WO2022210673A1 - 硬化性接着剤組成物、硬化物、及び硬化物の製造方法 - Google Patents

硬化性接着剤組成物、硬化物、及び硬化物の製造方法 Download PDF

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WO2022210673A1
WO2022210673A1 PCT/JP2022/015344 JP2022015344W WO2022210673A1 WO 2022210673 A1 WO2022210673 A1 WO 2022210673A1 JP 2022015344 W JP2022015344 W JP 2022015344W WO 2022210673 A1 WO2022210673 A1 WO 2022210673A1
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adhesive composition
curable adhesive
cured product
mass
carbon
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PCT/JP2022/015344
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English (en)
French (fr)
Japanese (ja)
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健太 西嶋
幹広 樫尾
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リンテック株式会社
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Priority to JP2023511356A priority Critical patent/JPWO2022210673A1/ja
Priority to KR1020237026432A priority patent/KR20230163357A/ko
Priority to CN202280025752.6A priority patent/CN117222721A/zh
Publication of WO2022210673A1 publication Critical patent/WO2022210673A1/ja

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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
    • C09J1/00—Adhesives based on inorganic constituents
    • C09J1/02—Adhesives based on inorganic constituents containing water-soluble alkali silicates
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/30—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by oxidation
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a curable adhesive composition that does not easily contaminate the surroundings in the bonding process, a cured product thereof, and a method for producing the cured product.
  • curable adhesives are sometimes used as materials for forming insulating resin layers, sealant layers, adhesive members, etc. of electronic devices.
  • Patent Document 1 discloses a thermosetting adhesive sheet containing an epoxy resin, wherein the cured product of the thermosetting adhesive sheet has a storage elastic modulus (x1) of 1 GPa or more at 25°C and a temperature of 100°C. describes a thermosetting adhesive sheet having a storage modulus (x2) of 1 GPa or more.
  • this document states that the thermosetting adhesive sheet described in the same document can effectively suppress minute deformation and displacement of an adherend at high temperatures, and can be repeatedly minutely deformed as an adherend. It is also described that even when used to fix an adherend, it is less likely to cause peeling over time.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable adhesive composition that does not easily contaminate the surroundings during the bonding process, a cured product thereof, and a method for producing the cured product.
  • the present inventors have diligently studied curable adhesive compositions. As a result, by blending the curable components so as to have a first curing system in which the reaction proceeds at a temperature of 120 ° C. or less and a second curing system in which the reaction proceeds at a temperature above 120 ° C., adhesion can be achieved.
  • the inventors have found that a curable adhesive composition that hardly contaminates the surroundings during the process can be obtained, and have completed the present invention.
  • curable adhesive compositions [1] to [10], cured products [11] to [14] and [16], and cured products [15] and [17] is provided.
  • a first curing system in which a binder resin having a reactive functional group and a cross-linking agent react with each other, in which the reaction proceeds at a temperature of 120° C. or less; a second curing system in which one or more compounds having a carbon-carbon double bond react, wherein the reaction proceeds at a temperature above 120° C.;
  • a curable adhesive composition comprising: [2] The curable adhesive composition according to [1], wherein the binder resin having a reactive functional group is a polyolefin resin. [3] The curable adhesive composition according to [1] or [2], wherein the binder resin having a reactive functional group is an acid-modified resin.
  • Step IIa A step of curing the curable adhesive composition according to any one of [1] to [10] at a temperature of 120° C. or less to form a cured product
  • Step IIb Formed in Step IIa Further curing the cured product at a temperature above 120°C
  • a curable adhesive composition that does not easily contaminate the surroundings in the bonding process, a cured product thereof, and a method for producing the cured product are provided.
  • FIG. 2 is a schematic diagram (plan view) of a part of a laminate used when evaluating the exudation of an adhesive component.
  • FIG. 2 is a schematic diagram showing a cross section taken along line AA of FIG. 1;
  • the upper and lower limits can be combined arbitrarily.
  • the numerical range is described as “preferably 30 to 100, more preferably 40 to 80”
  • the range of "30 to 80” and the range of "40 to 100” are also described in this specification. included in the specified numerical range.
  • the numerical range is described as “preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less”
  • “30 to 80” Ranges and ranges from “40 to 100” are also included in the numerical ranges described herein.
  • the description of "60 to 100” means a range of "60 or more and 100 or less”.
  • the number average molecular weight (Mn) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • the curable adhesive composition of the present invention is a curing system in which a binder resin having a reactive functional group and a cross-linking agent react, and the reaction proceeds at a temperature of 120°C or less. and a second curing system in which one or more compounds having a carbon-carbon double bond react with each other, wherein the reaction proceeds at a temperature exceeding 120 ° C., including.
  • the component contained in the curable adhesive composition of the present invention may be a component classified into one of the first curing system and the second curing system. It may be a component classified into both curing systems.
  • the curable adhesive composition of the present invention may contain components that are not classified into either the first curing system or the second curing system within the range that does not impair the effects of the present invention.
  • the first curing system contained in the curable adhesive composition of the present invention is a curing system in which a binder resin having a reactive functional group and a cross-linking agent react, and the reaction proceeds at a temperature of 120° C. or less. It is.
  • the first curing system is one in which the reaction proceeds at a temperature of 120°C or less. Since the reaction of the first curing system proceeds at a temperature of 120° C. or less, when using the curable adhesive composition of the present invention, the reaction of the first curing system is conducted under relatively mild conditions. can proceed. Therefore, a crosslinked structure can be efficiently formed in the coating film of the curable adhesive composition without advancing the reaction of the second curing system.
  • the first curing system comprises a binder resin having a reactive functional group (hereinafter sometimes referred to as "binder resin (A)”) and a cross-linking agent (B) ( Hereinafter, it may be described as “crosslinking agent (B)"). Therefore, the first curing system preferably contains a binder resin (A) and a cross-linking agent (B).
  • the first curing system may contain curing components other than the binder resin (A) and the cross-linking agent (B). Curable components other than the binder resin (A) and the cross-linking agent (B) contained in the first curing system can be appropriately selected according to the reaction characteristics of the first curing system.
  • the other curable component may also be a component that is also classified as the second curing system.
