WO2023008183A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2023008183A1
WO2023008183A1 PCT/JP2022/027449 JP2022027449W WO2023008183A1 WO 2023008183 A1 WO2023008183 A1 WO 2023008183A1 JP 2022027449 W JP2022027449 W JP 2022027449W WO 2023008183 A1 WO2023008183 A1 WO 2023008183A1
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WO
WIPO (PCT)
Prior art keywords
group
adhesive composition
styrene
acid
composition according
Prior art date
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PCT/JP2022/027449
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French (fr)
Japanese (ja)
Inventor
順平 村田
芳範 河村
歩海 松島
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田岡化学工業株式会社
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Publication of WO2023008183A1 publication Critical patent/WO2023008183A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated

Definitions

  • the present invention relates to an adhesive composition that has excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) and adhesiveness, and is suitable for manufacturing electronic components, particularly members related to flexible printed wiring boards (hereinafter referred to as FPC).
  • FPC flexible printed wiring boards
  • coverlay film a laminate with an adhesive layer called “coverlay film” is used in order to protect the wiring part when manufacturing the FPC. And it is also required to have strong adhesiveness to the base film.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive composition that has low dielectric properties and excellent adhesiveness between resin and metal.
  • the present inventors have made intensive studies to solve the above problems, and found that (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized and (C) free of tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators.
  • the present invention includes the following inventions.
  • An adhesive composition containing the following (A) and (B) and not containing the following (C).
  • (A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides;
  • [4] (B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of [1] to [3] The adhesive composition described.
  • X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .
  • the adhesive composition of the present invention has low dielectric properties and excellent adhesion between resin and metal. Therefore, the adhesive composition of the present invention is suitably used for applications such as laminates with an adhesive layer (coverlay films, bonding sheets), resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like. be able to.
  • the adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized.
  • A an acid-modified styrene-based elastomer
  • B an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized.
  • the adhesive composition of the present invention uses, as a main component, a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer).
  • a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer).
  • methods for modifying a styrene-based elastomer include a method of grafting a styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
  • styrene elastomers include styrene-butadiene block copolymers, styrene-ethylene propylene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS ), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and the like.
  • SBS styrene-butadiene block copolymers
  • SIS styrene-isoprene-styrene block copolymers
  • SEBS styrene-ethylenebutylene-styrene block copolymer
  • SEPS styrene-ethylenepropylene-styrene block copolymer
  • styrene-based elastomers styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) are preferable from the viewpoint of adhesiveness and low dielectric properties.
  • SEBS styrene-ethylenebutylene-styrene block copolymer
  • SEPS styrene-ethylenepropylene-styrene block copolymer
  • Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid.
  • Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and fumaric anhydride. Among these unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, maleic acid, fumaric acid and maleic anhydride are preferred, and maleic anhydride is more preferred.
  • the amount of modification with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides is usually about 0.1 to 10% by mass of the total acid-modified styrene elastomer.
  • at least part of all the acid groups in the acid-modified elastomer are preferably acid anhydrides.
  • the acid value of the acid-modified styrene-based elastomer is not particularly limited, but for example, the lower limit is 0.1 mg CH 3 ONa/g or more, preferably 0.5 mg CH 3 ONa/g or more, more preferably 1.0 mg CH 3 ONa/g or more. and the upper limit is 20 mg CH 3 ONa/g or less, preferably 18 mg CH 3 ONa/g or less, more preferably 15 mg CH 3 ONa/g or less.
  • the molecular weight of the acid-modified styrene-based elastomer is, for example, a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably. is less than 200,000.
  • the weight average molecular weight in the present invention is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).
  • Examples of commercially available acid-modified styrene-based elastomers include the Tuftec M series manufactured by Asahi Kasei Corporation and the Kraton FG series manufactured by Kraton Polymer Japan.
  • the above acid-modified styrene-based elastomers may be used alone, or two or more of them may be used in combination.
  • Alicyclic epoxy resins are epoxy resins containing an alicyclic structure.
  • the structure in which the unsaturated bond of the cyclic olefin structure is epoxidized includes a cycloalkane structure corresponding to the cyclic olefin structure and an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the cycloalkane structure. ,including.
  • Cyclic olefin structures may be monocyclic or polycyclic.
  • the cyclic olefin structure may have a substituent such as an alkyl group.
  • Examples of the alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized include compounds represented by the following formulas (1) to (4).
  • X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .
  • Examples of the compound represented by the above formula (1) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), 2 , 2-bis(3,4-epoxycyclohexyl)propane, the following formula (1-1):
  • alicyclic epoxy resins containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized include Celoxide 2021P, Celoxide 8010P, Celoxide 2081 from Daicel, Epolead GT401, and THI- from ENEOS. DE, DE-102, DE-103, Shin-Etsu Silicone Co., Ltd. X-40-2669, KR-470 and the like.
  • the alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized may be used alone or in combination of two or more.
  • the amount of (B) contained in the adhesive composition of the present invention is generally 0.1-50 parts by weight, preferably 0.4-30 parts by weight, more preferably 0.4-30 parts by weight, per 100 parts by weight of (A). 4 to 20 parts by weight, more preferably 0.4 to 4 parts by weight.
  • the adhesive composition of the present invention contains (A) a thermoplastic resin other than the acid-modified styrene elastomer, a tackifier, a flame retardant, a coupling agent, and an antioxidant. , a filler and (D) an organic solvent.
  • thermoplastic resins examples include styrene-based elastomers containing no acid anhydride groups, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene-based resins, and polypropylene-based resins. Examples thereof include resins and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
  • tackifiers examples include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
  • Examples of the flame retardant include organic flame retardants and inorganic flame retardants.
  • Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate.
  • inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, oxide Metal oxides such as zinc, molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants may be used alone or in combination of two or more.
