硬化型磁着性接着シートは、加熱硬化型磁着性接着剤組成物がアクリル系重合体（Ａ）としてアクリルゴムを含有することにより、上記のような剛軟度を達成することができる。かかる剛軟度を有する加熱硬化型磁着性接着シートは、優れた柔軟性を発揮し、被接着体が三次元曲面を有するものであっても、当該被接着体に追従し、確実に接着することができる。 In the heat-curable magnetic adhesive sheet according to the present embodiment, the heat-curable magnetic adhesive composition contains the acrylic rubber as the acrylic polymer (A) to obtain the above-mentioned hardness and hardness. Can be achieved. The heat-curable magnetic adhesive sheet having such a bending resistance exhibits excellent flexibility, and even if the adherend has a three-dimensional curved surface, it adheres to the adherend and adheres reliably. can do.
　本実施形態に係る加熱硬化型磁着性接着シートも、前述した加熱硬化型磁着性接着剤組成物と同様の用途に用いることができる。 The heat-curable magnetic adhesive sheet according to the present embodiment can also be used for the same application as the above-described heat-curable magnetic adhesive composition.
〔接合体の製造方法〕
　ここで、本発明の一実施形態に係る接合体の製造方法について説明する。
　本実施形態に係る接合体の製造方法は、少なくとも一つが強磁性材料からなる２以上の被接着体を接合することにより、接合体を製造する方法である。まず、前述した加熱硬化型磁着性接着剤組成物または加熱硬化型磁着性接着シートを使用して、２以上の被接着体を仮固定し、その後、上記加熱硬化型磁着性接着剤組成物または加熱硬化型磁着性接着シートを加熱し、上記２以上の被接着体を接合する。より具体的には、以下の方法が例示される。 [Method of producing a joined body]
Here, a method of manufacturing a joined body according to an embodiment of the present invention will be described.
The method for producing a joined body according to the present embodiment is a method for producing a joined body by joining two or more adherends of which at least one is made of a ferromagnetic material. First, two or more adherends are temporarily fixed using the above-mentioned heat-curable magnetic adhesive composition or heat-curable magnetic adhesive sheet, and then the above-mentioned heat-curable magnetic adhesive The composition or the heat-curable magnetic adhesive sheet is heated to bond the two or more adherends. More specifically, the following method is exemplified.
　第１の例として、強磁性材料からなる第１の部材と、強磁性材料からなる第２の部材とを、それらの接合面に上記加熱硬化型磁着性接着シートを介在させて接着する方法について説明する。最初に、第１の部材と第２の部材との接合面の形状をした加熱硬化型磁着性接着シートを用意する。その加熱硬化型磁着性接着シートを２つの部材の接合面の間に挟み、当該加熱硬化型磁着性接着シートの磁力（および粘着力）によって、第１の部材と第２の部材とを仮固定する。これにより、作業性が良好なものとなる。そして、加熱硬化型磁着性接着シートを加熱した後、冷却し、第１の部材と第２の部材とを強固に接着し、接合体を得る。なお、第１の部材および第２の部材の形状は、特に限定されない。 As a first example, a method of bonding a first member made of a ferromagnetic material and a second member made of a ferromagnetic material, with the above-mentioned heat-curable magnetic adhesive sheet interposed between the bonding surfaces thereof Will be explained. First, a heat-curable magnetically attachable adhesive sheet having the shape of the joint surface between the first member and the second member is prepared. The heat-curable magnetic adhesive sheet is held between the joining surfaces of two members, and the first member and the second member are separated by the magnetic force (and adhesive force) of the heat-curable magnetic adhesive sheet. Temporarily fix. This improves the workability. Then, the heat-curable magnetic adhesive sheet is heated and then cooled to firmly bond the first member and the second member to obtain a joined body. The shapes of the first member and the second member are not particularly limited.
　第２の例として、第１の部材と、強磁性材料からなる第２の部材とを、それらの接合面に加熱硬化型磁着性接着剤組成物を介在させて接着する方法について説明する。最初に、加熱硬化型磁着性接着剤組成物からなる接着剤部を、第１の部材に形成する。接着剤部の形成方法としては、加熱硬化型磁着性接着剤組成物を第１の部材に塗工してもよいし、加熱硬化型磁着性接着剤組成物に対して第１の部材を積み重ねてもよい。第１の部材は強磁性体であってもよいし、強磁性体でなくてもよい。 As a second example, a method of bonding a first member and a second member made of a ferromagnetic material with a heat-curable magnetic adhesive composition interposed therebetween on a bonding surface thereof will be described. First, an adhesive portion made of a heat-curable magnetic adhesive composition is formed on a first member. As a method of forming the adhesive part, a heat-curable magnetic adhesive composition may be applied to the first member, or the first member with respect to the heat-curable magnetic adhesive composition. May be stacked. The first member may or may not be ferromagnetic.