  • the reaction temperature of the first curing system considers the reactivity between the reactive functional groups in the binder resin (A) and the cross-linking agent (B), and the binder resin (A) and the cross-linking agent (B) are appropriately adjusted. can be adjusted by using in combination with
  • the total content of the components (A) and (B) is the total amount of active ingredients in the curable adhesive composition (100 %), may be 40% by mass or more, 50% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and 94% by mass or less, 90% by mass or less, 85% by mass % or less, 80 mass % or less, or 77 mass % or less.
  • active ingredient refers to a component in the composition other than the solvent.
  • the first curing system contains a binder resin (A) having a reactive functional group as a curable component. Since the first curing system contains the binder resin (A), contamination of the surroundings during the bonding process can be suppressed, as will be described later. Binder resin (A) can be used individually by 1 type or in combination of 2 or more types.
  • the number average molecular weight (Mn) of the binder resin (A) is not particularly limited. 000, more preferably 10,000 to 100,000.
  • the number average molecular weight (Mn) of the binder resin (A) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and specific measurement The conditions are as described above.
  • the content of the binder resin (A) (when two or more binder resins (A) are included, the total amount thereof) is preferably based on the total amount (100% by mass) of the active ingredients of the curable adhesive composition. is 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and more More preferably, it is 80% by mass or less.
  • the content of the binder resin (A) is 50% by mass or more, it becomes easier to obtain a curable adhesive composition that does not easily stain the surroundings.
  • binder resin (A) examples include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamideimide-based resins, polyvinyl butyral-based resins, and polycarbonate-based resins. Among these, polyolefin-based resins are preferable as the binder resin (A). When the binder resin (A) is a polyolefin resin, it becomes easier to obtain a curable adhesive composition that gives a cured product with excellent low dielectric properties.
  • the curable adhesive composition may contain a binder resin other than the polyolefin resin as another component. good.
  • the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 100 parts by mass of the total polyolefin resin. 0 to 10 parts by weight, more preferably 0 to 5 parts by weight.
  • a polyolefin resin is a polymer containing repeating units derived from an olefin monomer.
  • the polyolefin resin may be a polymer consisting only of repeating units derived from an olefinic monomer, or a repeating unit derived from an olefinic monomer and a monomer copolymerizable with the olefinic monomer. It may be a polymer composed of repeating units derived from
  • the olefinic monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and still more preferably ethylene or propylene.
  • These olefinic monomers can be used singly or in combination of two or more.
  • monomers copolymerizable with olefinic monomers include vinyl acetate, (meth)acrylic acid esters, and styrene.
  • (meth)acrylic acid means acrylic acid or methacrylic acid (same below).
  • Polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), ethylene-propylene Copolymers, olefinic elastomers (TPO), ethylene-vinyl acetate copolymers (EVA), ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, and the like.
  • VLDPE very low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • TPO ethylene-propylene Copolymers
  • EVA ethylene-vinyl acetate copolymers
  • EVA ethylene-(meth)acrylic acid copolymers
  • ethylene-(meth)acrylic acid ester copolymers and the like.
  • Reactive functional groups contained in the binder resin (A) include a carboxy group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, and an isocyanate group. group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphon group, nitro group, urethane group, halogen atom, alkoxysilyl and the like.
  • Binder resin (A) is preferably a modified resin.
  • the modified resin is a resin into which a reactive functional group is introduced, which is obtained by modifying a resin as a precursor using a modifying agent.
  • a modifier used for modifying the binder resin is a compound having a reactive functional group in the molecule. Reactive functional groups include those previously described.
  • modified resins include resins into which acid groups have been introduced (acid-modified resins) and resins into which hydroxyl groups have been introduced, and acid-modified resins are preferred.
  • acid-modified resins resins into which an acid anhydride structure is introduced are preferable.
  • an acid-modified resin as the binder resin (A)
  • a resin into which an acid anhydride structure is introduced as the acid-modified resin there is a tendency to easily maintain a long pot life.
  • the curable adhesive composition may contain other binder resins other than the acid-modified resin as other components.
  • the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 100 parts by mass of the total amount of the acid-modified resin. 0 to 10 parts by weight, more preferably 0 to 5 parts by weight.
  • a resin is reacted with an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (hereinafter sometimes referred to as "unsaturated carboxylic acid or the like") to form a carboxy group or a carboxylic anhydride group. is introduced (graft modification).
  • unsaturated carboxylic acid or an unsaturated carboxylic anhydride hereinafter sometimes referred to as "unsaturated carboxylic acid or the like
  • Unsaturated carboxylic acids to be reacted with the resin include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid; maleic anhydride, itaconic anhydride, and glutaconic anhydride. acids, unsaturated carboxylic anhydrides such as citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride; These can be used individually by 1 type or in combination of 2 or more types. Among these, maleic anhydride is preferable because it is easy to obtain a curable adhesive composition that gives a cured product with higher adhesive strength.
  • the amount of the unsaturated carboxylic acid or the like to be reacted with the resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 1 part by mass with respect to 100 parts by mass of the resin. part by mass.
  • the method of introducing unsaturated carboxylic acid units or unsaturated carboxylic anhydride units into the resin is not particularly limited.
  • a radical generator such as organic peroxides or azonitriles, a resin and an unsaturated carboxylic acid, etc.
  • a method of heating and melting above the melting point of the resin to react or a method of reacting the resin and the unsaturated carboxylic acid.
  • the resin is graft-copolymerized with an unsaturated carboxylic acid or the like by heating and stirring in the presence of a radical generator.
  • the binder resin (A) a modified polyolefin resin is preferable, and an acid-modified polyolefin resin is more preferable.
  • the binder resin (A) is an acid-modified polyolefin resin, it becomes easier to obtain a curable adhesive composition that gives a cured product with excellent low dielectric properties and low staining properties.
  • a modified polyolefin resin is a polyolefin resin into which a reactive functional group has been introduced, obtained by modifying a polyolefin resin as a precursor using a modifier.
  • the curable adhesive composition contains, as another component, a binder resin other than the acid-modified polyolefin resin.
  • a binder resin other than the acid-modified polyolefin resin may be included in the curable adhesive composition.
  • the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and more preferably 0 to 30 parts by mass, based on 100 parts by mass of the total amount of the acid-modified polyolefin resin. It is preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight.
