WO2016067966A1 - Thermosetting adhesive composition and thermosetting adhesive sheet - Google Patents

Thermosetting adhesive composition and thermosetting adhesive sheet Download PDF

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Publication number
WO2016067966A1
WO2016067966A1 PCT/JP2015/079518 JP2015079518W WO2016067966A1 WO 2016067966 A1 WO2016067966 A1 WO 2016067966A1 JP 2015079518 W JP2015079518 W JP 2015079518W WO 2016067966 A1 WO2016067966 A1 WO 2016067966A1
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epoxy resin
thermosetting adhesive
mass
solid
parts
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PCT/JP2015/079518
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French (fr)
Japanese (ja)
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大助 本村
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デクセリアルズ株式会社
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Publication of WO2016067966A1 publication Critical patent/WO2016067966A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a reinforcing adhesive for fixing a reinforcing plate to a flexible printed wiring board, a thermosetting adhesive composition that can be used as a binder for dispersing thermal conductive particles, conductive particles, and the like, and thermosetting adhesion Regarding the sheet.
  • the adhesive sheet When a member such as a reinforcing plate is closely fixed to the surface of a substrate such as a flexible printed wiring board using a thermosetting adhesive sheet, the adhesive sheet is temporarily fixed by exhibiting tackiness at room temperature or bonded. It is conceivable to heat the sheet so as not to be cured by heat and develop tackiness to temporarily fix the sheet.
  • the present invention has been proposed in view of such a conventional situation, and provides a thermosetting adhesive composition and a thermosetting adhesive sheet capable of easily temporarily fixing a member to a substrate.
  • the inventor contains acrylic rubber having a low glass transition temperature, and the value of the ratio of the content of the liquid epoxy resin to the content of the solid epoxy resin and the solid phenol resin is within a predetermined range.
  • the member can be easily temporarily fixed to the substrate.
  • thermosetting adhesive composition according to the present invention is An acrylic rubber having a glass transition temperature of ⁇ 50 to ⁇ 30 ° C .; Liquid epoxy resin, A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin; Containing solid phenolic resin, The ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is 0.4 to 0.8.
  • thermosetting adhesive sheet according to the present invention is An acrylic rubber having a glass transition temperature of ⁇ 50 to ⁇ 30 ° C .; Liquid epoxy resin, A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin; Containing solid phenolic resin, The ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is 0.4 to 0.8.
  • thermosetting adhesive composition and the thermosetting adhesive sheet of the present invention include an acrylic rubber having a low glass transition temperature, a solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin, and a solid phenol resin. Since the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is set within a predetermined range, the member can be easily attached to the substrate like an adhesive tape. Can be fixed. Moreover, the outstanding adhesiveness and heat resistance can be obtained by heating.
  • Thermosetting adhesive composition includes an acrylic rubber (A) having a glass transition temperature of ⁇ 50 to ⁇ 30 ° C., a liquid epoxy resin (B), a solid epoxy resin (C), and a solid phenol.
  • the ratio of the content of the liquid epoxy resin (B) to the total content of the solid epoxy resin (C) and the solid phenol resin (D) is 0.4 to 0.8. is there.
  • the acrylic rubber means an acrylic polymer or a methacrylic polymer.
  • the liquid epoxy resin means an epoxy resin that is liquid at room temperature.
  • the solid epoxy resin means an epoxy resin that is solid at normal temperature.
  • the solid phenol resin means a phenol resin that is solid at normal temperature.
  • the normal temperature means a temperature range of 5 to 35 ° C. defined by JIS Z 8703.
  • the glass transition temperature is a temperature obtained by a method defined in JIS K 7121.
  • Acrylic rubber has a glass transition temperature (Tg) of ⁇ 50 to ⁇ 30 ° C.
  • Tg glass transition temperature
  • the acrylic rubber has a Tg of ⁇ 50 to ⁇ 30 ° C.
  • the tackiness expression temperature of the film is appropriately lowered, and the tackiness can be exhibited at room temperature.
  • Acrylic rubber is a copolymer of (meth) acrylic monomers. Although it does not specifically limit as a polymerization method for obtaining acrylic rubber from a (meth) acryl monomer, It is preferable to use pearl polymerization from a viewpoint of obtaining high molecular weight.
  • (meth) acrylic monomers examples include butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), ethyl acrylate (EA), nitrile acrylate (AN), and glycidyl methacrylate (GMA).
  • BA butyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • EA ethyl acrylate
  • AN nitrile acrylate
  • GMA glycidyl methacrylate
  • butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), nitrile acrylate (AN), and glycidyl methacrylate (GMA) are used in combination as a (meth) acryl monomer, and these are subjected to pearl polymerization.
  • BA butyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • AN nitrile acrylate
  • GMA glycidyl methacrylate
  • the glass transition temperature (Tg) of acrylic rubber can be calculated by the following formula (1) (FOX formula).
  • W 1, W 2 ⁇ W n is the weight fraction of each monomer
  • T 1, T 2 ⁇ T n is the glass transition temperature of each monomer (K).
  • the liquid epoxy resin is not particularly limited as long as it is liquid at normal temperature, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac phenol type epoxy resin, naphthalene type epoxy resin, and the like. Can be used alone or in combination of two or more. In particular, it is preferable to use a bisphenol A type epoxy resin or a bisphenol F type epoxy resin from the viewpoint of tackiness and flexibility of the film.
  • the amount is preferably 15 to 55 parts by mass, more preferably 25 to 100 parts by mass of the acrylic rubber. ⁇ 45 parts by mass.
  • the solid epoxy resin is compatible with the liquid epoxy resin and contains a polyfunctional epoxy resin and a monofunctional epoxy resin that are solid at room temperature.
  • the polyfunctional epoxy resin is an epoxy resin having three or more epoxy groups in the molecule
  • the monofunctional epoxy resin is an epoxy resin having one epoxy group in the molecule.
  • polyfunctional epoxy resin a known polyfunctional epoxy resin can be employed. Specifically, a polyfunctional phenol novolac type epoxy resin (for example, 1031S of Mitsubishi Chemical Corporation), tri (glycidyloxymethyl) Propane (for example, ED-505 of ADEKA Corporation), (2- (glycidyloxyphenyl) propylphenyl) -1,1-di (glycidyloxyphenyl) ethane (for example, VG3101L of Printec Corporation), etc. Can be mentioned.
  • a polyfunctional phenol novolac type epoxy resin for example, 1031S of Mitsubishi Chemical Corporation
  • tri (glycidyloxymethyl) Propane for example, ED-505 of ADEKA Corporation
  • (2- (glycidyloxyphenyl) propylphenyl) -1,1-di (glycidyloxyphenyl) ethane for example, VG3101L of Printec Corporation
  • monofunctional epoxy resins examples include monofunctional dicyclopentadiene type epoxy resins, monofunctional novolac phenol type epoxy resins, monofunctional biphenyl type epoxy resins, and monofunctional naphthalene type epoxy resins. Or in combination of two or more. Among these, monofunctional dicyclopentadiene type epoxy resins can be preferably used.
  • the solid epoxy resin preferably contains the above-mentioned polyfunctional epoxy resin and monofunctional epoxy resin in a mass ratio of 1: 4 to 1:10.
  • the amount is 45 parts by mass, more preferably 30 to 35 parts by mass.
  • the solid phenol resin is not particularly limited as long as it is compatible with a liquid epoxy resin and is solid at room temperature.
  • a resin etc. are mentioned, Among these, 1 type can be used individually or in combination of 2 or more types. In particular, it is preferable to use a resol type phenol resin that functions as an epoxy resin curing agent.
  • the content of the solid phenol resin is preferably 10 to 50 parts by mass, more preferably 20 parts per 100 parts by mass of the acrylic rubber. ⁇ 40 parts by mass.
  • the content of the liquid epoxy resin (B) with respect to the total content of the solid epoxy resin (C) and the solid phenol resin (D) is 0.4 to 0.8, preferably 0.5 to 0.65. If it is this range, the adhesiveness and heat resistance which were excellent in the thermosetting adhesive composition can be provided.
  • thermosetting adhesive composition for dilution of latent curing agents, inorganic fillers, conductive particles, heat conductive particles, film-forming resins, various acrylic monomers, etc., if necessary Monomers, fillers, softeners, colorants, flame retardants, thixotropic agents, silane coupling agents, and the like may be blended.
  • the latent curing agent includes dicyandiamide (DICY), 7,11-octadecadiene-1,18-dicarbohydrazide (UDH), diaminodiphenylsulfone (DDS), a microcapsule comprising a reaction product of an epoxy resin and an amine compound.
