WO2023002970A1 - 硬化性接着剤組成物、及び硬化性接着シート - Google Patents

硬化性接着剤組成物、及び硬化性接着シート Download PDF

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Publication number
WO2023002970A1
WO2023002970A1 PCT/JP2022/027985 JP2022027985W WO2023002970A1 WO 2023002970 A1 WO2023002970 A1 WO 2023002970A1 JP 2022027985 W JP2022027985 W JP 2022027985W WO 2023002970 A1 WO2023002970 A1 WO 2023002970A1
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mass
curable adhesive
component
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group
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PCT/JP2022/027985
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 西嶋
幹広 樫尾
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Lintec Corp
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Lintec Corp
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Priority to JP2023536748A priority Critical patent/JPWO2023002970A1/ja
Priority to CN202280048731.6A priority patent/CN117616097A/zh
Priority to KR1020247000736A priority patent/KR20240036556A/ko
Publication of WO2023002970A1 publication Critical patent/WO2023002970A1/ja
Anticipated expiration legal-status Critical
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a curable adhesive composition and a curable adhesive sheet.
  • FPC flexible printed wiring boards
  • An FPC can be manufactured by, for example, etching the copper foil of a copper-clad laminate in which a copper foil is bonded to an insulating resin film such as polyimide to form an electric circuit.
  • a coverlay sheet having an insulating resin base material and an adhesive layer is attached to a copper foil on which an electric circuit is formed to protect the electric circuit.
  • Patent Document 1 discloses an adhesive composition containing a base film, a styrene-based elastomer containing a carboxyl group, and an epoxy resin on at least one surface of the base film.
  • Patent Document 1 The laminate described in Patent Document 1 is said to have high adhesiveness to, for example, a base film made of a polyimide resin or the like and a copper foil, but further improvements are required including other properties.
  • a curable adhesive composition capable of forming an adhesive layer or a cured product thereof that is excellent in various properties and is suitable for use as a coverlay sheet.
  • the present invention provides a binder resin having a reactive functional group, a polyphenylene ether resin having a vinyl group and having a number average molecular weight within a predetermined range, and a polyfunctional polyphenylene ether resin having two or more unsaturated hydrocarbon groups having a double bond at the end. and a curable adhesive sheet having an adhesive layer formed from the curable adhesive composition.
  • a curable adhesive sheet having an adhesive layer formed from the curable adhesive composition.
  • one aspect provided by the present invention is as follows. [1] Binder resin (A) having a reactive functional group, A polyphenylene ether resin (B) having a vinyl group and having a number average molecular weight of 1500 or more and less than 5000, and a polyfunctional compound (C) having two or more unsaturated hydrocarbon groups having terminal double bonds.
  • a curable adhesive composition comprising: [2] The curable adhesive composition according to [1], further comprising a cationic polymerization initiator (D). [3] The curable adhesive composition according to [1] or [2] above, wherein the content of component (B) is 99.0 parts by mass or less with respect to 100 parts by mass of the total amount of component (A). thing. [4] Any one of [1] to [3] above, wherein the content of component (A) is more than 20% by mass with respect to the total amount of active ingredients in the curable adhesive composition. curable adhesive composition. [5] The curable adhesive composition according to any one of [1] to [4] above, further comprising a cross-linking agent (E) capable of reacting with the reactive functional group of component (A).
  • curable adhesive composition [10] The curable adhesive composition according to any one of [1] to [9] above, wherein the component (C) comprises a polyfunctional compound (C1) having two unsaturated hydrocarbon groups. thing. [11] The curable adhesive composition according to [10] above, wherein the component (C1) is a polyfunctional compound having two unsaturated hydrocarbon groups and one saturated hydrocarbon group.
  • component (C) contains a compound (C11) represented by the following general formula (c-11): .
  • R a represents a saturated hydrocarbon group.
  • component (A) comprises an olefin resin (A1) having a reactive functional group.
  • the content of the inorganic filler is 0 to 30% by mass with respect to the total amount of active ingredients in the curable adhesive composition. curable adhesive composition.
  • the curable adhesive composition of a preferred embodiment of the present invention has excellent balance of various properties (e.g., adhesive strength, dielectric properties, effect of suppressing bleeding of adhesive components, etc.) that can be suitably applied to coverlay sheets.