  • the first curing system contains, as a curable component, a cross-linking agent (B) capable of reacting with the binder resin (A). Since the first curing system contains the cross-linking agent (B), contamination of the surroundings during the bonding process can be suppressed, as will be described later.
  • a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
  • the molecular weight of the cross-linking agent (B) is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, still more preferably 600 or less, and particularly preferably 500 or less.
  • the molecular weight of the cross-linking agent (B) is 1000 or less, the collision probability of the reaction with the binder resin (A) increases, the cross-linked structure is easily formed, and the curability with a high effect of suppressing the surrounding contamination in the adhesion process. It can be an adhesive composition.
  • the molecular weight of the cross-linking agent (B) it is usually 100 or more, preferably 200 or more.
  • the molecular weight of the cross-linking agent (B) is a formula weight determined from the structural formula of the compound used as the cross-linking agent (B).
  • the content of the cross-linking agent (B) (the total amount of these when two or more cross-linking agents (B) are included) is preferably is 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, even more preferably 0.7% by mass or more, especially
  • the content is preferably 0.9% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.
  • the content of the cross-linking agent (B) is 0.1% by mass or more relative to the total amount of active ingredients in the curable adhesive composition, it becomes easier to obtain a curable adhesive composition that does not easily stain the surroundings. .
  • the content of the cross-linking agent (B) is 5% by mass or less with respect to the total amount of active ingredients in the curable adhesive composition, so that the curable adhesive composition gives a cured product having excellent low dielectric properties. easier to obtain.
  • the content of the cross-linking agent (B) is preferably 0.1 part by mass or more, more preferably 100 parts by mass of component (A) 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, particularly preferably 1.2 parts by mass or more, and preferably 10 parts by mass or less, more It is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.
  • the cross-linking agent (B) is a compound capable of reacting with the binder resin (A). Therefore, as the cross-linking agent (B), it is necessary to appropriately select one having a reactive group or a reactive site that is reactive with the reactive functional group in the binder resin (A).
  • an isocyanate-based cross-linking agent an epoxy-based cross-linking agent, a metal chelate-based cross-linking agent, an aziridine-based cross-linking agent, or the like can be used.
  • one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents are preferable from the viewpoint of storage stability.
  • a cross-linking agent ( B) is preferably one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents.
  • An isocyanate-based cross-linking agent is a compound having two or more isocyanate groups in the molecule.
  • isocyanate cross-linking agents include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene.
  • Epoxy crosslinking agent is a compound having two or more epoxy groups in its molecule.
  • Epoxy crosslinking agents include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
  • a metal chelate-based cross-linking agent is a chelate compound having metal ions functioning as cross-linking points.
  • metal chelate-based cross-linking agents for example, metal chelate compounds whose metal ions are aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, tin ions, and the like can be used. Among these, aluminum chelate compounds are preferred.
  • aluminum chelate compounds include aluminum tris(acetylacetonate), acetylacetonate aluminum bis(ethylacetoacetate), diisopropoxyaluminum monooleyl acetoacetate, monoisopropoxyaluminum bisoleyl acetoacetate, and the like.
  • the cross-linking agent (B) is preferably a compound having an isocyanurate skeleton, more preferably a compound having an isocyanurate skeleton and two or more isocyanate groups.
  • the cross-linking agent (B) is a compound having an isocyanurate skeleton, it becomes easier to obtain a curable adhesive composition that gives a cured product with excellent low dielectric properties.
  • the component (B) is a curable adhesive composition that is a compound having an isocyanurate skeleton
  • the curable adhesive composition contains, as another component, a cross-linking compound other than the compound having an isocyanurate skeleton. It may contain an agent.
  • the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 100 parts by mass of the total amount of the compound having an isocyanurate skeleton. More preferably 0 to 30 parts by mass, still more preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass.
  • a curable adhesive composition that gives a cured product having excellent low dielectric properties can be easily obtained.
  • an isocyanurate of a polyisocyanate compound is more preferred, and an isocyanurate of 1,5-pentamethylene diisocyanate [1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2, 4,6-trione] or isocyanurate of 1,6-hexamethylene diisocyanate [1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione] More preferred.
  • the curable adhesive composition contains, as another component, a cross-linking agent other than the isocyanate-based cross-linking agent.
  • the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 100 parts by mass of the total amount of the isocyanate-based cross-linking agent. It is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass.
  • the cross-linking agent (B) is preferably an epoxy-based cross-linking agent, since a curable adhesive composition capable of suppressing contamination of the surroundings in the bonding process can be easily obtained.
  • the curable adhesive composition may contain, as another component, a cross-linking agent other than the epoxy-based cross-linking agent. good.
  • the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 100 parts by mass of the total epoxy cross-linking agent. is 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, and particularly preferably 0 to 5 parts by weight.
  • the cross-linking agent (B) is a compound that can react with the binder resin (A), the binder resin (A) and the cross-linking agent ( B) can be reacted to build a crosslinked structure in the coating film.
  • a coating film having a crosslinked structure inside is difficult to fluidize even when heated. Therefore, by building a cross-linked structure in the coating film before adhering the two adherends, even if heat treatment is performed when adhering the two adherends, staining of the adhesive component in the coating film can be prevented.
  • the coating film can be completely cured while suppressing extrusion.
  • the reaction between the binder resin (A) and the cross-linking agent (B) proceeds before performing the adhesion step. Therefore, contamination of the surroundings in the bonding process can be suppressed.
  • the second curing system contained in the curable adhesive composition of the present invention is a curing system in which one or more compounds having a carbon-carbon double bond react at a temperature above 120°C. The reaction proceeds. Since the reaction of the second curing system proceeds at a temperature above 120° C., the curable adhesive composition of the present invention has sufficient adhesion ability even after the reaction of the first curing system is completed. will be provided.
  • a second curable system contains a compound having a carbon-carbon double bond as a curable component.
  • the initiation of the reaction can be relatively easily controlled, so that while the reaction of the first curing system is in progress, the second curing system , the reaction of the second curing system can be reliably progressed after the reaction of the first curing system is completed.
  • cured products of curable adhesive compositions containing compounds having carbon-carbon double bonds tend to be excellent in low dielectric properties.