  • the coupling agent examples include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane-based coupling agents such as imidazole silane; titanate-based coupling agents; aluminate-based coupling agents; and zirconium-based coupling agents. These coupling agents may be used alone or in combination of two or more.
  • antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate , tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, tri Phenolic antioxidants such as ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3' - sulfur-based antioxidants such as dithiopropionate; may be used alone or in combination of two or more.
  • filler examples include polyacrylate powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as multi-layered core shells using silicone, acrylic, styrene-butadiene rubber, butadiene rubber, etc.
  • Polymer filler silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate , sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Inorganic fillers such as nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate. These fillers may be used alone or in combination of two or more. As for the shape, for example, spherical, powdery, fibrous, needle-like, scale-like, etc. can be used.
  • Examples of the organic solvent (D) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cyclohexane, methylcyclohexane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tetrahydrofuran.
  • N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, dioxane, cyclopentyl methyl ether, methylene chloride, chloroform, 1 , 2-dichloroethane, ⁇ -butyrolactone, cellosolve, butyl cellosolve, carbitol, butyl carbitol and the like.
  • These organic solvents may be used alone or in combination of two or more.
  • the adhesive composition of the present invention includes, for example, light stabilizers, weather stabilizers, stabilizers such as heat stabilizers, leveling agents, anionic and cationic stabilizers such as antifoaming agents. , nonionic surfactants, dyes, pigments, plasticizers and the like can also be contained to such an extent that the functions of the adhesive composition are not affected.
  • the adhesive composition of the present invention is usually used for the purpose of promoting the reaction between the elastomer and the epoxy resin, as is clear from the comparison with the examples and comparative examples of Patent Document 1.
  • (C) Does not contain tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators (so-called curing accelerators). By not containing these, excellent adhesiveness is exhibited as shown in the section of Examples described later.
  • tertiary amines examples include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N-dimethyl piperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like.
  • tertiary amine salts include the formate, ethylhexanoate, octylate, p-toluenesulfonate, o-phthalate of 1,8-diazabicyclo[5.4.0]undecene.
  • phenol salts or phenol novolac resin salts and 1,5-diazabicyclo[4.3.0]nonene formates, ethylhexanoates, octylates, p-toluenesulfonates, o-phthalates. , phenol salts, phenol novolac resin salts, and the like.
  • imidazoles examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4- Diamino-6-[2-undecylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]ethyl-s-triazine, 2 , 4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine isocyanurate,
  • the adhesive composition of the present invention comprises (A) an acid-modified styrene elastomer, (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized, and other components as necessary. It can be manufactured by mixing. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution (hereinafter referred to as a liquid adhesive composition), the (D) organic solvent is also usually used. By using a liquid adhesive composition, when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
  • a liquid adhesive composition when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
  • the solid content concentration is, for example, 3 to 80% by weight, preferably 10 to 50% by weight, more preferably 20 to 20% by weight, from the viewpoint of workability including formation of an adhesive layer. 35% by weight.
  • the adhesive composition of the present invention has low dielectric properties and excellent adhesiveness between resin and metal, it can be suitably used as an adhesive (e.g., adhesive film, etc.) for manufacturing FPC-related members.
  • an adhesive e.g., adhesive film, etc.
  • FPC-related members in the present invention include coverlay films, bonding sheets, resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like.
  • the adhesive layer being in a B-stage state refers to a semi-cured state in which a part of the adhesive composition has begun to cure, and curing of the adhesive composition further progresses by heating or the like. is in a state to
  • Examples 1 to 7, Comparative Examples 1 to 6 Each component was added to a 1000 ml flask equipped with a stirrer in the proportions (parts by weight) shown in Table 1 or Table 2, and dispersed by stirring at room temperature for 6 hours to prepare an adhesive composition. Using the obtained adhesive composition, each physical property was measured by the following methods. The obtained results are shown in Table 1 or Table 2.
  • Dielectric Constant, Dielectric Loss Tangent A release-treated glass plate was prepared, and the adhesive composition prepared as described above was applied so that the thickness after drying was 100 ⁇ m. Next, the coated glass plate is placed in an oven and dried at 100° C. for 10 minutes to form a B-stage adhesive layer (thickness: 100 ⁇ m). It was left to stand inside and subjected to heat curing treatment at 160° C. for 60 minutes to prepare a test piece. The dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece at a measurement temperature of 25° C. and a measurement frequency of 10 GHz were obtained by the cavity resonator method using a dielectric constant measuring device manufactured by AET Corporation.
  • Dk dielectric constant
  • Df dielectric loss tangent
  • a flexible copper-clad laminate was obtained by thermocompression bonding under these conditions for 60 minutes. Cut this flexible copper-clad laminate into a width of 10 mm x length of 100 mm, and use an Autograph AGS-500 manufactured by Shimadzu Corporation to measure the peel adhesion strength in the 90 ° direction (direction perpendicular to the plane direction of the laminate) as follows. was measured under the measurement conditions of The measurement conditions were a test speed of 50 mm/min.
  • each component in Table 1 and Table 2 is as follows.
  • B-1 Celoxide 2021P (3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
  • B-2) Celoxide 8010P (4,4′-bis(1,2-epoxycyclohexane), manufactured by Daicel Corporation)
  • B-3 DE-103 (compound represented by the above formula (4), manufactured by Eneos)
  • C-1 U-CAT SA102 (manufactured by San-Apro, tertiary amine salts, 2-ethylhexanoate of DBU)
  • C-2 San-Aid 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic sulfonium salt)
  • C-3 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)
  • D Toluene
  • E HP-7200L (glycidyl ether type epoxy resin, manufactured by DIC Corporation)
  • F Tuftec H1041 (acid-unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epoxy Resins (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is an adhesive composition that: includes (A) an acid-modified styrene elastomer and (B) an alicyclic epoxy resin that includes a structure formed by epoxidation of the unsaturated bond of a cyclic olefin structure; but does not include (C) a tertiary amine, a tertiary amine salt, an imidazole, or a cationic polymerization initiator.