  • DIY dicyandiamide
  • UDH 7,11-octadecadiene-1,18-dicarbohydrazide
  • DDS diaminodiphenylsulfone
  • a microcapsule comprising a reaction product of an epoxy resin and an amine compound.
  • Novacure trade name, Asahi Kasei E-Materials Co., Ltd.
  • the content of the latent curing agent is preferably 0.5 to 3.0 parts by mass, more preferably 100 parts by mass with respect to the acrylic rubber. 1 to 1.5 parts by mass.
  • An example of the inorganic filler is an oxide such as silica.
  • the inorganic filler is used for adjusting the viscosity and viscosity of the binder in forming a sheet, and controlling the resin flow property during heat curing.
  • the content of the inorganic filler is preferably 1 to 10 parts by mass, more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the acrylic rubber.
  • thermosetting adhesive composition composed of such components has tackiness, the member can be easily temporarily fixed to the substrate like an adhesive tape. Moreover, the outstanding adhesiveness and heat resistance can be obtained by heating. Therefore, it can use suitably for the use which bonds a flexible printed wiring board and the member for reinforcement, for example, a metal plate.
  • Thermosetting adhesive sheet includes an acrylic rubber (A) having a glass transition temperature of ⁇ 50 to ⁇ 30 ° C., a liquid epoxy resin (B), a solid epoxy resin (C), and a solid phenol resin.
  • the ratio of the content of the liquid epoxy resin (B) to the total content of the solid epoxy resin (C) and the solid phenol resin (D) is 0.4 to 0.8, preferably Is 0.5 to 0.65.
  • thermosetting adhesive composition can be prepared by uniformly mixing by a conventional method. Then, the thermosetting adhesive composition is applied on the base film with a bar coater or roll coater so that the dry thickness is 10 to 60 ⁇ m, and is dried by a conventional method to provide a thermosetting adhesive layer. A curable adhesive sheet can be produced.
  • a base material film a base material such as a polyethylene terephthalate film or a polyimide film, which is a base material that is peel-treated with silicone or the like as required, can be used.
  • An adhesive layer made of a curable adhesive composition is formed on the base film with a thickness of 10 to 60 ⁇ m, for example.
  • thermosetting adhesive sheet includes, for example, a terminal portion of a flexible printed wiring board and a reinforcing sheet having a thickness of 50 ⁇ m to 2 mm made of polyethylene terephthalate, polyimide, glass epoxy, stainless steel, aluminum, or the like for lining it. It can be preferably applied for adhesive fixing. Moreover, workability can be improved because it can be easily adhered to the reinforcing sheet by thermal lamination.
  • Example> Examples of the present invention will be described below.
  • an acrylic rubber, a liquid epoxy resin, a solid epoxy resin, a solid phenol resin, a latent curing agent, and an inorganic filler shown below were blended to prepare a thermosetting adhesive composition.
  • thermosetting adhesive composition is applied to a polyethylene terephthalate film (release PET film) that has been subjected to a release treatment, dried in a drying oven at 50 to 130 ° C., and further laminated with a release treatment PET film.
  • release PET film polyethylene terephthalate film
  • a thermosetting adhesive sheet having a thermosetting adhesive layer having a thickness of 35 ⁇ m was prepared.
  • the following items (1) to (5) were evaluated.
  • thermosetting adhesive sheet was cut into strips (1 cm ⁇ 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 ⁇ m thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. And superimposed. And the 90 degree peeling test was done with respect to the polyimide film at the peeling speed of 50 mm / min, and the force required for peeling was measured.
  • thermosetting adhesive sheet [(2) Evaluation of tackiness before curing of thermosetting adhesive sheet]
  • a tackiness tester a RHESCA tacking tester TAC-II was used, and an aluminum cylindrical probe having a diameter of 10 mm was applied to the thermosetting adhesive layer from which the release-treated PET film was removed, with a pressing speed of 30 mm / min.
  • the probe tackiness when peeled by pressing under the conditions of a peeling speed of 120 mm / min, a load of 196 g, a pressing time of 5.0 seconds, a pulling distance of 5 mm, a probe heating of 40 ° C. and a sheet stage heating of 40 ° C. was measured.
  • Tack of the thermosetting adhesive sheet " ⁇ " a of less than 10 kN / m 2 was evaluated 10 kN / m 2 or more as the " ⁇ ".
  • thermosetting adhesive sheet was cut into strips (1 cm ⁇ 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 ⁇ m thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. And superimposed. Then, a cut was made at 25 mm from the end of the SUS304 plate, put in an oven at 100 ° C., a load of 1 kg was applied, and the deviation after 1 hour was observed. The evaluation of the case where the deviation was 1 mm or less and did not fall was “ ⁇ ”, and the evaluation of the case where the deviation exceeded 1 mm or was dropped was “x”.
  • thermosetting adhesive sheet was cut into strips (1 cm ⁇ 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 ⁇ m thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller.
  • thermosetting adhesive sheet was cut into strips (1 cm ⁇ 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 ⁇ m thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller.
  • thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 6 parts by mass of filler.
  • the value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.50, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 2.0 N / cm, (2) The evaluation of the tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property is evaluated before curing of the thermosetting adhesive sheet is “good”.
  • the peel strength after curing of the thermosetting adhesive sheet was 8.7 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 8.7 N / cm.
  • thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 6 parts by mass of filler.
  • the value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 3.0 N / cm, (2) The evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is “good”.
  • the peel strength after curing of the curable adhesive sheet was 7.7 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 7.7 N / cm.
  • thermosetting adhesive sheet was prepared using the thermosetting adhesive composition.
  • thermosetting pressure-sensitive adhesive sheet The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 1.25, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 1.2 N / cm, (2) The evaluation of the tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is poor “ ⁇ ”. (4) The peel strength after curing of the thermosetting adhesive sheet was 2.0 N / cm, and (5) the peel strength after heat resistance test of the thermosetting adhesive sheet was 1.4 N / cm.
  • thermosetting adhesive sheet was prepared using the thermosetting adhesive composition.
  • the value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 1.00, and (1) peel strength before curing of the thermosetting adhesive sheet 0.8 N / cm, (2) The evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is poor “ ⁇ ”.
  • the peel strength after curing of the thermosetting adhesive sheet was 1.8 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 1.4 N / cm.
  • thermosetting adhesive sheet was produced using the thermosetting adhesive composition containing a mass part and 6 mass parts of inorganic fillers.
  • thermosetting pressure-sensitive adhesive sheet The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet 1.0 N / cm, (2) Evaluation of tackiness before curing of thermosetting adhesive sheet is poor “x”, (3) Evaluation of creep characteristics before curing of thermosetting adhesive sheet is “poor” (4) The peel strength after curing of the thermosetting adhesive sheet was 3.3 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 0.8 N / cm.
  • thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 1.5 parts by mass and 6 parts by mass of an inorganic filler.
  • thermosetting pressure-sensitive adhesive sheet The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 2.0 N / cm, (2) the evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) the creep property evaluation before curing of the thermosetting adhesive sheet is poor “ ⁇ ”. (4) The peel strength after curing of the thermosetting adhesive sheet was 7.0 N / cm, and (5) the peel strength after heat resistance test of the thermosetting adhesive sheet was 5.5 N / cm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is a thermosetting adhesive composition capable of temporarily fixing a member easily, comprising: an acrylic rubber having a glass transition temperature of -50 to -30 °C; a liquid epoxy resin; a solid epoxy resin comprising a polyfunctional epoxy resin and a monofunctional resin; and a solid phenol resin. With respect to the total content of the solid epoxy resin and the solid phenol resin, the ratio of the liquid epoxy resin content is 0.4-0.8. With respect to 100 parts by mass of the acrylic rubber, the contents of the liquid epoxy resin, the solid epoxy resin and the solid phenol resin are respectively 15-55 parts by mass, 20-45 parts by mass and 10-50 parts by mass.

Description

熱硬化性接着組成物、及び熱硬化性接着シートThermosetting adhesive composition and thermosetting adhesive sheet
　本発明は、フレキシブルプリント配線板などに補強板を固定させる補強用接着剤や、熱伝導性粒子、導電性粒子などを分散させるバインダーとして使用可能な熱硬化性接着組成物、及び熱硬化性接着シートに関する。 The present invention relates to a reinforcing adhesive for fixing a reinforcing plate to a flexible printed wiring board, a thermosetting adhesive composition that can be used as a binder for dispersing thermal conductive particles, conductive particles, and the like, and thermosetting adhesion Regarding the sheet.