  • An adhesive layer or a cured product thereof can be formed.
  • FIG. 2 is a schematic cross-sectional view in the thickness direction of the adhesive sheet, showing an example of the configuration of the curable adhesive sheet of one embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing the state of a test sample after hot pressing for explaining the procedure for evaluating the exudation of the adhesive component.
  • the term "active ingredient" of the curable adhesive composition means a component excluding water and a diluent such as an organic solvent among the components contained in the curable adhesive composition.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the curable adhesive composition of the present invention has a binder resin (A) having a reactive functional group (hereinafter also referred to as “component (A)”), a vinyl group, and a number average molecular weight of 1500 or more and less than 5000.
  • component (A) a reactive functional group
  • component (B) a certain polyphenylene ether resin
  • component (C) a polyfunctional compound having two or more unsaturated hydrocarbon groups having double bonds at the ends
  • a curable adhesive sheet having an adhesive layer is obtained by applying the adhesive layer to an adherend such as a circuit board, curing the cured product, and adhering it to the adherend.
  • adherends such as circuit boards
  • further improvement in adhesive strength of the cured product to adherends such as circuit boards is desired.
  • the frequency of electric signals has been increased in order to handle larger amounts of data. Since electric signals in a high frequency range (for example, 1 GHz or higher) are likely to be converted into heat, transmission loss tends to increase as the frequency of electric signals increases.
  • the curable adhesive composition of one embodiment of the present invention contains component (A), component (B), and component (C), thereby achieving adhesive strength, low dielectric properties, and adhesive components.
  • the curable adhesive composition of one aspect of the present invention can react with the cationic polymerization initiator (D) (hereinafter also referred to as “component (D)”) and the reactive functional group of component (A). Further containing one or more selected from a cross-linking agent (E) (hereinafter also referred to as “component (E)”) and a silane coupling agent (F) (hereinafter also referred to as “component (F)”) is preferred.
  • the curable adhesive composition of one embodiment of the present invention may contain additives other than these components (A) to (F) within a range that does not impair the effects of the present invention.
  • the curable adhesive composition of one aspect of the present invention it is possible to form an adhesive layer or a cured product thereof in which various properties such as adhesive strength, low dielectric properties, and effect of suppressing bleeding of adhesive components are improved in a well-balanced manner.
  • the total content of component (A), component (B) and component (C) is preferably 50% by mass or more with respect to the total amount of active ingredients in the curable adhesive composition, More preferably 55% by mass or more, more preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, still more preferably 80% by mass or more, and even more Preferably 85% by mass or more, particularly preferably 90% by mass or more, and 100% by mass or less, 99.99% by mass or less, 99.90% by mass or less, 99.70% by mass or less, or 99.50% by mass % or less.
  • the content is preferably 50% by mass or more, more preferably 55% by mass or more, more preferably 60% by mass or more, more preferably 65% by mass or more, relative to the total amount of active ingredients in the curable adhesive composition. , More preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and 100% by mass or less If it is Details of each component contained in the curable adhesive composition of one embodiment of the present invention are described below.
  • a curable adhesive composition of one aspect of the present invention contains a binder resin (A) having a reactive functional group.
  • the adhesive layer formed from the composition is applied to an adherend such as a circuit board and cured to adhere to the adherend in the adhesion step. , the phenomenon in which the adhesive component oozes out from the ends is less likely to occur.
  • the curable adhesive composition of one embodiment of the present invention can form an adhesive layer that is highly effective in suppressing bleeding of the adhesive component by containing the binder resin (A).
  • the binder resin (A) may be used alone or in combination of two or more.
  • the content of component (A) is such that the adhesive component seeps out with respect to the total amount (100% by mass) of the active ingredients of the curable adhesive composition. From the viewpoint of making the composition capable of forming an adhesive layer with a high inhibitory effect and making it possible to form a cured product with further improved low dielectric properties, it is preferably more than 20% by mass, more preferably 22% by mass.
