WO2013073380A1 - Thermosetting adhesive sheet and laminate - Google Patents

Thermosetting adhesive sheet and laminate Download PDF

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Publication number
WO2013073380A1
WO2013073380A1 PCT/JP2012/078316 JP2012078316W WO2013073380A1 WO 2013073380 A1 WO2013073380 A1 WO 2013073380A1 JP 2012078316 W JP2012078316 W JP 2012078316W WO 2013073380 A1 WO2013073380 A1 WO 2013073380A1
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WO
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Prior art keywords
thermosetting adhesive
adhesive sheet
thermosetting
present
weight
Prior art date
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PCT/JP2012/078316
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French (fr)
Japanese (ja)
Inventor
桑原理恵
野中崇弘
大學紀二
堀口計
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日東電工株式会社
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Publication of WO2013073380A1 publication Critical patent/WO2013073380A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • 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
    • C09J133/18—Homopolymers or copolymers of nitriles
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/04—Crosslinking with phenolic resin
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2461/00—Presence of condensation polymers of aldehydes or ketones
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials

Definitions

  • the present invention relates to a thermosetting adhesive sheet having a thermosetting adhesive layer. More specifically, the present invention relates to a thermosetting adhesive sheet that can be preferably used for a flexible printed circuit board or the like. The present invention also relates to a laminate having the thermosetting adhesive sheet and a flexible printed circuit board.
  • FPC flexible printed circuit boards
  • a process of manufacturing an FPC by bonding and laminating a conductive metal foil such as a copper foil or an aluminum foil on a heat-resistant substrate such as a polyimide substrate or a polyamide substrate
  • An adhesive is used in the process of bonding the FPC to a reinforcing plate such as an aluminum plate, a stainless steel plate, or a polyimide plate.
  • thermosetting adhesive containing a thermosetting resin such as a phenol resin or an epoxy resin is known as an adhesive used for bonding such an FPC.
  • thermosetting adhesives exhibit an adhesive force when, for example, the thermosetting resin contained in the adhesive is cured by heating at 150 ° C. or higher.
  • thermosetting adhesive When a laminated body produced by bonding an adherend (FPC or the like) using the thermosetting adhesive is processed in a high temperature process such as a reflow process, the adhesive, moisture contained in the adherend, etc. As a result of evaporation of the adhesive, foaming (blowing) or lifting off of the adhesive may occur. These phenomena often occur due to insufficient curing of the adhesive, and there is a problem that the curing temperature must be increased and the curing time must be increased for sufficient curing.
  • thermosetting adhesive sheet that solves the above problems and has a thermosetting adhesive layer excellent in curability
  • a thermosetting adhesive composition that contains an acrylic polymer as a main component and further contains an etherified phenol resin
  • a thermosetting adhesive sheet having a thermosetting adhesive layer formed from a product is known (see Patent Document 1).
  • an adhesive used for bonding the FPC is required to have thermal conductivity.
  • an object of the present invention is to provide a thermosetting adhesive sheet that can exhibit excellent adhesiveness and heat resistance after moist heat even when the curing time is short, and is excellent in heat dissipation, that is, thermal conductivity.
  • thermosetting adhesive layer having a specific thickness formed from a specific thermosetting adhesive composition. Even in this case, the present inventors have found that a thermosetting adhesive sheet that can exhibit excellent adhesiveness and heat resistance after wet heat and has excellent thermal conductivity can be obtained.
  • the present invention has a thermosetting adhesive layer formed from a thermosetting adhesive composition, the thermosetting adhesive composition contains an acrylic polymer (X) as a main component, Also provided is a thermosetting adhesive sheet comprising an etherified phenol resin (Y), wherein the thermosetting adhesive layer has a thickness of 1 to 20 ⁇ m.
  • thermosetting adhesive sheet of the present invention has a total thermal resistance of 2.0 (cm 2 ⁇ K) / W or less after being cured at 150 ° C. for 60 minutes. Preferably there is.
  • the acrylic polymer (X) is an acrylic polymer comprising, as an essential monomer component, a (meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms. It is preferable that
  • the acrylic polymer (X) is preferably an acrylic polymer composed of a cyano group-containing monomer (b) and a carboxyl group-containing monomer (c) as essential monomer components.
  • the content of the etherified phenol resin (Y) is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the acrylic polymer (X).
  • thermosetting adhesive sheet of the present invention preferably comprises only a thermosetting adhesive layer and does not have a substrate.
  • thermosetting adhesive sheet of the present invention is preferably a thermosetting adhesive sheet for flexible printed circuit boards.
  • the present invention also provides a laminate having the above thermosetting adhesive sheet on a flexible printed circuit board.
  • the present invention also provides a thermoset thermosetting adhesive sheet obtained by thermosetting the thermosetting adhesive sheet.
  • the present invention also provides a laminate having the above thermosetting thermosetting adhesive sheet on a flexible printed circuit board.
  • thermosetting adhesive sheet of the present invention Since the thermosetting adhesive sheet of the present invention has the above-described structural characteristics, it can exhibit excellent adhesiveness, heat resistance after moist heat even when the curing time is short, and is excellent in thermal conductivity.
  • thermosetting thermosetting adhesive sheet obtained by thermosetting the thermosetting adhesive sheet of the present invention can exhibit excellent adhesiveness and heat resistance after wet heat even when the curing time is short, and Excellent thermal conductivity.
  • (A) is the front schematic of the apparatus used when measuring total thermal resistance in an Example
  • (b) is the side schematic of the apparatus shown to (a).
  • thermosetting adhesive sheet of the present invention contains an acrylic polymer (X) as a main component and is formed from a thermosetting adhesive composition containing an etherified phenol resin (Y). Having at least a layer.
  • thermosetting adhesive composition containing acrylic polymer (X) as a main component and containing etherified phenol resin (Y) is referred to as “thermosetting type of the present invention. It may be referred to as “adhesive composition”.
  • thermosetting adhesive layer formed from a thermosetting adhesive composition containing acrylic polymer (X) as a main component and containing etherified phenol resin (Y) that is, the present invention
  • thermosetting adhesive layer formed from the thermosetting adhesive composition of the invention may be referred to as “thermosetting adhesive layer of the invention”.
  • “contains acrylic polymer (X) as a main component” means that acrylic polymer (X) in the total nonvolatile content (100% by weight) of the thermosetting adhesive composition of the present invention. It means that the content of is 50% by weight or more.
  • thermosetting adhesive sheet includes the meaning of “thermosetting adhesive tape”. That is, the thermosetting adhesive sheet of the present invention may be a thermosetting adhesive tape having a tape-like form.
  • thermosetting adhesive composition of the present invention contains an acrylic polymer (X) and an etherified phenol resin (Y) as essential components.
  • the thermosetting adhesive composition of the present invention may contain a solvent (solvent and / or dispersion medium) in addition to the acrylic polymer (X) and the etherified phenol resin (Y). You may contain.
  • solvent solvent and / or dispersion medium
  • Each of the above components can be used alone or in combination of two or more.
  • the acrylic polymer (X) is not particularly limited, but comprises a (meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms as an essential monomer component.
  • a (or formed) acrylic polymer is preferred.
  • the “(meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms” is referred to as “(meth) acrylic acid C 1. -14 alkyl ester (a) "or simply” (meth) acrylic acid alkyl ester (a) ".
  • “(Meth) acryl” means “acryl” and / or “methacryl” (one or both of “acryl” and “methacryl”), and the same applies to the following.
  • the acrylic polymer (X) is an acrylic polymer composed of (meth) acrylic acid C 1-14 alkyl ester (a), cyano group-containing monomer (b) and carboxyl group-containing monomer (c) as essential monomer components. More preferably, it is a polymer.
  • the content of the (meth) acrylic acid C 1-14 alkyl ester (a) in the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X) is 50 to 75% by weight, and contains a cyano group
  • the content of the monomer (b) is 20 to 49.5% by weight and the content of the carboxyl group-containing monomer (c) is 0.5 to 10% by weight.
  • the monomer component constituting the acrylic polymer (X) includes monomers other than the (meth) acrylic acid C 1-14 alkyl ester (a), the cyano group-containing monomer (b), and the carboxyl group-containing monomer (c). Components (other monomer components) may be used.
  • the acrylic polymer (X) is preferably an acrylic polymer (acrylic elastomer) that exhibits rubber elasticity (elastomeric properties).
  • the (meth) acrylic acid C 1-14 alkyl ester (a) is not particularly limited.
  • (meth) acrylic acid alkyl ester ((meth) acrylic acid C 4-12 alkyl ester) having a linear or branched alkyl group having 4 to 12 carbon atoms is preferred, and n-butyl acrylate is preferred. Particularly preferred.
  • the said (meth) acrylic-acid C1-14 alkylester (a) can be used individually or in combination of 2 or more types.
  • the content (content ratio) of the (meth) acrylic acid C 1-14 alkyl ester (a) in the monomer component constituting the acrylic polymer (X) is the total amount of the monomer component constituting the acrylic polymer (X) ( 100% by weight) to 50% by weight or more, preferably 50 to 75% by weight, more preferably 55 to 75% by weight, and still more preferably 60 to 72% by weight.
  • the acrylic polymer (X) becomes a relatively hard polymer, improves the strength (bulk strength) of the thermosetting adhesive layer of the present invention, and improves heat resistance after wet heat. Can be improved.
  • the cyano group-containing monomer (b) is a monomer having a cyano group and is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred.
  • the said cyano group containing monomer (b) can be used individually or in combination of 2 or more types. Use of the cyano group-containing monomer (b) is preferable because the strength (bulk strength) of the thermosetting adhesive layer of the present invention can be improved and the heat resistance after wet heat can be improved. Moreover, since it can prevent that the thermosetting adhesive layer of this invention becomes weak, it is preferable.
  • the content of the cyano group-containing monomer (b) in the monomer component constituting the acrylic polymer (X) is 20 to 49 with respect to the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X).
  • 0.5 wt% is preferable, more preferably 24 to 40 wt%, and still more preferably 26 to 35 wt%.
  • the content is 20% by weight or more because the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is further improved.
  • the content exceeds 49.5% by weight, the flexibility of the thermosetting adhesive layer may be lowered.
  • the carboxyl group-containing monomer (c) is a monomer having a carboxyl group and is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acid anhydrides of these carboxyl group-containing monomers for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride
  • acrylic acid, methacrylic acid, and itaconic acid are preferable, and acrylic acid is particularly preferable.
  • the said carboxyl group-containing monomer (c) can be used individually or in combination of 2 or more types. It is preferable to use the carboxyl group-containing monomer (c) because the heat resistance and adhesive strength after wet heat of the thermosetting adhesive sheet of the present invention can be improved.
  • the content of the carboxyl group-containing monomer (c) in the monomer component constituting the acrylic polymer (X) is 0.5% relative to the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X). It is preferably ⁇ 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight. It is preferable that the content is 0.5% by weight or more because the heat resistance after wet heat and the adhesive force of the thermosetting adhesive sheet of the present invention are improved. On the other hand, if the content exceeds 10% by weight, the flexibility of the thermosetting adhesive layer may be lowered.
  • Examples of the monomer component constituting the acrylic polymer (X) include the (meth) acrylic acid C 1-14 alkyl ester (a), the cyano group-containing monomer (b), and the carboxyl group-containing monomer (c).
  • other monomer components copolymerizable monomers
  • the said other monomer component (copolymerizable monomer) can be used individually or in combination of 2 or more types.
  • Examples of the other monomer components include, for example, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate (Meth) acrylic acid alkyl ester ((meth) acrylic acid C 15-20 alkyl ester) having a linear or branched alkyl group having 15 to 20 carbon atoms, such as eicosyl (meth) acrylate; Non-aromatic ring-containing (meth) acrylic esters such as (meth) acrylic acid cycloalkyl esters [cyclohexyl (meth) acrylate] and isobornyl (meth) acrylate; (meth) acrylic acid aryl esters [(meth) acrylic Acid phenyl], (meth) acrylic acid aryloxy
  • the other monomer components include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa
  • Polyfunctional monomers such as (meth) acrylate and divinylbenzene can also be used.
  • the acrylic polymer (X) comprises a structural unit derived from the (meth) acrylic acid C 1-14 alkyl ester (a), a structural unit derived from the cyano group-containing monomer (b), and a carboxyl group-containing monomer ( An acrylic polymer containing at least the structural unit derived from c) is preferred.
  • Each structural unit may be one kind or two or more kinds.
  • the content of the structural unit derived from the (meth) acrylic acid C 1-14 alkyl ester (a) in the acrylic polymer (X) (100% by weight) is preferably 50% by weight or more, more preferably 50 to 50%. It is 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight.
  • the content of the structural unit derived from the cyano group-containing monomer (b) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, and still more preferably 26 to 35% by weight.
  • the content of the structural unit derived from the carboxyl group-containing monomer (c) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
  • the acrylic polymer (X) can be used alone or in combination of two or more.
  • the acrylic polymer (X) may be used in combination with at least two acrylic polymers (X) in order to achieve both adhesiveness and heat resistance.
  • At least the acrylic polymer (X1) and the acrylic polymer (X2) may be used in combination.
  • acrylic polymer (X1) examples include a (meth) acrylic acid alkyl ester (a1) (“(meth) acrylic acid C 1 ) having a linear or branched alkyl group having 1 to 3 carbon atoms. -3 alkyl ester (a1) ”)) as an essential monomer component (or formed), (meth) acrylic acid C 1-3 alkyl ester (a1), cyano group
  • the monomer component constituting the acrylic polymer (X1) is a monomer other than the (meth) acrylic acid C 1-3 alkyl ester (a1), the cyano group-containing monomer (b1), and the carboxyl group-containing monomer (c1). Components (other monomer components) may be used.
  • the (meth) acrylic acid C 1-3 alkyl ester (a1) is, for example, a linear or branched chain having 1 to 3 carbon atoms in the above (meth) acrylic acid C 1-14 alkyl ester (a).
  • (Meth) acrylic acid alkyl ester having an alkyl group in a shape can be used.
  • cyano group-containing monomer (b1) for example, a cyano group-containing monomer selected from the above-mentioned cyano group-containing monomers (b) can be used.
  • carboxyl group-containing monomer (c1) a carboxyl group-containing monomer selected from the above-mentioned carboxyl group-containing monomers (c) can be used.
  • the content of the (meth) acrylic acid C 1-3 alkyl ester (a1) in the total amount (100% by weight) of the monomer components constituting the acrylic polymer (X1) is preferably 50% by weight or more, more preferably It is 50 to 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight.
  • the content of the cyano group-containing monomer (b1) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, and still more preferably 26 to 35% by weight.
  • the content of the carboxyl group-containing monomer (c1) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
  • acrylic polymer (X2) examples include (meth) acrylic acid alkyl ester (a2) (“(meth) acrylic acid C 4 having a linear or branched alkyl group having 4 to 14 carbon atoms”. -14 alkyl ester (a2) ”)) as an essential monomer component (or formation) acrylic polymer, (meth) acrylic acid C 4-14 alkyl ester (a2), cyano group-containing Examples thereof include an acrylic polymer composed of the monomer (b2) and the carboxyl group-containing monomer (c2) as essential monomer components. Each structural unit may be one kind or two or more kinds.
  • the monomer component constituting the acrylic polymer (X2) includes monomers other than the (meth) acrylic acid C 4-14 alkyl ester (a2), the cyano group-containing monomer (b2), and the carboxyl group-containing monomer (c2). Components (other monomer components) may be used.
  • the (meth) acrylic acid C 4-14 alkyl ester (a2) is, for example, a linear or branched chain having 4 to 14 carbon atoms in the above (meth) acrylic acid C 1-14 alkyl ester (a).
  • (Meth) acrylic acid alkyl ester having an alkyl group in a shape can be used.
  • cyano group-containing monomer (b2) for example, a cyano group-containing monomer selected from the above-mentioned cyano group-containing monomers (b) can be used.
  • carboxyl group-containing monomer (c2) a carboxyl group-containing monomer selected from the above-mentioned carboxyl group-containing monomers (c) can be used.
  • the content of (meth) acrylic acid C 4-14 alkyl ester (a2) in the total amount (100% by weight) of the monomer components constituting the acrylic polymer (X2) is preferably 50% by weight or more, more preferably It is 50 to 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight.
  • the content of the cyano group-containing monomer (b2) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, still more preferably 26 to 35% by weight.
  • the content of the carboxyl group-containing monomer (c2) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
  • the acrylic polymer (X) can be prepared by a known or conventional polymerization method (for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a polymerization method by ultraviolet irradiation, etc.).
  • a known or conventional polymerization method for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a polymerization method by ultraviolet irradiation, etc.
  • the polymerization initiator, the emulsifier, the chain transfer agent and the like that are used as necessary in the polymerization of the acrylic polymer (X) are not particularly limited, and can be appropriately selected from known or commonly used ones.
  • examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis ( 2,4,4-trimethylpentane), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazoline- Azo polymerization initiators such as 2-yl] propane ⁇ dihydrochloride; benzoyl perfluoride,
  • chain transfer agent examples include 1-dodecanethiol, tert-lauryl mercaptan, sec-lauryl mercaptan, 2-mercaptoethanol, glycidyl mercaptan, mercaptoacetic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1- Examples include propanol and ⁇ -methylstyrene dimer.
  • the emulsifier examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxy Nonionic emulsifiers such as ethylene alkyl ether and polyoxyethylene alkyl phenyl ether are listed.
  • the chain transfer agent and the emulsifier can be used alone or in combination of two or more.
  • solvents such as esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the said solvent can be used individually or in combination of 2 or more types.
  • the weight average molecular weight (Mw) of the acrylic polymer (X) is not particularly limited, but the viewpoint of improving productivity by improving the coating property of the thermosetting adhesive composition of the present invention, and the heat of the present invention. From the viewpoint of improving the strength of the curable adhesive layer and improving the heat resistance after wet heat, it is preferably 500,000 to 4,000,000, more preferably 600,000 to 3,500,000, still more preferably 800,000 to 3,200,000.
  • the weight average molecular weight of the acrylic polymer (X) can be controlled by the monomer concentration, the monomer dropping rate, etc., in addition to the type and amount of polymerization initiator and chain transfer agent, the temperature and time during polymerization.
  • the weight average molecular weight can be measured by gel permeation chromatograph (GPC). More specifically, it can be determined by, for example, the following ⁇ GPC measurement method>.
  • ⁇ GPC measurement method> Preparation of measurement sample
  • the acrylic polymer to be measured is dissolved in the eluent to prepare a 0.1% THF solution of the acrylic polymer, left for 1 day, and then filtered through a 0.45 ⁇ m membrane filter.
  • GPC measurement is performed under the following measurement conditions.
  • GPC device HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel GMH-H (S) (manufactured by Tosoh Corporation) Column size: 7.8 mm I.D. D. ⁇ 300mm Column temperature: 40 ° C Eluent: THF (tetrahydrofuran) Flow rate: 0.5 ml / min Inlet pressure: 4.6 MPa Injection volume: 100 ⁇ l Detector: Differential refractometer Standard sample: Polystyrene Data processing device: GPC-8020 (manufactured by Tosoh Corporation)
  • the content (content ratio, blending ratio) of the acrylic polymer (X) in the thermosetting adhesive composition of the present invention is not particularly limited, but from the viewpoint of coexistence of heat resistance after wet heat and adhesive strength, It is 50% by weight or more with respect to the total nonvolatile content (100% by weight) of the thermosetting adhesive composition of the present invention, preferably 70 to 99% by weight, more preferably 80 to 95% by weight, and still more preferably. 85 to 95% by weight.
  • the acrylic polymer (X) includes, for example, the acrylic polymer (X1) and the acrylic polymer (X2)
  • the total non-volatile content (100% by weight) of the thermosetting adhesive composition of the present invention is 50% by weight or more, preferably 70 to 99% by weight, more preferably 80 to It is 95% by weight, more preferably 85 to 95% by weight.
  • the content (content ratio, blending ratio) of the acrylic polymer (X2) with respect to the acrylic polymer (X1) is not particularly limited, but the acrylic polymer (X1) 100 is compatible with both adhesiveness and heat resistance.
  • the amount is preferably 1 to 100 parts by weight, more preferably 2 to 45 parts by weight, still more preferably 4 to 25 parts by weight, and most preferably 5 to 20 parts by weight with respect to parts by weight.
  • the content of the acrylic polymer (X2) is 1 part by weight or more, it is preferable because the adhesive force of the thermosetting adhesive sheet of the present invention is improved and the heat resistance after wet heat is improved. Further, the content of 100 parts by weight or less is preferable because the strength of the thermosetting adhesive layer of the present invention is improved and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved.
  • the etherified phenol resin (Y) is a phenol resin in which a part of the methylol group (methylol group in the phenol resin) of the phenol resin is etherified. That is, it is a phenol resin having at least a non-etherified methylol group and an etherified methylol group.
  • the etherified phenol resin (Y) is used for imparting thermosetting properties.
  • thermosetting adhesive sheet of the present invention can be thinned.
  • the etherified phenol resin (Y) is preferably an alkyl etherified phenol resin which is a phenol resin in which a part of the methylol group of the phenol resin is etherified with an alkyl group.
  • alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, Octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl
  • the phenol resin as a skeleton is not particularly limited.
  • the etherified phenol resin (Y) include an etherified novolac type phenol resin, an etherified resol type phenol resin, and an etherified cresol resin.
  • etherified cresol resins are preferable, and butyl etherified cresol resins (cresol resins in which a part of the methylol group is butyl etherified) are more preferable.
  • the etherified phenol resin (Y) can be used alone or in combination of two or more.
  • the ratio of etherified methylol groups in the etherified phenol resin (Y) is, for example, etherified with respect to the total (100 mol%) of etherified methylol groups and non-etherified methylol groups.
  • the proportion of the methylol group is preferably 50 mol% or more (50 mol% or more and less than 100 mol%), more preferably 70 mol% or more. If the ratio of the etherified methylol group is less than 50 mol%, the reaction of the etherified phenol resin at room temperature may be accelerated, or the reactivity during heat curing may be reduced.
  • etherified phenol resin a commercially available etherified phenol resin can also be used.
  • trade name “Sumilite Resin PR-55317” Suditomo Bakelite Co., Ltd., butyl etherified cresol resin, The ratio of etherified methylol groups: 90 mol%)
  • trade name “CKS-3898” butyl etherified cresol resin, manufactured by Showa Denko KK
  • the like can be used.
  • the content (content ratio, blending ratio) of the etherified phenol resin (Y) in the thermosetting adhesive composition of the present invention is 1 to 40 weights per 100 weight parts of the acrylic polymer (X). Parts, preferably 5 to 20 parts by weight, more preferably 10 to 15 parts by weight.
  • the content of the etherified phenol resin (Y) of 1 part by weight or more is preferable because the thermosetting property of the thermosetting adhesive layer of the present invention is improved. Moreover, it is preferable to make it 40 parts by weight or less because the adhesive does not protrude during high-temperature pressing.
  • the thermosetting adhesive composition of the present invention preferably contains a solvent.
  • the solvent include esters such as ethyl acetate and n-butyl acetate; alcohols such as methanol, ethanol, butanol, propanol and isopropanol; aromatic hydrocarbons such as toluene and benzene; n-hexane and n- Examples include aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the said solvent can be used individually or in combination of 2 or more types. Note that the solvent includes the meaning of a dispersion medium.
  • the thermosetting adhesive composition of the present invention includes an anti-aging agent, a filler (filler), a colorant (pigment) as necessary. And dyes), UV absorbers, antioxidants, crosslinking agents, tackifiers, plasticizers, softeners, surfactants, antistatic agents, and other known additives are included within the range that does not impair the characteristics of the present invention. It may be.