　次いで、第１の部材に形成された接着剤部を、当該接着剤部の磁力（および粘着力）により第２の部材に吸着させて、第１の部材と第２の部材とを仮固定する。これにより、作業性が良好なものとなる。そして、加熱硬化型磁着性接着剤組成物を加熱した後、冷却し、第１の部材と第２の部材とを強固に接着し、接合体を得る。 Then, the adhesive portion formed on the first member is adsorbed to the second member by the magnetic force (and adhesive force) of the adhesive portion, and the first member and the second member are temporarily fixed. . This improves the workability. Then, the heat-curable magnetic adhesive composition is heated and then cooled to strongly bond the first member and the second member to obtain a joined body.
　上記のようにして得られる接合体における接着剤は、接着力およびせん断力が高く、また、再加熱しても軟化・溶融しないため、耐熱性にも優れる。さらに、当該接着剤は溶融しないため、磁力線による肉厚変化が生じない。 The adhesive in the joined body obtained as described above has high adhesion and shear force, and does not soften / melt even after reheating, so it is also excellent in heat resistance. Furthermore, since the adhesive does not melt, no thickness change occurs due to magnetic lines of force.
　以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.
　以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔実施例１〕
　アクリル系重合体（Ａ）として、アクリル酸エチル（ＥＡ）と、（メタ）アクリル酸ｎ－ブチル（ＢＡ）と、アクリル酸（ＡＡ）とを、３７：６０：３の質量比で共重合させた質量平均分子量１３０万、分子量分布２．７０のアクリルゴムを用意した。 Example 1
As acrylic polymer (A), ethyl acrylate (EA), n-butyl (meth) acrylate (BA), and acrylic acid (AA) are copolymerized at a mass ratio of 37: 60: 3. An acrylic rubber having a mass average molecular weight of 1,300,000 and a molecular weight distribution of 2.70 was prepared.
　上記アクリル系重合体（Ａ）１００質量部（固形分換算；以下同じ）と、エポキシ樹脂（Ｂ）としてのクレゾールノボラック型エポキシ樹脂（ＤＩＣ社製，製品名「Ｎ－６６０」，エポキシ当量：２００～２１５ｇ／ｅｑ，軟化点：６１～６９℃，固形）３０．８質量部と、硬化剤（Ｃ）としてのジシアンアミド０．６８質量部と、硬化触媒としての２－フェニル－４，５－ジヒドロキシメチルイミダゾール０．３４質量部と、強磁性体（Ｄ）としてのストロンチウムフェライト粉末（平均粒径２μｍ）２３０質量部（２９体積％）とを、混合機（東洋精機製作所社製，製品名「３０Ｃ１５０」）に入れて６０℃に加熱し、１０分間混合し、加熱硬化型磁着性接着剤組成物を得た。 100 parts by mass of the above acrylic polymer (A) (solid content conversion; the same below) and a cresol novolac epoxy resin (product of DIC, product name “N-660”, epoxy equivalent weight: 200 as epoxy resin (B) 30.8 parts by mass of a softening point: 61-69 ° C. (solid), 0.68 parts by mass of dicyanamide as a curing agent (C), and 2-phenyl-4,5-dihydroxy as a curing catalyst 0.34 part by mass of methyl imidazole and 230 parts by mass (29% by volume) of strontium ferrite powder (average particle diameter 2 μm) as a ferromagnetic substance (D) The mixture was heated to 60 ° C. and mixed for 10 minutes to obtain a heat-curable magnetic adhesive composition.