  • % or more more preferably 25 mass % or more, more preferably 27 mass % or more, still more preferably 30 mass % or more, still more preferably 35 mass % or more, still more preferably 40 mass % or more, still more preferably 45 mass %
  • it is particularly preferably 50% by mass or more, and may be 52% by mass or more, 55% by mass or more, 57% by mass or more, 60% by mass or more, 62% by mass or more, or 65% by mass or more
  • it is preferably 95% by mass or less, more preferably 90% by mass or less. , more preferably 85% by mass or less, still more preferably 80% by mass or less, still more preferably 75% by mass or less, even more preferably 72% by mass or less, and particularly preferably 70% by mass or less.
  • the number average molecular weight (Mn) of the binder resin (A) used in one embodiment of the present invention is preferably 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, and 10. 000 or more, more preferably 12,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, still more preferably 25,000 or more, still more preferably 30,000 or more, still more preferably 32, 000 or more, particularly preferably 35,000 or more, and may be 37,000 or more, 39,000 or more, 40,000 or more, 42,000 or more, or 45,000 or more. is preferably 200,000 or less, more preferably 150,000, from the viewpoint of obtaining good solubility in the dilution solvent of component (A) and making the composition excellent in coatability. Below, more preferably 100,000 or less, still more preferably 80,000 or less, still more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 55,000 or less.
  • the binder resin (A) used in one aspect of the present invention may have a reactive functional group as a side chain with respect to the main chain resin.
  • Reactive functional groups possessed by the binder resin (A) include, for example, a carboxy group, a carboxylic anhydride structure, a carboxylic acid ester, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, and isocyanate. groups, acetyl groups, thiol groups, sulfone groups, phosphonic groups, nitro groups, halogen atoms, alkoxysilyl groups, and the like.
  • the reactive functional groups possessed by the binder resin (A) may be composed of one type alone, or may be composed of a combination of two or more types.
  • the reactive functional groups possessed by the binder resin (A) include a carboxy group, a group having a carboxylic anhydride structure, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, an isocyanate group, A composition that is preferably a group selected from an acetyl group, a thiol group, an ether group, a thioether group, a sulfone group, a phosphonic group, a nitro group, a urethane group, a halogen atom, and an alkoxysilyl group, and which can form a cured product with excellent adhesive strength.
  • a group selected from groups having a carboxy group and a carboxylic anhydride structure is more preferable, and from the viewpoint of a composition capable of forming a cured product having excellent adhesive strength and low dielectric properties, a carboxylic acid Groups having an anhydride structure are more preferred.
  • resins that form the main chain of the binder resin (A) include polyolefin resins, phenoxy resins, polyimide resins, polyamideimide resins, polyvinyl butyral resins, polycarbonate resins, and styrene resins.
  • the binder resin (A) used in one aspect of the invention preferably contains one or more selected from a polyolefin resin having a reactive functional group and a styrene resin having a reactive functional group. It is more preferable to include at least a polyolefin resin (A1) having
  • the content of the polyolefin resin (A1) is, from the viewpoint of forming a composition capable of forming a cured product having excellent low dielectric properties, the curable adhesive composition Preferably 50 to 100% by mass, more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, more preferably 80 to 100% by mass, relative to the total amount (100% by mass) of component (A) contained in % by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass.
  • the polyolefin-based resin (A1) used in one aspect of the present invention may be a polymer having a structural unit derived from an olefin-based monomer, and may be a polymer consisting only of structural units derived from an olefin-based monomer. It may be a copolymer having a structural unit derived from an olefinic monomer and a structural unit derived from a monomer copolymerizable with the olefinic monomer.
  • the olefinic monomer constituting the polyolefinic resin (A1) includes ⁇ -olefins having 2 or more carbon atoms, preferably ⁇ -olefins having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene are more preferred, and at least one selected from ethylene and propylene is even more preferred. These olefinic monomers may be used alone or in combination of two or more.
  • Examples of monomers copolymerizable with olefinic monomers that constitute the polyolefinic resin (A1) include vinyl acetate, (meth)acrylic acid esters, and styrene. These monomers may be used alone or in combination of two or more.
  • the polyolefin-based resin (A1) used in one aspect of the present invention includes very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), straight Chain low density polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefinic elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, 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 copolymer
  • EVA ethylene-vinyl acetate copolymer
  • EVA ethylene-(meth)acrylic acid copolymer
  • the binder resin (A) used in one aspect of the present invention may be a modified resin obtained by modifying a main chain resin using a modifying agent to introduce the reactive functional groups described above.