  • the said additive can be used individually or in combination of 2 or more types.
  • the filler is not particularly limited, and known and commonly used organic fillers and inorganic fillers can be used. Especially, a silica filler and a copper filler are preferable from the viewpoint of improving the strength of the thermosetting adhesive layer of the present invention and further improving the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention.
  • the said filler can be used individually or in combination of 2 or more types.
  • the shape of the silica filler or the copper filler is not particularly limited, and examples thereof include a spherical shape, a filament shape, a flake shape, a dendritic shape, and an irregular shape. Especially, it is preferable that the shape of the said silica filler or the said copper filler is spherical from the point disperse
  • the average particle diameter of the silica filler or the copper filler is not particularly limited, but is preferably 0.005 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m. It is preferable that the average particle size is 0.005 ⁇ m or more because the wettability and adhesive strength of the thermosetting adhesive layer of the present invention are improved. The average particle size is preferably 10 ⁇ m or less because the strength of the thermosetting adhesive layer of the present invention is improved and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved.
  • the average particle size of the filler can be determined by, for example, a photometric particle size distribution meter (device name “LA-910”, manufactured by Horiba, Ltd.).
  • the silica filler or the copper filler may be subjected to a surface treatment.
  • thermosetting adhesive composition of the present invention preferably contains at least one filler of the silica filler and the copper filler. That is, the thermosetting adhesive composition of the present invention may contain both a silica filler and a copper filler, or may contain only one of the silica filler and the copper filler.
  • the total amount of the silica filler content and the copper filler content (total content, total content ratio, total blending ratio) in the thermosetting adhesive composition of the present invention is not particularly limited.
  • the amount is preferably 1 to 150 parts by weight, more preferably 5 to 140 parts by weight, and still more preferably 10 to 120 parts by weight with respect to 100 parts by weight of the polymer (X).
  • the strength of the thermosetting adhesive layer of the present invention is improved, and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved.
  • it can prevent that the thermosetting adhesive layer of this invention becomes weak and the intensity
  • thermosetting adhesive composition of the present invention includes, for example, (meth) acrylic acid C 1-14 alkyl ester (a), cyano group-containing monomer (b) and carboxyl group-containing monomer (c) as essential monomer components. It is preferable that the structured acrylic polymer (X) is contained as a main component and the etherified phenol resin (Y) is contained.
  • thermosetting adhesive composition of the present invention can be prepared, for example, by mixing an acrylic polymer (X), an etherified phenol resin (Y), and various additives as necessary.
  • the acrylic polymer (X) and the etherified phenol resin (Y) can be dissolved in a solvent to form a solution, or dispersed in a dispersion medium to form a dispersion. It can also be used for the preparation of an agent composition.
  • thermosetting adhesive layer of the present invention is a thermosetting adhesive layer formed from the thermosetting adhesive composition of the present invention.
  • the thermosetting adhesive layer of the present invention may have either a single layer or multiple layers.
  • the thickness of the thermosetting adhesive layer of the present invention is 1 to 20 ⁇ m, preferably 5 to 20 ⁇ m, preferably 8 to 18 ⁇ m, more preferably 10 to 15 ⁇ m. It is preferable that the thickness is 1 ⁇ m or more because the adhesive force is improved. On the other hand, when the thickness is 20 ⁇ m or less, even when the curing time is short, the cured thermosetting adhesive layer is excellent in heat dissipation, adhesiveness, and heat resistance after wet heat.
  • the thermosetting adhesive layer of the present invention is not particularly limited, but the total thermal resistance after being cured at 150 ° C. for 60 minutes (total thermal resistance measured by a steady heat flow method) is 2.0 ( cm 2 ⁇ K) / W or less, preferably 0.01 to 1.8 (cm 2 ⁇ K) / W, more preferably 0.1 to 1.6 (cm 2 ⁇ K) / W 0.3 to 1.5 (cm 2 ⁇ K) / W is particularly preferable. That is, the total thermal resistance after curing at 150 ° C.
  • thermosetting adhesive layer has excellent heat dissipation (thermal conductivity).
  • the heat accumulated in the FPC is reinforced through the thermosetting adhesive sheet of the present invention.
  • the plate can be efficiently dissipated.
  • the total thermal resistance means the sum of the thermal resistance of the thermosetting adhesive layer itself after curing and the contact thermal resistance.
  • the contact thermal resistance means that the air is interposed between the surface of the adhesive layer and the adherend due to the surface roughness of the thermosetting adhesive layer after curing, and the adhesive layer and the adherend.
  • the thermal resistance that occurs between The total thermal resistance can be measured by the method described in “(3) Total thermal resistance” in (Evaluation) described later.
  • thermosetting adhesive layer of the present invention is not particularly limited, but the total heat resistance after being cured at 150 ° C. for 20 minutes (total heat resistance measured by a steady heat flow method) is a viewpoint of heat dissipation. Therefore, it is preferably 0.1 to 1.6 (cm 2 ⁇ K) / W, more preferably 0.2 to 1.5 (cm 2 ⁇ K) / W, still more preferably 0.3 to 1 0.5 (cm 2 ⁇ K) / W.
  • the gel fraction of the thermosetting adhesive layer of the present invention (before curing) is not particularly limited, but is less than 70% (% by weight) from the viewpoint of flexibility of the thermosetting adhesive layer of the present invention (for example, 0% or more and less than 70%), preferably less than 60%, more preferably less than 50%.
  • the gel fraction can be obtained as methyl ethyl ketone insoluble matter. Specifically, the weight fraction (unit: weight) of the insoluble matter after immersion in methyl ethyl ketone for 7 days at room temperature (23 ° C.). %). It is preferable that the gel fraction is less than 70% because the flexibility of the thermosetting adhesive layer of the present invention is improved and the adhesive force is improved.
  • the gel fraction (ratio of methyl ethyl ketone insoluble matter) can be measured and calculated by, for example, the following ⁇ Method for measuring gel fraction>.
  • ⁇ Method for measuring gel fraction> About 0.1 g of the thermosetting adhesive layer of the present invention is sampled from the thermosetting adhesive sheet of the present invention to obtain a thermosetting adhesive layer for gel fraction measurement.
  • a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Corporation) having pores having an average pore diameter of 0.2 ⁇ m
  • the weight before immersion is the total weight of the thermosetting adhesive layer, the tetrafluoroethylene sheet, and the kite string. Further, the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is defined as the wrapping weight.
  • the above thermosetting adhesive layer wrapped with a tetrafluoroethylene sheet and tied with a kite string (referred to as “sample”) is placed in a 50 mL container filled with methyl ethyl ketone and 1 at room temperature (23 ° C.). Leave for a week (7 days). Thereafter, the sample (after methyl ethyl ketone treatment) is taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C.
  • Gel fraction (% by weight) (AB) / (CB) ⁇ 100 (In the above formula, A is the weight after immersion, B is the weight of the bag, and C is the weight before immersion.)
  • the gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the thermosetting adhesive layer of the present invention is not particularly limited, but is preferably 90% (% by weight) or more, more preferably 92% or more, and still more preferably. 96% or more.
  • the upper limit of the gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the thermosetting adhesive layer of the present invention is not particularly limited and is, for example, 100%.
  • the gel fraction is 90% or more, the thermosetting treatment of the thermosetting adhesive layer of the present invention can be rapidly and sufficiently advanced, and the adhesiveness after thermosetting and the heat resistance after wet heat are superior. preferable.
  • the gel fraction is less than 90%, the thermosetting treatment at 150 ° C. for 1 hour does not proceed sufficiently, and the adhesive strength after thermosetting and the heat resistance after wet heat may be insufficient. In order to achieve this, a higher curing temperature and a longer curing time are required, which may increase the cost.
  • thermosetting adhesive layer for gel fraction measurement The gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the above thermosetting adhesive layer is specifically, for example, by heating the thermosetting adhesive sheet of the present invention at 150 ° C. for 1 hour,
  • thermosetting adhesive sheet of the present invention has at least one thermosetting adhesive layer of the present invention (a thermosetting adhesive layer formed by the thermosetting adhesive composition of the present invention).
  • the thermosetting adhesive sheet of the present invention may have a substrate, a thermosetting adhesive layer other than the thermosetting adhesive layer of the present invention, and the like in addition to the thermosetting adhesive layer of the present invention. Good. Moreover, you may have another layer (for example, intermediate
  • Each of the layers other than the thermosetting adhesive layer of the present invention may be provided as only one layer, or may be provided as two or more layers.
  • the thermosetting adhesive sheet of the present invention may be a single-sided adhesive sheet in which only one surface of the sheet is the adhesive layer surface (adhesive surface) (that is, the thermosetting adhesive layer surface of the present invention). And the double-sided adhesive sheet whose both surfaces of this sheet
  • the thermosetting adhesive sheet of the present invention is not particularly limited, it is preferably a double-sided adhesive sheet from the viewpoint of being used for bonding articles (adherents) to each other, and more preferably, both surfaces of the sheet are It is a double-sided adhesive sheet that is the surface of a thermosetting adhesive layer.
  • thermosetting adhesive sheet of the present invention may be a thermosetting adhesive sheet having a base material (thermosetting adhesive sheet with a base material), or a thermosetting adhesive sheet having no base material (base material). Less thermosetting adhesive sheet).
  • thermosetting adhesive sheet of the present invention for example, (1) a thermosetting adhesive sheet comprising only the thermosetting adhesive layer of the present invention and having no base material (baseless thermosetting adhesive sheet) ), (2) Thermosetting adhesive sheet (thermosetting adhesive sheet with substrate) having the thermosetting adhesive layer of the present invention on at least one side (both sides or one side) of the substrate, and the like. It is done.
  • thermosetting adhesive sheet of the present invention a substrate-less thermosetting adhesive sheet is preferable, and among these, from the viewpoint of ease of production and heat dissipation (thermal conductivity), A substrate-less thermosetting adhesive sheet consisting only of the thermosetting adhesive layer of the invention and having no substrate is preferred.
  • the “base material” does not include a release liner (separator) that is peeled off when the thermosetting adhesive sheet is used.
  • thermosetting adhesive sheet of the present invention is a thermosetting adhesive sheet with a substrate
  • the thermosetting adhesive layer of the present invention may be provided on at least one surface side of the substrate.
  • a thermosetting adhesive layer other than the thermosetting adhesive layer of the present invention or a thermosetting adhesive
  • a known adhesive layer for example, a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) or the like] other than the layer may be provided.
  • the substrate is not particularly limited.
  • a paper-based substrate such as paper; a fiber-based substrate such as cloth, nonwoven fabric, or net; a metal-based substrate such as metal foil or metal plate;
  • Plastic base materials such as films and sheets made of resin, polyester resin, polyvinyl chloride resin, vinyl acetate resin, polyamide resin, polyimide resin, polyether ether ketone (PEEK), polyphenylene sulfide (PPS), etc.
  • Rubber base materials such as rubber sheets; foam-based base materials such as foam sheets, and laminates thereof (particularly laminates of plastic base materials and other base materials, and laminates of plastic films (or sheets))
  • An appropriate sheet-like material such as a body can be used.
  • the thickness of the substrate is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m from the viewpoint of workability.
  • the base material may have a single layer form or may have a multiple layer form.
  • the substrate may be subjected to various treatments such as back treatment, antistatic treatment, and undercoating treatment as necessary.
  • thermosetting adhesive sheet of the present invention may have, for example, a form wound in a roll shape or a form in which sheets are laminated. That is, the thermosetting adhesive sheet of the present invention can have forms such as a sheet form and a tape form.
  • thermosetting adhesive sheet of the present invention has a form wound in a roll shape, for example, a release treatment in which the thermosetting adhesive layer is formed on the back side of the release liner or the base material The form wound by the roll shape in the state protected by the layer may be sufficient.
  • the surface of the adhesive layer (for example, the thermosetting adhesive layer of the present invention) in the thermosetting adhesive sheet of the present invention may be protected by a release liner (separator).
  • the release liner is not particularly limited, and can be appropriately selected from known release liners.
  • a release liner for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicon, or the surface of a base material (liner base material) such as paper or plastic film is a polyolefin.
  • a release liner laminated with a resin is preferable.
  • the polyolefin resin is not particularly limited, but a polyethylene resin is preferable.
  • the thickness of the thermosetting adhesive sheet of the present invention is not particularly limited, but is preferably 190 ⁇ m or less (4 to 190 ⁇ m), more preferably 140 ⁇ m or less (4 to 140 ⁇ m), and still more preferably 90 ⁇ m or less.
  • the said thickness is 190 micrometers or less, the total thermal resistance of the thermosetting type adhesive sheet of this invention becomes low, and it is excellent in heat dissipation.
  • thermosetting adhesive sheet of the present invention can be produced according to a known or commonly used method for producing an adhesive sheet.
  • the thickness after drying of the thermosetting adhesive composition of the present invention is predetermined on the release surface of the release liner.
  • the thermosetting adhesive sheet of the present invention can be produced by forming the thermosetting adhesive layer of the present invention by a method of applying and drying to a thickness.
  • the thermosetting adhesive sheet of the present invention is a thermosetting adhesive sheet with a substrate, after the thermosetting adhesive layer of the present invention is formed on the release surface of the release liner, the heat
  • the thermosetting adhesive sheet of the present invention can be produced by a method of transferring the curable adhesive layer onto the surface of the substrate. Further, the thermosetting adhesive layer of the present invention is applied to the surface of the base material by applying the thermosetting adhesive composition of the present invention so that the thickness after drying becomes a predetermined thickness and drying. To form the thermosetting adhesive sheet of the present invention.
  • thermosetting adhesive composition of the present invention a conventional coater (for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.) Can be used.
  • a conventional coater for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.
  • thermosetting adhesive sheet of the present invention and the thermosetting adhesive layer of the present invention can exhibit an excellent adhesive force by causing a curing reaction to proceed (thermosetting) by heating.
  • the thermosetting adhesive sheet of the present invention is heated to cure (thermoset) the thermosetting adhesive layer of the present invention, whereby an adhesive sheet having a strong adhesive force (thermoset thermosetting adhesive sheet) ) Is obtained.
  • the curing temperature in the thermosetting is not particularly limited, but is preferably 100 ° C. or higher (eg, 100 to 200 ° C.), more preferably 140 ° C. or higher (eg, 140 to 200 ° C., preferably 140 to 170 ° C.), More preferably, it is 150 ° C. or higher (for example, 150 to 170 ° C.).
  • thermosetting time in the said thermosetting, Less than 60 minutes (for example, 20 minutes or more and less than 60 minutes) is preferable, More preferably, it is less than 30 minutes (for example, 20 minutes or more and less than 30 minutes). Even when the curing time is less than 60 minutes, the cured thermosetting adhesive layer of the present invention and the cured thermosetting adhesive sheet of the present invention exhibit excellent adhesiveness, heat resistance after wet heat, and heat dissipation. it can. Moreover, in the laminated body which has the thermosetting type adhesive sheet of this invention on FPC, the heat
  • the curing conditions are not particularly limited, but are less than 60 minutes (eg, 20 minutes to less than 60 minutes, preferably 20 minutes to less than 30 minutes) at a temperature of 100 ° C. or higher (eg, 100 to 200 ° C.). ) It is preferable to heat, more preferably 140 ° C. or higher (for example, 140 to 200 ° C., preferably 140 to 170 ° C.) for less than 60 minutes (for example, 20 minutes to less than 60 minutes, preferably 20 minutes or more Less than 30 minutes), particularly preferably less than 60 minutes (for example, 20 minutes to less than 60 minutes, preferably 20 minutes to less than 30 minutes) at a temperature of 150 ° C. or more (eg, 150 to 170 ° C.).
  • thermosetting adhesive layer of the present invention has high adhesive force (adhesiveness) because the thermosetting adhesive composition of the present invention contains the acrylic polymer (X). Moreover, since the thermosetting adhesive composition of the present invention contains an etherified phenol resin (Y), the thermosetting adhesive layer of the present invention is easily heat-cured and has excellent thermosetting properties, and also has an adhesive force. Excellent heat resistance after wet heat. In addition, since the thickness of the thermosetting adhesive layer of the thermosetting adhesive layer of the present invention is 1 to 20 ⁇ m, the thermosetting adhesive layer after curing has adhesiveness, after wet heat, even when the curing time is short. Excellent heat resistance, low total thermal resistance, and excellent heat dissipation (thermal conductivity).
  • thermosetting adhesive sheet of the present invention can exhibit high adhesive strength, excellent heat resistance after moist heat, and excellent heat dissipation even after the curing time is short. Therefore, the thermosetting adhesive sheet of the present invention is required to have excellent post-humidity heat resistance that does not cause foaming or peeling even when firmly bonded and processed under extremely severe temperature conditions after bonding, and It can be preferably used in applications where excellent thermal conductivity is required to dissipate the heat of the adherend.
  • the thermosetting adhesive sheet of the present invention can be preferably used for bonding on a flexible printed circuit board (FPC), for example. That is, the thermosetting adhesive sheet of the present invention is preferably an FPC thermosetting adhesive sheet.
  • the adhesion in the FPC means, for example, adhesion when the FPC is manufactured or adhesion when the FPC is bonded to the reinforcing plate.
  • the FPC often passes through a high-temperature reflow process before being incorporated into the final product, and the thermosetting adhesive sheet used is required to be free from foaming and peeling off after passing through the reflow process.
  • the FPC inside the electronic device often has heat, and the adhesive (adhesive sheet) used for bonding the FPC is required to have heat dissipation (thermal conductivity).
  • heat resistance after wet heat and “heat dissipation” are regarded as important from the viewpoint of reliability.
  • the “heat resistance after wet heat” refers to a laminate produced by bonding an adherend using a thermosetting adhesive sheet under high temperature and high humidity (for example, temperature 40 to 60 ° C., humidity 60 to 95).
  • thermosetting adhesive sheet thermosetting adhesive layer
  • thermosetting adhesive sheet thermosetting adhesive layer
  • the thermosetting adhesive sheet of the present invention can exhibit heat dissipation as well as high adhesive strength and excellent heat resistance after moist heat after thermosetting, it is highly reliable thermosetting adhesive particularly in FPC applications.
  • FPC which has the thermosetting type adhesive sheet of this invention can be obtained by producing FPC using the thermosetting type adhesive sheet of this invention.
  • thermosetting adhesive sheet of the present invention is not particularly limited.
  • the heat-curable adhesive sheet of the present invention is used to form a heat resistant group.
  • a method of manufacturing an FPC by bonding and laminating a conductive metal foil to a material is mentioned.
  • the heat-resistant substrate is not particularly limited, and examples thereof include a polyimide substrate and a polyamide substrate. Although it does not specifically limit as said electroconductive metal foil, For example, copper foil and aluminum foil are mentioned.
  • thermosetting adhesive sheet of the present invention has the FPC and the reinforcing plate bonded (used) through the thermosetting adhesive sheet of the present invention and has the thermosetting adhesive sheet of the present invention on the FPC. It can be used in a method for producing a laminate (FPC with reinforcing plate).
  • the method for producing the laminate having the thermosetting adhesive sheet of the present invention on the FPC is not particularly limited.
  • the thermosetting adhesive sheet of the present invention is pasted on the FPC or the reinforcing plate, and the thermosetting type is applied.
  • the laminate having the thermosetting adhesive sheet of the present invention on the FPC is manufactured by bonding the FPC or the reinforcing plate through the thermosetting thermosetting adhesive sheet obtained by thermosetting the adhesive sheet.
  • a method is mentioned.
  • the laminate having the thermosetting adhesive sheet of the present invention on the FPC may be bonded to the entire surface of the FPC (or reinforcing plate) using the thermosetting adhesive sheet of the present invention, or may be used in part. It may be pasted.
  • the laminated body which has the thermosetting adhesive sheet of this invention on FPC may be provided with the film and board (another board
  • FPC manufactured using the thermosetting type adhesive sheet of this invention may be sufficient, and well-known thru
  • the reinforcing plate is not particularly limited, and examples thereof include an aluminum plate, a stainless plate (such as a stainless steel plate), and a polyimide plate. Among these, a stainless plate and a polyimide plate are preferable.
  • the laminate having the thermosetting adhesive sheet of the present invention on an FPC is obtained by thermosetting the thermosetting adhesive sheet of the present invention, thereby providing a thermosetting adhesive sheet excellent in heat dissipation, adhesive strength, and heat resistance after wet heat.
  • the laminated body which has (The laminated body which has the thermosetting type adhesive sheet thermosetted on FPC) can be obtained.
  • the thermosetting conditions of the thermosetting adhesive sheet in the said laminated body can be performed on the conditions similar to the thermosetting conditions of the thermosetting adhesive sheet of this invention mentioned above.
  • Table 1 shows the monomer composition of the acrylic polymer (X) and the content (blending amount) in the thermosetting adhesive composition and the thermosetting type of the etherified phenol resin (Y) in Examples and Comparative Examples. The content (blending amount) in the adhesive composition and the thickness of the thermosetting adhesive layer were shown.
  • the monomer composition of the acrylic polymer (X) is represented by the content (% by weight) of each monomer in the total amount of monomer components (100% by weight) constituting the acrylic polymer (X).
  • content of acrylic polymer (X) and etherified phenol resin (Y) was represented by content (weight part) as a non volatile matter.
  • Example 1 Preparation of acrylic polymer (X)
  • a reactor equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer 2,2′-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride (Product name “VA-060”, manufactured by Wako Pure Chemical Industries, Ltd.) (Polymerization initiator) 0.279 g and ion-exchanged water 100 g were added and stirred for 1 hour while introducing nitrogen gas.
  • acrylic polymer (X) weight average molecular weight 1 million
  • thermosetting adhesive composition Acrylic polymer (X) [copolymer comprising butyl acrylate (BA) 66% by weight, acrylonitrile (AN) 29% by weight, acrylic acid (AA) 5% by weight as monomer components]: 100 parts by weight dissolved A butanol solution in which 12 parts by weight (non-volatile content) of the trade name “CKS-3898” (manufactured by Showa Denko KK) as an etherified phenol resin (Y) was dissolved in the ethyl acetate solution was mixed and stirred, A curable adhesive composition (solution) was prepared. That is, the thermosetting adhesive composition contains 100 parts by weight of the acrylic polymer (X) and 12 parts by weight of the etherified phenol resin (Y).
  • thermosetting adhesive sheet (Preparation of thermosetting adhesive sheet)
  • the thermosetting adhesive composition is applied to the release surface of the release liner so that the thickness after drying is 5 ⁇ m, and dried at 100 ° C. for 3 minutes to form a thermosetting adhesive layer (thickness 5 ⁇ m).
  • a thermosetting adhesive sheet (a baseless thermosetting adhesive sheet consisting only of a thermosetting adhesive layer) was obtained.
  • thermosetting adhesive composition As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 13 ⁇ m.
  • thermosetting adhesive composition As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 25 ⁇ m.
  • thermosetting adhesive composition As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 35 ⁇ m.
  • thermosetting adhesive sheet obtained in Examples and Comparative Examples For each thermosetting adhesive sheet obtained in Examples and Comparative Examples, the adhesive strength after curing of the thermosetting adhesive layer, heat resistance after wet heat, and total thermal resistance are measured by the following measurement method or evaluation method. Or evaluated.
  • thermosetting type adhesive layer after hardening in each thermosetting type adhesive sheet obtained in the examples and comparative examples the adhesive strength (N / cm) at 23 ° C was determined by the following method. It was measured.
  • a flexible printed circuit board (FPC; size: width 5 cm ⁇ length 8 cm, thickness 0.2 mm) and a thermosetting adhesive sheet were laminated at 130 ° C. and then cut to 1 cm width (the thermosetting adhesive sheet is an FPC).