Description

接着剤組成物adhesive composition
　本発明は、低誘電特性（低誘電率、低誘電正接）及び接着性に優れ、電子部品、特にフレキシブルプリント配線板（以下、ＦＰＣ）の関連部材の製造に適した接着剤組成物に関する。 The present invention relates to an adhesive composition that has excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) and adhesiveness, and is suitable for manufacturing electronic components, particularly members related to flexible printed wiring boards (hereinafter referred to as FPC).
　近年、スマートフォンやモバイルパソコンなど無線通信技術の進展に伴って大容量の情報を高速で処理することが要求され、伝送信号の高周波化が進展している。高周波化に伴い、無線通信デバイスの構成要素の１つであるＦＰＣ及びその関連部材にも高周波帯域での低誘電特性（低誘電率、低誘電正接）が求められている（例えば、国際公開第２０１６／０１７４７３号（特許文献１））。 In recent years, with the progress of wireless communication technology such as smartphones and mobile personal computers, there is a demand for high-speed processing of large amounts of information, and transmission signals are becoming higher frequency. With the increase in frequency, low dielectric properties (low dielectric constant, low dielectric loss tangent) in high frequency bands are required for FPC and its related members, which are one of the components of wireless communication devices (for example, International Publication No. 2016/017473 (Patent Document 1)).
　また、上記関連部材として、例えば、ＦＰＣを製造する際に配線部分を保護するために、「カバーレイフィルム」と呼ばれる接着剤層付き積層体が用いられるが、該接着剤層には、配線部分及び基材フィルムに対して強固な接着性を有することも求められている。 Further, as the related member, for example, a laminate with an adhesive layer called "coverlay film" is used in order to protect the wiring part when manufacturing the FPC. And it is also required to have strong adhesiveness to the base film.
国際公開第２０１６／０１７４７３号WO2016/017473
　本発明は、このような事情に鑑み為されたものであって、低誘電特性及び樹脂と金属との接着性に優れる接着剤組成物を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive composition that has low dielectric properties and excellent adhesiveness between resin and metal.
　本発明者らは、上記課題を解決するために鋭意検討した結果、（Ａ）酸変性スチレン系エラストマー及び（Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂を含み、且つ（Ｃ）第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤を含まない接着剤組成物によれば、上記課題が解決可能であることを見出した。具体的には、本発明は以下の発明を含む。 The present inventors have made intensive studies to solve the above problems, and found that (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized and (C) free of tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators. Specifically, the present invention includes the following inventions.
〔１〕
　下記（Ａ）及び（Ｂ）を含み、且つ下記（Ｃ）を含まない、接着剤組成物。
（Ａ）酸変性スチレン系エラストマー
（Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂
（Ｃ）第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤 [1]
An adhesive composition containing the following (A) and (B) and not containing the following (C).
(A) Acid-modified styrene elastomer (B) Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized (C) Tertiary amines, tertiary amine salts, imidazoles and cations polymerization initiator
〔２〕
　（Ａ）１００重量部に対し、（Ｂ）を０．１～５０重量部含有する、〔１〕に記載の接着剤組成物。 [2]
The adhesive composition according to [1], which contains 0.1 to 50 parts by weight of (B) per 100 parts by weight of (A).
〔３〕
　（Ａ）が、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレンブロック共重合体からなる群より選択される少なくとも１種のスチレン系エラストマーを不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種によりで変性したものである、〔１〕又は〔２〕に記載の接着剤組成物。 [3]
(A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; The adhesive composition according to [1] or [2], which is modified with at least one selected from the group consisting of:
〔４〕
　（Ｂ）が、下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種の脂環式エポキシ樹脂である、〔１〕～〔３〕のいずれか一項に記載の接着剤組成物。 [4]
(B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of [1] to [3] The adhesive composition described.
Figure JPOXMLDOC01-appb-C000005
（上記式（１）におけるＸは、単結合、又は２価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。）
Figure JPOXMLDOC01-appb-C000005
(X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
〔５〕
　更に、（Ｄ）有機溶媒を含む、〔１〕～〔４〕のいずれか一項に記載の接着剤組成物。 [5]
The adhesive composition according to any one of [1] to [4], further comprising (D) an organic solvent.
〔６〕
　〔１〕～〔５〕のいずれか一項に記載の接着剤組成物を用いてなる接着フィルム。 [6]
An adhesive film using the adhesive composition according to any one of [1] to [5].
　本発明の接着剤組成物は、低誘電特性及び樹脂と金属との接着性に優れる。そのため、本発明の接着剤組成物は、例えば、接着剤層付き積層体（カバーレイフィルム、ボンディングシート）、樹脂付き銅箔、フレキシブル銅張積層板、及びフレキシブルフラットケーブル等の用途に好適に用いることができる。 The adhesive composition of the present invention has low dielectric properties and excellent adhesion between resin and metal. Therefore, the adhesive composition of the present invention is suitably used for applications such as laminates with an adhesive layer (coverlay films, bonding sheets), resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like. be able to.
　以下、本発明について詳細に記載する。なお、本発明は以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 The present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
＜本発明の接着剤組成物＞
　本発明の接着剤組成物は、（Ａ）酸変性スチレン系エラストマー及び（Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂を含む。以下、上記（Ａ）及び（Ｂ）について、具体的に説明する。 <Adhesive composition of the present invention>
The adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized. The above (A) and (B) will be specifically described below.