  • the second curing system may contain one type of compound having a carbon-carbon double bond, or may contain two or more types.
  • a compound having a carbon-carbon double bond of the second curing system a compound having two or more hydrocarbon groups having a double bond at the end and being liquid at 25 ° C. (hereinafter referred to as "carbon-carbon two Sometimes referred to as a “liquid compound containing a double bond (C)”.) and a polymer having a hydrocarbon group with a double bond at the end (hereinafter referred to as a “carbon-carbon double bond-containing polymer (D)" It may be described as.) can be mentioned.
  • the total content of the components (C) and (D) is the total amount of active ingredients in the curable adhesive composition (100 %), 6% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 23% by mass or more, or 60% by mass or less, 50% by mass or less, or 40% by mass % or less, 35 mass % or less, or 30 mass % or less.
  • the carbon-carbon double bond-containing liquid compound (C) has two or more hydrocarbon groups having double bonds at their terminals. Since the carbon-carbon double bond-containing liquid compound (C) has two or more hydrocarbon groups having a double bond at the end, a curable adhesive composition that provides a cured product with excellent adhesive strength and heat resistance can be obtained. becomes easier.
  • the carbon-carbon double bond-containing liquid compound (C) can be used singly or in combination of two or more.
  • the number of hydrocarbon groups having a double bond at the end of the carbon-carbon double bond-containing liquid compound (C) is preferably 2 to 4, more preferably 2.
  • the carbon number of the hydrocarbon group having a double bond at the end contained in the carbon-carbon double bond-containing liquid compound (C) is preferably 2-10, more preferably 2-5.
  • Hydrocarbon groups having a double bond at the end include vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, 1-methyl-2-propenyl group and vinylbenzyl group. , a vinyl naphthyl group, and the like. Among these, an allyl group is preferred.
  • the carbon-carbon double bond-containing liquid compound (C) is a compound that is liquid at 25°C. Since the carbon-carbon double bond-containing liquid compound (C) is a compound that is liquid at 25° C., the curable adhesive composition of the present invention remains stable during lamination even after undergoing the reaction of the first curing system. It has good wetting and spreading properties and is excellent in lamination aptitude. "Liquid at 25°C” means having fluidity at 25°C.
  • a compound that is liquid at 25° C. is a compound with a viscosity of 2 to 10000 mPa ⁇ s measured at 25° C. and 1.0 rpm using an E-type viscometer.
  • the carbon-carbon double bond-containing liquid compound (C) is preferably a non-aromatic compound.
  • a non-aromatic compound means a compound without an aromatic ring. Since the carbon-carbon double bond-containing liquid compound (C) is a non-aromatic compound, the cured product of the curable adhesive composition containing the carbon-carbon double bond-containing liquid compound (C) is more It tends to have excellent low dielectric properties.
  • the carbon-carbon double bond-containing liquid compound (C) is preferably a compound having a heterocyclic skeleton.
  • the carbon-carbon double bond-containing liquid compound (C) is a compound having a heterocyclic skeleton, it becomes easier to obtain a curable adhesive composition that gives a cured product with excellent adhesive strength and low dielectric properties.
  • the component (C) is a curable adhesive composition that is a compound having a heterocyclic skeleton, the curable adhesive composition contains, as another component, other carbon- It may contain a carbon double bond-containing liquid compound.
  • the content of the other carbon-carbon double bond-containing liquid compound is preferably 0 to 50 parts by mass, more than 100 parts by mass of the total amount of the compound having a heterocyclic skeleton. It is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
  • the heterocyclic skeleton includes an isocyanurate skeleton and a glycoluril skeleton.
  • the heterocyclic skeleton preferably has an n-fold rotation axis as a symmetry element.
  • a cured product of a curable adhesive composition containing such a carbon-carbon double bond-containing liquid compound (C) having a heterocyclic skeleton tends to be more excellent in low dielectric properties.
  • the molecular weight of the carbon-carbon double bond-containing liquid compound (C) is preferably 1,000 or less, more preferably 800 or less, still more preferably 650 or less, and even more preferably 500 or less. Compounds with a molecular weight of 1,000 or less tend to meet the requirement of being liquid at 25°C. Further, the molecular weight of the carbon-carbon double bond-containing liquid compound (C) is preferably 100 or more, more preferably 200 or more, and even more preferably 275 or more. If the compound has a molecular weight of 100 or more, the carbon-carbon double bond-containing liquid compound (C) is difficult to volatilize even in the drying process and the heat curing process of the curable adhesive composition, so it has the desired physical properties. A cured product can be easily obtained.
  • Examples of the carbon-carbon double bond-containing liquid compound (C) include compounds having an isocyanurate skeleton and compounds having a glycoluril skeleton.
  • Examples of the carbon-carbon double bond-containing liquid compound (C) having an isocyanurate skeleton include compounds represented by the following formula (1) or (2).
  • R 1 and R 2 each independently represent a hydrocarbon group having a double bond at the end;
  • R 3 is a saturated hydrocarbon group having 1 to 15 carbon atoms; represents an alkoxy group-substituted alkyl group.
  • R 4 to R 6 each independently represent a hydrocarbon group having a double bond at its end.
  • hydrocarbon groups having a double bond at the end represented by R 1 , R 2 , R 4 , R 5 and R 6 are as explained above.
  • the saturated hydrocarbon group represented by R 3 has 1 to 15 carbon atoms, preferably 5 to 15 carbon atoms, and more preferably 8 to 15 carbon atoms.
  • saturated hydrocarbon groups represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, etc. is mentioned.
  • the alkoxy group-substituted alkyl group represented by R 3 has 2 to 15 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.
  • the alkoxy-substituted alkyl group represented by R 3 includes methoxymethyl group, ethoxymethyl group, 2-methoxyethoxymethyl group, benzyloxymethyl group and the like.
  • Examples of the carbon-carbon double bond-containing liquid compound (C) having a glycoluril skeleton include compounds represented by the following formula (3).
  • R 7 to R 10 each independently represent a hydrocarbon group having 1 to 15 carbon atoms, at least two of which are hydrocarbon groups having double bonds at their ends.
  • R 11 and R 12 each represent a hydrogen atom or a saturated hydrocarbon group having 1 to 15 carbon atoms.