  • FPC flexible printed circuit board
  • thermosetting adhesive sheet is an FPC.
  • the specimen was prepared by curing (heating and curing) at 150 ° C. for 20 minutes.
  • thermosetting adhesive layer after hardening in each thermosetting adhesive sheet obtained in Examples and Comparative Examples the heat resistance after wet heat was evaluated.
  • a copper-clad laminate (CCL; polyimide / copper laminate, size: width 5 cm ⁇ length 8 cm, thickness 45 ⁇ m) and a thermosetting adhesive sheet were laminated at 130 ° C. and then cut to 1 cm width (thermosetting).
  • the mold adhesive sheet is laminated on the entire CCL polyimide surface). This was laminated to a stainless steel plate (SUS304BA plate) (SUS; size: length 5 cm ⁇ width 5 cm, thickness 0.4 mm) at 130 ° C.
  • the specimen was prepared by curing (heating and curing) at 150 ° C. for 20 minutes.
  • the test specimen was allowed to stand for 24 hours under conditions of heating and humidity (temperature: 60 ° C., humidity: 90% RH), and then the stainless steel plate side surface of the test specimen was dipped in a solder bath at 260 ° C. for 3 minutes ( Dipping).
  • the heat-hardened adhesive layer after curing in the above test specimen was visually observed for floating and foaming, and the heat resistance after wet heat was evaluated according to the following criteria. The evaluation results are shown in the column of “heat resistance after wet heat, 20 minutes cure, SUS” in Table 1.
  • heat resistance after wet heat was evaluated according to the following criteria in the same manner as above except that the heat curing was performed at 150 ° C. for 60 minutes.
  • the evaluation results are shown in the column of “heat resistance after wet heat 60 minutes cure SUS” in Table 1.
  • Excellent heat resistance after wet heat (O): Floating off the thermosetting adhesive layer and no foaming was confirmed.
  • heat resistance after wet heat is slightly inferior, it can be used ( ⁇ ): it was lifted off part of the thermosetting adhesive layer, and foaming was confirmed.
  • heat resistance after wet heat was similarly evaluated using a polyimide plate (PI; size: length 5 cm ⁇ width 5 cm, thickness 0.13 mm) instead of the stainless steel plate.
  • PI polyimide plate
  • the evaluation results are shown in the columns of “heat resistance after wet heat 20 minutes cure PI” and “heat resistance after wet heat 60 minutes cure PI” in Table 1.
  • thermosetting adhesive sheet S (20 mm ⁇ 20 mm) is formed between a pair of rods L made of aluminum (A5052, thermal conductivity: 140 W / m ⁇ K) formed so as to be a legitimate body having a side of 20 mm.
  • thermosetting adhesive sheet S 20 mm
  • the rod L was arrange
  • the heating element H is disposed on the upper rod L
  • the radiator C is disposed below the lower rod L.
  • the pair of rods L bonded together by the thermosetting adhesive sheet S that is thermally cured is located between the pair of pressure adjusting screws T that penetrate the heating element H and the radiator C.
  • a load cell R is installed between the pressure adjusting screw T and the heating element H, and is configured to measure the pressure when the pressure adjusting screw T is tightened.
  • the pressure applied to the thermosetting thermosetting adhesive sheet S was used.
  • three probes P (1 mm in diameter) of a contact-type displacement meter were installed so as to penetrate the lower rod L and the heat-cured thermosetting adhesive sheet S from the radiator C side. At this time, the upper end of the probe P is in contact with the lower surface of the upper rod L, and the distance between the upper and lower rods L (thickness of the thermosetting thermosetting adhesive sheet S) can be measured. It is configured.
  • a temperature sensor D was attached to the heating element H and the upper and lower rods L (see FIG. 1B).
  • the temperature sensor D was attached at one place on the heating element H and five places at intervals of 5 mm in the vertical direction of each rod L.
  • the pressure adjusting screw T is tightened to apply pressure to the heat-cured thermosetting adhesive sheet S
  • the temperature of the heating element H is set to 80 ° C.
  • the cooling body C is cooled to 20 ° C. Water was circulated.
  • the temperature of the upper and lower rods L is measured by each temperature sensor D, and the heat curing is performed by the thermal conductivity and temperature gradient of the upper and lower rods L.
  • the heat flux passing through the mold adhesive sheet S was calculated, and the temperature at the interface between the upper and lower rods L and the thermosetting thermosetting adhesive sheet S was calculated. And using these, the total thermal resistance (cm ⁇ 2 > * K) / W in the said pressure was computed. In addition, the pressure applied to the heat-cured thermosetting adhesive sheet S was 250 kPa, and the total thermal resistance was measured. The measurement results are shown in the column of “total thermal resistance (cm 2 ⁇ K) / W 20 minutes cure” in Table 1.
  • the total heat resistance was similarly measured using the thermosetting thermosetting adhesive sheet heat-hardened on 150 degreeC on the conditions for 60 minutes.
  • the measurement results are shown in the column of “Total thermal resistance (cm 2 ⁇ K) / W 60 minutes cure” in Table 1.
  • thermosetting adhesive sheet of the present invention has a high adhesive strength after curing and excellent adhesiveness even when the thermosetting time is as short as 20 minutes, and further, it is severe after being placed under humidified heat conditions. Even when the solder dipping process was performed under the temperature condition (260 ° C.), no peeling or foaming was observed, and the film had high heat resistance after wet heat. Moreover, even when the curing time was short, the total thermal resistance of the thermosetting adhesive layer after curing was low, and the heat dissipation (thermal conductivity) was excellent (Examples 1 and 2).
  • thermosetting adhesive sheet having a thermosetting adhesive layer having a thickness of more than 20 ⁇ m is subjected to a solder dip treatment under severe temperature conditions after being placed under humidified heat conditions when the curing time is short, Peeling and foaming were observed in the thermosetting adhesive layer, and the heat resistance after wet heat was poor.
  • thermosetting adhesive layer having a thickness of more than 20 ⁇ m had a high total thermal resistance and a poor heat dissipation (thermal conductivity) (Comparative Examples 1 and 2).
  • thermosetting adhesive sheet of the present invention can exhibit excellent adhesion, heat resistance after moist heat even when the curing time is short, and is excellent in thermal conductivity. Therefore, the thermosetting adhesive sheet of the present invention is required to have excellent post-humidity heat resistance that does not cause foaming or peeling even when firmly bonded and processed under extremely severe temperature conditions after bonding, and It can be preferably used for bonding applications of flexible printed circuit boards (FPCs) that require excellent thermal conductivity in order to dissipate the heat of the adherend.
  • FPCs flexible printed circuit boards

Abstract

The purpose of the present invention is to provide a thermosetting adhesive sheet which exhibits excellent adhesiveness and excellent heat resistance after exposure to humidity and heat even in cases where the curing time is short, while having excellent thermal conductivity. A thermosetting adhesive sheet of the present invention has a thermosetting adhesive layer that is formed from a thermosetting adhesive composition, and is characterized in that: the thermosetting adhesive composition contains an acrylic polymer (X) as a main component; the thermosetting adhesive composition also contains an etherified phenolic resin (Y); and the thermosetting adhesive layer has a thickness of 1-20 μm.

Description

熱硬化型接着シート及び積層体Thermosetting adhesive sheet and laminate
　本発明は、熱硬化型接着剤層を有する熱硬化型接着シートに関する。さらに詳細には、フレキシブル印刷回路基板等に好ましく用いることができる熱硬化型接着シートに関する。また、該熱硬化型接着シートとフレキシブル印刷回路基板を有する積層体に関する。 The present invention relates to a thermosetting adhesive sheet having a thermosetting adhesive layer. More specifically, the present invention relates to a thermosetting adhesive sheet that can be preferably used for a flexible printed circuit board or the like. The present invention also relates to a laminate having the thermosetting adhesive sheet and a flexible printed circuit board.
　電子機器では、フレキシブル印刷回路基板（「ＦＰＣ」と称する場合がある）が広く利用されている。このようなＦＰＣでは、（１）ポリイミド製基材やポリアミド製基材等の耐熱基材に、銅箔やアルミニウム箔等の導電性金属箔を接着積層して、ＦＰＣを作製する過程や、（２）ＦＰＣをアルミニウム板、ステンレス板、ポリイミド板等の補強板に接着する過程などで、接着剤が使用される。 In electronic devices, flexible printed circuit boards (sometimes referred to as “FPC”) are widely used. In such an FPC, (1) a process of manufacturing an FPC by bonding and laminating a conductive metal foil such as a copper foil or an aluminum foil on a heat-resistant substrate such as a polyimide substrate or a polyamide substrate, 2) An adhesive is used in the process of bonding the FPC to a reinforcing plate such as an aluminum plate, a stainless steel plate, or a polyimide plate.
　このようなＦＰＣの接着の際に用いられる接着剤としては、フェノール樹脂やエポキシ樹脂などの熱硬化性樹脂を含む熱硬化型接着剤が知られている。これら熱硬化型接着剤は、例えば、１５０℃以上の加熱により、接着剤に含まれる熱硬化性樹脂が硬化することで接着力を発揮する。 A thermosetting adhesive containing a thermosetting resin such as a phenol resin or an epoxy resin is known as an adhesive used for bonding such an FPC. These thermosetting adhesives exhibit an adhesive force when, for example, the thermosetting resin contained in the adhesive is cured by heating at 150 ° C. or higher.
　上記熱硬化型接着剤を用いて被着体（ＦＰＣ等）を接着して作製した積層体を、リフロー工程等の高温工程で処理する際には、接着剤や被着体に含まれる水分等が蒸発することにより、接着剤の発泡（膨れ）や浮き剥がれが生じることがあった。これらの現象は、接着剤の硬化不足が原因でおこる場合が多く、十分に硬化させるためには硬化温度を上げ、硬化時間を増やさなければならないという問題があった。そこで、上記問題を解決し、硬化性に優れた熱硬化型接着剤層を有する熱硬化型接着シートとして、アクリル系ポリマーを主成分とし、さらにエーテル化フェノール樹脂を含有する熱硬化型接着剤組成物から形成された熱硬化型接着剤層を有する熱硬化型接着シートが知られている（特許文献１参照）。 When a laminated body produced by bonding an adherend (FPC or the like) using the thermosetting adhesive is processed in a high temperature process such as a reflow process, the adhesive, moisture contained in the adherend, etc. As a result of evaporation of the adhesive, foaming (blowing) or lifting off of the adhesive may occur. These phenomena often occur due to insufficient curing of the adhesive, and there is a problem that the curing temperature must be increased and the curing time must be increased for sufficient curing. Therefore, as a thermosetting adhesive sheet that solves the above problems and has a thermosetting adhesive layer excellent in curability, a thermosetting adhesive composition that contains an acrylic polymer as a main component and further contains an etherified phenol resin A thermosetting adhesive sheet having a thermosetting adhesive layer formed from a product is known (see Patent Document 1).
国際公開第２０１１／００４７１０号パンフレットInternational Publication No. 2011/004710 Pamphlet
　しかしながら、近年、生産性向上の観点から、より一層硬化時間を短くすることが要求されてきている。そのため、硬化時間を短くした場合でも、優れた接着性、湿熱後耐熱性（高温高湿条件下で保存後、高温工程で処理した場合にも接着剤層の発泡や浮き剥がれが生じにくい特性）を発揮できる接着シートが要求されてきている。 However, in recent years, it has been required to further shorten the curing time from the viewpoint of improving productivity. Therefore, even when the curing time is shortened, excellent adhesion and heat resistance after wet heat (property that foaming and floating of the adhesive layer hardly occur even if it is stored in high temperature and high humidity conditions and then processed in a high temperature process) There has been a demand for an adhesive sheet capable of exhibiting the above.
　また、近年では、ＦＰＣを利用した電子機器の小型化、薄型化に伴い、電子機器内の電子部品の集積度が増す傾向にあり、ＦＰＣが熱を持つことが多くなってきている。ＦＰＣにたまった熱を放熱させるために、ＦＰＣの接着の際に用いられる接着剤（接着シート）には熱伝導性が求められるようになってきている。 Also, in recent years, with the downsizing and thinning of electronic devices using FPC, the degree of integration of electronic components in electronic devices has been increasing, and FPCs are often heated. In order to dissipate heat accumulated in the FPC, an adhesive (adhesive sheet) used for bonding the FPC is required to have thermal conductivity.
　従って、本発明の目的は、硬化時間が短い場合でも優れた接着性、湿熱後耐熱性を発揮でき、且つ放熱性、即ち熱伝導性に優れた熱硬化型接着シートを提供することにある。 Therefore, an object of the present invention is to provide a thermosetting adhesive sheet that can exhibit excellent adhesiveness and heat resistance after moist heat even when the curing time is short, and is excellent in heat dissipation, that is, thermal conductivity.
　そこで、上記問題を解決するために本発明者は鋭意検討した結果、特定の熱硬化型接着剤組成物から形成された特定の厚みの熱硬化型接着剤層を設けることで、硬化時間が短い場合でも優れた接着性、湿熱後耐熱性を発揮でき、且つ熱伝導性に優れた熱硬化型接着シートが得られることを見出し、本発明を完成した。 Accordingly, as a result of intensive studies by the present inventors in order to solve the above problems, a curing time is short by providing a thermosetting adhesive layer having a specific thickness formed from a specific thermosetting adhesive composition. Even in this case, the present inventors have found that a thermosetting adhesive sheet that can exhibit excellent adhesiveness and heat resistance after wet heat and has excellent thermal conductivity can be obtained.
　すなわち、本発明は、熱硬化型接着剤組成物から形成された熱硬化型接着剤層を有し、上記熱硬化型接着剤組成物は、アクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有し、上記熱硬化型接着剤層の厚さが１～２０μｍであることを特徴とする熱硬化型接着シートを提供する。 That is, the present invention has a thermosetting adhesive layer formed from a thermosetting adhesive composition, the thermosetting adhesive composition contains an acrylic polymer (X) as a main component, Also provided is a thermosetting adhesive sheet comprising an etherified phenol resin (Y), wherein the thermosetting adhesive layer has a thickness of 1 to 20 μm.
　本発明の熱硬化型接着シートは、１５０℃、６０分の条件下で硬化させた後の、上記熱硬化型接着剤層の全熱抵抗が２．０（ｃｍ2・Ｋ）／Ｗ以下であることが好ましい。 The thermosetting adhesive sheet of the present invention has a total thermal resistance of 2.0 (cm 2 · K) / W or less after being cured at 150 ° C. for 60 minutes. Preferably there is.
　上記アクリル系ポリマー（Ｘ）は、炭素数が１～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ）を必須のモノマー成分として構成されたアクリル系ポリマーであることが好ましい。 The acrylic polymer (X) is an acrylic polymer comprising, as an essential monomer component, a (meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms. It is preferable that
　上記アクリル系ポリマー（Ｘ）は、さらに、シアノ基含有モノマー（ｂ）及びカルボキシル基含有モノマー（ｃ）を必須のモノマー成分として構成されたアクリル系ポリマーであることが好ましい。 The acrylic polymer (X) is preferably an acrylic polymer composed of a cyano group-containing monomer (b) and a carboxyl group-containing monomer (c) as essential monomer components.
　上記エーテル化フェノール樹脂（Ｙ）の含有量が、上記アクリル系ポリマー（Ｘ）１００重量部に対して、１～４０重量部であることが好ましい。 The content of the etherified phenol resin (Y) is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the acrylic polymer (X).
　本発明の熱硬化型接着シートは、熱硬化型接着剤層のみからなり、基材を有していないことが好ましい。 The thermosetting adhesive sheet of the present invention preferably comprises only a thermosetting adhesive layer and does not have a substrate.
　本発明の熱硬化型接着シートは、フレキシブル印刷回路基板用熱硬化型接着シートであることが好ましい。 The thermosetting adhesive sheet of the present invention is preferably a thermosetting adhesive sheet for flexible printed circuit boards.
　また本発明は、フレキシブル印刷回路基板上に、上記熱硬化型接着シートを有する積層体を提供する。 The present invention also provides a laminate having the above thermosetting adhesive sheet on a flexible printed circuit board.
　また本発明は、上記熱硬化型接着シートを熱硬化して得られた、熱硬化された熱硬化型接着シートを提供する。 The present invention also provides a thermoset thermosetting adhesive sheet obtained by thermosetting the thermosetting adhesive sheet.
　また本発明は、フレキシブル印刷回路基板上に、上記熱硬化された熱硬化型接着シートを有する積層体を提供する。 The present invention also provides a laminate having the above thermosetting thermosetting adhesive sheet on a flexible printed circuit board.
　本発明の熱硬化型接着シートは、上記構成上の特徴を有することにより、硬化時間が短い場合でも優れた接着性、湿熱後耐熱性を発揮でき、且つ熱伝導性に優れる。特に、本発明の熱硬化型接着シートを熱硬化して得られた、熱硬化された熱硬化型接着シートは、硬化時間が短い場合でも優れた接着性、湿熱後耐熱性を発揮でき、且つ熱伝導性に優れる。 Since the thermosetting adhesive sheet of the present invention has the above-described structural characteristics, it can exhibit excellent adhesiveness, heat resistance after moist heat even when the curing time is short, and is excellent in thermal conductivity. In particular, the thermosetting thermosetting adhesive sheet obtained by thermosetting the thermosetting adhesive sheet of the present invention can exhibit excellent adhesiveness and heat resistance after wet heat even when the curing time is short, and Excellent thermal conductivity.
（ａ）は、実施例において全熱抵抗の測定を行う際に用いた装置の正面概略図、（ｂ）は（ａ）に示す装置の側面概略図である。(A) is the front schematic of the apparatus used when measuring total thermal resistance in an Example, (b) is the side schematic of the apparatus shown to (a).
　以下に、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の熱硬化型接着シートは、アクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有する熱硬化型接着剤組成物から形成された熱硬化型接着剤層を少なくとも有する。なお、本明細書においては、上記「アクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有する熱硬化型接着剤組成物」を「本発明の熱硬化型接着剤組成物」と称する場合がある。また、上記「アクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有する熱硬化型接着剤組成物から形成された熱硬化型接着剤層」（即ち、本発明の熱硬化型接着剤組成物から形成された熱硬化型接着剤層）を「本発明の熱硬化型接着剤層」と称する場合がある。 The thermosetting adhesive sheet of the present invention contains an acrylic polymer (X) as a main component and is formed from a thermosetting adhesive composition containing an etherified phenol resin (Y). Having at least a layer. In the present specification, the above-mentioned “thermosetting adhesive composition containing acrylic polymer (X) as a main component and containing etherified phenol resin (Y)” is referred to as “thermosetting type of the present invention. It may be referred to as “adhesive composition”. Further, the above-mentioned “thermosetting adhesive layer formed from a thermosetting adhesive composition containing acrylic polymer (X) as a main component and containing etherified phenol resin (Y)” (that is, the present invention The thermosetting adhesive layer formed from the thermosetting adhesive composition of the invention may be referred to as “thermosetting adhesive layer of the invention”.
　本明細書において、「アクリル系ポリマー（Ｘ）を主成分として含有する」とは、本発明の熱硬化型接着剤組成物の全不揮発分（１００重量％）中の、アクリル系ポリマー（Ｘ）の含有量が５０重量％以上であることを意味する。 In this specification, “contains acrylic polymer (X) as a main component” means that acrylic polymer (X) in the total nonvolatile content (100% by weight) of the thermosetting adhesive composition of the present invention. It means that the content of is 50% by weight or more.
　また、「熱硬化型接着シート」には、「熱硬化型接着テープ」の意味も含むものとする。即ち、本発明の熱硬化型接着シートは、テープ状の形態を有する熱硬化型接着テープであってもよい。 In addition, “thermosetting adhesive sheet” includes the meaning of “thermosetting adhesive tape”. That is, the thermosetting adhesive sheet of the present invention may be a thermosetting adhesive tape having a tape-like form.
［本発明の熱硬化型接着剤組成物］
　本発明の熱硬化型接着剤組成物は、アクリル系ポリマー（Ｘ）、及びエーテル化フェノール樹脂（Ｙ）を、必須の成分として含有する。本発明の熱硬化型接着剤組成物は、アクリル系ポリマー（Ｘ）及びエーテル化フェノール樹脂（Ｙ）の他に、溶剤（溶剤及び／又は分散媒）を含有していてもよく、添加剤を含有していてもよい。上記の各成分（アクリル系ポリマー（Ｘ）、エーテル化フェノール樹脂（Ｙ）、溶剤や添加剤）は、それぞれ、単独で又は２種以上を組み合わせて使用できる。 [Thermosetting adhesive composition of the present invention]
The thermosetting adhesive composition of the present invention contains an acrylic polymer (X) and an etherified phenol resin (Y) as essential components. The thermosetting adhesive composition of the present invention may contain a solvent (solvent and / or dispersion medium) in addition to the acrylic polymer (X) and the etherified phenol resin (Y). You may contain. Each of the above components (acrylic polymer (X), etherified phenol resin (Y), solvent or additive) can be used alone or in combination of two or more.
（アクリル系ポリマー（Ｘ））
　上記アクリル系ポリマー（Ｘ）は、特に限定されないが、炭素数が１～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ）を必須のモノマー成分として構成（又は形成）されたアクリル系ポリマーであることが好ましい。なお、本明細書においては、上記「炭素数が１～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ）」を、「（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）」又は単に「（メタ）アクリル酸アルキルエステル（ａ）」と称する場合がある。また、「（メタ）アクリル」とは、「アクリル」及び／又は「メタクリル」（「アクリル」及び「メタクリル」のうち一方又は両方）を意味し、以下も同様である。 (Acrylic polymer (X))
The acrylic polymer (X) is not particularly limited, but comprises a (meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms as an essential monomer component. A (or formed) acrylic polymer is preferred. In the present specification, the “(meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms” is referred to as “(meth) acrylic acid C 1. -14 alkyl ester (a) "or simply" (meth) acrylic acid alkyl ester (a) ". “(Meth) acryl” means “acryl” and / or “methacryl” (one or both of “acryl” and “methacryl”), and the same applies to the following.
　上記アクリル系ポリマー（Ｘ）は、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）、シアノ基含有モノマー（ｂ）及びカルボキシル基含有モノマー（ｃ）を必須のモノマー成分として構成されたアクリル系ポリマーであることがより好ましい。中でも、上記アクリル系ポリマー（Ｘ）を構成するモノマー成分全量（１００重量％）中の、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）の含有量が５０～７５重量％、シアノ基含有モノマー（ｂ）の含有量が２０～４９．５重量％、カルボキシル基含有モノマー（ｃ）の含有量が０．５～１０重量％であることが好ましい。なお、アクリル系ポリマー（Ｘ）を構成するモノマー成分としては、上記（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）、シアノ基含有モノマー（ｂ）及びカルボキシル基含有モノマー（ｃ）以外のモノマー成分（他のモノマー成分）が用いられてもよい。 The acrylic polymer (X) is an acrylic polymer composed of (meth) acrylic acid C 1-14 alkyl ester (a), cyano group-containing monomer (b) and carboxyl group-containing monomer (c) as essential monomer components. More preferably, it is a polymer. In particular, the content of the (meth) acrylic acid C 1-14 alkyl ester (a) in the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X) is 50 to 75% by weight, and contains a cyano group It is preferable that the content of the monomer (b) is 20 to 49.5% by weight and the content of the carboxyl group-containing monomer (c) is 0.5 to 10% by weight. The monomer component constituting the acrylic polymer (X) includes monomers other than the (meth) acrylic acid C 1-14 alkyl ester (a), the cyano group-containing monomer (b), and the carboxyl group-containing monomer (c). Components (other monomer components) may be used.