　一方、剥離シートとして、ポリエチレンテレフタレートフィルムの片面がシリコーン系剥離剤によって剥離処理された剥離シート（リンテック社製，製品名「ＳＰ－ＰＥＴ３８１１３０」，厚さ：３８μｍ）を２枚用意した。上記で得られた加熱硬化型磁着性接着剤組成物を、上記２枚の剥離シートでサンドイッチするように、かつそれら剥離シートの剥離処理面が加熱硬化型磁着性接着剤組成物に接触するように、ホットプレス機（テスター産業社製，製品名「ＳＡ－３０２」，加熱温度：６０℃）により、厚さ１ｍｍにシート化した後、磁場中にある金型を用いて着磁を行い、両面に剥離シートが積層された加熱硬化型磁着性接着シートを得た。 On the other hand, as a release sheet, two release sheets (made by Lintec Co., Ltd., product name “SP-PET 381130, thickness: 38 μm) were prepared in which one side of a polyethylene terephthalate film was release-treated with a silicone release agent. The heat-curable magnetic adhesive composition obtained above is sandwiched between the two release sheets, and the release-treated surface of the release sheet is in contact with the heat-curable magnetic adhesive composition. Sheet to a thickness of 1 mm with a hot press (product name “SA-302”, product name “SA-302”, product name made by Tester Sangyo Co., Ltd.) and magnetize it using a mold in a magnetic field Then, a heat-curable magnetic adhesive sheet was obtained, in which release sheets were laminated on both sides.
〔実施例２～２８，比較例１～２〕
　加熱硬化型磁着性接着剤組成物を構成する各成分の種類および配合量、ならびに加熱硬化型磁着性接着シートの厚さを表１に示すように変更する以外、実施例１と同様にして加熱硬化型磁着性接着シートを製造した。なお、実施例２０～２３では、２種類のエポキシ樹脂（Ｂ）（エポキシ樹脂（Ｂ）－１およびエポキシ樹脂（Ｂ）－２）を使用した。 [Examples 2-28, Comparative Examples 1-2]
The same procedure as in Example 1 was carried out except that the types and blending amounts of the components constituting the heat-curable magnetic adhesive composition and the thickness of the heat-curable magnetic adhesive sheet were changed as shown in Table 1. A heat-curable magnetic adhesive sheet was produced. In Examples 20 to 23, two types of epoxy resins (B) (epoxy resin (B) -1 and epoxy resin (B) -2) were used.
　なお、表１に記載のエポキシ樹脂（Ｂ）（エポキシ樹脂（Ｂ）－１およびエポキシ樹脂（Ｂ）－２）の詳細は以下の通りである。
・「Ｎ－６６０」：クレゾールノボラック型エポキシ樹脂（ＤＩＣ社製，製品名「Ｎ－６６０」，エポキシ当量：２００～２１５ｇ／ｅｑ，軟化点：６１～６９℃，質量平均分子量：２１００，固形）
・「ＥＯＣＮ－１０４Ｓ」：クレゾールノボラック型エポキシ樹脂（日本化薬社製，製品名「ＥＯＣＮ－１０４Ｓ」，エポキシ当量：２１３～２２３ｇ／ｅｑ，軟化点：９０～９４℃，質量平均分子量：３６００，固形）
・「Ｎ－７４０」：フェノールノボラック型エポキシ樹脂（ＤＩＣ社製，製品名「Ｎ－７４０」，エポキシ当量：１７０～１９０ｇ／ｅｑ，質量平均分子量：１６００，半固形）
・「１０５５」：ビスフェノールＡ型エポキシ樹脂（三菱樹脂社製，製品名「１０５５」，エポキシ当量：８００～９００ｇ／ｅｑ，軟化点：９３℃，質量平均分子量：５７００，固形） The details of the epoxy resin (B) (epoxy resin (B) -1 and epoxy resin (B) -2) described in Table 1 are as follows.