  • modified resins include acid-modified resins into which acid groups have been introduced and resins into which hydroxyl groups have been introduced.
  • the introduced acid-modified resin is preferred, and the acid anhydride-modified resin into which the acid anhydride structure is introduced is more preferred from the viewpoint of making the composition capable of forming a cured product having excellent adhesive strength and low dielectric properties.
  • Acid-modified resins or acid anhydride-modified resins are produced, for example, by reacting unsaturated carboxylic acids or the like with resins that serve as the main chain to form carboxy groups or carboxylic acid anhydrides. It is obtained by introducing a structure and graft-denaturing it.
  • the method of introducing the unsaturated carboxylic acid or the like into the resin is not particularly limited. A method of heating and melting the reaction as described above, or a method of dissolving the resin and the unsaturated carboxylic acid or the like in an organic solvent, followed by heating and stirring in the presence of a radical generator, and the like.
  • Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid.
  • Examples of unsaturated carboxylic anhydrides include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride. These may be used alone or in combination of two or more.
  • maleic anhydride is preferable from the viewpoint of forming a composition capable of forming a cured product having excellent adhesive strength and low dielectric properties.
  • the amount of unsaturated carboxylic acid or the like to be reacted with the resin is preferably 0.1 to 5 parts per 100 parts by mass of the resin, from the viewpoint of making the composition capable of forming a cured product having excellent adhesive strength and low dielectric properties. parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.2 to 1 part by mass.
  • a curable adhesive composition of one aspect of the present invention contains a polyphenylene ether resin (B) having a vinyl group and a number average molecular weight of 1,500 or more and less than 5,000.
  • the curable adhesive composition of one aspect of the present invention contains the polyphenylene ether resin (B) described above together with a polyfunctional compound (C) described later, thereby improving heat resistance and low dielectric properties, A cured product with improved adhesive strength can be formed.
  • polyphenylene ether resin (B) may be used independently and may use 2 or more types together.
  • the content of component (B) is a composition capable of forming a cured product with further improved adhesive strength relative to the total amount of component (A) of 100 parts by mass.
  • a composition capable of forming an adhesive layer having a high effect of suppressing bleeding of the adhesive component preferably 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 12 parts by mass parts or more, more preferably 15 parts by mass or more, even more preferably 17 parts by mass or more, and particularly preferably 20 parts by mass or more, and a composition capable of forming an adhesive layer having a high effect of suppressing bleeding of the adhesive component.
  • the content of the component (B) is, relative to the total amount (100% by mass) of the curable adhesive composition, a cured product with improved adhesive strength.
  • the number average molecular weight (Mn) of the polyphenylene ether resin (B) used in one embodiment of the present invention is 1500 or more, preferably 1600 or more, more preferably 1700 or more, more preferably 1800 or more, still more preferably 1900 or more, still more preferably 2000 or more, particularly preferably 2100 or more.
  • the form of from the viewpoint of good solubility in the dilution solvent of the component (B) and a composition with excellent coatability, it is less than 5000, preferably 4900 or less, more preferably more preferably is 4800 or less, more preferably 4700 or less, more preferably 4600 or less, still more preferably 4500 or less, even more preferably 4400 or less, particularly preferably 4300 or less, and further 4200 or less, 4000 or less, 3700 or less, 3500 or less , 3300 or less, or 3000 or less.
  • the polyphenylene ether resin (B) used in one aspect of the present invention may be a resin having a structural unit represented by at least one of the following general formulas (bi) and (b-ii) in the main chain.
  • R a1 and R a2 each independently represent a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom) having 1 to 6 alkyl group or phenyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, methyl groups or ethyl groups are even more preferred, and methyl groups are particularly preferred.
  • halogen atom fluorine atom, chlorine atom, bromine atom, or iodine atom
  • alkyl groups having 1 to 6 carbon atoms that can be selected as R a1 and R a2 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 and the like.
  • m1 and m2 are each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 2.
  • the polyphenylene ether resin (B) used in one embodiment of the present invention has a main chain of the following formula ( A resin having a skeleton represented by b-1) is preferable.