［（Ａ）酸変性スチレン系エラストマー］
　本発明の接着剤組成物は、主成分として、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種により変性したスチレン系エラストマー（酸変性スチレン系エラストマー）を用いる。スチレン系エラストマーを変性する方法としては、例えば、スチレン系エラストマーと不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種とをグラフト化反応させる方法等が挙げられる。 [(A) Acid-modified styrene-based elastomer]
The adhesive composition of the present invention uses, as a main component, a styrene elastomer modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (acid-modified styrene elastomer). Examples of methods for modifying a styrene-based elastomer include a method of grafting a styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
　スチレン系エラストマーの具体例としては、スチレン－ブタジエンブロック共重合体、スチレン－エチレンプロピレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－エチレンブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレンプロピレン－スチレンブロック共重合体（ＳＥＰＳ）等が挙げられる。これらスチレン系エラストマーの中でも、接着性と低誘電特性の観点から、スチレン－エチレンブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレンプロピレン－スチレンブロック共重合体（ＳＥＰＳ）が好ましい。 Specific examples of styrene elastomers include styrene-butadiene block copolymers, styrene-ethylene propylene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS ), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and the like. Among these styrene-based elastomers, styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) are preferable from the viewpoint of adhesiveness and low dielectric properties.
　不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸等が挙げられる。不飽和カルボン酸無水物としては、例えば、無水マレイン酸、無水イタコン酸、無水フマル酸等が挙げられる。これら不飽和カルボン酸及び不飽和カルボン酸無水物の中でも、マレイン酸、フマル酸、無水マレイン酸が好ましく、無水マレイン酸がより好ましい。不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種による変性量は、通常、酸変性スチレン系エラストマー全体の０．１～１０質量％程度である。また、酸変性スチレン系エラストマーは、該酸変性エラストマー中の全酸性基の少なくとも一部が酸無水物であることが好ましい。 Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and fumaric anhydride. Among these unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, maleic acid, fumaric acid and maleic anhydride are preferred, and maleic anhydride is more preferred. The amount of modification with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides is usually about 0.1 to 10% by mass of the total acid-modified styrene elastomer. Moreover, in the acid-modified styrene-based elastomer, at least part of all the acid groups in the acid-modified elastomer are preferably acid anhydrides.
　酸変性スチレン系エラストマーの酸価は特に限定されないが、例えば、下限が０．１ｍｇＣＨ３ＯＮａ／ｇ以上、好ましくは０．５ｍｇＣＨ３ＯＮａ／ｇ以上、より好ましくは１．０ｍｇＣＨ３ＯＮａ／ｇ以上であり、上限が２０ｍｇＣＨ３ＯＮａ／ｇ以下、好ましくは１８ｍｇＣＨ３ＯＮａ／ｇ以下、より好ましくは１５ｍｇＣＨ３ＯＮａ／ｇ以下である。 The acid value of the acid-modified styrene-based elastomer is not particularly limited, but for example, the lower limit is 0.1 mg CH 3 ONa/g or more, preferably 0.5 mg CH 3 ONa/g or more, more preferably 1.0 mg CH 3 ONa/g or more. and the upper limit is 20 mg CH 3 ONa/g or less, preferably 18 mg CH 3 ONa/g or less, more preferably 15 mg CH 3 ONa/g or less.
　酸変性スチレン系エラストマーの分子量は、例えば、重量平均分子量で１万以上、好ましくは３万以上、より好ましくは５万以上であり、また、例えば、５０万以下、好ましくは３０万以下、より好ましくは２０万以下である。なお、本発明における重量平均分子量とは、ゲル・パーミエーションクロマトグラフィー（ＧＰＣ）により測定したポリスチレン換算の分子量である。 The molecular weight of the acid-modified styrene-based elastomer is, for example, a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably. is less than 200,000. In addition, the weight average molecular weight in the present invention is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).
　酸変性スチレン系エラストマーの市販品としては、例えば、旭化成社製のタフテックＭシリーズや、クレイトンポリマージャパン社製のクレイトンＦＧシリーズ等が挙げられる。 Examples of commercially available acid-modified styrene-based elastomers include the Tuftec M series manufactured by Asahi Kasei Corporation and the Kraton FG series manufactured by Kraton Polymer Japan.
　本発明において、上記した酸変性スチレン系エラストマーは、単独で用いてもよく、２種以上を併用してもよい。 In the present invention, the above acid-modified styrene-based elastomers may be used alone, or two or more of them may be used in combination.
［（Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂］
　脂環式エポキシ樹脂は、脂環構造を含むエポキシ樹脂である。環状オレフィン構造の不飽和結合がエポキシ化された構造は、環状オレフィン構造に対応するシクロアルカン構造と、前記シクロアルカン構造を構成する隣接する２つの炭素原子と酸素原子とで構成されたエポキシ基と、を含む。環状オレフィン構造は単環式でも多環式でもよい。環状オレフィン構造は、アルキル基等の置換基を有していてもよい。環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂としては、例えば、下記式（１）～（４）で表される化合物等が挙げられる。 [(B) Alicyclic Epoxy Resin Containing Structure in which Unsaturated Bond of Cyclic Olefin Structure is Epoxidized]
Alicyclic epoxy resins are epoxy resins containing an alicyclic structure. The structure in which the unsaturated bond of the cyclic olefin structure is epoxidized includes a cycloalkane structure corresponding to the cyclic olefin structure and an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the cycloalkane structure. ,including. Cyclic olefin structures may be monocyclic or polycyclic. The cyclic olefin structure may have a substituent such as an alkyl group. Examples of the alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized include compounds represented by the following formulas (1) to (4).
Figure JPOXMLDOC01-appb-C000009
（上記式（１）におけるＸは、単結合、又は２価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。）
Figure JPOXMLDOC01-appb-C000009
(X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記式（１）で表される化合物としては、例えば、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、４，４’－ビス（１，２－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、以下式（１－１）： Examples of the compound represented by the above formula (1) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), 2 , 2-bis(3,4-epoxycyclohexyl)propane, the following formula (1-1):
Figure JPOXMLDOC01-appb-C000013
で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-C000013
Compounds represented by and the like.
　これら環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂の中でも、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、４，４’－ビス（１，２－エポキシシクロヘキサン）、上記式（１－１）で表される化合物、上記式（２）で表される化合物、上記式（３）で表される化合物、上記式（４）で表される化合物が好ましい。 Among these alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4′-bis( 1,2-epoxycyclohexane), a compound represented by the above formula (1-1), a compound represented by the above formula (2), a compound represented by the above formula (3), a compound represented by the above formula (4) are preferred.