　熱硬化性の接着シートを用いて、フレキシブルプリント配線板等の基板の表面に補強板等の部材を密着固定する場合、接着シートに常温でタック性を発現させて仮固定を行うか、又は接着シートが熱硬化してしまわないように加熱してタック性を発現させて仮固定することが考えられる。 When a member such as a reinforcing plate is closely fixed to the surface of a substrate such as a flexible printed wiring board using a thermosetting adhesive sheet, the adhesive sheet is temporarily fixed by exhibiting tackiness at room temperature or bonded. It is conceivable to heat the sheet so as not to be cured by heat and develop tackiness to temporarily fix the sheet.
　しかし、後者の場合は、タック性を発現させるために、加熱する工程が必要となり、生産性が低下してしまう。 However, in the latter case, a heating step is required to develop tackiness, and productivity is lowered.
特開２００１－３０１５号公報JP 2001-3015 A
　本発明は、このような従来の実情に鑑みて提案されたものであり、基板に部材を容易に仮固定させることができる熱硬化性接着組成物、及び熱硬化性接着シートを提供する。 The present invention has been proposed in view of such a conventional situation, and provides a thermosetting adhesive composition and a thermosetting adhesive sheet capable of easily temporarily fixing a member to a substrate.
　本発明者は、鋭意検討を行った結果、低いガラス転移温度を有するアクリルゴムを含有し、固形エポキシ樹脂及び固形フェノール樹脂の含有量に対する液状エポキシ樹脂の含有量の比の値が、所定の範囲であることにより、基板に部材を容易に仮固定させることができることを見出した。 As a result of intensive studies, the inventor contains acrylic rubber having a low glass transition temperature, and the value of the ratio of the content of the liquid epoxy resin to the content of the solid epoxy resin and the solid phenol resin is within a predetermined range. Thus, it has been found that the member can be easily temporarily fixed to the substrate.
　すなわち、本発明に係る熱硬化性接着組成物は、
　ガラス転移温度が－５０～－３０℃であるアクリルゴムと、
　液状エポキシ樹脂と、
　多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂と、
　固形フェノール樹脂とを含有し、
　前記固形エポキシ樹脂及び前記固形フェノール樹脂の合計含有量に対する前記液状エポキシ樹脂の含有量の比の値が、０．４～０．８であることを特徴とする。 That is, the thermosetting adhesive composition according to the present invention is
An acrylic rubber having a glass transition temperature of −50 to −30 ° C .;
Liquid epoxy resin,
A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin;
Containing solid phenolic resin,
The ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is 0.4 to 0.8.
　また、本発明に係る熱硬化性接着シートは、
　ガラス転移温度が－５０～－３０℃であるアクリルゴムと、
　液状エポキシ樹脂と、
　多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂と、
　固形フェノール樹脂とを含有し、
　前記固形エポキシ樹脂及び前記固形フェノール樹脂の合計含有量に対する前記液状エポキシ樹脂の含有量の比の値が、０．４～０．８であることを特徴とする。 In addition, the thermosetting adhesive sheet according to the present invention is
An acrylic rubber having a glass transition temperature of −50 to −30 ° C .;
Liquid epoxy resin,
A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin;
Containing solid phenolic resin,
The ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is 0.4 to 0.8.
　本発明の熱硬化性接着剤組成物及び熱硬化性接着シートは、低いガラス転移温度を有するアクリルゴムと、多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂と、固形フェノール樹脂とを含有し、固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値が所定の範囲に設定されているので、粘着テープのように、基板に部材を容易に仮固定させることができる。また、加熱により、優れた接着性及び耐熱性を得ることができる。 The thermosetting adhesive composition and the thermosetting adhesive sheet of the present invention include an acrylic rubber having a low glass transition temperature, a solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin, and a solid phenol resin. Since the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin is set within a predetermined range, the member can be easily attached to the substrate like an adhesive tape. Can be fixed. Moreover, the outstanding adhesiveness and heat resistance can be obtained by heating.
　以下、本発明の実施の形態について、図面を参照しながら下記順序にて詳細に説明する。
１．熱硬化性接着組成物
２．熱硬化性接着シート
３．実施例 Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. 1. Thermosetting adhesive composition 2. Thermosetting adhesive sheet Example
　＜１．熱硬化性接着組成物＞
　本実施の形態に係る熱硬化性接着組成物は、ガラス転移温度が－５０～－３０℃であるアクリルゴム（Ａ）と、液状エポキシ樹脂（Ｂ）と、固形エポキシ樹脂（Ｃ）、固形フェノール樹脂（Ｄ）とを含有し、固形エポキシ樹脂（Ｃ）及び固形フェノール樹脂（Ｄ）の合計含有量に対する液状エポキシ樹脂（Ｂ）の含有量の比の値が、０．４～０．８である。 <1. Thermosetting adhesive composition>
The thermosetting adhesive composition according to the present embodiment includes an acrylic rubber (A) having a glass transition temperature of −50 to −30 ° C., a liquid epoxy resin (B), a solid epoxy resin (C), and a solid phenol. The ratio of the content of the liquid epoxy resin (B) to the total content of the solid epoxy resin (C) and the solid phenol resin (D) is 0.4 to 0.8. is there.
　以下、熱硬化性接着組成物の各成分（Ａ）～（Ｄ）について詳細に説明する。なお、本明細書において、アクリルゴムとは、アクリル重合体又はメタアクリル重合体を意味する。また、液状エポキシ樹脂とは、常温で液状であるエポキシ樹脂を意味する。また、固形エポキシ樹脂とは、常温で固体状であるエポキシ樹脂を意味する。また、固形フェノール樹脂とは、常温で固体状であるフェノール樹脂を意味する。また、常温とは、ＪＩＳ Ｚ ８７０３で規定される５～３５℃の温度範囲を意味する。また、ガラス転移温度とは、ＪＩＳ Ｋ ７１２１に規定される方法により求められる温度である。 Hereinafter, each component (A) to (D) of the thermosetting adhesive composition will be described in detail. In the present specification, the acrylic rubber means an acrylic polymer or a methacrylic polymer. The liquid epoxy resin means an epoxy resin that is liquid at room temperature. The solid epoxy resin means an epoxy resin that is solid at normal temperature. The solid phenol resin means a phenol resin that is solid at normal temperature. The normal temperature means a temperature range of 5 to 35 ° C. defined by JIS Z 8703. Further, the glass transition temperature is a temperature obtained by a method defined in JIS K 7121.
　［（Ａ）アクリルゴム］
　アクリルゴムは、ガラス転移温度（Ｔｇ）が－５０～－３０℃である。アクリルゴムのＴｇが－５０～－３０℃であることにより、フィルムのタック性発現温度が適度に低くなり、常温でタック性を発現させることができる。 [(A) Acrylic rubber]
Acrylic rubber has a glass transition temperature (Tg) of −50 to −30 ° C. When the acrylic rubber has a Tg of −50 to −30 ° C., the tackiness expression temperature of the film is appropriately lowered, and the tackiness can be exhibited at room temperature.
　アクリルゴムは、（メタ）アクリルモノマーの共重合体である。（メタ）アクリルモノマーからアクリルゴムを得るための重合方法としては、特に限定されないが、高分子量を得る観点からパール重合を用いることが好ましい。 Acrylic rubber is a copolymer of (meth) acrylic monomers. Although it does not specifically limit as a polymerization method for obtaining acrylic rubber from a (meth) acryl monomer, It is preferable to use pearl polymerization from a viewpoint of obtaining high molecular weight.
（メタ）アクリルモノマーとしては、アクリル酸ブチル（ＢＡ）、アクリル酸２－エチルヘキシル（２ＥＨＡ）、アクリル酸エチル（ＥＡ）、アクリル酸ニトリル（ＡＮ）、グリシジルメタクリレート（ＧＭＡ）などが挙られ、これらの中から１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of (meth) acrylic monomers include butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), ethyl acrylate (EA), nitrile acrylate (AN), and glycidyl methacrylate (GMA). One of them can be used alone, or two or more of them can be used in combination.