  • R a1 and R a2 , and m1 and m2 are the same as defined in general formula (bi) or formula (b-ii) above; The same applies to types and numerical ranges.
  • X is a divalent organic group, and at least one hydrogen atom of the organic group may be substituted with a substituent.
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater. * indicates the bonding position with the terminal group.
  • Examples of divalent hydrocarbon groups that can be selected as X include an alkylene group having 1 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, and a ring-forming carbon atom number of 3. to 10 cycloalkylene groups, cycloalkenylene groups having 3 to 10 ring-forming carbon atoms, phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, groups formed by combining two or more of these groups, and the like.
  • the alkylene group, oxyalkylene group, and alkenylene group described above may be linear or branched.
  • the alkylene group, oxyalkylene group, and alkenylene group have a substituent selected from a halogen atom, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a cycloalkyl group having 3 to 10 carbon atoms.
  • cycloalkylene group, cycloalkenylene group, phenylene group, biphenylene group, terphenylene group, and naphthylene group are halogen atoms, alkyl groups having 1 to 6 carbon atoms, oxyalkyl groups having 1 to 6 carbon atoms, and may have a substituent selected from alkenyl groups having 1 to 6 carbon atoms.
  • X is preferably a group represented by the following formula (b-2) from the viewpoint of making the composition capable of forming a cured product with improved adhesive strength.
  • R b1 and R b2 each independently represent a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), an alkyl group having 1 to 6 carbon atoms, and an oxyalkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and 1 to 6 carbon atoms;
  • An alkyl group of 3 is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred.
  • alkyl groups having 1 to 6 carbon atoms that can be selected as R b1 and R b2 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 and the like.
  • n1 and n2 are each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 3.
  • A is a single bond or a divalent hydrocarbon group.
  • the divalent hydrocarbon group that can be selected as A includes, for example, an alkylene group having 1 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, and a ring-forming carbon atom number of 3. to 10 cycloalkylene groups and 3 to 10 ring-forming carbon atoms cycloalkenylene groups.
  • the alkylene group, oxyalkylene group, and alkenylene group may be linear or branched.
  • the hydrocarbon group that can be selected as A may have the substituents described above.
  • A is preferably a single bond or an alkylene group having 1 to 20 carbon atoms, and is preferably a single bond, from the viewpoint of a composition capable of forming a cured product with improved adhesive strength. more preferred.
  • the polyphenylene ether resin (B) used in one embodiment of the present invention has a main chain represented by the following formula (b-3).
  • a resin having a skeleton is more preferable.
  • R a1 and R a2 are the same as defined in general formula (bi) or formula (b-ii) above. are the same. Further, R b1 and R b2 are the same as defined in the general formula (b-2) above, and the types and numerical ranges of suitable groups are also the same.
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater. * indicates the bonding position with the terminal group.
  • R a1 , R a2 , R b1 , and R b2 in the general formula (b-3) are each independently preferably an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms. is more preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred.
  • the cured product formed from the curable adhesive composition is excellent in low dielectric properties, crosslinkability, and heat resistance.
  • the vinyl group that the polyphenylene ether resin (B) has may be one that constitutes a part of the hydrocarbon substituent, such as vinylbenzyl group and vinylnaphthyl group. That is, the polyphenylene ether resin (B) is formed by bonding a vinyl group or a vinyl group-containing hydrocarbon group to a polyphenylene ether skeleton.
  • the polyphenylene ether resin (B) used in one embodiment of the present invention has vinyl groups or A resin having a vinyl group-containing hydrocarbon group is preferred.
  • a polyphenylene ether resin (B) having a vinyl group or a vinyl group-containing hydrocarbon group at both ends of the main chain forms a polyphenylene ether skeleton to be the main chain, and then has a vinyl group or a vinyl group-containing hydrocarbon group at both ends.
  • a bifunctional phenol compound and a monofunctional phenol compound are reacted to obtain a polymer having phenolic hydroxyl groups at both ends, and then 4-(chloromethyl)styrene is used to convert the terminal phenolic hydroxyl groups to vinyl.
  • 4-(chloromethyl)styrene is used to convert the terminal phenolic hydroxyl groups to vinyl.
  • benzyl etherifying a polyphenylene ether resin (B) having vinylbenzyl groups at both ends of the polyphenylene ether skeleton can be obtained.