　上記アクリル系ポリマー（Ｘ）は、ゴム弾性（エラストマー性）を発現するアクリル系ポリマー（アクリル系エラストマー）であることが好ましい。 The acrylic polymer (X) is preferably an acrylic polymer (acrylic elastomer) that exhibits rubber elasticity (elastomeric properties).
　上記（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）としては、特に限定されないが、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）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（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）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシルなどが挙げられる。中でも、炭素数が４～１２である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（（メタ）アクリル酸Ｃ4-12アルキルエステル）が好ましく、アクリル酸ｎ－ブチルが特に好ましい。上記（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）は、単独で又は２種以上を組み合わせて使用できる。 The (meth) acrylic acid C 1-14 alkyl ester (a) is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate , Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Decyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and (meth) tetradecyl acrylate. Among them, (meth) acrylic acid alkyl ester ((meth) acrylic acid C 4-12 alkyl ester) having a linear or branched alkyl group having 4 to 12 carbon atoms is preferred, and n-butyl acrylate is preferred. Particularly preferred. The said (meth) acrylic-acid C1-14 alkylester (a) can be used individually or in combination of 2 or more types.
　アクリル系ポリマー（Ｘ）を構成するモノマー成分中の、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）の含有量（含有割合）は、アクリル系ポリマー（Ｘ）を構成するモノマー成分全量（１００重量％）に対して、５０重量％以上であり、好ましくは５０～７５重量％、より好ましくは５５～７５重量％、さらに好ましくは６０～７２重量％である。
　上記含有量が５０重量％以上であることにより、アクリル系ポリマー（Ｘ）が比較的硬いポリマーとなり、本発明の熱硬化型接着剤層の強度（バルク強度）を向上させ、湿熱後耐熱性を向上させることができる。 The content (content ratio) of the (meth) acrylic acid C 1-14 alkyl ester (a) in the monomer component constituting the acrylic polymer (X) is the total amount of the monomer component constituting the acrylic polymer (X) ( 100% by weight) to 50% by weight or more, preferably 50 to 75% by weight, more preferably 55 to 75% by weight, and still more preferably 60 to 72% by weight.
When the content is 50% by weight or more, the acrylic polymer (X) becomes a relatively hard polymer, improves the strength (bulk strength) of the thermosetting adhesive layer of the present invention, and improves heat resistance after wet heat. Can be improved.
　上記シアノ基含有モノマー（ｂ）は、シアノ基を有するモノマーであり、特に限定されないが、例えば、アクリロニトリル、メタクリロニトリルなどが挙げられる。中でも、アクリロニトリルが好ましい。上記シアノ基含有モノマー（ｂ）は、単独で又は２種以上を組み合わせて使用できる。
　シアノ基含有モノマー（ｂ）を用いることにより、本発明の熱硬化型接着剤層の強度（バルク強度）を向上させ、湿熱後耐熱性を向上させることができるため好ましい。また、本発明の熱硬化型接着剤層が脆くなることを防ぐことができるため好ましい。 The cyano group-containing monomer (b) is a monomer having a cyano group and is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. The said cyano group containing monomer (b) can be used individually or in combination of 2 or more types.
Use of the cyano group-containing monomer (b) is preferable because the strength (bulk strength) of the thermosetting adhesive layer of the present invention can be improved and the heat resistance after wet heat can be improved. Moreover, since it can prevent that the thermosetting adhesive layer of this invention becomes weak, it is preferable.
　アクリル系ポリマー（Ｘ）を構成するモノマー成分中の、シアノ基含有モノマー（ｂ）の含有量は、アクリル系ポリマー（Ｘ）を構成するモノマー成分全量（１００重量％）に対して、２０～４９．５重量％が好ましく、より好ましくは２４～４０重量％、さらに好ましくは２６～３５重量％である。
　上記含有量が２０重量％以上であることにより、本発明の熱硬化型接着シートの湿熱後耐熱性がより向上するため好ましい。一方、上記含有量が４９．５重量％を超えると、熱硬化型接着剤層の柔軟性が低下する場合がある。 The content of the cyano group-containing monomer (b) in the monomer component constituting the acrylic polymer (X) is 20 to 49 with respect to the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X). 0.5 wt% is preferable, more preferably 24 to 40 wt%, and still more preferably 26 to 35 wt%.
It is preferable that the content is 20% by weight or more because the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is further improved. On the other hand, if the content exceeds 49.5% by weight, the flexibility of the thermosetting adhesive layer may be lowered.
　上記カルボキシル基含有モノマー（ｃ）は、カルボキシル基を有するモノマーであり、特に限定されないが、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸などが挙げられる。また、これらのカルボキシル基含有モノマーの酸無水物（例えば、無水マレイン酸、無水イタコン酸などの酸無水物基含有モノマー）も、カルボキシル基含有モノマーに含まれるものとする。中でも、アクリル酸、メタクリル酸、イタコン酸が好ましく、特に好ましくはアクリル酸である。上記カルボキシル基含有モノマー（ｃ）は、単独で又は２種以上を組み合わせて使用できる。カルボキシル基含有モノマー（ｃ）を用いることにより、本発明の熱硬化型接着シートの湿熱後耐熱性及び接着力を向上させることができるため好ましい。 The carboxyl group-containing monomer (c) is a monomer having a carboxyl group and is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. In addition, acid anhydrides of these carboxyl group-containing monomers (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride) are also included in the carboxyl group-containing monomers. Among these, acrylic acid, methacrylic acid, and itaconic acid are preferable, and acrylic acid is particularly preferable. The said carboxyl group-containing monomer (c) can be used individually or in combination of 2 or more types. It is preferable to use the carboxyl group-containing monomer (c) because the heat resistance and adhesive strength after wet heat of the thermosetting adhesive sheet of the present invention can be improved.
　アクリル系ポリマー（Ｘ）を構成するモノマー成分中の、カルボキシル基含有モノマー（ｃ）の含有量は、アクリル系ポリマー（Ｘ）を構成するモノマー成分全量（１００重量％）に対して、０．５～１０重量％が好ましく、より好ましくは１～８重量％、さらに好ましくは２～６重量％である。
　上記含有量が０．５重量％以上であることにより、本発明の熱硬化型接着シートの湿熱後耐熱性及び接着力が向上するため好ましい。一方、上記含有量が１０重量％を超えると、熱硬化型接着剤層の柔軟性が低下する場合がある。 The content of the carboxyl group-containing monomer (c) in the monomer component constituting the acrylic polymer (X) is 0.5% relative to the total amount (100% by weight) of the monomer component constituting the acrylic polymer (X). It is preferably ˜10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
It is preferable that the content is 0.5% by weight or more because the heat resistance after wet heat and the adhesive force of the thermosetting adhesive sheet of the present invention are improved. On the other hand, if the content exceeds 10% by weight, the flexibility of the thermosetting adhesive layer may be lowered.
　上記アクリル系ポリマー（Ｘ）を構成するモノマー成分としては、上記（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）、上記シアノ基含有モノマー（ｂ）及び上記カルボキシル基含有モノマー（ｃ）の他に、他のモノマー成分（共重合性モノマー）が用いられていてもよい。上記他のモノマー成分（共重合性モノマー）は、単独で又は２種以上を組み合わせて使用できる。上記他のモノマー成分（共重合性モノマー）としては、例えば、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシル等の炭素数が１５～２０である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（（メタ）アクリル酸Ｃ15-20アルキルエステル）；（メタ）アクリル酸シクロアルキルエステル［（メタ）アクリル酸シクロヘキシルなど］や（メタ）アクリル酸イソボルニル等の非芳香族性環含有（メタ）アクリル酸エステル；（メタ）アクリル酸アリールエステル［（メタ）アクリル酸フェニルなど］、（メタ）アクリル酸アリールオキシアルキルエステル［（メタ）アクリル酸フェノキシエチルなど］、（メタ）アクリル酸アリールアルキルエステル［（メタ）アクリル酸ベンジルエステルなど］等の芳香族性環含有（メタ）アクリル酸エステル；（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジル等のエポキシ基含有アクリル系モノマー；酢酸ビニル、プロピオン酸ビニル等のビニルエステル系モノマー；スチレン、α－メチルスチレン等のスチレン系モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル等のヒドロキシル基含有モノマー；（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系モノマー；（メタ）アクリル酸アミノエチル、（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ｔ－ブチルアミノエチル等の（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリル酸アミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヒドロキシ（メタ）アクリルアミド等の（Ｎ－置換）アミド系モノマー；エチレン、プロピレン、イソプレン、ブタジエン等のオレフィン系モノマー；メチルビニルエーテル等のビニルエーテル系モノマーなどが挙げられる。 Examples of the monomer component constituting the acrylic polymer (X) include the (meth) acrylic acid C 1-14 alkyl ester (a), the cyano group-containing monomer (b), and the carboxyl group-containing monomer (c). In addition, other monomer components (copolymerizable monomers) may be used. The said other monomer component (copolymerizable monomer) can be used individually or in combination of 2 or more types. Examples of the other monomer components (copolymerizable monomers) include, for example, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate (Meth) acrylic acid alkyl ester ((meth) acrylic acid C 15-20 alkyl ester) having a linear or branched alkyl group having 15 to 20 carbon atoms, such as eicosyl (meth) acrylate; Non-aromatic ring-containing (meth) acrylic esters such as (meth) acrylic acid cycloalkyl esters [cyclohexyl (meth) acrylate] and isobornyl (meth) acrylate; (meth) acrylic acid aryl esters [(meth) acrylic Acid phenyl], (meth) acrylic acid aryloxyalkyl ester (Meth) acrylic acid phenoxyethyl etc.], (meth) acrylic acid arylalkyl ester [(meth) acrylic acid benzyl ester etc.] etc. aromatic ring containing (meth) acrylic acid ester; (meth) acrylic acid glycidyl, ( Epoxy group-containing acrylic monomers such as methyl glycidyl acrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; styrene monomers such as styrene and α-methylstyrene; hydroxyethyl (meth) acrylate, (meta ) Hydroxypropyl-containing monomers such as hydroxypropyl acrylate and hydroxybutyl (meth) acrylate; (meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; (meth) Acrylic acid (Meth) acrylic acid aminoalkyl monomers such as noethyl, N, N-dimethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (meth) acrylic acid amide, N, N-dimethyl ( (N-substituted) amide monomers such as (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxy (meth) acrylamide; olefin monomers such as ethylene, propylene, isoprene and butadiene; vinyl ether monomers such as methyl vinyl ether Etc.
　また、上記他のモノマー成分（共重合性モノマー）としては、ヘキサンジオールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジビニルベンゼンなどの多官能モノマーを用いることもできる。 The other monomer components (copolymerizable monomers) include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( Polyfunctional monomers such as (meth) acrylate and divinylbenzene can also be used.
　言い換えると、アクリル系ポリマー（Ｘ）は、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）に由来する構成単位、シアノ基含有モノマー（ｂ）に由来する構成単位、及びカルボキシル基含有モノマー（ｃ）に由来する構成単位を少なくとも含むアクリル系ポリマーであることが好ましい。各構成単位は、それぞれ、１種であってもよいし、２種以上であってもよい。アクリル系ポリマー（Ｘ）（１００重量％）中の、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）に由来する構成単位の含有量は、５０重量％以上が好ましく、より好ましくは５０～７５重量％、さらに好ましくは５５～７５重量％、最も好ましくは６０～７２重量％である。シアノ基含有モノマー（ｂ）に由来する構成単位の含有量は、２０～４９．５重量％が好ましく、より好ましくは２４～４０重量％、さらに好ましくは２６～３５重量％である。カルボキシル基含有モノマー（ｃ）に由来する構成単位の含有量は０．５～１０重量％が好ましく、より好ましくは１～８重量％、さらに好ましくは２～６重量％である。 In other words, the acrylic polymer (X) comprises a structural unit derived from the (meth) acrylic acid C 1-14 alkyl ester (a), a structural unit derived from the cyano group-containing monomer (b), and a carboxyl group-containing monomer ( An acrylic polymer containing at least the structural unit derived from c) is preferred. Each structural unit may be one kind or two or more kinds. The content of the structural unit derived from the (meth) acrylic acid C 1-14 alkyl ester (a) in the acrylic polymer (X) (100% by weight) is preferably 50% by weight or more, more preferably 50 to 50%. It is 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight. The content of the structural unit derived from the cyano group-containing monomer (b) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, and still more preferably 26 to 35% by weight. The content of the structural unit derived from the carboxyl group-containing monomer (c) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
　上記アクリル系ポリマー（Ｘ）は、単独で又は２種以上を組み合わせて使用できる。上記アクリル系ポリマー（Ｘ）は、接着性と耐熱性を両立させるため、少なくとも２種のアクリル系ポリマー（Ｘ）を組み合わせて使用してもよく、少なくともアクリル系ポリマー（Ｘ１）、及びアクリル系ポリマー（Ｘ２）を組み合わせて用いてもよい。 The acrylic polymer (X) can be used alone or in combination of two or more. The acrylic polymer (X) may be used in combination with at least two acrylic polymers (X) in order to achieve both adhesiveness and heat resistance. At least the acrylic polymer (X1) and the acrylic polymer (X2) may be used in combination.
　上記アクリル系ポリマー（Ｘ１）としては、例えば、炭素数が１～３である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ１）（「（メタ）アクリル酸Ｃ1-3アルキルエステル（ａ１）」と称する場合がある。）を必須のモノマー成分として構成（又は形成）されたアクリル系ポリマーや、（メタ）アクリル酸Ｃ1-3アルキルエステル（ａ１）、シアノ基含有モノマー（ｂ１）、及びカルボキシル基含有モノマー（ｃ１）を必須のモノマー成分として構成されたアクリル系ポリマーが挙げられる。各構成単位は、それぞれ、１種であってもよいし、２種以上であってもよい。なお、アクリル系ポリマー（Ｘ１）を構成するモノマー成分としては、上記（メタ）アクリル酸Ｃ1-3アルキルエステル（ａ１）、シアノ基含有モノマー（ｂ１）及びカルボキシル基含有モノマー（ｃ１）以外のモノマー成分（他のモノマー成分）が用いられてもよい。
　上記（メタ）アクリル酸Ｃ1-3アルキルエステル（ａ１）は、例えば、上述の（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）のうち炭素数が１～３である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルを用いることができる。上記シアノ基含有モノマー（ｂ１）は、例えば、上述のシアノ基含有モノマー（ｂ）から選ばれるシアノ基含有モノマーを用いることができる。上記カルボキシル基含有モノマー（ｃ１）は、上述のカルボキシル基含有モノマー（ｃ）から選ばれるカルボキシル基含有モノマーを用いることができる。 Examples of the acrylic polymer (X1) include a (meth) acrylic acid alkyl ester (a1) (“(meth) acrylic acid C 1 ) having a linear or branched alkyl group having 1 to 3 carbon atoms. -3 alkyl ester (a1) ”)) as an essential monomer component (or formed), (meth) acrylic acid C 1-3 alkyl ester (a1), cyano group Examples thereof include acrylic polymers composed of the containing monomer (b1) and the carboxyl group-containing monomer (c1) as essential monomer components. Each structural unit may be one kind or two or more kinds. The monomer component constituting the acrylic polymer (X1) is a monomer other than the (meth) acrylic acid C 1-3 alkyl ester (a1), the cyano group-containing monomer (b1), and the carboxyl group-containing monomer (c1). Components (other monomer components) may be used.
The (meth) acrylic acid C 1-3 alkyl ester (a1) is, for example, a linear or branched chain having 1 to 3 carbon atoms in the above (meth) acrylic acid C 1-14 alkyl ester (a). (Meth) acrylic acid alkyl ester having an alkyl group in a shape can be used. As the cyano group-containing monomer (b1), for example, a cyano group-containing monomer selected from the above-mentioned cyano group-containing monomers (b) can be used. As the carboxyl group-containing monomer (c1), a carboxyl group-containing monomer selected from the above-mentioned carboxyl group-containing monomers (c) can be used.
　上記アクリル系ポリマー（Ｘ１）を構成するモノマー成分全量（１００重量％）中の、（メタ）アクリル酸Ｃ1-3アルキルエステル（ａ１）の含有量は、５０重量％以上が好ましく、より好ましくは５０～７５重量％、さらに好ましくは５５～７５重量％、最も好ましくは６０～７２重量％である。シアノ基含有モノマー（ｂ１）の含有量は、２０～４９．５重量％が好ましく、より好ましくは２４～４０重量％、さらに好ましくは２６～３５重量％である。カルボキシル基含有モノマー（ｃ１）の含有量は、０．５～１０重量％が好ましく、より好ましくは１～８重量％、さらに好ましくは２～６重量％である。 The content of the (meth) acrylic acid C 1-3 alkyl ester (a1) in the total amount (100% by weight) of the monomer components constituting the acrylic polymer (X1) is preferably 50% by weight or more, more preferably It is 50 to 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight. The content of the cyano group-containing monomer (b1) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, and still more preferably 26 to 35% by weight. The content of the carboxyl group-containing monomer (c1) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
　上記アクリル系ポリマー（Ｘ２）としては、例えば、炭素数が４～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ２）（「（メタ）アクリル酸Ｃ4-14アルキルエステル（ａ２）」と称する場合がある。）を必須のモノマー成分として構成（又は形成）されたアクリル系ポリマーや（メタ）アクリル酸Ｃ4-14アルキルエステル（ａ２）、シアノ基含有モノマー（ｂ２）、及びカルボキシル基含有モノマー（ｃ２）を必須のモノマー成分として構成されたアクリル系ポリマーが挙げられる。各構成単位は、それぞれ、１種であってもよいし、２種以上であってもよい。なお、アクリル系ポリマー（Ｘ２）を構成するモノマー成分としては、上記（メタ）アクリル酸Ｃ4-14アルキルエステル（ａ２）、シアノ基含有モノマー（ｂ２）及びカルボキシル基含有モノマー（ｃ２）以外のモノマー成分（他のモノマー成分）が用いられてもよい。
　上記（メタ）アクリル酸Ｃ4-14アルキルエステル（ａ２）は、例えば、上述の（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）のうち炭素数が４～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルを用いることができる。上記シアノ基含有モノマー（ｂ２）は、例えば、上述のシアノ基含有モノマー（ｂ）から選ばれるシアノ基含有モノマーを用いることができる。上記カルボキシル基含有モノマー（ｃ２）は、上述のカルボキシル基含有モノマー（ｃ）から選ばれるカルボキシル基含有モノマーを用いることができる。 Examples of the acrylic polymer (X2) include (meth) acrylic acid alkyl ester (a2) (“(meth) acrylic acid C 4 having a linear or branched alkyl group having 4 to 14 carbon atoms”. -14 alkyl ester (a2) ”)) as an essential monomer component (or formation) acrylic polymer, (meth) acrylic acid C 4-14 alkyl ester (a2), cyano group-containing Examples thereof include an acrylic polymer composed of the monomer (b2) and the carboxyl group-containing monomer (c2) as essential monomer components. Each structural unit may be one kind or two or more kinds. The monomer component constituting the acrylic polymer (X2) includes monomers other than the (meth) acrylic acid C 4-14 alkyl ester (a2), the cyano group-containing monomer (b2), and the carboxyl group-containing monomer (c2). Components (other monomer components) may be used.
The (meth) acrylic acid C 4-14 alkyl ester (a2) is, for example, a linear or branched chain having 4 to 14 carbon atoms in the above (meth) acrylic acid C 1-14 alkyl ester (a). (Meth) acrylic acid alkyl ester having an alkyl group in a shape can be used. As the cyano group-containing monomer (b2), for example, a cyano group-containing monomer selected from the above-mentioned cyano group-containing monomers (b) can be used. As the carboxyl group-containing monomer (c2), a carboxyl group-containing monomer selected from the above-mentioned carboxyl group-containing monomers (c) can be used.
　上記アクリル系ポリマー（Ｘ２）を構成するモノマー成分全量（１００重量％）中の、（メタ）アクリル酸Ｃ4-14アルキルエステル（ａ２）の含有量は、５０重量％以上が好ましく、より好ましくは５０～７５重量％、さらに好ましくは５５～７５重量％、最も好ましくは６０～７２重量％である。シアノ基含有モノマー（ｂ２）の含有量は、２０～４９．５重量％が好ましく、より好ましくは２４～４０重量％、さらに好ましくは２６～３５重量％である。カルボキシル基含有モノマー（ｃ２）の含有量は、０．５～１０重量％が好ましく、より好ましくは１～８重量％、さらに好ましくは２～６重量％である。 The content of (meth) acrylic acid C 4-14 alkyl ester (a2) in the total amount (100% by weight) of the monomer components constituting the acrylic polymer (X2) is preferably 50% by weight or more, more preferably It is 50 to 75% by weight, more preferably 55 to 75% by weight, and most preferably 60 to 72% by weight. The content of the cyano group-containing monomer (b2) is preferably 20 to 49.5% by weight, more preferably 24 to 40% by weight, still more preferably 26 to 35% by weight. The content of the carboxyl group-containing monomer (c2) is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight.
　上記アクリル系ポリマー（Ｘ）は、公知乃至慣用の重合方法（例えば、溶液重合方法、エマルション重合方法、懸濁重合方法、塊状重合方法や紫外線照射による重合方法など）により調製することができる。 The acrylic polymer (X) can be prepared by a known or conventional polymerization method (for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a polymerization method by ultraviolet irradiation, etc.).
　なお、アクリル系ポリマー（Ｘ）の重合に際して必要に応じて用いられる重合開始剤、乳化剤、連鎖移動剤などは、特に限定されず、公知乃至慣用のものの中から適宜選択して使用することができる。より具体的には、上記重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス（２，４，４－トリメチルペンタン）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス｛２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン｝ジハイドロクロライド等のアゾ系重合開始剤；ベンゾイルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）シクロドデカン等の過酸化物系重合開始剤などが挙げられる。上記重合開始剤は、単独で又は２種以上を組み合わせて使用できる。上記重合開始剤の使用量は、特に限定されず、通常の使用量の範囲から適宜選択することができる。 In addition, the polymerization initiator, the emulsifier, the chain transfer agent and the like that are used as necessary in the polymerization of the acrylic polymer (X) are not particularly limited, and can be appropriately selected from known or commonly used ones. . More specifically, examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis ( 2,4,4-trimethylpentane), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline- Azo polymerization initiators such as 2-yl] propane} dihydrochloride; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxide Peroxides such as xylbenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane A polymerization initiator etc. are mentioned. The said polymerization initiator can be used individually or in combination of 2 or more types. The usage-amount of the said polymerization initiator is not specifically limited, It can select suitably from the range of a normal usage-amount.
　上記連鎖移動剤としては、例えば、１－ドデカンチオール、ｔｅｒｔ－ラウリルメルカプタン、ｓｅｃ－ラウリルメルカプタン、２－メルカプトエタノール、グリシジルメルカプタン、メルカプト酢酸、チオグリコール酸２－エチルヘキシル、２，３－ジメルカプト－１－プロパノール、α－メチルスチレンダイマーなどが挙げられる。上記乳化剤としては、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウムなどのアニオン系乳化剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテルなどのノニオン系乳化剤などが挙げられる。上記連鎖移動剤及び上記乳化剤は、それぞれ、単独で又は２種以上を組み合わせて使用できる。 Examples of the chain transfer agent include 1-dodecanethiol, tert-lauryl mercaptan, sec-lauryl mercaptan, 2-mercaptoethanol, glycidyl mercaptan, mercaptoacetic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1- Examples include propanol and α-methylstyrene dimer. Examples of the emulsifier include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxy Nonionic emulsifiers such as ethylene alkyl ether and polyoxyethylene alkyl phenyl ether are listed. The chain transfer agent and the emulsifier can be used alone or in combination of two or more.