　また、環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂の市販品としては、例えば、ダイセル社のセロキサイド２０２１Ｐ、セロキサイド８０１０Ｐ、セロキサイド２０８１、エポリードＧＴ４０１、ＥＮＥＯＳ社のＴＨＩ－ＤＥ、ＤＥ－１０２、ＤＥ－１０３、信越シリコーン社のＸ－４０－２６６９、ＫＲ－４７０等が挙げられる。 Commercially available alicyclic epoxy resins containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized include Celoxide 2021P, Celoxide 8010P, Celoxide 2081 from Daicel, Epolead GT401, and THI- from ENEOS. DE, DE-102, DE-103, Shin-Etsu Silicone Co., Ltd. X-40-2669, KR-470 and the like.
　本発明において、上記した環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂は、単独で用いても、２種以上を併用してもよい。 In the present invention, the alicyclic epoxy resins containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized may be used alone or in combination of two or more.
　本発明の接着剤組成物に含まれる（Ｂ）の量は、（Ａ）１００重量部に対し、通常０．１～５０重量部、好ましくは０．４～３０重量部、より好ましくは０．４～２０重量部、更に好ましくは０．４～４重量部である。 The amount of (B) contained in the adhesive composition of the present invention is generally 0.1-50 parts by weight, preferably 0.4-30 parts by weight, more preferably 0.4-30 parts by weight, per 100 parts by weight of (A). 4 to 20 parts by weight, more preferably 0.4 to 4 parts by weight.
［その他の成分］
　本発明の接着剤組成物は、上記（Ａ）及び（Ｂ）の他、（Ａ）酸変性スチレン系エラストマー以外の他の熱可塑性樹脂、粘着付与剤、難燃剤、カップリング剤、酸化防止剤、フィラー及び（Ｄ）有機溶媒等を含有することができる。 [Other ingredients]
In addition to the above (A) and (B), the adhesive composition of the present invention contains (A) a thermoplastic resin other than the acid-modified styrene elastomer, a tackifier, a flame retardant, a coupling agent, and an antioxidant. , a filler and (D) an organic solvent.
　上記他の熱可塑性樹脂としては、例えば、酸無水物基を含有しないスチレン系エラストマー、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキシド樹脂、ポリウレタン樹脂、ポリアセタール樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂及びポリビニル系樹脂等が挙げられる。これらの熱可塑性樹脂は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the other thermoplastic resins include styrene-based elastomers containing no acid anhydride groups, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene-based resins, and polypropylene-based resins. Examples thereof include resins and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
　上記粘着付与剤としては、例えば、クマロン－インデン樹脂、テルペン樹脂、テルペン－フェノール樹脂、ロジン樹脂、ｐ－ｔ－ブチルフェノール－アセチレン樹脂、フェノール－ホルムアルデヒド樹脂、キシレン－ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、テレピン系樹脂等が挙げられる。これらの粘着付与剤は、単独で用いてもよいし、２種以上を併用してもよい。 Examples of the tackifier include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
　上記難燃剤としては、例えば、有機系難燃剤、無機系難燃剤等が挙げられる。有機系難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート、トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタン等のリン系難燃剤；メラミン、メラム、メラミンシアヌレート等のトリアジン系化合物や、シアヌル酸化合物、イソシアヌル酸化合物、トリアゾール系化合物、テトラゾール化合物、ジアゾ化合物、尿素等の窒素系難燃剤；シリコーン化合物、シラン化合物等のケイ素系難燃剤等が挙げられる。また、無機系難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム等の金属水酸化物；酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化ニッケル等の金属酸化物；炭酸亜鉛、炭酸マグネシウム、炭酸バリウム、ホウ酸亜鉛、水和ガラス等が挙げられる。これらの難燃剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the flame retardant include organic flame retardants and inorganic flame retardants. Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. , aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , Titanyl bismethylethylphosphinate, Titanium tetrakismethylethylphosphinate, Titanyl bisdiphenylphosphinate, Titanium tetrakisdiphenylphosphinate, etc.; , isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea, and other nitrogen-based flame retardants; silicone compounds, silane compounds, and other silicon-based flame retardants. Examples of inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, oxide Metal oxides such as zinc, molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants may be used alone or in combination of two or more.
　上記カップリング剤としては、例えば、ビニルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトシキシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシラン、イミダゾールシラン等のシラン系カップリング剤；チタネート系カップリング剤；アルミネート系カップリング剤；ジルコニウム系カップリング剤等が挙げられる。これらカップリング剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane-based coupling agents such as imidazole silane; titanate-based coupling agents; aluminate-based coupling agents; and zirconium-based coupling agents. These coupling agents may be used alone or in combination of two or more.
　上記酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、ｎ－オクタデシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、テトラキス〔メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕メタン、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェノール、トリエチレングリコール－ビス〔３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート等のフェノール系酸化防止剤；ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－ジチオプロピオネート等のイオウ系酸化防止剤；トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト等のリン系酸化防止剤等が挙げられる。これら酸化防止剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate , tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, tri Phenolic antioxidants such as ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3' - sulfur-based antioxidants such as dithiopropionate; may be used alone or in combination of two or more.