  • the polyphenylene ether resin (B) used in one aspect of the present invention is preferably a compound represented by the following general formula (b-4).
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater.
  • a commercially available product can also be used as the polyphenylene ether resin (B) used in one aspect of the present invention.
  • Examples of commercially available products include OPE-2St (compound represented by the above general formula (b-4)) manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.
  • a curable adhesive composition of one aspect of the present invention contains a polyfunctional compound (C) having two or more unsaturated hydrocarbon groups with double bonds at their terminals.
  • the polyfunctional compound (C) in the present invention excludes compounds corresponding to the components (A) and (B).
  • a composition containing a polyfunctional compound (C) together with the polyphenylene ether resin (B) described above a cured product having improved low dielectric properties and adhesive strength in a well-balanced manner can be formed.
  • the polyfunctional compound (C) has two or more unsaturated hydrocarbon groups, a crosslinked structure is formed in the obtained cured product, thereby forming a cured product with further improved adhesive strength.
  • polyfunctional compound (C) may be used independently and may use 2 or more types together.
  • the content of the component (C) is a cured product with a well-balanced improvement in low dielectric properties and adhesive strength with respect to 100 parts by mass of the total amount of the component (A). is preferably 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, More preferably 12 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 17 parts by mass or more, particularly preferably 20 parts by mass or more, and a composition capable of forming an adhesive layer with excellent adhesiveness From the viewpoint of a product, preferably less than 99 parts by mass, more preferably 95 parts by mass or less, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 60 parts by mass parts or less, more preferably 50 parts by mass or less, even more preferably 40 parts
  • the content of component (C) is such that low dielectric properties and adhesive strength are is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, more preferably is 3.0% by mass or more, more preferably 5.0% by mass or more, still more preferably 7.0% by mass or more, still more preferably 10.0% by mass or more, even more preferably 12.0% by mass or more, especially It is preferably 15.0% by mass or more, and from the viewpoint of making the composition capable of forming an adhesive layer with excellent adhesiveness, it is preferably less than 50% by mass, more preferably 45% by mass or less, more preferably 45% by mass or less.
  • the component (B) and the component ( The content ratio [(B)/(C)] with C) is preferably 5/95 or more, more preferably 10/90 or more, more preferably 15/85 or more, more preferably 20/(C) in mass ratio.
  • the total content of component (B) and component (C) is, with respect to the total amount of component (A) of 100 parts by mass, the effect of suppressing bleeding of the adhesive component.
  • a cured product with improved adhesive strength is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, It is more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, and particularly preferably 40 parts by mass or more.
  • the number of carbon atoms in the unsaturated hydrocarbon group per one of the polyfunctional compound (C) used in one aspect of the present invention is preferably 2 to 10, more preferably 2 to 7, still more preferably 2 to 5, more preferably 2-4, particularly preferably 2-3.
  • the unsaturated hydrocarbon group 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.
  • the unsaturated hydrocarbon group possessed by the polyfunctional compound (C) is preferably an allyl group.
  • the number of the unsaturated hydrocarbon groups possessed by the polyfunctional compound (C) used in one aspect of the present invention is 2 or more, but the crosslinked structure is moderately sparse, and a cured product in which the generation of cracks is suppressed is obtained.
  • a composition that can be formed and from the viewpoint of suppressing curing shrinkage in the bonding process from the adhesive layer to the cured product, it is a composition that can reduce warping of a plate-like member such as a circuit board that is an adherend. From the point of view, it is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.
  • the polyfunctional compound (C) used in one embodiment of the present invention has two unsaturated hydrocarbon groups.
  • a polyfunctional compound having the above and further having a saturated hydrocarbon group is preferred.
  • the number of saturated hydrocarbon groups possessed by the polyfunctional compound (C) used in one aspect of the present invention is preferably 1 or more, more preferably 1 to 4, still more preferably 1 to 3, and even more preferably is 1 to 2, particularly preferably 1.
  • Examples of the saturated hydrocarbon group include an alkyl group and an alkyl group substituted with an alkoxy group.
  • alkyl group 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 and the like.
  • the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 4-18, even more preferably 6-16, and even more preferably 8-15.