  • a compound having an isocyanurate skeleton is preferable as the carbon-carbon double bond-containing liquid compound (C) because it has an appropriate cross-linking density and is easy to obtain a cured product having excellent low dielectric properties.
  • a compound represented by formula (1) and more preferably a compound represented by the following formula.
  • R represents a saturated hydrocarbon group having 5 to 15 carbon atoms, preferably a saturated hydrocarbon group having 8 to 15 carbon atoms.
  • the content of the carbon-carbon double bond-containing liquid compound (C) (two or more (C) When containing components, the total amount of these) is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably It is 8.5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • a curable adhesive that has a carbon-carbon double bond-containing liquid compound (C) content of 25% by mass or less in the total amount of active ingredients in the curable adhesive composition, thereby providing a cured product having excellent low dielectric properties. It becomes easy to obtain a composition.
  • the content of the curable compound (C) (two or more curable compounds (C)
  • the total amount of these when containing) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 30 It is not more than 25 parts by mass, more preferably not more than 20 parts by mass, and even more preferably not more than 16 parts by mass.
  • the carbon-carbon double bond-containing polymer (D) is a polymer having a hydrocarbon group with a double bond at its end. By including the carbon-carbon double bond-containing polymer (D) in the second curing system, it becomes easier to obtain a curable adhesive composition that gives a cured product with excellent adhesive strength and heat resistance.
  • the carbon-carbon double bond-containing polymer (D) can be used singly or in combination of two or more.
  • the number of hydrocarbon groups having double bonds at their ends contained in the carbon-carbon double bond-containing polymer (D) is preferably 2 to 4, more preferably 2.
  • a curable adhesive composition that provides a cured product with excellent adhesive strength and heat resistance and with suppressed crack generation can be obtained. easier to get.
  • the carbon number of the hydrocarbon group having a double bond at the end contained in the carbon-carbon double bond-containing polymer (D) is preferably 2-20, more preferably 2-15.
  • Hydrocarbon groups having a double bond at the end include vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, 1-methyl-2-propenyl group and vinylbenzyl group. , a vinyl naphthyl group, and the like.
  • a vinylbenzyl group is preferable because a cured product having excellent low dielectric properties can be easily obtained.
  • the number average molecular weight (Mn) of the carbon-carbon double bond-containing polymer (D) is preferably 500-5,000, more preferably 500-3,000.
  • the number average molecular weight (Mn) of the carbon-carbon double bond-containing polymer (D) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. , the specific measurement conditions are as described above.
  • Examples of the carbon-carbon double bond-containing polymer (D) include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamideimide-based resins, polyvinyl butyral-based resins, polycarbonate-based resins, and polyphenylene ether-based resins.
  • the content of the carbon-carbon double bond-containing polymer (D) (two or more (D) When containing components, the total amount of these) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably It is 10% by mass or more, more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.
  • the content of the carbon-carbon double bond-containing polymer (D) is 30% by mass or less based on the total amount of active ingredients in the curable adhesive composition, it becomes easier to impart sticking properties.
  • the content of the carbon-carbon double bond-containing polymer (D) is based on 100 parts by mass of component (A).
  • the amount (when two or more components (D) are included, the total amount thereof) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and even more preferably 20 parts by mass. parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the carbon-carbon double bond-containing polymer (D) is a modified hydrocarbon group having a double bond at the end.
  • a polyphenylene ether resin (hereinafter sometimes referred to as "carbon-carbon double bond-containing polymer (D')") is preferred.
  • the curable adhesive composition contains, as another component, the component (D') Other carbon-carbon double bond-containing polymers may be contained.
  • the content of the other carbon-carbon double bond-containing polymer is preferably 0 to 50 parts by mass, more preferably 0 to 50 parts by mass, based on 100 parts by mass of the total amount of the component (D'). is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
  • a polyphenylene ether resin is a resin having a polyphenylene skeleton in its main chain.
  • a polyphenylene skeleton refers to a skeleton having a repeating unit represented by the following formula or a repeating unit in which hydrogen atoms in the above formula are substituted.
  • the carbon-carbon double bond-containing polymer (D') is a compound having a polyphenylene ether skeleton and a hydrocarbon group having a double bond at its end. Since the carbon-carbon double bond-containing polymer (D') has a polyphenylene ether skeleton, the cured product of the curable adhesive composition containing the carbon-carbon double bond-containing polymer (D') has a low dielectric Excellent properties.
  • Examples of the polyphenylene ether skeleton in the carbon-carbon double bond-containing polymer (D') include those represented by the following formula (4).
  • X is a divalent group represented by the following formula (5) or formula (6)
  • each Y is independently a divalent group represented by the following formula (7) is a group
  • a and b are integers of 0 to 100, and at least one of a and b is 1 or more.
  • * represents a bond (same below).
  • R 13 to R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
  • R 21 to R 28 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
  • A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
  • R 29 to R 32 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
  • Examples of the polyphenylene ether skeleton in the carbon-carbon double bond-containing polymer (D') include those represented by the following formula (8).
  • Examples of the hydrocarbon group having a double bond at the end in the carbon-carbon double bond-containing polymer (D') include those described above. Among them, a vinylbenzyl group is more preferable because a cured product having excellent low dielectric properties can be easily obtained.
  • the carbon-carbon double bond-containing polymer (D') As the carbon-carbon double bond-containing polymer (D'), a resin having a hydrocarbon group having a double bond at both ends of a polyphenylene ether skeleton, since a cured product having excellent low dielectric properties can be easily obtained. is preferred.
  • the component (D) is a curable adhesive composition that is a resin having a hydrocarbon group having a double bond at the end at both ends of a polyphenylene ether skeleton
  • the curable adhesive composition includes other components may contain a carbon-carbon double bond-containing polymer other than the resin.
  • the content of the other carbon-carbon double bond-containing polymer is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the resin. parts by weight, more preferably 0 to 10 parts by weight, and even more preferably 0 to 5 parts by weight.
  • the carbon-carbon double bond-containing polymer (D') can be obtained by forming a polyphenylene ether skeleton and then introducing a "hydrocarbon group having a double bond at the end" at the end.