　なお、溶液重合では、各種の一般的な溶剤を用いることができる。上記溶剤としては、例えば、酢酸エチル、酢酸ｎ－ブチル等のエステル類；トルエン、ベンゼン等の芳香族炭化水素類；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類；メチルエチルケトン、メチルイソブチルケトン等のケトン類などの有機溶剤が挙げられる。上記溶剤は単独で又は２種以上を組み合わせて使用できる。 In solution polymerization, various common solvents can be used. Examples of the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. The said solvent can be used individually or in combination of 2 or more types.
　上記アクリル系ポリマー（Ｘ）の重量平均分子量（Ｍｗ）は、特に限定されないが、本発明の熱硬化型接着剤組成物の塗工性を向上させ生産性を向上させる観点や、本発明の熱硬化型接着剤層の強度を向上させ湿熱後耐熱性を向上させる観点から、５０万～４００万が好ましく、より好ましくは６０万～３５０万、さらに好ましくは８０万～３２０万である。
　アクリル系ポリマー（Ｘ）の重量平均分子量は、重合開始剤や連鎖移動剤の種類やその使用量、重合の際の温度や時間の他、モノマー濃度、モノマー滴下速度などによりコントロールすることができる。 The weight average molecular weight (Mw) of the acrylic polymer (X) is not particularly limited, but the viewpoint of improving productivity by improving the coating property of the thermosetting adhesive composition of the present invention, and the heat of the present invention. From the viewpoint of improving the strength of the curable adhesive layer and improving the heat resistance after wet heat, it is preferably 500,000 to 4,000,000, more preferably 600,000 to 3,500,000, still more preferably 800,000 to 3,200,000.
The weight average molecular weight of the acrylic polymer (X) can be controlled by the monomer concentration, the monomer dropping rate, etc., in addition to the type and amount of polymerization initiator and chain transfer agent, the temperature and time during polymerization.
　上記重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により測定することができる。より具体的には、例えば、以下の＜ＧＰＣの測定方法＞で測定して求めることができる。
＜ＧＰＣの測定方法＞
　（測定試料の調製）
　測定対象であるアクリル系ポリマーを溶離液に溶解して、該アクリル系ポリマーの０．１％ＴＨＦ溶液を調製し、１日放置した後、０．４５μｍメンブレンフィルターにてろ過し、得られたろ液を測定試料として、下記測定条件でＧＰＣ測定を行う。
　（測定条件）
　ＧＰＣ装置：ＨＬＣ－８３２０ＧＰＣ（東ソー株式会社製）
　カラム：ＴＳＫｇｅｌ　ＧＭＨ－Ｈ（Ｓ）（東ソー株式会社製）
　カラムサイズ：７．８ｍｍＩ．Ｄ．×３００ｍｍ
　カラム温度：４０℃
　溶離液：ＴＨＦ（テトラヒドロフラン）
　流速：０．５ｍｌ／ｍｉｎ
　入口圧：４．６ＭＰａ
　注入量：１００μｌ
　検出器：示差屈折計
　標準試料：ポリスチレン
　データ処理装置：ＧＰＣ－８０２０（東ソー株式会社製） The weight average molecular weight can be measured by gel permeation chromatograph (GPC). More specifically, it can be determined by, for example, the following <GPC measurement method>.
<GPC measurement method>
(Preparation of measurement sample)
The acrylic polymer to be measured is dissolved in the eluent to prepare a 0.1% THF solution of the acrylic polymer, left for 1 day, and then filtered through a 0.45 μm membrane filter. As a measurement sample, GPC measurement is performed under the following measurement conditions.
(Measurement condition)
GPC device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TSKgel GMH-H (S) (manufactured by Tosoh Corporation)
Column size: 7.8 mm I.D. D. × 300mm
Column temperature: 40 ° C
Eluent: THF (tetrahydrofuran)
Flow rate: 0.5 ml / min
Inlet pressure: 4.6 MPa
Injection volume: 100 μl
Detector: Differential refractometer Standard sample: Polystyrene Data processing device: GPC-8020 (manufactured by Tosoh Corporation)
　本発明の熱硬化型接着剤組成物中の、上記アクリル系ポリマー（Ｘ）の含有量（含有割合、配合割合）は、特に限定されないが、湿熱後耐熱性と接着力の両立の観点から、本発明の熱硬化性接着剤組成物の全不揮発分（１００重量％）に対して、５０重量％以上であり、７０～９９重量％が好ましく、より好ましくは８０～９５重量％、さらに好ましくは８５～９５重量％である。 The content (content ratio, blending ratio) of the acrylic polymer (X) in the thermosetting adhesive composition of the present invention is not particularly limited, but from the viewpoint of coexistence of heat resistance after wet heat and adhesive strength, It is 50% by weight or more with respect to the total nonvolatile content (100% by weight) of the thermosetting adhesive composition of the present invention, preferably 70 to 99% by weight, more preferably 80 to 95% by weight, and still more preferably. 85 to 95% by weight.
　上記アクリル系ポリマー（Ｘ）が、例えば、アクリル系ポリマー（Ｘ１）、及びアクリル系ポリマー（Ｘ２）を含む場合、本発明の熱硬化型接着剤組成物の全不揮発分（１００重量％）中の、アクリル系ポリマー（Ｘ１）の含有量とアクリル系ポリマー（Ｘ２）の含有量の合計量（合計含有量）は、５０重量％以上であり、７０～９９重量％が好ましく、より好ましくは８０～９５重量％、さらに好ましくは８５～９５重量％である。
　また、アクリル系ポリマー（Ｘ１）に対するアクリル系ポリマー（Ｘ２）の含有量（含有割合、配合割合）は、特に限定されないが、接着性と耐熱性を両立できる点から、アクリル系ポリマー（Ｘ１）１００重量部に対して、１～１００重量部が好ましく、より好ましくは２～４５重量部、さらに好ましくは４～２５重量部、最も好ましくは５～２０重量部である。上記アクリル系ポリマー（Ｘ２）の含有量を１重量部以上とすることにより、本発明の熱硬化型接着シートの接着力が向上し、湿熱後耐熱性も向上するため好ましい。また、１００重量部以下とすることにより、本発明の熱硬化型接着剤層の強度が向上し、本発明の熱硬化型接着シートの湿熱後耐熱性が向上するため好ましい。 When the acrylic polymer (X) includes, for example, the acrylic polymer (X1) and the acrylic polymer (X2), the total non-volatile content (100% by weight) of the thermosetting adhesive composition of the present invention. The total content (total content) of the acrylic polymer (X1) content and the acrylic polymer (X2) content is 50% by weight or more, preferably 70 to 99% by weight, more preferably 80 to It is 95% by weight, more preferably 85 to 95% by weight.
Further, the content (content ratio, blending ratio) of the acrylic polymer (X2) with respect to the acrylic polymer (X1) is not particularly limited, but the acrylic polymer (X1) 100 is compatible with both adhesiveness and heat resistance. The amount is preferably 1 to 100 parts by weight, more preferably 2 to 45 parts by weight, still more preferably 4 to 25 parts by weight, and most preferably 5 to 20 parts by weight with respect to parts by weight. By setting the content of the acrylic polymer (X2) to 1 part by weight or more, it is preferable because the adhesive force of the thermosetting adhesive sheet of the present invention is improved and the heat resistance after wet heat is improved. Further, the content of 100 parts by weight or less is preferable because the strength of the thermosetting adhesive layer of the present invention is improved and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved.
（エーテル化フェノール樹脂（Ｙ））
　上記エーテル化フェノール樹脂（Ｙ）は、フェノール樹脂の有するメチロール基（フェノール樹脂中のメチロール基）の一部がエーテル化されているフェノール樹脂である。即ち、エーテル化されていないメチロール基及びエーテル化されたメチロール基を少なくとも有するフェノール樹脂である。エーテル化フェノール樹脂（Ｙ）は、熱硬化性を付与するために用いられる。エーテル化フェノール樹脂（Ｙ）は加熱硬化時の反応性に優れるため、エーテル化フェノール樹脂（Ｙ）を用いると、本発明の熱硬化型接着剤層の接着力及び湿熱後耐熱性が向上し、本発明の熱硬化型接着シートを薄くすることができる。 (Etherized phenol resin (Y))
The etherified phenol resin (Y) is a phenol resin in which a part of the methylol group (methylol group in the phenol resin) of the phenol resin is etherified. That is, it is a phenol resin having at least a non-etherified methylol group and an etherified methylol group. The etherified phenol resin (Y) is used for imparting thermosetting properties. Since the etherified phenol resin (Y) is excellent in reactivity at the time of heat curing, the use of the etherified phenol resin (Y) improves the adhesive strength of the thermosetting adhesive layer of the present invention and the heat resistance after wet heat, The thermosetting adhesive sheet of the present invention can be thinned.
　さらに、上記エーテル化フェノール樹脂（Ｙ）は、フェノール樹脂の有するメチロール基の一部がアルキル基でエーテル化されているフェノール樹脂である、アルキルエーテル化フェノール樹脂が好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基などの炭素数が１～２０のアルキル基が挙げられる。中でも、メチル基、エチル基、ｎ－ブチル基が好ましく、さらに好ましくはｎ－ブチル基である。 Furthermore, the etherified phenol resin (Y) is preferably an alkyl etherified phenol resin which is a phenol resin in which a part of the methylol group of the phenol resin is etherified with an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, Octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms such as an eicosyl group. Of these, a methyl group, an ethyl group, and an n-butyl group are preferable, and an n-butyl group is more preferable.
　上記エーテル化フェノール樹脂（Ｙ）において、骨格となるフェノール樹脂は、特に限定されない。上記エーテル化フェノール樹脂（Ｙ）としては、例えば、エーテル化ノボラック型フェノール樹脂、エーテル化レゾール型フェノール樹脂、エーテル化クレゾール樹脂などが挙げられる。中でも、エーテル化クレゾール樹脂が好ましく、より好ましくはブチルエーテル化クレゾール樹脂（メチロール基の一部がブチルエーテル化されたクレゾール樹脂）である。上記エーテル化フェノール樹脂（Ｙ）は、単独で又は２種以上を組み合わせて使用できる。 In the etherified phenol resin (Y), the phenol resin as a skeleton is not particularly limited. Examples of the etherified phenol resin (Y) include an etherified novolac type phenol resin, an etherified resol type phenol resin, and an etherified cresol resin. Among these, etherified cresol resins are preferable, and butyl etherified cresol resins (cresol resins in which a part of the methylol group is butyl etherified) are more preferable. The etherified phenol resin (Y) can be used alone or in combination of two or more.
　上記エーテル化フェノール樹脂（Ｙ）における、エーテル化されたメチロール基の割合としては、例えば、エーテル化されたメチロール基とエーテル化されていないメチロール基の合計（１００モル％）に対する、エーテル化されたメチロール基の割合が、５０モル％以上（５０モル％以上、１００モル％未満）であることが好ましく、より好ましくは７０モル％以上である。エーテル化されたメチロール基の割合が５０モル％未満では、エーテル化フェノール樹脂の常温での反応が促進されたり、加熱硬化時の反応性が低下する場合がある。 The ratio of etherified methylol groups in the etherified phenol resin (Y) is, for example, etherified with respect to the total (100 mol%) of etherified methylol groups and non-etherified methylol groups. The proportion of the methylol group is preferably 50 mol% or more (50 mol% or more and less than 100 mol%), more preferably 70 mol% or more. If the ratio of the etherified methylol group is less than 50 mol%, the reaction of the etherified phenol resin at room temperature may be accelerated, or the reactivity during heat curing may be reduced.
　上記エーテル化フェノール樹脂（Ｙ）としては、市販されているエーテル化フェノール樹脂を使用することもでき、例えば、商品名「スミライトレジンＰＲ－５５３１７」（住友ベークライト株式会社製、ブチルエーテル化クレゾール樹脂、エーテル化されたメチロール基の割合：９０モル％）、商品名「ＣＫＳ－３８９８」（昭和電工株式会社製、ブチルエーテル化クレゾール樹脂）などを使用することができる。 As the etherified phenol resin (Y), a commercially available etherified phenol resin can also be used. For example, trade name “Sumilite Resin PR-55317” (Sumitomo Bakelite Co., Ltd., butyl etherified cresol resin, The ratio of etherified methylol groups: 90 mol%), trade name “CKS-3898” (Butyl etherified cresol resin, manufactured by Showa Denko KK), and the like can be used.
　本発明の熱硬化型接着剤組成物中の、上記エーテル化フェノール樹脂（Ｙ）の含有量（含有割合、配合割合）は、アクリル系ポリマー（Ｘ）１００重量部に対して、１～４０重量部が好ましく、より好ましくは５～２０重量部、さらに好ましくは１０～１５重量部である。上記エーテル化フェノール樹脂（Ｙ）の含有量１重量部以上とすることにより、本発明の熱硬化型接着剤層の熱硬化性が向上するため好ましい。また、４０重量部以下とすることにより、高温プレス時に接着剤がはみ出さないため好ましい。 The content (content ratio, blending ratio) of the etherified phenol resin (Y) in the thermosetting adhesive composition of the present invention is 1 to 40 weights per 100 weight parts of the acrylic polymer (X). Parts, preferably 5 to 20 parts by weight, more preferably 10 to 15 parts by weight. The content of the etherified phenol resin (Y) of 1 part by weight or more is preferable because the thermosetting property of the thermosetting adhesive layer of the present invention is improved. Moreover, it is preferable to make it 40 parts by weight or less because the adhesive does not protrude during high-temperature pressing.
（溶剤、添加剤）
　本発明の熱硬化型接着剤組成物は、溶剤を含むことが好ましい。上記溶剤としては、例えば、酢酸エチル、酢酸ｎ－ブチル等のエステル類；メタノール、エタノール、ブタノール、プロパノール、イソプロパノール等のアルコール類；トルエン、ベンゼン等の芳香族炭化水素類；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類；メチルエチルケトン、メチルイソブチルケトン等のケトン類などの有機溶剤が挙げられる。上記溶剤は単独で又は２種以上を組み合わせて使用できる。なお、上記溶剤には分散媒の意味も含むものとする。 (Solvent, additive)
The thermosetting adhesive composition of the present invention preferably contains a solvent. Examples of the solvent include esters such as ethyl acetate and n-butyl acetate; alcohols such as methanol, ethanol, butanol, propanol and isopropanol; aromatic hydrocarbons such as toluene and benzene; n-hexane and n- Examples include aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. The said solvent can be used individually or in combination of 2 or more types. Note that the solvent includes the meaning of a dispersion medium.
　本発明の熱硬化型接着剤組成物には、アクリル系ポリマー（Ｘ）、及びエーテル化フェノール樹脂（Ｙ）以外に、必要に応じて、老化防止剤、充填剤（フィラー）、着色剤（顔料や染料など）、紫外線吸収剤、酸化防止剤、架橋剤、粘着付与剤、可塑剤、軟化剤、界面活性剤、帯電防止剤などの公知の添加剤が本発明の特性を損なわない範囲で含まれていてもよい。上記添加剤は単独で又は２種以上を組み合わせて使用できる。 In addition to the acrylic polymer (X) and the etherified phenol resin (Y), the thermosetting adhesive composition of the present invention includes an anti-aging agent, a filler (filler), a colorant (pigment) as necessary. And dyes), UV absorbers, antioxidants, crosslinking agents, tackifiers, plasticizers, softeners, surfactants, antistatic agents, and other known additives are included within the range that does not impair the characteristics of the present invention. It may be. The said additive can be used individually or in combination of 2 or more types.
　上記充填剤（フィラー）としては、特に限定されず、公知慣用の有機充填剤や無機充填剤を用いることができる。中でも、本発明の熱硬化型接着剤層の強度を向上させ、本発明の熱硬化型接着シートの湿熱後耐熱性をさらに向上させる観点から、シリカフィラー、銅フィラーが好ましい。上記充填剤は単独で又は２種以上を組み合わせて使用できる。 The filler (filler) is not particularly limited, and known and commonly used organic fillers and inorganic fillers can be used. Especially, a silica filler and a copper filler are preferable from the viewpoint of improving the strength of the thermosetting adhesive layer of the present invention and further improving the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention. The said filler can be used individually or in combination of 2 or more types.
　上記シリカフィラーや上記銅フィラーの形状としては、特に限定されないが、例えば、球状、フィラメント状、フレーク状、樹枝状、不規則形状などが挙げられる。中でも、上記シリカフィラーや上記銅フィラーの形状は、本発明の熱硬化型接着剤層で均一に分散させる点から、球状であることが好ましい。 The shape of the silica filler or the copper filler is not particularly limited, and examples thereof include a spherical shape, a filament shape, a flake shape, a dendritic shape, and an irregular shape. Especially, it is preferable that the shape of the said silica filler or the said copper filler is spherical from the point disperse | distributed uniformly with the thermosetting type adhesive layer of this invention.
　上記シリカフィラーや上記銅フィラーの平均粒径は、特に限定されないが、０．００５～１０μｍが好ましく、より好ましくは０．０５～５μｍである。上記平均粒径を０．００５μｍ以上とすることにより、本発明の熱硬化型接着剤層の濡れ性及び接着力が向上するため好ましい。また、上記平均粒径を１０μｍ以下とすることにより、本発明の熱硬化型接着剤層の強度が向上し、本発明の熱硬化型接着シートの湿熱後耐熱性が向上するため好ましい。なお、フィラーの平均粒径は、例えば、光度式の粒度分布計（装置名「ＬＡ－９１０」、株式会社堀場製作所製）により求めることができる。 The average particle diameter of the silica filler or the copper filler is not particularly limited, but is preferably 0.005 to 10 μm, more preferably 0.05 to 5 μm. It is preferable that the average particle size is 0.005 μm or more because the wettability and adhesive strength of the thermosetting adhesive layer of the present invention are improved. The average particle size is preferably 10 μm or less because the strength of the thermosetting adhesive layer of the present invention is improved and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved. The average particle size of the filler can be determined by, for example, a photometric particle size distribution meter (device name “LA-910”, manufactured by Horiba, Ltd.).
　上記のシリカフィラーや上記銅フィラーには、表面処理が施されていてよい。 The silica filler or the copper filler may be subjected to a surface treatment.
　本発明の熱硬化型接着剤組成物は、上記シリカフィラー及び上記銅フィラーのうち、少なくとも１のフィラーを含有することが好ましい。すなわち、本発明の熱硬化型接着剤組成物は、シリカフィラー及び銅フィラーの両方を含有していてもよいし、シリカフィラー及び銅フィラーのうち、どちらか一方のみを含有していてもよい。 The thermosetting adhesive composition of the present invention preferably contains at least one filler of the silica filler and the copper filler. That is, the thermosetting adhesive composition of the present invention may contain both a silica filler and a copper filler, or may contain only one of the silica filler and the copper filler.
　本発明の熱硬化型接着剤組成物中の、上記シリカフィラーの含有量と上記銅フィラーの含有量の合計量（合計含有量、合計含有割合、合計配合割合）は、特に限定されないが、アクリル系ポリマー（Ｘ）１００重量部に対して、１～１５０重量部が好ましく、より好ましくは５～１４０重量部、さらに好ましくは１０～１２０重量部である。上記含有量を１重量部以上とすることにより、本発明の熱硬化型接着剤層の強度が向上し、本発明の熱硬化型接着シートの湿熱後耐熱性が向上する。また、上記含有量を１５０重量部以下とすることにより、本発明の熱硬化型接着剤層が、脆くなり、その強度が低下することを防ぐことができる。なお、本発明の熱硬化型接着剤組成物中にシリカフィラー又は銅フィラーのどちらか一方が含まれる場合、その含まれるシリカフィラー又は銅フィラーの含有量である。 The total amount of the silica filler content and the copper filler content (total content, total content ratio, total blending ratio) in the thermosetting adhesive composition of the present invention is not particularly limited. The amount is preferably 1 to 150 parts by weight, more preferably 5 to 140 parts by weight, and still more preferably 10 to 120 parts by weight with respect to 100 parts by weight of the polymer (X). By setting the content to 1 part by weight or more, the strength of the thermosetting adhesive layer of the present invention is improved, and the heat resistance after wet heat of the thermosetting adhesive sheet of the present invention is improved. Moreover, it can prevent that the thermosetting adhesive layer of this invention becomes weak and the intensity | strength falls because the said content shall be 150 weight part or less. In addition, when either one of a silica filler or a copper filler is contained in the thermosetting adhesive composition of the present invention, it is the content of the silica filler or copper filler contained therein.
　本発明の熱硬化型接着剤組成物は、例えば、（メタ）アクリル酸Ｃ1-14アルキルエステル（ａ）、シアノ基含有モノマー（ｂ）及びカルボキシル基含有モノマー（ｃ）を必須のモノマー成分として構成されたアクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有することが好ましい。 The thermosetting adhesive composition of the present invention includes, for example, (meth) acrylic acid C 1-14 alkyl ester (a), cyano group-containing monomer (b) and carboxyl group-containing monomer (c) as essential monomer components. It is preferable that the structured acrylic polymer (X) is contained as a main component and the etherified phenol resin (Y) is contained.
　本発明の熱硬化型接着剤組成物は、例えば、アクリル系ポリマー（Ｘ）、エーテル化フェノール樹脂（Ｙ）と、必要に応じて各種添加剤等を混合することにより調製することができる。なお、アクリル系ポリマー（Ｘ）、エーテル化フェノール樹脂（Ｙ）は、溶剤に溶解させることにより溶液の状態として、又は分散媒に分散させることにより分散液の状態として、本発明の熱硬化型接着剤組成物の調製に用いることもできる。 The thermosetting adhesive composition of the present invention can be prepared, for example, by mixing an acrylic polymer (X), an etherified phenol resin (Y), and various additives as necessary. The acrylic polymer (X) and the etherified phenol resin (Y) can be dissolved in a solvent to form a solution, or dispersed in a dispersion medium to form a dispersion. It can also be used for the preparation of an agent composition.
［本発明の熱硬化型接着剤層］
　本発明の熱硬化型接着剤層は、本発明の熱硬化型接着剤組成物から形成された熱硬化型の接着剤層である。本発明の熱硬化型接着剤層は単層、複層のいずれの形態を有していてもよい。 [Thermosetting adhesive layer of the present invention]
The thermosetting adhesive layer of the present invention is a thermosetting adhesive layer formed from the thermosetting adhesive composition of the present invention. The thermosetting adhesive layer of the present invention may have either a single layer or multiple layers.
　本発明の熱硬化型接着剤層の厚さは、１～２０μｍであり、好ましくは５～２０μｍ、好ましくは８～１８μｍ、より好ましくは１０～１５μｍである。上記厚みが１μｍ以上であることにより、接着力が向上するため好ましい。一方、上記厚みが２０μｍ以下であることにより、硬化時間が短い場合でも硬化後の熱硬化型接着剤層が、放熱性、接着性、湿熱後耐熱性に優れる。 The thickness of the thermosetting adhesive layer of the present invention is 1 to 20 μm, preferably 5 to 20 μm, preferably 8 to 18 μm, more preferably 10 to 15 μm. It is preferable that the thickness is 1 μm or more because the adhesive force is improved. On the other hand, when the thickness is 20 μm or less, even when the curing time is short, the cured thermosetting adhesive layer is excellent in heat dissipation, adhesiveness, and heat resistance after wet heat.