　上記フィラーとしては、例えば、ポリアクリル酸エステル粉末、エポキシ樹脂粉末、ポリアミド粉末、ポリウレタン粉末、ポリシロキサン粉末等の他、シリコーン、アクリル、スチレンブタジエンゴム、ブタジエンゴム等を用いた多層構造のコアシェル等の高分子フィラー；シリカ、マイカ、タルク、カオリン、クレー、ハイドロタルサイト、ウォラストナイト、ゾノトライト、窒化ケイ素、窒化ホウ素、窒化アルミニウム、リン酸水素カルシウム、リン酸カルシウム、ガラスフレーク、水和ガラス、チタン酸カルシウム、セピオライト、硫酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム、酸化チタン、酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化アンチモン、酸化ニッケル、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、ホウ酸亜鉛、ホウ酸アルミニウム等の無機フィラー等が挙げられる。これらフィラーは、単独で用いてもよく、２種以上を併用してもよい。また、形状としては、例えば、球状、粉状、繊維状、針状、鱗片状等を用いることができる。 Examples of the filler include polyacrylate powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as multi-layered core shells using silicone, acrylic, styrene-butadiene rubber, butadiene rubber, etc. Polymer filler; silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate , sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Inorganic fillers such as nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate. These fillers may be used alone or in combination of two or more. As for the shape, for example, spherical, powdery, fibrous, needle-like, scale-like, etc. can be used.
　上記（Ｄ）有機溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、シクロヘキサン、メチルシクロヘキサン、トルエン、キシレン、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、テトラヒドロフラン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、ジメチルスルホキサイド、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールジメチルエーテル、ジオキサン、シクロペンチルメチルエーテル、塩化メチレン、クロロホルム、１，２－ジクロロエタン、γ－ブチロラクトン、セロソルブ、ブチルセロソルブ、カルビトール、ブチルカルビトール等が挙げられる。これらの有機溶媒は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the organic solvent (D) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cyclohexane, methylcyclohexane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tetrahydrofuran. , N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, dioxane, cyclopentyl methyl ether, methylene chloride, chloroform, 1 , 2-dichloroethane, γ-butyrolactone, cellosolve, butyl cellosolve, carbitol, butyl carbitol and the like. These organic solvents may be used alone or in combination of two or more.
　また、本発明の接着剤組成物は、上記したその他の成分の他、例えば、耐光安定剤、耐候安定剤、熱安定剤等の安定剤、レベリング剤、消泡剤等のアニオン系、カチオン系、ノニオン系の界面活性剤、染料、顔料、可塑剤等も、接着剤組成物の機能に影響を与えない程度に含有することができる。 In addition to the above-described other components, the adhesive composition of the present invention includes, for example, light stabilizers, weather stabilizers, stabilizers such as heat stabilizers, leveling agents, anionic and cationic stabilizers such as antifoaming agents. , nonionic surfactants, dyes, pigments, plasticizers and the like can also be contained to such an extent that the functions of the adhesive composition are not affected.
　なお、本発明の接着剤組成物は、例えば、特許文献１の各実施例及び比較例との対比からも明らかな通り、通常、エラストマーとエポキシ樹脂との反応を促進させる目的で使用される、（Ｃ）第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤（所謂、硬化促進剤）を含まない。これらを含まないことにより、後述する実施例の項にて示す通り、優れた接着性を示す。 The adhesive composition of the present invention is usually used for the purpose of promoting the reaction between the elastomer and the epoxy resin, as is clear from the comparison with the examples and comparative examples of Patent Document 1. (C) Does not contain tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators (so-called curing accelerators). By not containing these, excellent adhesiveness is exhibited as shown in the section of Examples described later.
　第三級アミン類の例としては、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、テトラメチルグアニジン、トリエタノールアミン、Ｎ，Ｎ－ジメチルピペラジン、トリエチレンジアミン、１，８－ジアザビシクロ［５．４．０］ウンデセン等が挙げられる。第三級アミン塩類の例としては、１，８－ジアザビシクロ［５．４．０］ウンデセンの、ギ酸塩、エチルへキサン酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩や、１，５－ジアザビシクロ［４．３．０］ノネンの、ギ酸塩、エチルへキサン酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩等が挙げられる。イミダゾール類の例としては、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－メチル－４－エチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、２，４－ジアミノ－６－［２－メチルイミダゾリル－（１）］エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２－ウンデシルイミダゾリル－（１）］エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２－エチル－４－メチルイミダゾリル－（１）］エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２－メチルイミダゾリル－（１）］エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等が挙げられる。カチオン重合開始剤の例としては、芳香族ヨードニウム塩、芳香族スルホニウム塩等が挙げられる。 Examples of tertiary amines include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N-dimethyl piperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like. Examples of tertiary amine salts include the formate, ethylhexanoate, octylate, p-toluenesulfonate, o-phthalate of 1,8-diazabicyclo[5.4.0]undecene. , phenol salts or phenol novolac resin salts, and 1,5-diazabicyclo[4.3.0]nonene formates, ethylhexanoates, octylates, p-toluenesulfonates, o-phthalates. , phenol salts, phenol novolac resin salts, and the like. Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4- Diamino-6-[2-undecylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]ethyl-s-triazine, 2 , 4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- phenyl-4-methyl-5-hydroxymethylimidazole and the like. Examples of cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts and the like.
　本発明の接着剤組成物は、（Ａ）酸変性スチレン系エラストマー、（Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂、及び必要に応じてその他成分を混合することにより製造することができる。混合方法は特に限定されず、接着剤組成物が均一になればよい。接着剤組成物は、溶液の状態（以下、液状の接着剤組成物と称する。）で好ましく用いられることから、通常は、上記（Ｄ）有機溶媒も使用される。液状の接着剤組成物とすることにより、ＦＰＣ関連部材を製造する際に、基材フィルムへの塗工及び接着剤層の形成を円滑に行うことができ、所望の厚さの接着剤層をより容易に得ることができる。 The adhesive composition of the present invention comprises (A) an acid-modified styrene elastomer, (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of a cyclic olefin structure is epoxidized, and other components as necessary. It can be manufactured by mixing. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution (hereinafter referred to as a liquid adhesive composition), the (D) organic solvent is also usually used. By using a liquid adhesive composition, when manufacturing an FPC-related member, coating on the base film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained more easily.