・ "N-660": Cresol novolac epoxy resin (product of DIC, product name "N-660", epoxy equivalent: 200 to 215 g / eq, softening point: 61 to 69 ° C, mass average molecular weight: 2100, solid)
・ “EOCN-104S”: cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name “EOCN-104S”, epoxy equivalent: 213 to 223 g / eq, softening point: 90 to 94 ° C., weight average molecular weight: 3600, solid)
-"N-740": Phenolic novolac epoxy resin (manufactured by DIC, product name "N-740", epoxy equivalent weight: 170 to 190 g / eq, weight average molecular weight: 1600, semisolid)
・ "1055": bisphenol A type epoxy resin (Mitsubishi resin company make, product name "1055", epoxy equivalent: 800-900 g / eq, softening point: 93 ° C, mass average molecular weight: 5700, solid)
〔試験例１〕（せん断力測定）
　実施例および比較例で得られた加熱硬化型磁着性接着シートを、１ｃｍ×１ｃｍの正方形に裁断した。そして、一方の剥離シートを剥離し、当該加熱硬化型磁着性接着シートをステンレス鋼板（ＳＵＳ４３０（２Ｂ）＃２８０ＨＬ，厚さ０．５ｍｍ）に貼付した（貼付面積は１ｃｍ２）。次いで、他方の剥離シートを剥離し、当該加熱硬化型磁着性接着シートを別に用意したステンレス鋼板（厚さ０．５ｍｍ）に貼付して、１５０℃で４０分間加熱した後、常温に戻した。このようにして加熱硬化した接着剤について、材料試験機（インストロン社製，製品名「５５８１」）を使用し、ＪＩＳ　Ｋ６８５０に従って、一方のステンレス鋼板を固定しつつ他方のステンレス鋼板を試験速度５０ｍｍ／ｍｉｎで動かしてせん断力（Ｎ／ｃｍ２）を測定した。結果を表１に示す。 [Test Example 1] (Shear force measurement)
The heat-curable magnetic adhesive sheets obtained in Examples and Comparative Examples were cut into squares of 1 cm × 1 cm. Then, one of the release sheets was released, and the heat-curable magnetic adhesive sheet was attached to a stainless steel plate (SUS430 (2B) # 280 HL, thickness 0.5 mm) (adhesion area: 1 cm 2 ). Next, the other release sheet was peeled off, and the heat-curable magnetic adhesive sheet was attached to a separately prepared stainless steel plate (0.5 mm in thickness), heated at 150 ° C. for 40 minutes, and returned to normal temperature. . Using a material tester (product name “5581” manufactured by Instron Co., Ltd.) for the heat-cured adhesive in this manner, the other stainless steel plate is tested at a test speed of 50 mm while fixing one stainless steel plate according to JIS K6850. The shear force (N / cm 2 ) was measured by moving at / min. The results are shown in Table 1.
〔試験例２〕（表面磁力測定）
　実施例および比較例で得られた加熱硬化型磁着性接着シートから一方の剥離シートを剥離し、露出した加熱硬化型磁着性接着シートの表面から１ｃｍ離れた距離で、ガウスメーター（東洋テクニカ社製，製品名「５０８０型ハンディガウスメータ」）により常温での表面磁力（ｍＴ）を測定した。結果を表１に示す。 [Test Example 2] (Surface Magnetic Force Measurement)
A gauss meter (Toyo Technica Co., Ltd.) at a distance of 1 cm from the surface of the heat-curable magnetic adhesive sheet obtained by peeling one release sheet from the heat-curable magnetic adhesive sheet obtained in Examples and Comparative Examples. The surface magnetic force (mT) at room temperature was measured by a product name “5080 Handy Gauss Meter”. The results are shown in Table 1.
〔試験例３〕（剛軟度測定）
　実施例および比較例で得られた加熱硬化型磁着性接着シートを長さ３８ｍｍ、幅２５ｍｍに裁断し、両面の剥離シートを剥離し、これを測定用サンプルとした。当該測定用サンプルについて、剛軟度試験機（東洋精機社製，製品名「ガーレ式柔軟度試験機」）を使用し、ＪＩＳ Ｌ １０９６（１９９９）８．２０．１のガーレ法に準じて、剛軟度（ｍＮ）を測定した。結果を表１に示す。 [Test Example 3] (Boughness Measurement)
The heat-curable magnetic adhesive sheet obtained in Examples and Comparative Examples was cut into a length of 38 mm and a width of 25 mm, and the release sheets on both sides were peeled off, and this was used as a measurement sample. For the sample for measurement, using a stiffness tester (product name “Gare type flexibility tester” manufactured by Toyo Seiki Co., Ltd.), according to the Gare method of JIS L 1096 (1999) 8.20.1, The bending resistance (mN) was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１から分かるように、実施例で得られた加熱硬化型磁着性接着シートは、良好な表面磁力を有するとともに、加熱硬化後には高いせん断力を発揮した。また、実施例１～２３，２５～２８で得られた加熱硬化型磁着性接着シートは、剛軟度が低く、柔軟性に優れていた。 As can be seen from Table 1, the heat-curable magnetic adhesive sheet obtained in the examples had a good surface magnetic force and exhibited high shear force after heat-hardening. In addition, the heat-curable magnetic adhesive sheet obtained in Examples 1 to 23 and 25 to 28 had a low bending resistance and was excellent in flexibility.