　好ましいアクリルゴムとしては、（メタ）アクリルモノマーとして、アクリル酸ブチル（ＢＡ）、アクリル酸２－エチルヘキシル（２ＥＨＡ）、アクリル酸ニトリル（ＡＮ）、及びグリシジルメタクリレート（ＧＭＡ）を併用し、これらをパール重合して得た共重合体である。この場合、アクリルゴムに低Ｔｇを実現するためにはＢＡ、２ＥＨＡの使用量を増加させ、また、アクリルゴムに良好な耐熱性を実現のためにはＡＮ、ＧＭＡの使用量を増加させることが好ましい。 As a preferable acrylic rubber, butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), nitrile acrylate (AN), and glycidyl methacrylate (GMA) are used in combination as a (meth) acryl monomer, and these are subjected to pearl polymerization. The copolymer obtained as above. In this case, it is necessary to increase the amount of BA and 2EHA used to achieve a low Tg in acrylic rubber, and to increase the amount of AN and GMA used to achieve good heat resistance in acrylic rubber. preferable.
　なお、アクリルゴムのガラス転移温度（Ｔｇ）は、下記（１）式（ＦＯＸ式）により計算することができる。（１）式中、Ｗ１、Ｗ２・・・Ｗｎは各モノマーの質量分率であり、Ｔ１、Ｔ２・・・Ｔｎは各モノマーのガラス転移温度（Ｋ）である。 In addition, the glass transition temperature (Tg) of acrylic rubber can be calculated by the following formula (1) (FOX formula). In (1), W 1, W 2 ··· W n is the weight fraction of each monomer, T 1, T 2 ··· T n is the glass transition temperature of each monomer (K).
　１／Ｔｇ＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋・・・Ｗｎ／Ｔｎ ・・・（１）
　 1 / Tg = W 1 / T 1 + W 2 / T 2 +... W n / T n (1)
　［（Ｂ）液状エポキシ樹脂］
　液状エポキシ樹脂としては、常温で液状であれば特に限定されず、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラックフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂などが挙げられ、これらの中から１種を単独で、又は２種以上を組み合わせて用いることができる。特に、フィルムのタック性、柔軟性などの観点から、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂を用いることが好ましい。 [(B) Liquid epoxy resin]
The liquid epoxy resin is not particularly limited as long as it is liquid at normal temperature, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac phenol type epoxy resin, naphthalene type epoxy resin, and the like. Can be used alone or in combination of two or more. In particular, it is preferable to use a bisphenol A type epoxy resin or a bisphenol F type epoxy resin from the viewpoint of tackiness and flexibility of the film.
　液状エポキシ樹脂の含有量は、少なすぎるとタック性が低下し、多すぎるとクリープ特性が低下する傾向があるので、アクリルゴム１００質量部に対し、好ましくは１５～５５質量部、より好ましくは２５～４５質量部である。 If the content of the liquid epoxy resin is too small, tackiness is lowered, and if it is too large, the creep characteristics tend to be lowered. Therefore, the amount is preferably 15 to 55 parts by mass, more preferably 25 to 100 parts by mass of the acrylic rubber. ~ 45 parts by mass.
　［（Ｃ）固形エポキシ樹脂］
　固形エポキシ樹脂は、液状エポキシ樹脂と相溶し、常温で固体状の多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する。ここで、多官能エポキシ樹脂は分子中にエポキシ基が３個以上存在するエポキシ樹脂であり、単官能エポキシ樹脂は分子中にエポキシ基が１個存在するエポキシ樹脂である。 [(C) Solid epoxy resin]
The solid epoxy resin is compatible with the liquid epoxy resin and contains a polyfunctional epoxy resin and a monofunctional epoxy resin that are solid at room temperature. Here, the polyfunctional epoxy resin is an epoxy resin having three or more epoxy groups in the molecule, and the monofunctional epoxy resin is an epoxy resin having one epoxy group in the molecule.
　多官能エポキシ樹脂としては、公知の多官能エポキシ樹脂を採用することができ、具体的には、多官能フェノールノボラック型エポキシ樹脂（例えば、三菱化学（株）の１０３１Ｓ）、トリ（グリシジルオキシメチル）プロパン（例えば、（株）ＡＤＥＫＡのＥＤ－５０５）、（２－（グリシジルオキシフェニル）プロピルフェニル）－１，１－ジ（グリシジルオキシフェニル）エタン（例えば、プリンテック（株）のＶＧ３１０１Ｌ）等を挙げられる。 As the polyfunctional epoxy resin, a known polyfunctional epoxy resin can be employed. Specifically, a polyfunctional phenol novolac type epoxy resin (for example, 1031S of Mitsubishi Chemical Corporation), tri (glycidyloxymethyl) Propane (for example, ED-505 of ADEKA Corporation), (2- (glycidyloxyphenyl) propylphenyl) -1,1-di (glycidyloxyphenyl) ethane (for example, VG3101L of Printec Corporation), etc. Can be mentioned.
　単官能エポキシ樹脂としては、単官能ジシクロペンタジエン型エポキシ樹脂、単官能ノボラックフェノール型エポキシ樹脂、単官能ビフェニル型エポキシ樹脂、単官能ナフタレン型エポキシ樹脂などが挙られ、これらの中から１種を単独で、又は２種以上を組み合わせて用いることができる。中でも単官能ジシクロペンタジエン型エポキシ樹脂を好ましく使用することができる。 Examples of monofunctional epoxy resins include monofunctional dicyclopentadiene type epoxy resins, monofunctional novolac phenol type epoxy resins, monofunctional biphenyl type epoxy resins, and monofunctional naphthalene type epoxy resins. Or in combination of two or more. Among these, monofunctional dicyclopentadiene type epoxy resins can be preferably used.
　固形エポキシ樹脂は、上述の多官能エポキシ樹脂と単官能エポキシ樹脂とを、１：４～１：１０の質量比で含有することが好ましい。多官能エポキシ樹脂が多すぎると、フィルムのタック性が失われ、単官能エポキシ樹脂が多すぎると、耐熱性が低下する傾向にある。 The solid epoxy resin preferably contains the above-mentioned polyfunctional epoxy resin and monofunctional epoxy resin in a mass ratio of 1: 4 to 1:10. When there are too many polyfunctional epoxy resins, the tackiness of a film will be lost, and when there are too many monofunctional epoxy resins, it exists in the tendency for heat resistance to fall.
　固形エポキシ樹脂の熱硬化性接着組成物中の含有量は、少なすぎるとクリープ特性が低下し、多すぎると剥離強度が低下する傾向があるので、アクリルゴム１００質量部に対し、好ましくは２０～４５質量部、より好ましくは３０～３５質量部である。 If the content of the solid epoxy resin in the thermosetting adhesive composition is too small, the creep property is lowered, and if it is too much, the peel strength tends to be lowered. The amount is 45 parts by mass, more preferably 30 to 35 parts by mass.
　［（Ｄ）固形フェノール樹脂］
　固形フェノール樹脂としては、液状エポキシ樹脂と相溶し、常温で固体状であれば特に限定されず、アルキルフェノール樹脂、ｐ－フェニルフェノール樹脂、ビスフェノールＡ型フェノール樹脂などのレゾール型フェノール樹脂及びノボラック型フェノール樹脂などが挙げられ、これらの中から１種を単独で、又は２種以上を組み合わせて用いることができる。特に、エポキシ樹脂硬化剤として機能するレゾール型フェノール樹脂を用いることが好ましい。 [(D) Solid phenol resin]
The solid phenol resin is not particularly limited as long as it is compatible with a liquid epoxy resin and is solid at room temperature. A resin etc. are mentioned, Among these, 1 type can be used individually or in combination of 2 or more types. In particular, it is preferable to use a resol type phenol resin that functions as an epoxy resin curing agent.
　固形フェノール樹脂の含有量は、少なすぎるとクリープ特性が低下し、多すぎると剥離強度が低下する傾向があるので、アクリルゴム１００質量部に対し、好ましくは１０～５０質量部、より好ましくは２０～４０質量部である。 When the content of the solid phenol resin is too small, the creep characteristics are lowered, and when it is too much, the peel strength tends to be lowered. Therefore, the content is preferably 10 to 50 parts by mass, more preferably 20 parts per 100 parts by mass of the acrylic rubber. ~ 40 parts by mass.
　また、前述した熱硬化性接着組成物の各成分（Ａ）～（Ｄ）において、固形エポキシ樹脂（Ｃ）及び固形フェノール樹脂（Ｄ）の合計含有量に対する液状エポキシ樹脂（Ｂ）の含有量の比の値は０．４～０．８、好ましくは０．５～０．６５である。この範囲であれば、熱硬化性接着組成物に優れた接着性及び耐熱性を付与することができる。 Further, in each of the components (A) to (D) of the thermosetting adhesive composition described above, the content of the liquid epoxy resin (B) with respect to the total content of the solid epoxy resin (C) and the solid phenol resin (D) The value of the ratio is 0.4 to 0.8, preferably 0.5 to 0.65. If it is this range, the adhesiveness and heat resistance which were excellent in the thermosetting adhesive composition can be provided.