　液状の接着剤組成物とする場合、接着剤層の形成を含む作業性等の観点から、固形分濃度は、例えば、３～８０重量％、好ましくは１０～５０重量％、より好ましくは２０～３５重量％である。 When a liquid adhesive composition is used, the solid content concentration is, for example, 3 to 80% by weight, preferably 10 to 50% by weight, more preferably 20 to 20% by weight, from the viewpoint of workability including formation of an adhesive layer. 35% by weight.
＜用途＞
　本発明における接着剤組成物は、低誘電特性及び樹脂と金属との接着性に優れることから、ＦＰＣの関連部材を製造するための接着剤（例えば、接着フィルム等）として好適に用いることができる。本発明におけるＦＰＣの関連部材としては、例えば、カバーレイフィルム、ボンディングシート、樹脂付き銅箔、フレキシブル銅張積層板、フレキシブルフラットケーブル等が挙げられる。 <Application>
Since the adhesive composition of the present invention has low dielectric properties and excellent adhesiveness between resin and metal, it can be suitably used as an adhesive (e.g., adhesive film, etc.) for manufacturing FPC-related members. . Examples of FPC-related members in the present invention include coverlay films, bonding sheets, resin-coated copper foils, flexible copper-clad laminates, flexible flat cables, and the like.
　以下、実施例等を挙げて本発明をより詳細に説明するが、本発明はこれらに何ら限定されるものではない。なお、以下実施例等において、接着剤層がＢステージ状であるとは、接着剤組成物の一部が硬化し始めた半硬化状態をいい、加熱等により接着剤組成物の硬化が更に進行する状態である。 The present invention will be described in more detail below with reference to Examples, etc., but the present invention is not limited to these. In the following examples, etc., the adhesive layer being in a B-stage state refers to a semi-cured state in which a part of the adhesive composition has begun to cure, and curing of the adhesive composition further progresses by heating or the like. is in a state to
（実施例１～７、比較例１～６）
　撹拌装置付き１０００ｍｌフラスコに、各成分を表１又は表２に示す割合（重量部）で添加し、室温下で６時間撹拌して分散させることにより接着剤組成物を調製した。得られた接着剤組成物を用いて、以下の方法で各物性の測定を行った。得られた結果を表１又は表２に示す。 (Examples 1 to 7, Comparative Examples 1 to 6)
Each component was added to a 1000 ml flask equipped with a stirrer in the proportions (parts by weight) shown in Table 1 or Table 2, and dispersed by stirring at room temperature for 6 hours to prepare an adhesive composition. Using the obtained adhesive composition, each physical property was measured by the following methods. The obtained results are shown in Table 1 or Table 2.
（１）誘電率、誘電正接
　離型処理をしたガラス板を用意し、上記の通り調製した接着剤組成物を、乾燥後の厚さが１００μｍとなるように塗布した。次いで、この塗膜付きガラス板をオーブン内に静置して、１００℃で１０分間乾燥させてＢステージ状の接着剤層（厚さ１００μｍ）を形成し、次に、この接着剤層をオーブン内に静置して、１６０℃で６０分間加熱硬化処理をして、試験片を作製した。この試験片について、エー・イー・ティー社製の誘電率測定装置を用い、空洞共振器法により、測定温度２５℃、測定周波数１０ＧＨｚにおける誘電率（Ｄｋ）及び誘電正接（Ｄｆ）を求めた。 (1) Dielectric Constant, Dielectric Loss Tangent A release-treated glass plate was prepared, and the adhesive composition prepared as described above was applied so that the thickness after drying was 100 μm. Next, the coated glass plate is placed in an oven and dried at 100° C. for 10 minutes to form a B-stage adhesive layer (thickness: 100 μm). It was left to stand inside and subjected to heat curing treatment at 160° C. for 60 minutes to prepare a test piece. The dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece at a measurement temperature of 25° C. and a measurement frequency of 10 GHz were obtained by the cavity resonator method using a dielectric constant measuring device manufactured by AET Corporation.
（２）剥離接着強度
　厚さ２５μｍのポリイミドフィルム［東レ・デュポン社製「カプトン１００ＥＮ」］を用意し、その一方の表面に、上記の通り調製した接着剤組成物を塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、１００℃で５分間乾燥させてＢステージ状の接着剤層（厚さ約１５μｍ）を形成し、カバーレイフィルム（接着剤層付き積層体）を得た。その後、厚さ２０μｍの圧延銅箔を、カバーレイフィルムの接着剤層の表面に面接触するように重ね合わせ（ポリイミドフィルム／接着剤層／銅箔）、温度１６０℃、及び圧力４．５ＭＰａの条件で６０分間加熱圧着し、フレキシブル銅張積層板を得た。このフレキシブル銅張積層板を幅１０ｍｍ×長さ１００ｍｍにカットし、島津製作所社製オートグラフＡＧＳ－５００を用いて、９０°方向（積層板の面方向に直交する方向）における剥離接着強度を以下の測定条件にて測定した。測定条件は、テストスピードを５０ｍｍ／ｍｉｎとした。 (2) Peel Adhesive Strength A polyimide film [“Kapton 100EN” manufactured by DuPont Toray] having a thickness of 25 μm was prepared, and the adhesive composition prepared as described above was applied to one surface of the film. Next, the coated film is left in an oven and dried at 100° C. for 5 minutes to form a B-stage adhesive layer (thickness of about 15 μm), coverlay film (laminate with adhesive layer) body). After that, a rolled copper foil having a thickness of 20 μm was superimposed so as to be in surface contact with the surface of the adhesive layer of the coverlay film (polyimide film/adhesive layer/copper foil), and the temperature was 160 ° C. and the pressure was 4.5 MPa. A flexible copper-clad laminate was obtained by thermocompression bonding under these conditions for 60 minutes. Cut this flexible copper-clad laminate into a width of 10 mm x length of 100 mm, and use an Autograph AGS-500 manufactured by Shimadzu Corporation to measure the peel adhesion strength in the 90 ° direction (direction perpendicular to the plane direction of the laminate) as follows. was measured under the measurement conditions of The measurement conditions were a test speed of 50 mm/min.