　本発明の熱硬化型接着剤層は、特に限定されないが、１５０℃、６０分の条件下で硬化させた後の全熱抵抗（定常熱流法により測定した全熱抵抗）が、２．０（ｃｍ2・Ｋ）／Ｗ以下であることが好ましく、０．０１～１．８（ｃｍ2・Ｋ）／Ｗがより好ましく、０．１～１．６（ｃｍ2・Ｋ）／Ｗがさらに好ましく、０．３～１．５（ｃｍ2・Ｋ）／Ｗが特に好ましい。すなわち、１５０℃、６０分の条件下で硬化させた後の、全熱抵抗は２．０（ｃｍ2・Ｋ）／Ｗ以下であることが好ましく、０．０１～１．８（ｃｍ2・Ｋ）／Ｗがより好ましく、０．１～１．６（ｃｍ2・Ｋ）／Ｗがさらに好ましく、０．３～１．５（ｃｍ2・Ｋ）／Ｗが特に好ましい。上記全熱抵抗が、２．０（ｃｍ2・Ｋ）／Ｗ以下であることにより、硬化後の熱硬化型接着剤層が、放熱性（熱伝導性）に優れたものとなるため、本発明の熱硬化型接着シートを用いて二つの被着体を貼り付けた場合に、一方の被着体から他方の被着体へ熱を効率よく移動させることができる。具体的には、例えば、本発明の熱硬化型接着シートを介して、ＦＰＣと補強板とを接着させた場合、ＦＰＣにたまった熱を、本発明の熱硬化型接着シートを介して、補強板に効率的に放熱させることができる。
　なお、全熱抵抗とは、硬化後の熱硬化型接着剤層自体の熱抵抗と、接触熱抵抗の合計を意味する。また、接触熱抵抗とは、硬化後の熱硬化型接着剤層の表面粗さなどにより、接着剤層表面と被着体との間に空気が介在することによって、接着剤層と被着体との間に生じる熱抵抗である。また、上記全熱抵抗は、後述の（評価）の「（３）全熱抵抗」に記載の方法によって測定することができる。 The thermosetting adhesive layer of the present invention is not particularly limited, but the total thermal resistance after being cured at 150 ° C. for 60 minutes (total thermal resistance measured by a steady heat flow method) is 2.0 ( cm 2 · K) / W or less, preferably 0.01 to 1.8 (cm 2 · K) / W, more preferably 0.1 to 1.6 (cm 2 · K) / W 0.3 to 1.5 (cm 2 · K) / W is particularly preferable. That is, the total thermal resistance after curing at 150 ° C. for 60 minutes is preferably 2.0 (cm 2 · K) / W or less, 0.01 to 1.8 (cm 2 · K) / W is more preferable, 0.1 to 1.6 (cm 2 · K) / W is further preferable, and 0.3 to 1.5 (cm 2 · K) / W is particularly preferable. When the total thermal resistance is 2.0 (cm 2 · K) / W or less, the cured thermosetting adhesive layer has excellent heat dissipation (thermal conductivity). When two adherends are attached using the thermosetting adhesive sheet of the invention, heat can be efficiently transferred from one adherend to the other adherend. Specifically, for example, when the FPC and the reinforcing plate are bonded through the thermosetting adhesive sheet of the present invention, the heat accumulated in the FPC is reinforced through the thermosetting adhesive sheet of the present invention. The plate can be efficiently dissipated.
The total thermal resistance means the sum of the thermal resistance of the thermosetting adhesive layer itself after curing and the contact thermal resistance. The contact thermal resistance means that the air is interposed between the surface of the adhesive layer and the adherend due to the surface roughness of the thermosetting adhesive layer after curing, and the adhesive layer and the adherend. The thermal resistance that occurs between The total thermal resistance can be measured by the method described in “(3) Total thermal resistance” in (Evaluation) described later.
　本発明の熱硬化型接着剤層は、特に限定されないが、１５０℃、２０分の条件下で硬化させた後の全熱抵抗（定常熱流法により測定した全熱抵抗）が、放熱性の観点から、０．１～１．６（ｃｍ2・Ｋ）／Ｗであることが好ましく、より好ましくは０．２～１．５（ｃｍ2・Ｋ）／Ｗ、さらに好ましくは０．３～１．５（ｃｍ2・Ｋ）／Ｗである。 The thermosetting adhesive layer of the present invention is not particularly limited, but the total heat resistance after being cured at 150 ° C. for 20 minutes (total heat resistance measured by a steady heat flow method) is a viewpoint of heat dissipation. Therefore, it is preferably 0.1 to 1.6 (cm 2 · K) / W, more preferably 0.2 to 1.5 (cm 2 · K) / W, still more preferably 0.3 to 1 0.5 (cm 2 · K) / W.
　本発明の熱硬化型接着剤層（硬化前）のゲル分率は、特に限定されないが、本発明の熱硬化型接着剤層の柔軟性の観点から、７０％（重量％）未満（例えば、０％以上７０％未満）が好ましく、より好ましくは６０％未満、より好ましくは５０％未満である。上記ゲル分率は、メチルエチルケトン不溶分として求めることができ、具体的には、メチルエチルケトン中に室温（２３℃）で７日間浸漬した後の不溶分の浸漬前の試料に対する重量分率（単位：重量％）として求められる。上記ゲル分率が７０％未満であることにより、本発明の熱硬化型接着剤層の柔軟性が向上し接着力が向上するため好ましい。 The gel fraction of the thermosetting adhesive layer of the present invention (before curing) is not particularly limited, but is less than 70% (% by weight) from the viewpoint of flexibility of the thermosetting adhesive layer of the present invention (for example, 0% or more and less than 70%), preferably less than 60%, more preferably less than 50%. The gel fraction can be obtained as methyl ethyl ketone insoluble matter. Specifically, the weight fraction (unit: weight) of the insoluble matter after immersion in methyl ethyl ketone for 7 days at room temperature (23 ° C.). %). It is preferable that the gel fraction is less than 70% because the flexibility of the thermosetting adhesive layer of the present invention is improved and the adhesive force is improved.
　上記ゲル分率（メチルエチルケトン不溶分の割合）は、具体的には、例えば、以下の＜ゲル分率の測定方法＞により測定し、算出できる。
＜ゲル分率の測定方法＞
　本発明の熱硬化型接着シートより、本発明の熱硬化型接着剤層を約０．１ｇ採取し、ゲル分率測定用の熱硬化型接着剤層とする。上記ゲル分率測定用の熱硬化型接着剤層を、平均孔径０．２μｍの孔を有する多孔質テトラフルオロエチレンシート（商品名「ＮＴＦ１１２２」、日東電工（株）製）に包んだ後、凧糸で縛り、その際の重量を測定し、該重量を浸漬前重量とする。なお、該浸漬前重量は、熱硬化型接着剤層と、テトラフルオロエチレンシートと、凧糸の総重量である。また、テトラフルオロエチレンシートと凧糸の合計重量も測定しておき、該重量を包袋重量とする。
　次に、上記の熱硬化型接着剤層をテトラフルオロエチレンシートで包み凧糸で縛ったもの（「サンプル」と称する）を、メチルエチルケトンで満たした５０ｍＬ容器に入れ、室温（２３℃）にて１週間（７日間）静置する。その後、容器からサンプル（メチルエチルケトン処理後）を取り出して、アルミニウム製カップに移し、１３０℃で２時間、乾燥機中で乾燥してメチルエチルケトンを除去した後、重量を測定し、該重量を浸漬後重量とする。
　そして、下記の式からゲル分率を算出する。
　　　　ゲル分率（重量％）＝（Ａ－Ｂ）／（Ｃ－Ｂ）　×　１００
（上記式において、Ａは浸漬後重量であり、Ｂは包袋重量であり、Ｃは浸漬前重量である。） Specifically, the gel fraction (ratio of methyl ethyl ketone insoluble matter) can be measured and calculated by, for example, the following <Method for measuring gel fraction>.
<Method for measuring gel fraction>
About 0.1 g of the thermosetting adhesive layer of the present invention is sampled from the thermosetting adhesive sheet of the present invention to obtain a thermosetting adhesive layer for gel fraction measurement. After wrapping the thermosetting adhesive layer for measuring the gel fraction in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Corporation) having pores having an average pore diameter of 0.2 μm, It is bound with a thread, the weight at that time is measured, and this weight is defined as the weight before immersion. The weight before immersion is the total weight of the thermosetting adhesive layer, the tetrafluoroethylene sheet, and the kite string. Further, the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is defined as the wrapping weight.
Next, the above thermosetting adhesive layer wrapped with a tetrafluoroethylene sheet and tied with a kite string (referred to as “sample”) is placed in a 50 mL container filled with methyl ethyl ketone and 1 at room temperature (23 ° C.). Leave for a week (7 days). Thereafter, the sample (after methyl ethyl ketone treatment) is taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove methyl ethyl ketone, the weight is measured, and the weight is immersed in the weight. And
Then, the gel fraction is calculated from the following formula.
Gel fraction (% by weight) = (AB) / (CB) × 100
(In the above formula, A is the weight after immersion, B is the weight of the bag, and C is the weight before immersion.)
　本発明の熱硬化型接着剤層の１５０℃１時間の熱硬化処理後のゲル分率は、特に限定されないが、９０％（重量％）以上が好ましく、より好ましくは９２％以上、さらに好ましくは９６％以上である。本発明の熱硬化型接着剤層の１５０℃１時間の熱硬化処理後のゲル分率の上限については、特に限定されず、例えば、１００％である。上記ゲル分率が９０％以上であることにより、本発明の熱硬化型接着剤層の熱硬化処理をすばやく十分に進行させることができ、熱硬化後の接着性、湿熱後耐熱性により優れるため好ましい。上記ゲル分率が９０％未満では、１５０℃１時間の熱硬化処理では熱硬化反応の進行が十分でなく、熱硬化後の接着力や湿熱後耐熱性が不足する場合があり、十分に接着させるためにさらに高い硬化温度や長い硬化時間を必要とするためコストが高くなる場合がある。 The gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the thermosetting adhesive layer of the present invention is not particularly limited, but is preferably 90% (% by weight) or more, more preferably 92% or more, and still more preferably. 96% or more. The upper limit of the gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the thermosetting adhesive layer of the present invention is not particularly limited and is, for example, 100%. When the gel fraction is 90% or more, the thermosetting treatment of the thermosetting adhesive layer of the present invention can be rapidly and sufficiently advanced, and the adhesiveness after thermosetting and the heat resistance after wet heat are superior. preferable. When the gel fraction is less than 90%, the thermosetting treatment at 150 ° C. for 1 hour does not proceed sufficiently, and the adhesive strength after thermosetting and the heat resistance after wet heat may be insufficient. In order to achieve this, a higher curing temperature and a longer curing time are required, which may increase the cost.
　なお、上記の熱硬化型接着剤層の１５０℃１時間の熱硬化処理後のゲル分率は、具体的には、例えば、本発明の熱硬化型接着シートを１５０℃で１時間加熱し、熱硬化処理を施した後の熱硬化型接着シートから採取した熱硬化型接着剤層（硬化後の熱硬化型接着剤層）を「ゲル分率測定用の熱硬化型接着剤層」として、上記の＜ゲル分率の測定方法＞と同様にして、測定し算出できる。 The gel fraction after the thermosetting treatment at 150 ° C. for 1 hour of the above thermosetting adhesive layer is specifically, for example, by heating the thermosetting adhesive sheet of the present invention at 150 ° C. for 1 hour, The thermosetting adhesive layer (thermosetting adhesive layer after curing) taken from the thermosetting adhesive sheet after being subjected to the thermosetting treatment as a “thermosetting adhesive layer for gel fraction measurement” It can be measured and calculated in the same manner as in the above <Method for measuring gel fraction>.
［本発明の熱硬化型接着シート］
　本発明の熱硬化型接着シートは、本発明の熱硬化型接着剤層（本発明の熱硬化型接着剤組成物により形成された熱硬化型接着剤層）を少なくとも１層有する。本発明の熱硬化型接着シートは、本発明の熱硬化型接着剤層以外にも、基材、本発明の熱硬化型接着剤層以外の熱硬化型接着剤層等を有していてもよい。また、本発明の効果を損なわない範囲で、他の層（例えば、中間層、下塗り層など）を有していてもよい。本発明の熱硬化型接着剤層以外の層は、それぞれ、１層のみ設けられていても、２層以上設けられていてもよい。 [Thermosetting adhesive sheet of the present invention]
The thermosetting adhesive sheet of the present invention has at least one thermosetting adhesive layer of the present invention (a thermosetting adhesive layer formed by the thermosetting adhesive composition of the present invention). The thermosetting adhesive sheet of the present invention may have a substrate, a thermosetting adhesive layer other than the thermosetting adhesive layer of the present invention, and the like in addition to the thermosetting adhesive layer of the present invention. Good. Moreover, you may have another layer (for example, intermediate | middle layer, undercoat etc.) in the range which does not impair the effect of this invention. Each of the layers other than the thermosetting adhesive layer of the present invention may be provided as only one layer, or may be provided as two or more layers.
　本発明の熱硬化型接着シートは、該シートの片面のみが接着剤層表面（接着面）である（即ち、本発明の熱硬化型接着剤層表面である）片面接着シートであってもよいし、該シートの両面が接着剤層表面（接着面）である両面接着シートであってもよい。本発明の熱硬化型接着シートは、特に限定されないが、物品（被着体）同士の貼り合わせに用いる等の観点から、両面接着シートであることが好ましく、より好ましくは、該シートの両面が熱硬化型接着剤層の表面である両面接着シートである。 The thermosetting adhesive sheet of the present invention may be a single-sided adhesive sheet in which only one surface of the sheet is the adhesive layer surface (adhesive surface) (that is, the thermosetting adhesive layer surface of the present invention). And the double-sided adhesive sheet whose both surfaces of this sheet | seat are an adhesive bond layer surface (adhesion surface) may be sufficient. Although the thermosetting adhesive sheet of the present invention is not particularly limited, it is preferably a double-sided adhesive sheet from the viewpoint of being used for bonding articles (adherents) to each other, and more preferably, both surfaces of the sheet are It is a double-sided adhesive sheet that is the surface of a thermosetting adhesive layer.
　本発明の熱硬化型接着シートは、基材を有する熱硬化型接着シート（基材付き熱硬化型接着シート）であってもよく、基材を有していない熱硬化型接着シート（基材レス熱硬化型接着シート）であってもよい。本発明の熱硬化型接着シートとしては、例えば、（１）本発明の熱硬化型接着剤層のみからなり、基材を有していない熱硬化型接着シート（基材レス熱硬化型接着シート）、（２）基材の少なくとも一方の面側（両面側又は片面側）に本発明の熱硬化型接着剤層を有する熱硬化型接着シート（基材付き熱硬化型接着シート）などが挙げられる。本発明の熱硬化型接着シートとしては、基材レス熱硬化型接着シートが好ましく、中でも、製造の簡便さ、及び放熱性（熱伝導性）の観点から、上記（１）の構成の、本発明の熱硬化型接着剤層のみからなり、基材を有していない基材レス熱硬化型接着シートが好ましい。なお、上記「基材」には、熱硬化型接着シートの使用時に剥離される剥離ライナー（セパレータ）は含まない。 The thermosetting adhesive sheet of the present invention may be a thermosetting adhesive sheet having a base material (thermosetting adhesive sheet with a base material), or a thermosetting adhesive sheet having no base material (base material). Less thermosetting adhesive sheet). As the thermosetting adhesive sheet of the present invention, for example, (1) a thermosetting adhesive sheet comprising only the thermosetting adhesive layer of the present invention and having no base material (baseless thermosetting adhesive sheet) ), (2) Thermosetting adhesive sheet (thermosetting adhesive sheet with substrate) having the thermosetting adhesive layer of the present invention on at least one side (both sides or one side) of the substrate, and the like. It is done. As the thermosetting adhesive sheet of the present invention, a substrate-less thermosetting adhesive sheet is preferable, and among these, from the viewpoint of ease of production and heat dissipation (thermal conductivity), A substrate-less thermosetting adhesive sheet consisting only of the thermosetting adhesive layer of the invention and having no substrate is preferred. The “base material” does not include a release liner (separator) that is peeled off when the thermosetting adhesive sheet is used.
　なお、本発明の熱硬化型接着シートが基材付き熱硬化型接着シートである場合、基材の少なくとも一方の面側に、本発明の熱硬化型接着剤層が設けられていればよい。基材の、本発明の熱硬化型接着剤層が設けられた側とは反対面側には、本発明の熱硬化型接着剤層以外の熱硬化型接着剤層や、熱硬化型接着剤層以外の公知の接着剤層［例えば、粘着剤層（感圧性接着剤層）等］が設けられていてもよい。 In addition, when the thermosetting adhesive sheet of the present invention is a thermosetting adhesive sheet with a substrate, the thermosetting adhesive layer of the present invention may be provided on at least one surface side of the substrate. On the side of the substrate opposite to the side where the thermosetting adhesive layer of the present invention is provided, a thermosetting adhesive layer other than the thermosetting adhesive layer of the present invention, or a thermosetting adhesive A known adhesive layer [for example, a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) or the like] other than the layer may be provided.
　上記基材としては、特に限定されず、例えば、紙などの紙系基材；布、不織布、ネットなどの繊維系基材；金属箔、金属板などの金属系基材；各種樹脂（ポリオレフィン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、酢酸ビニル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリフェニレンスルフィド（ＰＰＳ）など）によるフィルムやシートなどのプラスチック系基材；ゴムシートなどのゴム系基材；発泡シートなどの発泡体系基材や、これらの積層体（特にプラスチック系基材と他の基材との積層体や、プラスチックフィルム（又はシート）同士の積層体など）等の適宜なシート状物を用いることができる。 The substrate is not particularly limited. For example, a paper-based substrate such as paper; a fiber-based substrate such as cloth, nonwoven fabric, or net; a metal-based substrate such as metal foil or metal plate; Plastic base materials such as films and sheets made of resin, polyester resin, polyvinyl chloride resin, vinyl acetate resin, polyamide resin, polyimide resin, polyether ether ketone (PEEK), polyphenylene sulfide (PPS), etc. Rubber base materials such as rubber sheets; foam-based base materials such as foam sheets, and laminates thereof (particularly laminates of plastic base materials and other base materials, and laminates of plastic films (or sheets)) An appropriate sheet-like material such as a body can be used.
　上記基材の厚みは、特に限定されないが、加工性の観点から、１０～１５０μｍが好ましく、より好ましくは１０～１００μｍ、さらに好ましくは１０～５０μｍである。なお、基材は単層の形態を有していてもよく、また、複層の形態を有していてもよい。また、基材には、必要に応じて、背面処理、帯電防止処理、下塗り処理などの各種処理が施されていてもよい。 The thickness of the substrate is not particularly limited, but is preferably 10 to 150 μm, more preferably 10 to 100 μm, and still more preferably 10 to 50 μm from the viewpoint of workability. In addition, the base material may have a single layer form or may have a multiple layer form. Further, the substrate may be subjected to various treatments such as back treatment, antistatic treatment, and undercoating treatment as necessary.
　本発明の熱硬化型接着シートは、例えば、ロール状に巻回された形態や、シートが積層された形態であってもよい。すなわち、本発明の熱硬化型接着シートは、シート状、テープ状などの形態を有することができる。なお、本発明の熱硬化型接着シートがロール状に巻回された形態を有している場合、例えば、熱硬化型接着剤層が、剥離ライナーや基材の背面側に形成された剥離処理層により保護された状態でロール状に巻回された形態であってもよい。 The thermosetting adhesive sheet of the present invention may have, for example, a form wound in a roll shape or a form in which sheets are laminated. That is, the thermosetting adhesive sheet of the present invention can have forms such as a sheet form and a tape form. In addition, when the thermosetting adhesive sheet of the present invention has a form wound in a roll shape, for example, a release treatment in which the thermosetting adhesive layer is formed on the back side of the release liner or the base material The form wound by the roll shape in the state protected by the layer may be sufficient.
　本発明の熱硬化型接着シートにおける接着剤層（例えば、本発明の熱硬化型接着剤層）の表面は、剥離ライナー（セパレータ）によって保護されていてもよい。上記剥離ライナーとしては、特に限定されず、公知の剥離ライナーから適宜選択して用いることができる。上記剥離ライナーとしては、例えば、紙やプラスチックフィルム等の基材（ライナー基材）の表面がシリコーン処理された剥離ライナー、又は、紙やプラスチックフィルム等の基材（ライナー基材）の表面がポリオレフィン系樹脂によりラミネートされた剥離ライナーが好ましい。上記ポリオレフィン系樹脂は、特に限定されないが、ポリエチレン系樹脂が好ましい。 The surface of the adhesive layer (for example, the thermosetting adhesive layer of the present invention) in the thermosetting adhesive sheet of the present invention may be protected by a release liner (separator). The release liner is not particularly limited, and can be appropriately selected from known release liners. As the release liner, for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicon, or the surface of a base material (liner base material) such as paper or plastic film is a polyolefin. A release liner laminated with a resin is preferable. The polyolefin resin is not particularly limited, but a polyethylene resin is preferable.
　本発明の熱硬化型接着シートの厚みは、特に限定されないが、１９０μｍ以下（４～１９０μｍ）が好ましく、より好ましくは１４０μｍ以下（４～１４０μｍ）、さらに好ましくは９０μｍ以下である。上記厚みが１９０μｍ以下であることにより、本発明の熱硬化型接着シートの全熱抵抗が低くなり、放熱性に優れる。 The thickness of the thermosetting adhesive sheet of the present invention is not particularly limited, but is preferably 190 μm or less (4 to 190 μm), more preferably 140 μm or less (4 to 140 μm), and still more preferably 90 μm or less. When the said thickness is 190 micrometers or less, the total thermal resistance of the thermosetting type adhesive sheet of this invention becomes low, and it is excellent in heat dissipation.
　本発明の熱硬化型接着シートは、公知乃至慣用の接着シートの製造方法に従って製造することができる。例えば、本発明の熱硬化型接着シートが基材レス熱硬化型接着シートである場合、剥離ライナーの剥離面に、本発明の熱硬化型接着剤組成物を、乾燥後の厚さが所定の厚さとなるように塗布し、乾燥させる方法により本発明の熱硬化型接着剤層を形成して、本発明の熱硬化型接着シートを作製することができる。
　本発明の熱硬化型接着シートが基材付き熱硬化型接着シートである場合、上記と同様にして、剥離ライナーの剥離面上に本発明の熱硬化型接着剤層を形成した後、該熱硬化型接着剤層を基材の表面上に転写する方法により、本発明の熱硬化型接着シートを作製することができる。また、基材の表面上に、本発明の熱硬化型接着剤組成物を、乾燥後の厚さが所定の厚さとなるように塗布し、乾燥させる方法により本発明の熱硬化型接着剤層を形成して、本発明の熱硬化型接着シートを作製することができる。 The thermosetting adhesive sheet of the present invention can be produced according to a known or commonly used method for producing an adhesive sheet. For example, when the thermosetting adhesive sheet of the present invention is a substrate-less thermosetting adhesive sheet, the thickness after drying of the thermosetting adhesive composition of the present invention is predetermined on the release surface of the release liner. The thermosetting adhesive sheet of the present invention can be produced by forming the thermosetting adhesive layer of the present invention by a method of applying and drying to a thickness.
When the thermosetting adhesive sheet of the present invention is a thermosetting adhesive sheet with a substrate, after the thermosetting adhesive layer of the present invention is formed on the release surface of the release liner, the heat The thermosetting adhesive sheet of the present invention can be produced by a method of transferring the curable adhesive layer onto the surface of the substrate. Further, the thermosetting adhesive layer of the present invention is applied to the surface of the base material by applying the thermosetting adhesive composition of the present invention so that the thickness after drying becomes a predetermined thickness and drying. To form the thermosetting adhesive sheet of the present invention.