　［他の添加物］
　また、熱硬化性接着組成物に配合する他の添加物として、必要に応じて、潜在性硬化剤、無機フィラー、導電性粒子、熱伝導性粒子、膜形成樹脂、各種アクリルモノマー等の希釈用モノマー、充填剤、軟化剤、着色剤、難燃化剤、チキソトロピック剤、シランカップリング剤などを配合してもよい。 [Other additives]
In addition, as other additives to be added to the thermosetting adhesive composition, for dilution of latent curing agents, inorganic fillers, conductive particles, heat conductive particles, film-forming resins, various acrylic monomers, etc., if necessary Monomers, fillers, softeners, colorants, flame retardants, thixotropic agents, silane coupling agents, and the like may be blended.
　潜在性硬化剤としては、ジシアンジアミド（ＤＩＣＹ）、７，１１－オクタデカジエン－１，１８－ジカルボヒドラジド（ＵＤＨ）、ジアミノジフェニルスルフォン（ＤＤＳ）、エポキシ樹脂とアミン化合物の反応物からなるマイクロカプセル型硬化剤であるノバキュア（商品名、旭化成イーマテリアルズ（株））などが挙げられる。 The latent curing agent includes dicyandiamide (DICY), 7,11-octadecadiene-1,18-dicarbohydrazide (UDH), diaminodiphenylsulfone (DDS), a microcapsule comprising a reaction product of an epoxy resin and an amine compound. Novacure (trade name, Asahi Kasei E-Materials Co., Ltd.), which is a mold curing agent.
　潜在性硬化剤の含有量は、少なすぎても多すぎても硬化性が低下する傾向があるので、アクリルゴム１００質量部に対し、好ましくは０．５～３．０質量部、より好ましくは１～１．５質量部である。 If the content of the latent curing agent is too small or too large, the curability tends to decrease. Therefore, the content is preferably 0.5 to 3.0 parts by mass, more preferably 100 parts by mass with respect to the acrylic rubber. 1 to 1.5 parts by mass.
　無機フィラーとしては、シリカなどの酸化物が挙げられる。無機フィラーは、シート化におけるバインダーの粘度、粘性の調整、及び加熱硬化時のレジンフロー性の制御のために用いられる。無機フィラーの含有量は、アクリルゴム１００質量部に対し、好ましくは１～１０質量部、より好ましくは４～８質量部である。 An example of the inorganic filler is an oxide such as silica. The inorganic filler is used for adjusting the viscosity and viscosity of the binder in forming a sheet, and controlling the resin flow property during heat curing. The content of the inorganic filler is preferably 1 to 10 parts by mass, more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the acrylic rubber.
　このような成分からなる熱硬化性接着組成物は、タック性を有するため、粘着テープのように、基板に部材を容易に仮固定させることができる。また、加熱により、優れた接着性及び耐熱性を得ることができる。よって、フレキシブルプリント配線板と補強用の部材、例えば金属板とを貼り合わせる用途に好適に用いることができる。 Since the thermosetting adhesive composition composed of such components has tackiness, the member can be easily temporarily fixed to the substrate like an adhesive tape. Moreover, the outstanding adhesiveness and heat resistance can be obtained by heating. Therefore, it can use suitably for the use which bonds a flexible printed wiring board and the member for reinforcement, for example, a metal plate.
　＜２．熱硬化性接着シート＞
　本実施の形態に係る熱硬化性接着シートは、ガラス転移温度が－５０～－３０℃であるアクリルゴム（Ａ）と、液状エポキシ樹脂（Ｂ）と、固形エポキシ樹脂（Ｃ）、固形フェノール樹脂（Ｄ）とを含有し、固形エポキシ樹脂（Ｃ）及び固形フェノール樹脂（Ｄ）の合計含有量に対する液状エポキシ樹脂（Ｂ）の含有量の比の値が、０．４～０．８、好ましくは０．５～０．６５となっているものである。 <2. Thermosetting adhesive sheet>
The thermosetting adhesive sheet according to the present embodiment includes an acrylic rubber (A) having a glass transition temperature of −50 to −30 ° C., a liquid epoxy resin (B), a solid epoxy resin (C), and a solid phenol resin. The ratio of the content of the liquid epoxy resin (B) to the total content of the solid epoxy resin (C) and the solid phenol resin (D) is 0.4 to 0.8, preferably Is 0.5 to 0.65.
　各成分（Ａ）～（Ｄ）は、前述の熱硬化性接着組成物と同様であるため、ここでは説明を省略する。前述の熱硬化性接着組成物は、常法により均一に混合することにより調製することができる。そして、熱硬化性接着組成物を、基材フィルム上にバーコーター、ロールコーターにより乾燥厚が１０～６０μｍとなるように塗布し、常法により乾燥することにより熱硬化性の接着層を有する熱硬化性接着シートを製造することができる。 Since each of the components (A) to (D) is the same as the thermosetting adhesive composition described above, the description thereof is omitted here. The aforementioned thermosetting adhesive composition can be prepared by uniformly mixing by a conventional method. Then, the thermosetting adhesive composition is applied on the base film with a bar coater or roll coater so that the dry thickness is 10 to 60 μm, and is dried by a conventional method to provide a thermosetting adhesive layer. A curable adhesive sheet can be produced.
　基材フィルムとしては、ポリエチレンテレフタレートフィルム、ポリイミドフィルムなどの基材に必要に応じてシリコーンなどで剥離処理した剥離基材を用いることができる。基材フィルム上には硬化性接着組成物からなる接着層が例えば１０～６０μｍの厚さで形成される。 As the base material film, a base material such as a polyethylene terephthalate film or a polyimide film, which is a base material that is peel-treated with silicone or the like as required, can be used. An adhesive layer made of a curable adhesive composition is formed on the base film with a thickness of 10 to 60 μm, for example.
　このような熱硬化性接着シートは、例えば、フレキシブルプリント配線板の端子部と、その裏打ちするためのポリエチレンテレフタレート、ポリイミド、ガラスエポキシ、ステンレス、アルミニウムなどの厚さ５０μｍ～２ｍｍの補強用シートとを接着固定するために好ましく適用できる。また、熱ラミネートにより容易に補強用シートと密着させることができるため、作業性を向上させることができる。 Such a thermosetting adhesive sheet includes, for example, a terminal portion of a flexible printed wiring board and a reinforcing sheet having a thickness of 50 μm to 2 mm made of polyethylene terephthalate, polyimide, glass epoxy, stainless steel, aluminum, or the like for lining it. It can be preferably applied for adhesive fixing. Moreover, workability can be improved because it can be easily adhered to the reinforcing sheet by thermal lamination.
　＜３．実施例＞
　以下、本発明の実施例について説明する。本実施例では、下記に示すアクリルゴムと、液状エポキシ樹脂と、固形エポキシ樹脂と、固形フェノール樹脂と、潜在性硬化剤と、無機フィラーとを配合し、熱硬化性接着組成物を作製した。 <3. Example>
Examples of the present invention will be described below. In this example, an acrylic rubber, a liquid epoxy resin, a solid epoxy resin, a solid phenol resin, a latent curing agent, and an inorganic filler shown below were blended to prepare a thermosetting adhesive composition.
（アクリルゴム）
　アクリル酸ブチル（ＢＡ）、アクリル酸２－エチルヘキシル（２ＥＨＡ）、アクリル酸ニトリル（ＡＮ）、及びグリシジルメタクリレート（ＧＭＡ）をパール重合して得た共重合体（ガラス転移温度（Ｔｇ）＝－４０℃）
（液状エポキシ樹脂）
　ｊＥＲ８２８、三菱化学（株）
（固形エポキシ樹脂）
　多官能エポキシ樹脂（ＥＤ－５０５、（株）ＡＤＥＫＡ）と単官能エポキシ樹脂としての単官能ジシクロペンタジエン型エポキシ樹脂（ＨＰ７２００Ｌ、ＤＩＣ（株））とを１：６の質量比でブレンドしたもの
（なお、比較例３では固形エポキシ樹脂として３官能エポキシ樹脂のみを使用し、比較例４では固形エポキシ樹脂として単官能エポキシ樹脂のみを使用した）
（固形フェノール樹脂）
　ＣＫＭ－９０８Ｅ（レゾール型）、昭和電工（株）
（潜在性硬化剤）
ノバキュア、旭化成イーマテリアルズ（株） (Acrylic rubber)
Copolymer obtained by pearl polymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), nitrile acrylate (AN), and glycidyl methacrylate (GMA) (glass transition temperature (Tg) = − 40 ° C. )
(Liquid epoxy resin)
jER828, Mitsubishi Chemical Corporation
(Solid epoxy resin)
A blend of polyfunctional epoxy resin (ED-505, ADEKA) and monofunctional dicyclopentadiene type epoxy resin (HP7200L, DIC Corporation) as a monofunctional epoxy resin in a mass ratio of 1: 6 ( In Comparative Example 3, only a trifunctional epoxy resin was used as the solid epoxy resin, and in Comparative Example 4, only a monofunctional epoxy resin was used as the solid epoxy resin.