　なお、表１及び表２中の各成分は以下の通りである。
［（Ａ）：酸変性スチレン系エラストマー］
（Ａ－１）：タフテックＭ１９１１（無水マレイン酸変性スチレン－エチレンブチレン－スチレンブロック共重合体、酸価：２ｍｇＣＨ３ＯＮａ／ｇ、重量平均分子量：１５万、旭化成ケミカルズ社製） In addition, each component in Table 1 and Table 2 is as follows.
[(A): acid-modified styrene-based elastomer]
(A-1): Tuftec M1911 (maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer, acid value: 2 mg CH 3 ONa/g, weight average molecular weight: 150,000, manufactured by Asahi Kasei Chemicals)
［（Ｂ）：環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂］
（Ｂ－１）：セロキサイド２０２１Ｐ（３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、ダイセル社製）
（Ｂ－２）：セロキサイド８０１０Ｐ（４，４’－ビス（１，２－エポキシシクロヘキサン）、ダイセル社製）
（Ｂ－３）：ＤＥ－１０３（上記式（４）で表される化合物、エネオス社製）
（Ｂ－４）：Ｘ－４０－２６６９（上記式（１－１）で表される化合物、信越シリコーン社製） [(B): Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized]
(B-1): Celoxide 2021P (3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
(B-2): Celoxide 8010P (4,4′-bis(1,2-epoxycyclohexane), manufactured by Daicel Corporation)
(B-3): DE-103 (compound represented by the above formula (4), manufactured by Eneos)
(B-4): X-40-2669 (compound represented by the above formula (1-1), manufactured by Shin-Etsu Silicone Co., Ltd.)
［その他］
（Ｃ－１）：Ｕ－ＣＡＴ　ＳＡ１０２（サンアプロ社製、第３級アミン塩類、ＤＢＵの２－エチルヘキサン酸塩）
（Ｃ－２）：サンエイド１００Ｌ（三新化学社製、カチオン重合開始剤、芳香族スルホニウム塩）
（Ｃ－３）：２Ｅ４ＭＺ（２－エチル－４－メチルイミダゾール、和光純薬工業社製）
（Ｄ）：トルエン
（Ｅ）：ＨＰ－７２００Ｌ（グリシジルエーテル型エポキシ樹脂、ＤＩＣ社製）
（Ｆ）：タフテックＨ１０４１（酸未変性スチレン系エラストマー、旭化成ケミカルズ社製） [others]
(C-1): U-CAT SA102 (manufactured by San-Apro, tertiary amine salts, 2-ethylhexanoate of DBU)
(C-2): San-Aid 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic sulfonium salt)
(C-3): 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)
(D): Toluene (E): HP-7200L (glycidyl ether type epoxy resin, manufactured by DIC Corporation)
(F): Tuftec H1041 (acid-unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals)
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015

Claims (6)

  1. 　下記（Ａ）及び（Ｂ）を含み、且つ下記（Ｃ）を含まない、接着剤組成物。
    （Ａ）酸変性スチレン系エラストマー
    （Ｂ）環状オレフィン構造の不飽和結合がエポキシ化された構造を含む脂環式エポキシ樹脂
    （Ｃ）第三級アミン類、第三級アミン塩類、イミダゾール類及びカチオン重合開始剤     An adhesive composition containing the following (A) and (B) and not containing the following (C).
    (A) Acid-modified styrene elastomer (B) Alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized (C) Tertiary amines, tertiary amine salts, imidazoles and cations polymerization initiator
  2. 　（Ａ）１００重量部に対し、（Ｂ）を０．１～５０重量部含有する、請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, which contains 0.1 to 50 parts by weight of (B) per 100 parts by weight of (A).
  3. 　（Ａ）が、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレンブロック共重合体からなる群より選択される少なくとも１種のスチレン系エラストマーを不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種により変性したものである、請求項１又は２に記載の接着剤組成物 (A) comprises at least one styrenic elastomer selected from the group consisting of styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene block copolymers, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; The adhesive composition according to claim 1 or 2, which is modified with at least one selected from the group consisting of
  4. 　（Ｂ）が、下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種の脂環式エポキシ樹脂である、請求項１～３のいずれか一項に記載の接着剤組成物。
    Figure JPOXMLDOC01-appb-C000001
    （上記式（１）におけるＸは、単結合、又は２価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、シロキサン結合もしくはこれらが複数連結した基を表す。）
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
         (B) is at least one alicyclic epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4), according to any one of claims 1 to 3. adhesive composition.
    Figure JPOXMLDOC01-appb-C000001
    (X in the above formula (1) represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, a siloxane bond, or a group in which a plurality of these are linked. .)
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
  5. 　更に、（Ｄ）有機溶媒を含む、請求項１～４のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, further comprising (D) an organic solvent.
  6. 　請求項１～５のいずれか一項に記載の接着剤組成物を用いてなる接着フィルム。 An adhesive film using the adhesive composition according to any one of claims 1 to 5.
PCT/JP2022/027449 2021-07-28 2022-07-12 Adhesive composition WO2023008183A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01261478A (en) * 1988-04-13 1989-10-18 Hitachi Chem Co Ltd Adhesive composition for circuit connection
WO2020048799A1 (en) * 2018-09-05 2020-03-12 Tesa Se Adhesive mass for a flexible display
WO2021145240A1 (en) * 2020-01-16 2021-07-22 住友精化株式会社 Laminated body having copper foil and epoxy resin composition layer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01261478A (en) * 1988-04-13 1989-10-18 Hitachi Chem Co Ltd Adhesive composition for circuit connection
WO2020048799A1 (en) * 2018-09-05 2020-03-12 Tesa Se Adhesive mass for a flexible display
WO2021145240A1 (en) * 2020-01-16 2021-07-22 住友精化株式会社 Laminated body having copper foil and epoxy resin composition layer

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