　なお、本発明の熱硬化型接着剤組成物の塗布に際しては、慣用のコーター（例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーロールコーターなど）を用いることができる。 In applying the thermosetting adhesive composition of the present invention, a conventional coater (for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.) Can be used.
　本発明の熱硬化型接着シート及び本発明の熱硬化型接着剤層は、加熱によって硬化反応を進行（熱硬化）させることにより、優れた接着力を発揮することができる。本発明の熱硬化型接着シートを加熱して本発明の熱硬化型接着剤層を硬化させる（熱硬化する）ことにより、強固な接着力を有する接着シート（熱硬化された熱硬化型接着シート）が得られる。 The thermosetting adhesive sheet of the present invention and the thermosetting adhesive layer of the present invention can exhibit an excellent adhesive force by causing a curing reaction to proceed (thermosetting) by heating. The thermosetting adhesive sheet of the present invention is heated to cure (thermoset) the thermosetting adhesive layer of the present invention, whereby an adhesive sheet having a strong adhesive force (thermoset thermosetting adhesive sheet) ) Is obtained.
　上記熱硬化における硬化温度としては、特に限定されないが、１００℃以上（例えば、１００～２００℃）が好ましく、さらに好ましくは１４０℃以上（例えば、１４０～２００℃、好ましくは１４０～１７０℃）、より好ましくは１５０℃以上（例えば、１５０～１７０℃）である。 The curing temperature in the thermosetting is not particularly limited, but is preferably 100 ° C. or higher (eg, 100 to 200 ° C.), more preferably 140 ° C. or higher (eg, 140 to 200 ° C., preferably 140 to 170 ° C.), More preferably, it is 150 ° C. or higher (for example, 150 to 170 ° C.).
　上記熱硬化における硬化時間としては、特に限定されないが、６０分未満（例えば、２０分以上６０分未満）が好ましく、より好ましくは３０分未満（例えば、２０分以上３０分未満）である。上記硬化時間が６０分未満でも、硬化後の本発明の熱硬化型接着剤層、及び硬化後の本発明の熱硬化型接着シートは、優れた接着性、湿熱後耐熱性、放熱性を発揮できる。また、ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体では、ＦＰＣにたまった熱を効率よく放熱できる。特に、硬化時間が３０分未満と短い場合でも、優れた接着性、湿熱後耐熱性、放熱性を発揮できる。そのため、例えば、ＦＰＣなどの優れた湿熱後耐熱性、放熱性が要求される製品の製造用途に用いられた場合に、生産効率が向上する。 Although it does not specifically limit as hardening time in the said thermosetting, Less than 60 minutes (for example, 20 minutes or more and less than 60 minutes) is preferable, More preferably, it is less than 30 minutes (for example, 20 minutes or more and less than 30 minutes). Even when the curing time is less than 60 minutes, the cured thermosetting adhesive layer of the present invention and the cured thermosetting adhesive sheet of the present invention exhibit excellent adhesiveness, heat resistance after wet heat, and heat dissipation. it can. Moreover, in the laminated body which has the thermosetting type adhesive sheet of this invention on FPC, the heat | fever accumulated in FPC can be thermally radiated efficiently. In particular, even when the curing time is as short as less than 30 minutes, excellent adhesiveness, heat resistance after wet heat and heat dissipation can be exhibited. Therefore, for example, when it is used for the manufacture of a product that requires excellent heat resistance and heat dissipation after wet heat such as FPC, the production efficiency is improved.
　上記硬化条件（加熱条件）は、特に限定されないが、１００℃以上（例えば、１００～２００℃）の温度にて６０分未満（例えば、２０分以上６０分未満、好ましくは２０分以上３０分未満）加熱することが好ましく、より好ましくは１４０℃以上（例えば、１４０～２００℃、好ましくは１４０～１７０℃）の温度にて６０分未満（例えば、２０分以上６０分未満、好ましくは２０分以上３０分未満）、特に好ましくは１５０℃以上（例えば、１５０～１７０℃）の温度にて６０分未満（例えば、２０分以上６０分未満、好ましくは２０分以上３０分未満）である。 The curing conditions (heating conditions) are not particularly limited, but are less than 60 minutes (eg, 20 minutes to less than 60 minutes, preferably 20 minutes to less than 30 minutes) at a temperature of 100 ° C. or higher (eg, 100 to 200 ° C.). ) It is preferable to heat, more preferably 140 ° C. or higher (for example, 140 to 200 ° C., preferably 140 to 170 ° C.) for less than 60 minutes (for example, 20 minutes to less than 60 minutes, preferably 20 minutes or more Less than 30 minutes), particularly preferably less than 60 minutes (for example, 20 minutes to less than 60 minutes, preferably 20 minutes to less than 30 minutes) at a temperature of 150 ° C. or more (eg, 150 to 170 ° C.).
　本発明の熱硬化型接着剤層は、本発明の熱硬化型接着剤組成物がアクリル系ポリマー（Ｘ）を含有するので、高い接着力（接着性）を有する。また、本発明の熱硬化型接着剤層は、本発明の熱硬化型接着剤組成物がエーテル化フェノール樹脂（Ｙ）を含有するので、加熱硬化しやすく熱硬化性に優れ、その上接着力及び湿熱後耐熱性に優れる。
　加えて、本発明の熱硬化型接着シートは、熱硬化型接着剤層の厚みが１～２０μｍであるため、硬化時間が短い場合でも硬化後の熱硬化型接着剤層は接着性、湿熱後耐熱性に優れ、その上全熱抵抗が低く、放熱性（熱伝導性）に優れる。 The thermosetting adhesive layer of the present invention has high adhesive force (adhesiveness) because the thermosetting adhesive composition of the present invention contains the acrylic polymer (X). Moreover, since the thermosetting adhesive composition of the present invention contains an etherified phenol resin (Y), the thermosetting adhesive layer of the present invention is easily heat-cured and has excellent thermosetting properties, and also has an adhesive force. Excellent heat resistance after wet heat.
In addition, since the thickness of the thermosetting adhesive layer of the thermosetting adhesive layer of the present invention is 1 to 20 μm, the thermosetting adhesive layer after curing has adhesiveness, after wet heat, even when the curing time is short. Excellent heat resistance, low total thermal resistance, and excellent heat dissipation (thermal conductivity).
　本発明の熱硬化型接着シートは、硬化時間が短くても、硬化後には高い接着力、優れた湿熱後耐熱性、及び優れた放熱性を発揮することができる。そのため、本発明の熱硬化型接着シートは、強固に接着し、接着後に極めて厳しい温度条件下で処理される場合でも発泡や浮き剥がれなどが生じない優れた湿熱後耐熱性が求められ、かつ、被着体の熱を放熱させるために優れた熱伝導性が求められる用途等に好ましく使用することができる。具体的には、本発明の熱硬化型接着シートは、例えば、フレキシブル印刷回路基板（ＦＰＣ）における接着の際に好ましく使用できる。即ち、本発明の熱硬化型接着シートは、好ましくは、ＦＰＣ用熱硬化型接着シートである。なお、ＦＰＣにおける接着とは、例えば、ＦＰＣを作製する際の接着や、ＦＰＣを補強板に貼り合わせる際の接着を意味している。 The thermosetting adhesive sheet of the present invention can exhibit high adhesive strength, excellent heat resistance after moist heat, and excellent heat dissipation even after the curing time is short. Therefore, the thermosetting adhesive sheet of the present invention is required to have excellent post-humidity heat resistance that does not cause foaming or peeling even when firmly bonded and processed under extremely severe temperature conditions after bonding, and It can be preferably used in applications where excellent thermal conductivity is required to dissipate the heat of the adherend. Specifically, the thermosetting adhesive sheet of the present invention can be preferably used for bonding on a flexible printed circuit board (FPC), for example. That is, the thermosetting adhesive sheet of the present invention is preferably an FPC thermosetting adhesive sheet. Note that the adhesion in the FPC means, for example, adhesion when the FPC is manufactured or adhesion when the FPC is bonded to the reinforcing plate.
　ＦＰＣは最終製品に組み込まれるまでに高温のリフロー工程を通ることが多く、使用される熱硬化型接着シートには、リフロー工程を通った後に、発泡や浮き剥がれが発生しないことが求められる。また、電子機器内部のＦＰＣは熱を持つことが多く、ＦＰＣの接着の際に用いられる接着剤（接着シート）には、放熱性（熱伝導性）が求められる。このようなＦＰＣ用途では、信頼性の観点から、「湿熱後耐熱性」及び「放熱性」が重要視されている。なお、上記「湿熱後耐熱性」とは、熱硬化型接着シートを用いて被着体を接着して作製した積層体を、高温高湿下（例えば、温度４０～６０℃、湿度６０～９５％ＲＨの環境下）で保存した後に、厳しい温度条件（例えば、温度２５０～２７０℃で１～３分間）で処理した場合にも、上記熱硬化型接着シート（熱硬化型接着剤層）に発泡や浮き剥がれが生じにくい特性を意味する。
　本発明の熱硬化型接着シートは、熱硬化後には、高い接着力と極めて優れた湿熱後耐熱性と共に、放熱性を発揮することができるため、特にＦＰＣ用途において信頼性の高い熱硬化型接着シートとして使用することができる。即ち、本発明の熱硬化型接着シートを用いてＦＰＣを作製することにより、本発明の熱硬化型接着シートを有するＦＰＣを得ることができる。 The FPC often passes through a high-temperature reflow process before being incorporated into the final product, and the thermosetting adhesive sheet used is required to be free from foaming and peeling off after passing through the reflow process. In addition, the FPC inside the electronic device often has heat, and the adhesive (adhesive sheet) used for bonding the FPC is required to have heat dissipation (thermal conductivity). In such FPC applications, “heat resistance after wet heat” and “heat dissipation” are regarded as important from the viewpoint of reliability. The “heat resistance after wet heat” refers to a laminate produced by bonding an adherend using a thermosetting adhesive sheet under high temperature and high humidity (for example, temperature 40 to 60 ° C., humidity 60 to 95). In the case of processing under severe temperature conditions (for example, at a temperature of 250 to 270 ° C. for 1 to 3 minutes) after storage in an environment of% RH, the above thermosetting adhesive sheet (thermosetting adhesive layer) It means the characteristic that foaming and peeling are hard to occur.
Since the thermosetting adhesive sheet of the present invention can exhibit heat dissipation as well as high adhesive strength and excellent heat resistance after moist heat after thermosetting, it is highly reliable thermosetting adhesive particularly in FPC applications. Can be used as a sheet. That is, FPC which has the thermosetting type adhesive sheet of this invention can be obtained by producing FPC using the thermosetting type adhesive sheet of this invention.
　本発明の熱硬化型接着シートを用いて、本発明の熱硬化型接着シートを有するＦＰＣを作製する方法は、特に限定されないが、例えば、本発明の熱硬化型接着シートを用いて、耐熱基材に導電性金属箔を接着積層させて、ＦＰＣを作製する方法が挙げられる。 A method for producing an FPC having the thermosetting adhesive sheet of the present invention using the thermosetting adhesive sheet of the present invention is not particularly limited. For example, the heat-curable adhesive sheet of the present invention is used to form a heat resistant group. A method of manufacturing an FPC by bonding and laminating a conductive metal foil to a material is mentioned.
　上記耐熱基材としては、特に限定されないが、例えば、ポリイミド製基材やポリアミド製基材が挙げられる。上記導電性金属箔としては、特に限定されないが、例えば、銅箔やアルミニウム箔が挙げられる。 The heat-resistant substrate is not particularly limited, and examples thereof include a polyimide substrate and a polyamide substrate. Although it does not specifically limit as said electroconductive metal foil, For example, copper foil and aluminum foil are mentioned.
　また、本発明の熱硬化型接着シートを用いてＦＰＣと補強板とを貼り合わせることにより、ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体を得ることができる。即ち、本発明の熱硬化型接着シートは、ＦＰＣと補強板とを本発明の熱硬化型接着シートを介して（使用して）貼り合わせ、ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体（補強板付ＦＰＣ）を製造する方法に用いることができる。 Also, by laminating the FPC and the reinforcing plate using the thermosetting adhesive sheet of the present invention, a laminate having the thermosetting adhesive sheet of the present invention on the FPC can be obtained. That is, the thermosetting adhesive sheet of the present invention has the FPC and the reinforcing plate bonded (used) through the thermosetting adhesive sheet of the present invention and has the thermosetting adhesive sheet of the present invention on the FPC. It can be used in a method for producing a laminate (FPC with reinforcing plate).
　ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体を製造する方法は、特に限定されないが、例えば、ＦＰＣ又は補強板上に、本発明の熱硬化型接着シートを貼付し、熱硬化型接着シートを熱硬化させて得られた熱硬化された熱硬化型接着シートを介して、ＦＰＣ又は補強板を接着させて、ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体を製造する方法が挙げられる。ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体は、ＦＰＣ（又は補強板）の全面に本発明の熱硬化型接着シートを用いて貼り合わされていてもよいし、一部に用いて貼り合わされていてもよい。また、ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体は、本発明の効果を損なわない範囲で、フィルムや板（他の基板や遮光板など）が設けられていてもよい。なお、ＦＰＣは、本発明の熱硬化型接着シートを用いて製造されたＦＰＣであってもよいし、公知乃至慣用のＦＰＣであってもよい。 The method for producing the laminate having the thermosetting adhesive sheet of the present invention on the FPC is not particularly limited. For example, the thermosetting adhesive sheet of the present invention is pasted on the FPC or the reinforcing plate, and the thermosetting type is applied. The laminate having the thermosetting adhesive sheet of the present invention on the FPC is manufactured by bonding the FPC or the reinforcing plate through the thermosetting thermosetting adhesive sheet obtained by thermosetting the adhesive sheet. A method is mentioned. The laminate having the thermosetting adhesive sheet of the present invention on the FPC may be bonded to the entire surface of the FPC (or reinforcing plate) using the thermosetting adhesive sheet of the present invention, or may be used in part. It may be pasted. Moreover, the laminated body which has the thermosetting adhesive sheet of this invention on FPC may be provided with the film and board (another board | substrate, a light shielding board, etc.) in the range which does not impair the effect of this invention. In addition, FPC manufactured using the thermosetting type adhesive sheet of this invention may be sufficient, and well-known thru | or usual FPC may be sufficient as it.
　上記補強板としては、特に限定されないが、例えば、アルミニウム板、ステンレス板（ステンレス鋼板など）、ポリイミド板が挙げられる。中でも、ステンレス板、ポリイミド板が好ましい。 The reinforcing plate is not particularly limited, and examples thereof include an aluminum plate, a stainless plate (such as a stainless steel plate), and a polyimide plate. Among these, a stainless plate and a polyimide plate are preferable.
　ＦＰＣ上に本発明の熱硬化型接着シートを有する積層体は、本発明の熱硬化型接着シートを熱硬化させることにより、放熱性、接着力、湿熱後耐熱性に優れる熱硬化型接着シートを有する積層体（ＦＰＣ上に熱硬化された熱硬化型接着シートを有する積層体）を得ることができる。なお、当該積層体における熱硬化型接着シートの熱硬化条件は、上述した本発明の熱硬化型接着シートの熱硬化条件と同様の条件で行うことができる。 The laminate having the thermosetting adhesive sheet of the present invention on an FPC is obtained by thermosetting the thermosetting adhesive sheet of the present invention, thereby providing a thermosetting adhesive sheet excellent in heat dissipation, adhesive strength, and heat resistance after wet heat. The laminated body which has (The laminated body which has the thermosetting type adhesive sheet thermosetted on FPC) can be obtained. In addition, the thermosetting conditions of the thermosetting adhesive sheet in the said laminated body can be performed on the conditions similar to the thermosetting conditions of the thermosetting adhesive sheet of this invention mentioned above.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
　表１には、実施例及び比較例における、アクリル系ポリマー（Ｘ）のモノマー組成、及び熱硬化型接着剤組成物中の含有量（配合量）、エーテル化フェノール樹脂（Ｙ）の熱硬化型接着剤組成物中の含有量（配合量）、並びに熱硬化型接着剤層の厚みを示した。なお、表１において、アクリル系ポリマー（Ｘ）のモノマー組成は、該アクリル系ポリマー（Ｘ）を構成するモノマー成分全量（１００重量％）中の各モノマーの含有量（重量％）で表した。また、アクリル系ポリマー（Ｘ）及びエーテル化フェノール樹脂（Ｙ）の含有量は、不揮発分としての含有量（重量部）で表した。 Table 1 shows the monomer composition of the acrylic polymer (X) and the content (blending amount) in the thermosetting adhesive composition and the thermosetting type of the etherified phenol resin (Y) in Examples and Comparative Examples. The content (blending amount) in the adhesive composition and the thickness of the thermosetting adhesive layer were shown. In Table 1, the monomer composition of the acrylic polymer (X) is represented by the content (% by weight) of each monomer in the total amount of monomer components (100% by weight) constituting the acrylic polymer (X). Moreover, content of acrylic polymer (X) and etherified phenol resin (Y) was represented by content (weight part) as a non volatile matter.
（実施例１）
（アクリル系ポリマー（Ｘ）の調製）
　冷却管、窒素導入管、温度計および攪拌機を備えた反応器に、２，２’－アゾビス｛２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン｝ジハイドロクロライド（商品名「ＶＡ－０６０」、和光純薬工業株式会社製）（重合開始剤）０．２７９ｇ、イオン交換水１００ｇを投入し、窒素ガスを導入しながら１時間攪拌した。これを６０℃に保ち、ここにブチルアクリレート（アクリル酸ｎ－ブチル）（ＢＡ）６６重量部、アクリロニトリル（ＡＮ）２９重量部、アクリル酸（ＡＡ）５重量部、１－ドデカンチオール（連鎖移動剤）０．０４重量部、及びポリオキシエチレンラウリルエーテル硫酸ナトリウム（乳化剤）２重量部をイオン交換水４１重量部に添加して乳化したもの（モノマー原料のエマルション）４００ｇを３時間かけて徐々に滴下して、乳化重合反応を進行させた。モノマー原料のエマルションの滴下終了後、さらに３時間同温度に保持して熟成させた。このようにして重合したアクリル系ポリマーの水分散液（エマルション）を乾燥し、アクリル系ポリマー（Ｘ）（重量平均分子量１００万）を得た。 Example 1
(Preparation of acrylic polymer (X))
In a reactor equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride (Product name “VA-060”, manufactured by Wako Pure Chemical Industries, Ltd.) (Polymerization initiator) 0.279 g and ion-exchanged water 100 g were added and stirred for 1 hour while introducing nitrogen gas. This was kept at 60 ° C., where butyl acrylate (n-butyl acrylate) (BA) 66 parts by weight, acrylonitrile (AN) 29 parts by weight, acrylic acid (AA) 5 parts by weight, 1-dodecanethiol (chain transfer agent) ) 400 g of 0.04 parts by weight and 2 parts by weight of polyoxyethylene lauryl ether sodium sulfate (emulsifier) added to 41 parts by weight of ion-exchanged water and emulsified (emulsion of monomer raw material) are gradually added dropwise over 3 hours. Then, the emulsion polymerization reaction was allowed to proceed. After completion of dropping of the monomer raw material emulsion, the mixture was further aged by maintaining the same temperature for 3 hours. The aqueous dispersion (emulsion) of the acrylic polymer thus polymerized was dried to obtain acrylic polymer (X) (weight average molecular weight 1 million).
（熱硬化型接着剤組成物の調製）
　上記アクリル系ポリマー（Ｘ）［ブチルアクリレート（ＢＡ）６６重量％、アクリロニトリル（ＡＮ）２９重量％、アクリル酸（ＡＡ）５重量％をモノマー成分として構成された共重合体］：１００重量部が溶解された酢酸エチル溶液に、エーテル化フェノール樹脂（Ｙ）として商品名「ＣＫＳ－３８９８」（昭和電工株式会社製）１２重量部（不揮発分）が溶解されたブタノール溶液を混合し攪拌して、熱硬化型接着剤組成物（溶液）を調製した。
　すなわち、該熱硬化型接着剤組成物中には、アクリル系ポリマー（Ｘ）が１００重量部、エーテル化フェノール樹脂（Ｙ）が１２重量部含まれている。 (Preparation of thermosetting adhesive composition)
Acrylic polymer (X) [copolymer comprising butyl acrylate (BA) 66% by weight, acrylonitrile (AN) 29% by weight, acrylic acid (AA) 5% by weight as monomer components]: 100 parts by weight dissolved A butanol solution in which 12 parts by weight (non-volatile content) of the trade name “CKS-3898” (manufactured by Showa Denko KK) as an etherified phenol resin (Y) was dissolved in the ethyl acetate solution was mixed and stirred, A curable adhesive composition (solution) was prepared.
That is, the thermosetting adhesive composition contains 100 parts by weight of the acrylic polymer (X) and 12 parts by weight of the etherified phenol resin (Y).
（熱硬化型接着シートの作製）
　上記熱硬化型接着剤組成物を、乾燥後の厚みが５μｍとなるように、剥離ライナーの剥離面に塗布し、１００℃で３分間乾燥して、熱硬化型接着剤層（厚み５μｍ）を形成し、熱硬化型接着シート（熱硬化型接着剤層のみからなる基材レス熱硬化型接着シート）を得た。 (Preparation of thermosetting adhesive sheet)
The thermosetting adhesive composition is applied to the release surface of the release liner so that the thickness after drying is 5 μm, and dried at 100 ° C. for 3 minutes to form a thermosetting adhesive layer (thickness 5 μm). Thus, a thermosetting adhesive sheet (a baseless thermosetting adhesive sheet consisting only of a thermosetting adhesive layer) was obtained.
（実施例２）
　表１に示すように、熱硬化型接着剤層の厚みを１３μｍに変更した以外は、実施例１と同様にして、熱硬化型接着剤組成物及び熱硬化型接着シートを得た。 (Example 2)
As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 13 μm.
（比較例１）
　表１に示すように、熱硬化型接着剤層の厚みを２５μｍに変更した以外は、実施例１と同様にして、熱硬化型接着剤組成物及び熱硬化型接着シートを得た。 (Comparative Example 1)
As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 25 μm.
（比較例２）
　表１に示すように、熱硬化型接着剤層の厚みを３５μｍに変更した以外は、実施例１と同様にして、熱硬化型接着剤組成物及び熱硬化型接着シートを得た。 (Comparative Example 2)
As shown in Table 1, a thermosetting adhesive composition and a thermosetting adhesive sheet were obtained in the same manner as in Example 1 except that the thickness of the thermosetting adhesive layer was changed to 35 μm.
（評価）
　実施例及び比較例で得られた各熱硬化型接着シートについて、熱硬化型接着剤層の硬化後の接着力、湿熱後耐熱性、及び全熱抵抗を、下記の測定方法又は評価方法により測定又は評価した。 (Evaluation)
For each thermosetting adhesive sheet obtained in Examples and Comparative Examples, the adhesive strength after curing of the thermosetting adhesive layer, heat resistance after wet heat, and total thermal resistance are measured by the following measurement method or evaluation method. Or evaluated.
（１）接着力の測定方法
　実施例及び比較例で得られた各熱硬化型接着シートにおける硬化後の熱硬化型接着剤層について、２３℃における接着力（Ｎ／ｃｍ）を以下の方法で測定した。
　フレキシブル印刷回路基板（ＦＰＣ；サイズ：幅５ｃｍ×長さ８ｃｍ、厚み０．２ｍｍ）と、熱硬化型接着シートとを１３０℃でラミネートした後、１ｃｍ幅に切断した（熱硬化型接着シートはＦＰＣの片面側（表面の材質：ポリイミド）の全面にラミネートされている）。これを、ステンレス鋼板（ＳＵＳ３０４ＢＡ板）（ＳＵＳ；サイズ：長さ５ｃｍ×幅５ｃｍ、厚み０．４ｍｍ）に、ラミネーターを用いて１３０℃でラミネートした後、１６０℃、２ＭＰａで９０秒間加熱圧着（プレス）して貼り付けた。さらに、１５０℃で２０分キュアー（加熱硬化）して試験体を作製した。 (1) Measuring method of adhesive force About the thermosetting type adhesive layer after hardening in each thermosetting type adhesive sheet obtained in the examples and comparative examples, the adhesive strength (N / cm) at 23 ° C was determined by the following method. It was measured.