  • a carbon-carbon double bond-containing polymer (D') having vinylbenzyl groups at both ends is reacted with a bifunctional phenol compound and a monofunctional phenol compound to obtain a polymer having phenolic hydroxyl groups at both ends.
  • it can be obtained by vinylbenzyl etherifying the terminal phenolic hydroxyl group using 4-(chloromethyl)styrene.
  • Examples of the carbon-carbon double bond-containing polymer (D') include those represented by the following formula (9).
  • the curable adhesive composition of the present invention preferably contains a cationic polymerization initiator, and the cationic polymerization initiator initiates the reaction of the second curing system.
  • the stability and reactivity of the second curing system can be adjusted by appropriately selecting a cationic polymerization initiator having reactivity according to the purpose. can be done.
  • a cationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
  • Thermal cationic polymerization initiators are compounds that can generate cationic species that initiate polymerization upon heating.
  • Thermal cationic polymerization initiators include sulfonium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.
  • Sulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris(4-methoxyphenyl)sulfonium hexafluoroalcinate, and diphenyl(4-phenylthiophenyl)sulfonium. hexafluoroalcinate and the like.
  • the quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N,N-dimethyl-N- benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyltrifluoromethanesulfonate , N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
  • Phosphonium salts include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.
  • iodonium salts include diphenyliodonium hexafluoroarsinate, bis(4-chlorophenyl)iodonium hexafluoroarsinate, bis(4-bromophenyl)iodonium hexafluoroarsinate, phenyl(4-methoxyphenyl)iodonium hexafluoroarsinate, and the like. is mentioned.
  • the curable adhesive composition of the present invention contains a cationic polymerization initiator
  • at least part of the cationic polymerization initiator has a peak top temperature of an exothermic peak obtained by differential scanning calorimetry under the following conditions. It is preferably a high temperature reactive thermal cationic polymerization initiator exceeding 120°C. (Differential scanning calorimetry conditions)
  • a mixture containing 0.1 part by mass of a cationic polymerization initiator to be measured, 100 parts by mass of bisphenol A diglycidyl ether, and 0.1 part by mass of ⁇ -butyrolactone was used as a measurement sample, and the temperature was changed from 30°C to 300°C. Differential scanning calorimetry is performed at a heating rate of 10° C./min to measure the peak temperature of the exothermic peak.
  • the temperature at which the reaction of the second curing system proceeds tends to exceed 120°C.
  • the peak top temperature of the exothermic peak of the high-temperature reactive thermal cationic polymerization initiator is preferably 250° C. or less from the viewpoint of preventing the temperature when curing the curable adhesive composition from becoming too high.
  • Examples of commercially available high-temperature reactive thermal cationic polymerization initiators include San-Aid SI-B3, San-Aid SI-B4, San-Aid SI-B5, and San-Aid SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.). .
  • the content of the cationic polymerization initiator is preferably 100 parts by mass in total of the cationic polymerizable compounds (C) and (D). is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 6 parts by mass or less, It is more preferably 5 parts by mass or less, still more preferably 4 parts by mass or less.
  • the content of the cationic polymerization initiator is 0.01 parts by mass or more, it becomes easier to prevent a decrease in reactivity.
  • the content of the cationic polymerization initiator is 6 parts by mass or less, it becomes easy to suppress corrosion of the adherend.
  • thermal cationic polymerization initiator When a thermal cationic polymerization initiator is used as the cationic polymerization initiator, differential scanning calorimetry is performed under the following conditions to grasp the thermal stability and reactivity of the thermal cationic polymerization initiator, and to determine the reaction of the second curing system. It is preferable to adjust the reaction initiation temperature.
  • the peak top temperature of the exothermic peak of benzyl(4-hydroxyphenyl)(methyl)sulfonium tetrakis(pentafluorophenyl)borate is 140.degree.
  • the thermal cationic polymerization initiator preferably has an exothermic peak top temperature of 120 to 180.degree. C., more preferably 130 to 160.degree.
  • the curable adhesive composition of the invention may contain a silane coupling agent.
  • the silane coupling agent may be involved in the reaction of the first curing system, or may be involved in the reaction of the second curing system. It may not be involved. Whether the silane coupling agent to be used participates in the reaction of the first curing system or the reaction of the second curing system is usually determined by the reactivity of the substituent in the silane coupling agent.
  • a silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
  • silane coupling agent can be used as the silane coupling agent.
  • organosilicon compounds having at least one alkoxysilyl group in the molecule are preferred.
  • Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri
  • a silane coupling agent having a (meth)acryloyl group such as methoxysilane
  • Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy)silane; 2-(3,4-epoxycyclohexyl)ethyltrimeth
  • a silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the silane coupling agent (the total amount when two or more silane coupling agents are included) is It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and preferably 5% by mass or less with respect to the total amount (100% by mass) of the active ingredient. , more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
  • the content of the silane coupling agent When the content of the silane coupling agent is 0.01% by mass or more based on the total amount of active ingredients in the curable adhesive composition, it becomes easier to maintain the adhesiveness after the high-temperature and high-humidity test. When the content of the silane coupling agent is 5% by mass or less in the total amount of active ingredients in the curable adhesive composition, it becomes easier to maintain the adhesiveness after the high-temperature and high-humidity test.
  • the content of the silane coupling agent with respect to 100 parts by mass of component (A) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.15 parts by mass or more, and is preferably is 3 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.7 parts by mass or less, and even more preferably 0.5 parts by mass or less.
  • the curable adhesive composition of the present invention may be in the form of a solution containing a solvent.
  • solvents include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like. These solvents can be used singly or in combination of two or more. When the curable adhesive composition contains a solvent, the content of the solvent can be appropriately determined in consideration of applicability and the like.
  • the curable adhesive composition of the present invention may contain components (other components) other than those described above as long as the effects of the present invention are not impaired.
  • Other components include additives such as UV absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders and softeners. These can be used individually by 1 type or in combination of 2 or more types. When the curable adhesive composition of the present invention contains these additives, the content thereof can be appropriately determined according to the purpose.
  • the curable adhesive composition of the present invention can be prepared by appropriately mixing and stirring a binder resin (A), a cross-linking agent (B), a compound having a carbon-carbon double bond, and other optional components in a conventional manner. can be prepared.