(Solid phenol resin)
CKM-908E (Resol type), Showa Denko K.K.
(Latent curing agent)
Novacure, Asahi Kasei E-Materials Corporation
　そして、熱硬化性接着組成物を、剥離処理が施されたポリエチレンテレフタレートフィルム（剥離処理ＰＥＴフィルム）に塗布し、５０～１３０℃の乾燥炉中で乾燥し、更に剥離処理ＰＥＴフィルムを積層することにより３５μｍ厚の熱硬化性接着層を有する熱硬化性接着シートを作製した。そして、下記（１）～（５）の項目について評価した。 Then, the thermosetting adhesive composition is applied to a polyethylene terephthalate film (release PET film) that has been subjected to a release treatment, dried in a drying oven at 50 to 130 ° C., and further laminated with a release treatment PET film. Thus, a thermosetting adhesive sheet having a thermosetting adhesive layer having a thickness of 35 μm was prepared. The following items (1) to (5) were evaluated.
　［（１）熱硬化性接着シートの硬化前のピール強度の測定］
　熱硬化性接着シートを所定の大きさの短冊（１ｃｍ×１０ｃｍ）にカットし、片面の剥離処理ＰＥＴフィルムを剥離し、ハンドローラー（加重２ｋｇ/１ｃｍ幅）によって貼り合わせた。その後、もう片面の剥離処理ＰＥＴフィルムを取り除いて熱硬化性接着層を露出させ、その露出面に対し、同じ大きさの５０μｍ厚のポリイミドフィルム（２００Ｈ、デュポン(株)）を上からハンドローラーにて重ね合わせた。そして、ポリイミドフィルムに対し、剥離速度５０ｍｍ／ｍｉｎで９０度剥離試験を行い、引き剥がすのに要した力を測定した。 [(1) Measurement of peel strength before curing of thermosetting adhesive sheet]
The thermosetting adhesive sheet was cut into strips (1 cm × 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 μm thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. And superimposed. And the 90 degree peeling test was done with respect to the polyimide film at the peeling speed of 50 mm / min, and the force required for peeling was measured.
　［（２）熱硬化性接着シートの硬化前のタック性の評価］
　タック性試験機として、ＲＨＥＳＣＡ社製タッキング試験機ＴＡＣ－IIを使用し、剥離処理ＰＥＴフィルムを取り除いた熱硬化性接着層に、直径１０ｍｍのアルミニウム製円柱状プローブを、押しつけ速度３０ｍｍ／ｍｉｎ、引き剥がし速度１２０ｍｍ/ｍｉｎ、荷重１９６ｇ、押しつけ時間５．０秒、引っ張り距離５ｍｍ、プローブ加熱４０℃、シートステージ加熱４０℃の条件で押しつけて引き剥がしたときのプローブタック性を測定した。熱硬化性接着シートのタック性が１０ｋＮ／ｍ２未満のものを「×」、１０ｋＮ／ｍ２以上のものを「○」と評価した。 [(2) Evaluation of tackiness before curing of thermosetting adhesive sheet]
As a tackiness tester, a RHESCA tacking tester TAC-II was used, and an aluminum cylindrical probe having a diameter of 10 mm was applied to the thermosetting adhesive layer from which the release-treated PET film was removed, with a pressing speed of 30 mm / min. The probe tackiness when peeled by pressing under the conditions of a peeling speed of 120 mm / min, a load of 196 g, a pressing time of 5.0 seconds, a pulling distance of 5 mm, a probe heating of 40 ° C. and a sheet stage heating of 40 ° C. was measured. Tack of the thermosetting adhesive sheet "×" a of less than 10 kN / m 2, was evaluated 10 kN / m 2 or more as the "○".
　［（３）熱硬化性接着シートの硬化前のクリープ特性の評価］
　熱硬化性接着シートを所定の大きさの短冊（１ｃｍ×１０ｃｍ）にカットし、片面の剥離処理ＰＥＴフィルムを剥離し、ハンドローラー（加重２ｋｇ/１ｃｍ幅）によって貼り合わせた。その後、もう片面の剥離処理ＰＥＴフィルムを取り除いて熱硬化性接着層を露出させ、その露出面に対し、同じ大きさの５０μｍ厚のポリイミドフィルム（２００Ｈ、デュポン(株)）を上からハンドローラーにて重ね合わせた。そして、ＳＵＳ３０４板の端から２５ｍｍのところに切れ込みを入れ、１００℃のオーブンに入れ、１ｋｇの荷重をかけ、１時間後のズレを観察した。ズレが１ｍｍ以下で落下しないものの評価を「○」とし、ズレが１ｍｍを超えたもの、又は落下したものの評価を「×」とした。 [(3) Evaluation of creep characteristics before curing of thermosetting adhesive sheet]
The thermosetting adhesive sheet was cut into strips (1 cm × 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 μm thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. And superimposed. Then, a cut was made at 25 mm from the end of the SUS304 plate, put in an oven at 100 ° C., a load of 1 kg was applied, and the deviation after 1 hour was observed. The evaluation of the case where the deviation was 1 mm or less and did not fall was “◯”, and the evaluation of the case where the deviation exceeded 1 mm or was dropped was “x”.
　［（４）熱硬化性接着シートの硬化後のピール強度の測定］
　熱硬化性接着シートを所定の大きさの短冊（１ｃｍ×１０ｃｍ）にカットし、片面の剥離処理ＰＥＴフィルムを剥離し、ハンドローラー（加重２ｋｇ/１ｃｍ幅）によって貼り合わせた。その後、もう片面の剥離処理ＰＥＴフィルムを取り除いて熱硬化性接着層を露出させ、その露出面に対し、同じ大きさの５０μｍ厚のポリイミドフィルム（２００Ｈ、デュポン(株)）を上からハンドローラーにて重ね合わせ、真空プレス機（Ｖａｃｕｕｍ　Ｓｔａｒ、ミカドテクノス(株)）を用い、温度１７０℃、圧力２．０ＭＰａ、真空保持時間１０秒＋プレス時間９０秒という条件で熱プレスした後、１５０℃のオーブン中に６０分間保持した。そして、ポリイミドフィルムに対し、剥離速度５０ｍｍ／ｍｉｎで９０度剥離試験を行い、引き剥がすのに要した力を測定した。 [(4) Measurement of peel strength after curing of thermosetting adhesive sheet]
The thermosetting adhesive sheet was cut into strips (1 cm × 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 μm thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. Then, using a vacuum press machine (Vacuum Star, Mikado Technos Co., Ltd.), after hot pressing under the conditions of temperature 170 ° C., pressure 2.0 MPa, vacuum holding time 10 seconds + press time 90 seconds, Hold in oven for 60 minutes. And the 90 degree peeling test was done with respect to the polyimide film at the peeling speed of 50 mm / min, and the force required for peeling was measured.