A flexible printed circuit board (FPC; size: width 5 cm × length 8 cm, thickness 0.2 mm) and a thermosetting adhesive sheet were laminated at 130 ° C. and then cut to 1 cm width (the thermosetting adhesive sheet is an FPC). (It is laminated on the entire surface of one side of the material (surface material: polyimide)). This was laminated to a stainless steel plate (SUS304BA plate) (SUS; size: length 5 cm × width 5 cm, thickness 0.4 mm) at 130 ° C. using a laminator, and then thermocompression-bonded (pressed at 160 ° C., 2 MPa for 90 seconds) ) And pasted. Furthermore, the specimen was prepared by curing (heating and curing) at 150 ° C. for 20 minutes.
　上記試験体について、引張試験機（装置商品名「ＴＣＭ－１ｋＮＢ」、ミネベア（株）製）を用いて、ＦＰＣ側を引っ張る方法により、９０°ピール接着力（引張速度：５０ｍｍ／分、２３℃、５０％ＲＨ；Ｎ／ｃｍ）を測定した。
　なお、測定結果は、表１の「接着力（Ｎ／ｃｍ）　２０分キュアー　ＳＵＳ」の欄に示した。 Using the tensile tester (equipment trade name “TCM-1kNB”, manufactured by Minebea Co., Ltd.), the above test specimen was 90 ° peel adhesive (tensile speed: 50 mm / min, 23 ° C.) by pulling the FPC side. , 50% RH; N / cm).
The measurement results are shown in the column of “Adhesive strength (N / cm) 20 minutes cure SUS” in Table 1.
　また、上記測定において、１５０℃で、６０分キュアーして作製した試験体を用いて、同様に９０°ピール接着力を測定した。測定結果は、表１の「接着力（Ｎ／ｃｍ）　６０分キュアー　ＳＵＳ」の欄に示した。 Also, in the above measurement, 90 ° peel adhesive strength was measured in the same manner using a test specimen prepared by curing at 150 ° C. for 60 minutes. The measurement results are shown in the column of “Adhesive strength (N / cm) 60 minutes cure SUS” in Table 1.
　また、上記測定において、ステンレス鋼板のかわりに、ポリイミド板（ＰＩ；サイズ：長さ５ｃｍ×幅５ｃｍ、厚み０．１３ｍｍ）を用いて、同様に９０°ピール接着力を測定した。
　測定結果は、表１の「接着力（Ｎ／ｃｍ）　２０分キュアー　ＰＩ」及び「接着力（Ｎ／ｃｍ）　６０分キュアー　ＰＩ」の欄に示した。 In the above measurement, a 90 ° peel adhesive force was measured in the same manner using a polyimide plate (PI; size: length 5 cm × width 5 cm, thickness 0.13 mm) instead of the stainless steel plate.
The measurement results are shown in the columns of “Adhesive strength (N / cm) 20 minutes cure PI” and “Adhesive strength (N / cm) 60 minutes cure PI” in Table 1.
（２）湿熱後耐熱性の評価方法（加湿後２６０℃はんだディップ）
　実施例及び比較例で得られた各熱硬化型接着シートにおける硬化後の熱硬化型接着剤層について、湿熱後耐熱性を評価した。
　銅張積層板（ＣＣＬ；ポリイミド／銅の積層体、サイズ：幅５ｃｍ×長さ８ｃｍ、厚み４５μｍ）と、熱硬化型接着シートとを１３０℃でラミネートした後、１ｃｍ幅に切断した（熱硬化型接着シートはＣＣＬのポリイミド面の全面にラミネートされている）。これを、ステンレス鋼板（ＳＵＳ３０４ＢＡ板）（ＳＵＳ；サイズ：長さ５ｃｍ×幅５ｃｍ、厚み０．４ｍｍ）に、ラミネーターを用いて１３０℃でラミネートした後、１６０℃、２ＭＰａで９０秒間加熱圧着（プレス）して貼り付けた。さらに、１５０℃で２０分キュアー（加熱硬化）して試験体を作製した。
　上記試験体を、加熱湿（温度：６０℃、湿度：９０％ＲＨ）の条件下で２４時間静置させた後、試験体のステンレス鋼板側の表面を２６０℃のはんだ浴に３分間ディップ（浸漬）させた。 (2) Evaluation method of heat resistance after wet heat (260 ° C solder dip after humidification)
About the thermosetting adhesive layer after hardening in each thermosetting adhesive sheet obtained in Examples and Comparative Examples, the heat resistance after wet heat was evaluated.
A copper-clad laminate (CCL; polyimide / copper laminate, size: width 5 cm × length 8 cm, thickness 45 μm) and a thermosetting adhesive sheet were laminated at 130 ° C. and then cut to 1 cm width (thermosetting). The mold adhesive sheet is laminated on the entire CCL polyimide surface). This was laminated to a stainless steel plate (SUS304BA plate) (SUS; size: length 5 cm × width 5 cm, thickness 0.4 mm) at 130 ° C. using a laminator, and then thermocompression-bonded (pressed at 160 ° C., 2 MPa for 90 seconds) ) And pasted. Furthermore, the specimen was prepared by curing (heating and curing) at 150 ° C. for 20 minutes.
The test specimen was allowed to stand for 24 hours under conditions of heating and humidity (temperature: 60 ° C., humidity: 90% RH), and then the stainless steel plate side surface of the test specimen was dipped in a solder bath at 260 ° C. for 3 minutes ( Dipping).
　上記試験体における硬化後の熱硬化型接着剤層の浮き剥がれ、発泡の状態を目視にて観察し、以下の基準で湿熱後耐熱性を評価した。なお、評価結果は、表１の「湿熱後耐熱性　２０分キュアー　ＳＵＳ」の欄に示した。 The heat-hardened adhesive layer after curing in the above test specimen was visually observed for floating and foaming, and the heat resistance after wet heat was evaluated according to the following criteria. The evaluation results are shown in the column of “heat resistance after wet heat, 20 minutes cure, SUS” in Table 1.
　また、加熱硬化を１５０℃で６０分キュアーとした以外は上記と同様にして、以下の基準で湿熱後耐熱性を評価した。なお、評価結果は、表１の「湿熱後耐熱性　６０分キュアー　ＳＵＳ」の欄に示した。
　湿熱後耐熱性に優れる（○）：熱硬化型接着剤層に浮き剥がれ、発泡が確認されなかった。
　湿熱後耐熱性がやや劣るが使用可能（△）：熱硬化型接着剤層の一部に浮き剥がれ、発泡が確認された。
　湿熱後耐熱性が劣る（×）：熱硬化型接着剤層の全面に浮き剥がれ、発泡が確認された。 Further, heat resistance after wet heat was evaluated according to the following criteria in the same manner as above except that the heat curing was performed at 150 ° C. for 60 minutes. The evaluation results are shown in the column of “heat resistance after wet heat 60 minutes cure SUS” in Table 1.
Excellent heat resistance after wet heat (O): Floating off the thermosetting adhesive layer and no foaming was confirmed.
Although heat resistance after wet heat is slightly inferior, it can be used (Δ): it was lifted off part of the thermosetting adhesive layer, and foaming was confirmed.
Heat resistance after wet heat is inferior (x): Floating off the entire surface of the thermosetting adhesive layer, and foaming was confirmed.
　また、上記評価において、ステンレス鋼板のかわりに、ポリイミド板（ＰＩ；サイズ：長さ５ｃｍ×幅５ｃｍ、厚み０．１３ｍｍ）を用いて、同様に湿熱後耐熱性を評価した。評価結果は、表１の「湿熱後耐熱性　２０分キュアー　ＰＩ」及び「湿熱後耐熱性　６０分キュアー　ＰＩ」の欄に示した。 Also, in the above evaluation, heat resistance after wet heat was similarly evaluated using a polyimide plate (PI; size: length 5 cm × width 5 cm, thickness 0.13 mm) instead of the stainless steel plate. The evaluation results are shown in the columns of “heat resistance after wet heat 20 minutes cure PI” and “heat resistance after wet heat 60 minutes cure PI” in Table 1.
（３）全熱抵抗
　実施例及び比較例で得られた各熱硬化型接着シートにおける硬化後の熱硬化型接着剤層について、８０℃の全熱抵抗を測定した。
　測定は、図１に示す熱特性評価装置を用いて行った。図１（ａ）は、実施例において全熱抵抗の測定を行う際に用いた装置を示す正面概略図、図１（ｂ）は図１（ａ）に示す装置の側面概略図である。
　具体的には、一辺が２０ｍｍの立法体となるように形成されたアルミニウム製（Ａ５０５２、熱伝導率：１４０Ｗ／ｍ・Ｋ）の一対のロッドＬ間に、熱硬化型接着シートＳ（２０ｍｍ×２０ｍｍ）を挟み込み、一対のロッドＬを熱硬化型接着シートＳで貼り合わせた。
　そして、一対のロッドＬが上下となるように、発熱体（ヒータブロック）Ｈと放熱体（冷却水が内部を循環するように構成された冷却ベース板）Ｃとの間にロッドＬを配置した。具体的には、上側のロッドＬ上に発熱体Ｈを配置し、下側のロッドＬの下に放熱体Ｃを配置した。
　この際、熱硬化された熱硬化型接着シートＳで貼り合わされた一対のロッドＬは、発熱体Ｈ及び放熱体Ｃを貫通する一対の圧力調整用ネジＴの間に位置している。なお、圧力調整用ネジＴと発熱体Ｈとの間にはロードセルＲが設置されており、圧力調整用ネジＴを締め込んだ際の圧力が測定されるように構成されており、かかる圧力を熱硬化された熱硬化型接着シートＳに加わる圧力として用いた。
　また、下側のロッドＬ及び熱硬化された熱硬化型接着シートＳを放熱体Ｃ側から貫通するように接触式変位計の３本のプローブＰ（直径１ｍｍ）を設置した。この際、プローブＰの上端部は、上側のロッドＬの下面に接触した状態となっており、上下のロッドＬ間の間隔（熱硬化された熱硬化型接着シートＳの厚み）を測定可能に構成されている。
　発熱体Ｈ及び上下のロッドＬには温度センサーＤを取り付けた（図１（ｂ）参照）。具体的には、発熱体Ｈの１箇所、各ロッドＬの上下方向に５ｍｍ間隔で５箇所、温度センサーＤを取り付けた。
　まず初めに、圧力調整用ネジＴを締め込んで、熱硬化された熱硬化型接着シートＳに圧力を加え、発熱体Ｈの温度を８０℃に設定すると共に、放熱体Ｃに２０℃の冷却水を循環させた。
　そして、発熱体Ｈ及び上下のロッドＬの温度が安定した後、上下のロッドＬの温度を各温度センサーＤで測定し、上下のロッドＬの熱伝導率と温度勾配から熱硬化された熱硬化型接着シートＳを通過する熱流束を算出すると共に、上下のロッドＬと熱硬化された熱硬化型接着シートＳとの界面の温度を算出した。そして、これらを用いて当該圧力における全熱抵抗（ｃｍ2・Ｋ）／Ｗを算出した。なお、熱硬化された熱硬化型接着シートＳに加える圧力は２５０ｋＰａとして全熱抵抗の測定を行った。
　なお、測定結果は、表１の「全熱抵抗（ｃｍ2・Ｋ）／Ｗ　２０分キュアー」の欄に示した。 (3) Total heat resistance The 80 degreeC total heat resistance was measured about the thermosetting adhesive layer after hardening in each thermosetting type adhesive sheet obtained by the Example and the comparative example.
The measurement was performed using the thermal characteristic evaluation apparatus shown in FIG. FIG. 1A is a schematic front view showing an apparatus used when measuring the total thermal resistance in the embodiment, and FIG. 1B is a schematic side view of the apparatus shown in FIG.
Specifically, a thermosetting adhesive sheet S (20 mm × 20 mm) is formed between a pair of rods L made of aluminum (A5052, thermal conductivity: 140 W / m · K) formed so as to be a legitimate body having a side of 20 mm. 20 mm) was sandwiched, and a pair of rods L were bonded together with a thermosetting adhesive sheet S.
And the rod L was arrange | positioned between the heat generating body (heater block) H and the heat radiating body (cooling base board comprised so that a cooling water circulates inside) C so that a pair of rod L might become up and down. . Specifically, the heating element H is disposed on the upper rod L, and the radiator C is disposed below the lower rod L.
At this time, the pair of rods L bonded together by the thermosetting adhesive sheet S that is thermally cured is located between the pair of pressure adjusting screws T that penetrate the heating element H and the radiator C. A load cell R is installed between the pressure adjusting screw T and the heating element H, and is configured to measure the pressure when the pressure adjusting screw T is tightened. The pressure applied to the thermosetting thermosetting adhesive sheet S was used.
Further, three probes P (1 mm in diameter) of a contact-type displacement meter were installed so as to penetrate the lower rod L and the heat-cured thermosetting adhesive sheet S from the radiator C side. At this time, the upper end of the probe P is in contact with the lower surface of the upper rod L, and the distance between the upper and lower rods L (thickness of the thermosetting thermosetting adhesive sheet S) can be measured. It is configured.
A temperature sensor D was attached to the heating element H and the upper and lower rods L (see FIG. 1B). Specifically, the temperature sensor D was attached at one place on the heating element H and five places at intervals of 5 mm in the vertical direction of each rod L.
First, the pressure adjusting screw T is tightened to apply pressure to the heat-cured thermosetting adhesive sheet S, the temperature of the heating element H is set to 80 ° C., and the cooling body C is cooled to 20 ° C. Water was circulated.
Then, after the temperature of the heating element H and the upper and lower rods L is stabilized, the temperature of the upper and lower rods L is measured by each temperature sensor D, and the heat curing is performed by the thermal conductivity and temperature gradient of the upper and lower rods L. The heat flux passing through the mold adhesive sheet S was calculated, and the temperature at the interface between the upper and lower rods L and the thermosetting thermosetting adhesive sheet S was calculated. And using these, the total thermal resistance (cm < 2 > * K) / W in the said pressure was computed. In addition, the pressure applied to the heat-cured thermosetting adhesive sheet S was 250 kPa, and the total thermal resistance was measured.
The measurement results are shown in the column of “total thermal resistance (cm 2 · K) / W 20 minutes cure” in Table 1.
　また、上記測定において、１５０℃で６０分の条件で加熱硬化した熱硬化された熱硬化型接着シートを用いて、同様に全熱抵抗を測定した。測定結果は、表１の「全熱抵抗（ｃｍ2・Ｋ）／Ｗ　６０分キュアー」の欄に示した。 Moreover, in the said measurement, the total heat resistance was similarly measured using the thermosetting thermosetting adhesive sheet heat-hardened on 150 degreeC on the conditions for 60 minutes. The measurement results are shown in the column of “Total thermal resistance (cm 2 · K) / W 60 minutes cure” in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、本発明の熱硬化型接着シートは熱硬化時間が２０分と短い場合でも、硬化後の接着力が高く接着性に優れ、さらに、加湿熱条件下においた後に厳しい温度条件（２６０℃）で、はんだディップの処理を施した場合においても、浮き剥がれや発泡が見られず、高い湿熱後耐熱性を有していた。また、硬化時間が短い場合でも、硬化後の熱硬化型接着剤層の全熱抵抗が低く、放熱性（熱伝導性）に優れていた（実施例１、２）。
　一方、厚さが２０μｍより厚い熱硬化型接着剤層を有する熱硬化型接着シートは、硬化時間が短い場合、加湿熱条件下においた後に厳しい温度条件で、はんだディップの処理を施した場合、熱硬化型接着剤層に浮き剥がれや発泡が見られ、湿熱後耐熱性が劣っていた。その上、厚さが２０μｍより厚い熱硬化型接着剤層は、全熱抵抗が高く、放熱性（熱伝導性）が劣っていた（比較例１、２）。 As is clear from Table 1, the thermosetting adhesive sheet of the present invention has a high adhesive strength after curing and excellent adhesiveness even when the thermosetting time is as short as 20 minutes, and further, it is severe after being placed under humidified heat conditions. Even when the solder dipping process was performed under the temperature condition (260 ° C.), no peeling or foaming was observed, and the film had high heat resistance after wet heat. Moreover, even when the curing time was short, the total thermal resistance of the thermosetting adhesive layer after curing was low, and the heat dissipation (thermal conductivity) was excellent (Examples 1 and 2).
On the other hand, if the thermosetting adhesive sheet having a thermosetting adhesive layer having a thickness of more than 20 μm is subjected to a solder dip treatment under severe temperature conditions after being placed under humidified heat conditions when the curing time is short, Peeling and foaming were observed in the thermosetting adhesive layer, and the heat resistance after wet heat was poor. In addition, the thermosetting adhesive layer having a thickness of more than 20 μm had a high total thermal resistance and a poor heat dissipation (thermal conductivity) (Comparative Examples 1 and 2).
　本発明の熱硬化型接着シートは、硬化時間が短い場合でも優れた接着性、湿熱後耐熱性を発揮でき、且つ熱伝導性に優れる。そのため、本発明の熱硬化型接着シートは、強固に接着し、接着後に極めて厳しい温度条件下で処理される場合でも発泡や浮き剥がれなどが生じない優れた湿熱後耐熱性が求められ、かつ、被着体の熱を放熱させるために優れた熱伝導性が求められるフレキシブル印刷回路基板（ＦＰＣ）の接着用途等に好ましく使用することができる。 The thermosetting adhesive sheet of the present invention can exhibit excellent adhesion, heat resistance after moist heat even when the curing time is short, and is excellent in thermal conductivity. Therefore, the thermosetting adhesive sheet of the present invention is required to have excellent post-humidity heat resistance that does not cause foaming or peeling even when firmly bonded and processed under extremely severe temperature conditions after bonding, and It can be preferably used for bonding applications of flexible printed circuit boards (FPCs) that require excellent thermal conductivity in order to dissipate the heat of the adherend.

Claims (10)

  1. 　熱硬化型接着剤組成物から形成された熱硬化型接着剤層を有し、
    　前記熱硬化型接着剤組成物は、アクリル系ポリマー（Ｘ）を主成分として含有し、かつエーテル化フェノール樹脂（Ｙ）を含有し、前記熱硬化型接着剤層の厚さが１～２０μｍであることを特徴とする熱硬化型接着シート。     Having a thermosetting adhesive layer formed from the thermosetting adhesive composition;
    The thermosetting adhesive composition contains an acrylic polymer (X) as a main component and an etherified phenol resin (Y), and the thermosetting adhesive layer has a thickness of 1 to 20 μm. There is a thermosetting adhesive sheet.
  2. 　１５０℃、６０分の条件下で硬化させた後の、前記熱硬化型接着剤層の全熱抵抗が２．０（ｃｍ2・Ｋ）／Ｗ以下である請求項１に記載の熱硬化型接着シート。 2. The thermosetting type according to claim 1, wherein the thermosetting adhesive layer has a total thermal resistance of 2.0 (cm 2 · K) / W or less after being cured at 150 ° C. for 60 minutes. Adhesive sheet.
  3. 　前記アクリル系ポリマー（Ｘ）が、炭素数が１～１４である直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（ａ）を必須のモノマー成分として構成されたアクリル系ポリマーである請求項１又は２に記載の熱硬化型接着シート。 Acrylic polymer in which the acrylic polymer (X) is composed of (meth) acrylic acid alkyl ester (a) having a linear or branched alkyl group having 1 to 14 carbon atoms as an essential monomer component. The thermosetting adhesive sheet according to claim 1 or 2.
  4. 　前記アクリル系ポリマー（Ｘ）が、さらに、シアノ基含有モノマー（ｂ）及びカルボキシル基含有モノマー（ｃ）を必須のモノマー成分として構成されたアクリル系ポリマーである請求項３に記載の熱硬化型接着シート。 The thermosetting adhesive according to claim 3, wherein the acrylic polymer (X) is an acrylic polymer further comprising a cyano group-containing monomer (b) and a carboxyl group-containing monomer (c) as essential monomer components. Sheet.
  5. 　前記エーテル化フェノール樹脂（Ｙ）の含有量が、前記アクリル系ポリマー（Ｘ）１００重量部に対して、１～４０重量部である請求項１～４のいずれか１項に記載の熱硬化型接着シート。 The thermosetting type according to any one of claims 1 to 4, wherein the content of the etherified phenol resin (Y) is 1 to 40 parts by weight with respect to 100 parts by weight of the acrylic polymer (X). Adhesive sheet.
  6. 　前記熱硬化型接着剤層のみからなり、基材を有していない請求項１～５のいずれか１項に記載の熱硬化型接着シート。 The thermosetting adhesive sheet according to any one of claims 1 to 5, which comprises only the thermosetting adhesive layer and has no substrate.
  7. 　フレキシブル印刷回路基板用熱硬化型接着シートである請求項１～６のいずれか１項に記載の熱硬化型接着シート。 The thermosetting adhesive sheet according to any one of claims 1 to 6, which is a thermosetting adhesive sheet for a flexible printed circuit board.
  8. 　フレキシブル印刷回路基板上に請求項７に記載の熱硬化型接着シートを有する積層体。 A laminate having the thermosetting adhesive sheet according to claim 7 on a flexible printed circuit board.
  9. 　請求項１～７のいずれか１項に記載の熱硬化型接着シートを熱硬化して得られた、熱硬化された熱硬化型接着シート。 A thermoset thermosetting adhesive sheet obtained by thermosetting the thermosetting adhesive sheet according to any one of claims 1 to 7.
  10. 　フレキシブル印刷回路基板上に請求項９に記載の熱硬化された熱硬化型接着シートを有する積層体。 A laminate having the thermosetting thermosetting adhesive sheet according to claim 9 on a flexible printed circuit board.
PCT/JP2012/078316 2011-11-16 2012-11-01 Thermosetting adhesive sheet and laminate WO2013073380A1 (en)

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JP2005247910A (en) * 2004-03-02 2005-09-15 Nitto Denko Corp Thermosetting hardenable adhesive tape or sheet and method for producing the same
JP2007049036A (en) * 2005-08-11 2007-02-22 Nitto Denko Corp Wiring circuit board
WO2011004710A1 (en) * 2009-07-09 2011-01-13 日東電工株式会社 Heat-curable adhesive tape or sheet and flexible printed circuit board
JP2012051994A (en) * 2010-08-31 2012-03-15 Nitto Denko Corp Thermosetting adhesive tape or sheet

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239830A (en) * 2004-02-25 2005-09-08 Nitto Denko Corp Thermosetting pressure-sensitive adhesive composition and thermosetting pressure-sensitive adhesive tape or sheet
JP2005247910A (en) * 2004-03-02 2005-09-15 Nitto Denko Corp Thermosetting hardenable adhesive tape or sheet and method for producing the same
JP2007049036A (en) * 2005-08-11 2007-02-22 Nitto Denko Corp Wiring circuit board
WO2011004710A1 (en) * 2009-07-09 2011-01-13 日東電工株式会社 Heat-curable adhesive tape or sheet and flexible printed circuit board
JP2012051994A (en) * 2010-08-31 2012-03-15 Nitto Denko Corp Thermosetting adhesive tape or sheet

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