  • the method of using the curable adhesive composition of the present invention is not particularly limited.
  • the curable adhesive composition of the present invention is applied to one adherend, the resulting coating film is dried, and the reaction of the first curing system is allowed to proceed to form a crosslinked structure in the coating film. Form. Then, after another adherend is superimposed on this coating film, these adherends can be adhered by advancing the reaction of the second curing system.
  • Examples of methods for applying the curable adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • Methods for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
  • the conditions for drying the coating film are, for example, 80 to 120° C. for 30 seconds to 5 minutes.
  • the drying treatment of the coating film can be combined with the reaction of the first curing system.
  • the thickness of the coating film is not particularly limited, it is usually 1 to 50 ⁇ m, preferably 1 to 25 ⁇ m, more preferably 5 to 25 ⁇ m.
  • an adhesive sheet may be produced using the curable adhesive composition of the present invention, and two adherends may be bonded using this adhesive sheet.
  • the curable adhesive composition of the present invention is applied onto a release film, the resulting coating film is dried, and the coating film having a crosslinked structure (adhesion adhesive layer of the sheet).
  • the method for applying the curable adhesive composition and the method for drying may be those described above.
  • the preferable thickness of the coating film and the point of combining the drying treatment of the coating film and the reaction of the first curing system are also as described above.
  • the curable adhesive composition of the present invention preferably gives a cured product having a dielectric loss tangent of less than 0.0050 at 23° C. and a frequency of 1 GHz by curing the curable adhesive composition, and preferably 0.0030 or less.
  • Those that give a cured product are more preferred, those that give a cured product of 0.0020 or less are more preferred, those that give a cured product of 0.0015 or less are more preferred, and those that give a cured product of 0.0012 or less are even more preferred.
  • the dielectric loss tangent it is usually 0.0001 or more.
  • the curable adhesive composition of the present invention preferably gives a cured product having a dielectric constant of 3.00 or less at 23° C. and a frequency of 1 GHz by curing the curable adhesive composition, and preferably 2.75 or less. more preferably give a cured product of 2.50 or less. Although there is no particular lower limit for the dielectric constant under these conditions, it is usually 2.00 or more.
  • the cured state of the sample used for the measurement of the dielectric loss tangent and the dielectric constant is not limited as long as the measurement is possible.
  • An example of a sample for measurement of dielectric loss tangent and dielectric constant is a coating film after drying and heat treatment at 100° C. for 2 minutes as a reaction of the first curing system.
  • the curable adhesive composition of the present invention gives a cured product having the above-described dielectric properties through a curing reaction
  • the curable adhesive composition of the present invention can be used as an adhesive member, protective member, or the like in an electronic device. , as a material for forming insulating members and the like.
  • the cured product of the present invention is the following cured product ( ⁇ ) or cured product ( ⁇ ).
  • Cured product ( ⁇ ) A cured product whose raw material composition is the curable adhesive composition of the present invention, and which satisfies the following requirement 3.
  • Requirement 3 The gel fraction is 50% by mass or more.
  • the cured product ( ⁇ ) is a cured product whose raw material composition is the curable adhesive composition of the present invention and which satisfies the requirements 1 and 2 above.
  • the gel fraction of the cured product ( ⁇ ) is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
  • a cured product having a gel fraction of 10% by mass or more has a sufficient internal crosslinked structure. Therefore, even if such a cured product is subjected to heat treatment such as hot press treatment, a large amount of the adhesive component does not ooze out, and contamination of the surroundings is suppressed.
  • the gel fraction of the cured product ( ⁇ ) is usually 70% by mass or less, preferably 60% by mass or less, and more preferably less than 50% by mass.
  • a cured product ( ⁇ ) having a gel fraction of 70% by mass or less tends to be excellent in curability and adhesion to an adherend.
  • the gel fraction of the cured product ( ⁇ ) can be calculated by conducting an experiment in which a measurement sample is immersed in toluene at 23° C. for 168 hours, as described in Examples.
  • the cured product ( ⁇ ) has further thermosetting properties.
  • the curability of the cured product ( ⁇ ) is usually due to both the reaction of the first curing system and the reaction of the second curing system (the components of the first curing system partially remain unreacted). or only due to the reaction of the second curing system (if the reaction of the first curing system is already complete).
  • the cured product ( ⁇ ) preferably has a sheet-like shape. Since the cured product ( ⁇ ) has a sheet-like shape, it is possible to efficiently bond two adherends by heat press treatment or the like.
  • thermosetting sheet-like adhesive A sheet-like cured product ( ⁇ ) (hereinafter sometimes referred to as “thermosetting sheet-like adhesive”) may be covered with a protective sheet or the like on one or both sides for protection during storage or transportation. may have
  • thermosetting sheet-like adhesive When the thermosetting sheet-like adhesive is excellent in low dielectric properties, the thermosetting sheet-like adhesive is suitable as a sheet-like adhesive for electronic devices and a sheet-like adhesive for coverlay films. Used.
  • Sheet-like adhesives for electronic devices are sheet-like adhesives used for bonding various parts in electronic devices and for protecting and insulating circuits in electronic devices.
  • Examples of electronic devices include communication devices such as smartphones and tablet terminals.
  • a sheet-like adhesive for a coverlay film is a sheet-like adhesive used when manufacturing a coverlay film.
  • a coverlay film is, for example, a laminated film used to protect the surface of a flexible printed wiring board, and usually has an insulating resin layer and an adhesive layer.
  • a thermosetting sheet adhesive is useful as this adhesive layer.
  • Step I Step of curing the curable adhesive composition of the present invention at a temperature of 120° C. or less
  • the curable adhesive composition of the present invention has a first curing system in which the reaction proceeds at a temperature of 120°C or less.
  • Step I advances the reaction of this first curing system to build a crosslinked structure within the curable adhesive composition.
  • the heating temperature in step I is 120° C. or lower, preferably 110° C. or lower.
  • the heating temperature in step I is usually 0° C. or higher, preferably 20° C. or higher.
  • the heating time in step I is usually 0.5 to 5 minutes, preferably 1 to 3 minutes.
  • the cured product ( ⁇ ) is a cured product whose raw material composition is the curable adhesive composition of the present invention and which satisfies requirement 3 above.