　［（５）熱硬化性接着シートの耐熱試験後のピール強度の測定］
　熱硬化性接着シートを所定の大きさの短冊（１ｃｍ×１０ｃｍ）にカットし、片面の剥離処理ＰＥＴフィルムを剥離し、ハンドローラー（加重２ｋｇ/１ｃｍ幅）によって貼り合わせた。その後、もう片面の剥離処理ＰＥＴフィルムを取り除いて熱硬化性接着層を露出させ、その露出面に対し、同じ大きさの５０μｍ厚のポリイミドフィルム（２００Ｈ、デュポン(株)）を上からハンドローラーにて重ね合わせ、真空プレス機（Ｖａｃｕｕｍ　Ｓｔａｒ、ミカドテクノス(株)）を用い、温度１７０℃、圧力２．０ＭＰａ、真空保持時間１０秒＋プレス時間９０秒という条件で熱プレスした後、１５０℃のオーブン中に６０分間保持した。また、この試験片に対し、１５０℃、１０００時間の耐熱試験を行った。そして、ポリイミドフィルムに対し、剥離速度５０ｍｍ／ｍｉｎで９０度剥離試験を行い、引き剥がすのに要した力を測定した。 [(5) Measurement of peel strength after heat resistance test of thermosetting adhesive sheet]
The thermosetting adhesive sheet was cut into strips (1 cm × 10 cm) of a predetermined size, the single-sided release-treated PET film was peeled off, and bonded by a hand roller (weighted 2 kg / 1 cm width). Then, the other side peeled PET film was removed to expose the thermosetting adhesive layer, and a 50 μm thick polyimide film (200H, DuPont) of the same size was applied to the exposed surface from the top to the hand roller. Then, using a vacuum press machine (Vacuum Star, Mikado Technos Co., Ltd.), after hot pressing under the conditions of temperature 170 ° C., pressure 2.0 MPa, vacuum holding time 10 seconds + press time 90 seconds, Hold in oven for 60 minutes. Further, a heat resistance test at 150 ° C. for 1000 hours was performed on the test piece. And the 90 degree peeling test was done with respect to the polyimide film at the peeling speed of 50 mm / min, and the force required for peeling was measured.
　＜実施例１＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂２５質量部と、固形エポキシ樹脂３０質量部と、固形フェノール樹脂２０質量部と、潜在性硬化剤１．５質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は０．５０であり、（１）熱硬化性接着シートの硬化前のピール強度は２．０Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は良好「○」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は良好「○」、（４）熱硬化性接着シートの硬化後のピール強度は８．７Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は８．７Ｎ／ｃｍであった。 <Example 1>
As shown in Table 1, 100 parts by mass of acrylic rubber, 25 parts by mass of liquid epoxy resin, 30 parts by mass of solid epoxy resin, 20 parts by mass of solid phenol resin, 1.5 parts by mass of latent curing agent, and inorganic A thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 6 parts by mass of filler. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.50, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 2.0 N / cm, (2) The evaluation of the tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property is evaluated before curing of the thermosetting adhesive sheet is “good”. (4) The peel strength after curing of the thermosetting adhesive sheet was 8.7 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 8.7 N / cm.
　＜実施例２＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂４５質量部と、固形エポキシ樹脂３５質量部と、固形フェノール樹脂４０質量部と、潜在性硬化剤１．５質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は０．６４であり、（１）熱硬化性接着シートの硬化前のピール強度は３．０Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は良好「○」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は良好「○」、（４）硬化性接着シートの硬化後のピール強度は７．７Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は７．７Ｎ／ｃｍであった。 <Example 2>
As shown in Table 1, 100 parts by mass of acrylic rubber, 45 parts by mass of liquid epoxy resin, 35 parts by mass of solid epoxy resin, 40 parts by mass of solid phenol resin, 1.5 parts by mass of latent curing agent, inorganic A thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 6 parts by mass of filler. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 3.0 N / cm, (2) The evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is “good”. (4) The peel strength after curing of the curable adhesive sheet was 7.7 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 7.7 N / cm.
　＜比較例１＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂２５質量部と、固形フェノール樹脂２０質量部と、潜在性硬化剤１．０質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は１．２５であり、（１）熱硬化性接着シートの硬化前のピール強度は１．２Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は良好「○」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は不良「×」、（４）熱硬化性接着シートの硬化後のピール強度は２．０Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は１．４Ｎ／ｃｍであった。 <Comparative Example 1>
As shown in Table 1, 100 parts by mass of acrylic rubber, 25 parts by mass of a liquid epoxy resin, 20 parts by mass of a solid phenol resin, 1.0 part by mass of a latent curing agent, and 6 parts by mass of an inorganic filler are contained. A thermosetting adhesive sheet was prepared using the thermosetting adhesive composition. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 1.25, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 1.2 N / cm, (2) The evaluation of the tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is poor “×”. (4) The peel strength after curing of the thermosetting adhesive sheet was 2.0 N / cm, and (5) the peel strength after heat resistance test of the thermosetting adhesive sheet was 1.4 N / cm.
　＜比較例２＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂１０質量部と、固形フェノール樹脂１０質量部と、潜在性硬化剤１．０質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は１．００であり、（１）熱硬化性接着シートの硬化前のピール強度は０．８Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は良好「○」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は不良「×」、（４）熱硬化性接着シートの硬化後のピール強度は１．８Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は１．４Ｎ／ｃｍであった。 <Comparative example 2>
As shown in Table 1, 100 parts by mass of acrylic rubber, 10 parts by mass of a liquid epoxy resin, 10 parts by mass of a solid phenol resin, 1.0 part by mass of a latent curing agent, and 6 parts by mass of an inorganic filler are contained. A thermosetting adhesive sheet was prepared using the thermosetting adhesive composition. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 1.00, and (1) peel strength before curing of the thermosetting adhesive sheet 0.8 N / cm, (2) The evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) The creep property evaluation of the thermosetting adhesive sheet before curing is poor “×”. (4) The peel strength after curing of the thermosetting adhesive sheet was 1.8 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 1.4 N / cm.
　＜比較例３＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂４５質量部と、固形エポキシ樹脂として３官能エポキシ樹脂３５質量部と、固形フェノール樹脂４０質量部と、潜在性硬化剤１．５質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は０．６４であり、（１）熱硬化性接着シートの硬化前のピール強度は１．０Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は不良「×」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は不良「×」、（４）熱硬化性接着シートの硬化後のピール強度は３．３Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は０．８Ｎ／ｃｍであった。 <Comparative Example 3>
As shown in Table 1, 100 parts by weight of acrylic rubber, 45 parts by weight of a liquid epoxy resin, 35 parts by weight of a trifunctional epoxy resin as a solid epoxy resin, 40 parts by weight of a solid phenol resin, and a latent curing agent 1.5 The thermosetting adhesive sheet was produced using the thermosetting adhesive composition containing a mass part and 6 mass parts of inorganic fillers. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet 1.0 N / cm, (2) Evaluation of tackiness before curing of thermosetting adhesive sheet is poor “x”, (3) Evaluation of creep characteristics before curing of thermosetting adhesive sheet is “poor” (4) The peel strength after curing of the thermosetting adhesive sheet was 3.3 N / cm, and (5) the peel strength after the heat resistance test of the thermosetting adhesive sheet was 0.8 N / cm.
　＜比較例４＞
　表１に示すように、アクリルゴム１００質量部と、液状エポキシ樹脂４５質量部と、固形エポキシ樹脂として単官能ＤＣＰＤ型のエポキシ樹脂３５質量部と、固形フェノール樹脂４０質量部と、潜在性硬化剤１．５質量部と、無機フィラー６質量部とを含有する熱硬化性接着組成物を用いて熱硬化性接着シートを作製した。この熱硬化性粘着シートの固形エポキシ樹脂及び固形フェノール樹脂の合計含有量に対する液状エポキシ樹脂の含有量の比の値は０．６４であり、（１）熱硬化性接着シートの硬化前のピール強度は２．０Ｎ／ｃｍ、（２）熱硬化性接着シートの硬化前のタック性の評価は良好「○」、（３）熱硬化性接着シートの硬化前のクリープ特性の評価は不良「×」、（４）熱硬化性接着シートの硬化後のピール強度は７．０Ｎ／ｃｍ、（５）熱硬化性接着シートの耐熱試験後のピール強度は５．５Ｎ／ｃｍであった。 <Comparative example 4>
As shown in Table 1, 100 parts by weight of acrylic rubber, 45 parts by weight of a liquid epoxy resin, 35 parts by weight of a monofunctional DCPD type epoxy resin as a solid epoxy resin, 40 parts by weight of a solid phenol resin, and a latent curing agent A thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 1.5 parts by mass and 6 parts by mass of an inorganic filler. The value of the ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of this thermosetting pressure-sensitive adhesive sheet is 0.64, and (1) the peel strength before curing of the thermosetting adhesive sheet Is 2.0 N / cm, (2) the evaluation of tackiness before curing of the thermosetting adhesive sheet is “good”, and (3) the creep property evaluation before curing of the thermosetting adhesive sheet is poor “×”. (4) The peel strength after curing of the thermosetting adhesive sheet was 7.0 N / cm, and (5) the peel strength after heat resistance test of the thermosetting adhesive sheet was 5.5 N / cm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　比較例１，２のように、固形エポキシ樹脂を使用せず、しかも「固形エポキシ樹脂及び固形フェノール樹脂」の含有量に対する液状エポキシ樹脂の含有量の質量比の値が、１．０以上である場合、クリープ特性の評価が低く、ピール強度も低かった。また、比較例３のように、固形エポキシ樹脂として、多官能エポキシ樹脂のみを添加した場合、タック性が発現せず、クリープ特性の評価が低かった。また、比較例４のように、固形エポキシ樹脂として、単官能エポキシ樹脂のみを添加した場合、タック性は発現したものの、クリープ特性の評価が低かった。 As in Comparative Examples 1 and 2, no solid epoxy resin is used, and the value of the mass ratio of the content of the liquid epoxy resin to the content of “solid epoxy resin and solid phenol resin” is 1.0 or more. In this case, the creep property was low and the peel strength was low. Further, as in Comparative Example 3, when only a polyfunctional epoxy resin was added as a solid epoxy resin, tackiness was not exhibited, and evaluation of creep characteristics was low. Moreover, when only a monofunctional epoxy resin was added as a solid epoxy resin like the comparative example 4, although tack property was expressed, evaluation of creep characteristics was low.