　本発明は、ある部材と強磁性材料からなる部材とを接合するのに、または強磁性材料からなる部材同士を接合するのに好適に利用することができる。 The present invention can be suitably used to bond a member and a member made of a ferromagnetic material, or to bond members made of a ferromagnetic material to each other.

Claims (8)

  1. 　アクリル系重合体（Ａ）と、
    　エポキシ樹脂（Ｂ）と、
    　硬化剤（Ｃ）と、
    　強磁性体（Ｄ）と
    を含有する加熱硬化型磁着性接着剤組成物であって、
    　前記エポキシ樹脂（Ｂ）が、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂およびビスフェノール型エポキシ樹脂からなる群から選ばれる少なくとも一種を含有する
    ことを特徴とする加熱硬化型磁着性接着剤組成物。     Acrylic polymer (A),
    Epoxy resin (B),
    A curing agent (C),
    A heat-curable magnetic adhesive composition containing a ferromagnetic material (D), which is
    Heat-curable magnetic adhesive composition characterized in that the epoxy resin (B) contains at least one selected from the group consisting of cresol novolac epoxy resin, phenol novolac epoxy resin and bisphenol epoxy resin. .
  2. 　前記加熱硬化型磁着性接着剤組成物中における前記強磁性体（Ｄ）の含有量は、５～６０体積％であることを特徴とする請求項１に記載の加熱硬化型磁着性接着剤組成物。 The heat-curable magnetic adhesion as set forth in claim 1, wherein the content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is 5 to 60% by volume. Agent composition.
  3. 　前記加熱硬化型磁着性接着剤組成物中における前記強磁性体（Ｄ）の含有量は、固形分換算で前記アクリル系重合体（Ａ）１００質量部に対して、１０～５０００質量部であることを特徴とする請求項１に記載の加熱硬化型磁着性接着剤組成物。 The content of the ferromagnetic material (D) in the heat-curable magnetic adhesive composition is 10 to 5000 parts by mass relative to 100 parts by mass of the acrylic polymer (A) in terms of solid content. The heat-curable magnetic adhesive composition according to claim 1, wherein
  4. 　前記加熱硬化型磁着性接着剤組成物中における前記エポキシ樹脂（Ｂ）の含有量は、固形分換算で前記アクリル系重合体（Ａ）１００質量部に対して、５～３０００質量部であることを特徴とする請求項１に記載の加熱硬化型磁着性接着剤組成物。 The content of the epoxy resin (B) in the heat-curable magnetic adhesive composition is 5 to 3000 parts by mass relative to 100 parts by mass of the acrylic polymer (A) in terms of solid content. The heat-curable magnetic adhesive composition according to claim 1, which is characterized in that
  5. 　前記硬化剤（Ｃ）は、アミン系硬化剤であることを特徴とする請求項１に記載の加熱硬化型磁着性接着剤組成物。 The heat-curable magnetic adhesive composition according to claim 1, wherein the curing agent (C) is an amine curing agent.
  6. 　請求項１に記載の加熱硬化型磁着性接着剤組成物をシート化した加熱硬化型磁着性接着シート。 A heat-curable magnetic adhesive sheet obtained by forming the heat-curable magnetic adhesive composition according to claim 1 into a sheet.
  7. 　厚さが０．１～５ｍｍであることを特徴とする請求項６に記載の加熱硬化型磁着性接着シート。 7. The heat-curable magnetic adhesive sheet according to claim 6, having a thickness of 0.1 to 5 mm.
  8. 　少なくとも一つが強磁性材料からなる２以上の被接着体を接合して得られる接合体の製造方法であって、
    　請求項１～５のいずれか一項に記載の加熱硬化型磁着性接着剤組成物または請求項６もしくは７に記載の加熱硬化型磁着性接着シートを使用して、前記２以上の被接着体を仮固定し、
    　前記仮固定後に、前記加熱硬化型磁着性接着剤組成物または前記加熱硬化型磁着性接着シートを加熱し、前記２以上の被接着体を接合する
    ことを特徴とする接合体の製造方法。     A method of manufacturing a joined body obtained by joining two or more adherends of which at least one is a ferromagnetic material,
    A heat-curable magnetic adhesive composition according to any one of claims 1 to 5 or a heat-curable magnetic adhesive sheet according to claim 6 or 7 Temporarily fix the adhesive body,
    A method of manufacturing a joined body comprising heating the heat-curable magnetic adhesive composition or the heat-curable magnetic adhesive sheet after the temporary fixing to bond the two or more adherends. .
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