  • the cured product ( ⁇ ) has a gel fraction of 50% by mass or more, preferably 55% by mass or more.
  • the cured product ( ⁇ ) is used, for example, as an adhesive member, protective member, insulating member, etc. for electronic devices.
  • the cured product ( ⁇ ) has a gel fraction of 50% by mass or more, sufficient performance can be exhibited in these applications.
  • the gel fraction of the cured product ( ⁇ ) is usually 95% by mass or less, preferably 90% by mass or less.
  • the gel fraction of the cured product ( ⁇ ) can be determined by a method similar to the method for calculating the gel fraction of the cured product ( ⁇ ).
  • Step IIa The curable adhesive composition of the present invention is cured at a temperature of 120°C or less to form a cured product.
  • Step IIb The cured product formed in Step IIa is further cured at a temperature above 120°C.
  • Step III Step of curing the curable adhesive composition of the present invention under elevated temperature conditions such that the reaction initiation temperature is 120°C or less and the reaction completion temperature is above 120°C.
  • the curable adhesive composition of the present invention comprises a first curing system in which the reaction proceeds at a temperature of 120°C or less and a second curing system in which the reaction proceeds at a temperature above 120°C. have.
  • the "method for producing a cured product ( ⁇ )" of the present invention is a method for producing a cured product by utilizing the reaction of the first curing system and the reaction of the second curing system.
  • the production method having Step IIa and Step IIb is a method for producing a cured product ( ⁇ ) in two steps from a curable adhesive composition. That is, the cured product ( ⁇ ) can be obtained by curing the curable adhesive composition of the present invention at a temperature of 120° C. or lower. Next, by heating the cured product ( ⁇ ) at a temperature higher than 120° C., the reaction of the second curing system can be advanced to obtain the cured product ( ⁇ ).
  • Step IIa is as described as the method for producing the cured product ( ⁇ ).
  • the heating temperature in step IIb is higher than 120° C., preferably 140° C. or higher, more preferably 150° C. or higher, and preferably 180° C. or lower.
  • the heating time in step IIb is generally 0.5 to 3 hours, preferably 1 to 2 hours.
  • Step III is a method of producing a cured product ( ⁇ ) in one step from a curable adhesive composition. That is, by curing the curable adhesive composition of the present invention under a temperature elevation condition in which the reaction start temperature is 120° C. or less and the reaction end temperature is more than 120° C., the first curing is mainly performed from the beginning to the middle stage. The reaction of the system is allowed to proceed, and from the middle stage to the end stage, the reaction of the second curing system is mainly allowed to proceed, and the cured product ( ⁇ ) can be obtained.
  • the reaction initiation temperature of the temperature rising conditions in step III is 120° C. or lower, preferably 110° C. or lower.
  • the reaction initiation temperature of the temperature rising conditions in step III is usually 0° C. or higher, preferably 20° C. or higher.
  • the temperature at which the reaction is completed in the elevated temperature conditions in step III is higher than 120°C, preferably 140°C or higher, and more preferably 150 to 180°C.
  • the heating time in step III is usually 0.5 to 3 hours, preferably 1 to 2 hours.
  • Binder resin (A1) maleic anhydride-modified ⁇ -olefin polymer [manufactured by Mitsui Chemicals, trade name: UNISTOL H-200, number average molecular weight: 47,000]
  • Isocyanate-based cross-linking agent (B1) 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione [manufactured by Mitsui Chemicals, Inc., trade name: Stabio D-370N, molecular weight: 462]
  • Binder resin (A1) 100 parts by mass, isocyanate cross-linking agent (B1) 0.5 parts by mass, curable compound (C1) 12.5 parts by mass, polyphenylene ether resin (D1) 25 parts by mass, cationic polymerization initiator (E1) 0.12 parts by mass and 0.2 parts by mass of the silane coupling agent (F1) were dissolved in toluene to prepare a curable adhesive composition.
  • the obtained curable adhesive composition is applied on the release-treated surface of a release sheet (first release sheet, manufactured by Lintec Corporation, trade name: SP-PET752150) to form a coating film, and the resulting coating is The film was dried at 100° C.
  • An adhesive sheet was obtained by laminating the release-treated surface of another release sheet (second release sheet, product name: SP-PET381130, manufactured by Lintec Corporation) on the exposed surface of the adhesive layer.
  • the test sample was taken out, dried in an oven at 100°C for 2 hours, and then allowed to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%.
  • FIG. 1 is a schematic plan view of the laminated body used for evaluating the exudation of the adhesive component in the examples after being subjected to a heat press treatment. As shown in FIG.
  • the maximum value X of the distance between the oozing adhesive component 2 and the polyimide film 3 when viewed from the top is defined as "the oozing length of the adhesive component", and is shown in Table 1. described.
  • the curable adhesive compositions obtained in Examples 1-5 have a first curing system and a second curing system. When these curable adhesive compositions are used, exudation of the adhesive component is suppressed by forming a crosslinked structure in the coating film using the reaction of the first curing system and then carrying out the adhesion step. can do.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2022/015344 2021-03-30 2022-03-29 硬化性接着剤組成物、硬化物、及び硬化物の製造方法 WO2022210673A1 (ja)

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JP2015086330A (ja) * 2013-10-31 2015-05-07 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、金属張積層板、及びプリント配線板
WO2016147984A1 (ja) * 2015-03-13 2016-09-22 京セラ株式会社 樹脂組成物、プリプレグ、金属張積層板および配線基板
JP2017031301A (ja) * 2015-07-31 2017-02-09 東洋インキＳｃホールディングス株式会社 熱硬化性接着シート、およびその利用
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JP2018173549A (ja) * 2017-03-31 2018-11-08 リンテック株式会社 粘着性組成物、粘着剤、粘着シートおよび表示体
JP2020029557A (ja) * 2018-08-21 2020-02-27 東洋紡株式会社 接着剤組成物、積層体、およびリチウムイオン電池用包装材料
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JP2011148919A (ja) * 2010-01-22 2011-08-04 Panasonic Electric Works Co Ltd 樹脂組成物、樹脂組成物の製造方法、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板
JP2015086330A (ja) * 2013-10-31 2015-05-07 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、金属張積層板、及びプリント配線板
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