　一方、実施例１，２のように、多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂を使用し、しかも「固形エポキシ樹脂及び固形フェノール樹脂」の合計含有量に対する液状エポキシ樹脂の含有量の質量比の値が、０．４～０．８である場合、タック性を発現し、クリープ特性の評価が高く、硬化後のピール強度も高く、耐熱性も高かった。 On the other hand, as in Examples 1 and 2, a solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin was used, and the liquid epoxy resin with respect to the total content of “solid epoxy resin and solid phenol resin” When the mass ratio value of the content was 0.4 to 0.8, tackiness was exhibited, creep characteristics were highly evaluated, peel strength after curing was high, and heat resistance was also high.

Claims (13)

  1. 　ガラス転移温度が－５０～－３０℃であるアクリルゴムと、
    液状エポキシ樹脂と、
    多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂と、
    固形フェノール樹脂を含有し、
    前記固形エポキシ樹脂及び前記固形フェノール樹脂の合計含有量に対する前記液状エポキシ樹脂の含有量の比の値が、０．４～０．８である熱硬化性接着組成物。     An acrylic rubber having a glass transition temperature of −50 to −30 ° C .;
    Liquid epoxy resin,
    A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin;
    Contains solid phenolic resin,
    A thermosetting adhesive composition having a ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of 0.4 to 0.8.
  2. 　前記液状エポキシ樹脂の含有量が、前記アクリルゴム１００質量部に対し、１５～５５質量部であり、
    　前記固形エポキシ樹脂の含有量が、前記アクリルゴム１００質量部に対し、２０～４５質量部であり、
    　前記固形フェノール樹脂の含有量が、前記アクリルゴム１００質量部に対し、１０～５０質量部である請求項１記載の熱硬化性接着組成物。     The content of the liquid epoxy resin is 15 to 55 parts by mass with respect to 100 parts by mass of the acrylic rubber,
    The solid epoxy resin content is 20 to 45 parts by mass with respect to 100 parts by mass of the acrylic rubber,
    The thermosetting adhesive composition according to claim 1, wherein the content of the solid phenol resin is 10 to 50 parts by mass with respect to 100 parts by mass of the acrylic rubber.
  3. 　前記固形エポキシ樹脂及び前記固形フェノール樹脂の合計含有量に対する前記液状エポキシ樹脂の含有量の比の値が、０．５～０．６５である請求項１又は２記載の熱硬化性接着組成物。 The thermosetting adhesive composition according to claim 1 or 2, wherein a value of a ratio of the content of the liquid epoxy resin to a total content of the solid epoxy resin and the solid phenol resin is 0.5 to 0.65.
  4. 　前記液状エポキシ樹脂の含有量が、前記アクリルゴム１００質量部に対し、２５～４５質量部であり、
    　前記固形エポキシ樹脂の含有量が、前記アクリルゴム１００質量部に対し、３０～３５質量部であり、
    　前記固形フェノール樹脂の含有量が、前記アクリルゴム１００質量部に対し、２０～４０質量部である請求項３記載の熱硬化性接着組成物。     The content of the liquid epoxy resin is 25 to 45 parts by mass with respect to 100 parts by mass of the acrylic rubber,
    The solid epoxy resin content is 30 to 35 parts by mass with respect to 100 parts by mass of the acrylic rubber,
    The thermosetting adhesive composition according to claim 3, wherein the content of the solid phenol resin is 20 to 40 parts by mass with respect to 100 parts by mass of the acrylic rubber.
  5. 前記固形エポキシ樹脂が、多官能エポキシ樹脂と単官能エポキシ樹脂とを、１：４～１：１０の比率で含有する請求項１～４のいずれかに記載の熱硬化性接着組成物。 The thermosetting adhesive composition according to any one of claims 1 to 4, wherein the solid epoxy resin contains a polyfunctional epoxy resin and a monofunctional epoxy resin in a ratio of 1: 4 to 1:10.
  6. 前記単官能エポキシ樹脂が、単官能ジシクロペンタジエン型エポキシ樹脂である請求項１～５のいずれかに記載の熱硬化性接着組成物。 6. The thermosetting adhesive composition according to claim 1, wherein the monofunctional epoxy resin is a monofunctional dicyclopentadiene type epoxy resin.
  7. 　前記固形フェノール樹脂が、レゾール型フェノール樹脂である請求項１～６のいずれかに記載の熱硬化性接着組成物。 The thermosetting adhesive composition according to any one of claims 1 to 6, wherein the solid phenol resin is a resol type phenol resin.
  8. 　前記アクリルゴムが、アクリル酸ブチル（ＢＡ）、アクリル酸２－エチルヘキシル（２ＥＨＡ）、アクリル酸ニトリル（ＡＮ）及びグリシジルメタクリレート（ＧＭＡ）がパール重合された共重合体である請求項１～７のいずれかに記載の熱硬化性接着組成物。 The acrylic rubber is a copolymer obtained by pearl polymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), nitrile acrylate (AN) and glycidyl methacrylate (GMA). A thermosetting adhesive composition according to claim 1.
  9. 　前記アクリルゴム１００質量部に対し、潜在性硬化剤を０．５～３．０質量部含有する請求項１～８のいずれかに記載の熱硬化性接着組成物。 The thermosetting adhesive composition according to any one of claims 1 to 8, comprising 0.5 to 3.0 parts by mass of a latent curing agent with respect to 100 parts by mass of the acrylic rubber.
  10. 　前記アクリルゴム１００質量部に対し、無機フィラーを１～１０質量部含有する請求項１～９のいずれかに記載の熱硬化性接着組成物。 10. The thermosetting adhesive composition according to claim 1, comprising 1 to 10 parts by mass of an inorganic filler with respect to 100 parts by mass of the acrylic rubber.
  11. 　ガラス転移温度が－５０～－３０℃であるアクリルゴムと、
    液状エポキシ樹脂と、
    多官能エポキシ樹脂と単官能エポキシ樹脂とを含有する固形エポキシ樹脂と、
    固形フェノール樹脂を含有し、
    前記固形エポキシ樹脂及び前記固形フェノール樹脂の合計含有量に対する前記液状エポキシ樹脂の含有量の比の値が、０．４～０．８である熱硬化性接着シート。     An acrylic rubber having a glass transition temperature of −50 to −30 ° C .;
    Liquid epoxy resin,
    A solid epoxy resin containing a polyfunctional epoxy resin and a monofunctional epoxy resin;
    Contains solid phenolic resin,
    A thermosetting adhesive sheet having a ratio of the content of the liquid epoxy resin to the total content of the solid epoxy resin and the solid phenol resin of 0.4 to 0.8.
  12. 前記固形エポキシ樹脂が、多官能エポキシ樹脂と単官能エポキシ樹脂とを、１：４～１：１０の比率で含有する請求項１１記載の熱硬化性接着シート。 The thermosetting adhesive sheet according to claim 11, wherein the solid epoxy resin contains a polyfunctional epoxy resin and a monofunctional epoxy resin in a ratio of 1: 4 to 1:10.
  13. 前記単官能エポキシ樹脂が、単官能ジシクロペンタジエン型エポキシ樹脂である請求項１１又は１２記載の熱硬化性接着シート。 The thermosetting adhesive sheet according to claim 11 or 12, wherein the monofunctional epoxy resin is a monofunctional dicyclopentadiene type epoxy resin.
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