  • alkyl group substituted with the alkoxy group examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethoxymethyl group, benzyloxymethyl group and the like.
  • the number of carbon atoms in the alkyl group substituted with the alkoxy group is preferably 2-15, more preferably 2-12, and still more preferably 3-10.
  • the polyfunctional compound (C) used in one aspect of the present invention preferably contains the polyfunctional compound (C1) having two unsaturated hydrocarbon groups.
  • the composition containing such a polyfunctional compound (C1) having two unsaturated hydrocarbon groups suppresses the occurrence of cracks and causes warping of a plate-like member such as a circuit board as an adherend.
  • the polyfunctional compound (C1) is more preferably a polyfunctional compound having two unsaturated hydrocarbon groups and at least one saturated hydrocarbon group.
  • the content of the polyfunctional compound (C1) is the total amount (100% by mass) of the component (C) contained in the curable adhesive composition. ), preferably 30 to 100% by mass, more preferably 40 to 100% by mass, more preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and further It is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
  • the polyfunctional compound (C) used in one aspect of the present invention is preferably a polyfunctional compound having a heterocyclic skeleton.
  • a polyfunctional compound having a heterocyclic skeleton By including a polyfunctional compound having a heterocyclic skeleton, it is possible to obtain a composition capable of forming a cured product with improved low dielectric properties and adhesive strength.
  • Specific heterocyclic skeletons include an isocyanurate skeleton and a glycoluril skeleton.
  • Examples of the polyfunctional compound (C) used in one embodiment of the present invention include compounds having an isocyanurate skeleton represented by the following general formula (c-1), glycoluril represented by the following general formula (c-2) A compound having a skeleton can be mentioned.
  • R 11 to R 13 are each independently an unsaturated hydrocarbon group having a double bond at the end or a saturated hydrocarbon group, are the unsaturated hydrocarbon groups.
  • R 21 to R 26 are each independently a hydrogen atom, an unsaturated hydrocarbon group having a double bond at the end, or a saturated hydrocarbon group, At least two of R 21 to R 26 are the unsaturated hydrocarbon groups.
  • Specific examples of unsaturated hydrocarbon groups and saturated hydrocarbon groups that can be selected as R 11 to R 13 and R 21 to R 26 are as described above, and the preferred carbon number ranges are also as described above. .
  • the polyfunctional compound (C) used in one embodiment of the present invention preferably contains a compound having an isocyanurate skeleton represented by the general formula (c-1), It more preferably contains a compound (C11) having an isocyanurate skeleton represented by the following general formula (c-11).
  • R a is a saturated hydrocarbon group, and specific examples thereof are as described above. Among these, R a is preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 4-18, even more preferably 6-16, and even more preferably 8-15.
  • the content of the compound (C11) is , preferably 30 to 100 mass%, more preferably 40 to 100 mass%, more preferably 50 to 100 mass%, more preferably 60 to 100 mass%, still more preferably 70 to 100 mass%, still more preferably 80 to 100% by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass.
  • a commercially available product may be used as the polyfunctional compound (C) used in one embodiment of the present invention.
  • Specific commercial products include, for example, L-DAIC (product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., compound represented by the general formula (c-11)), TAIC (registered trademark) (product name, Mitsubishi Chemical Co., Ltd., a compound in which R 11 to R 13 in the general formula (c-1) are allyl groups), TAG (product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., represented by the general formula (c-2) compound) and the like.
  • the molecular weight of the polyfunctional compound (C) used in one aspect of the present invention is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more, more preferably 230 or more, particularly preferably 270 or more. More preferably 700 or less, still more preferably 600 or less, and particularly preferably 500 or less.
  • the boiling point of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175 to 350°C, more preferably 200 to 300°C.
  • the 5% weight loss temperature of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175 to 350°C, more preferably 200 to 300°C.
  • the polyfunctional compound used in one embodiment of the present invention is preferably a compound that is liquid at 25°C.
  • a compound that is liquid at 25°C refers to a compound that has fluidity at 25°C. means a compound having a viscosity of 2 to 10,000 mPa ⁇ s as measured by
  • the curable adhesive composition of one aspect of the present invention preferably further contains a cationic polymerization initiator (D).
  • a cationic polymerization initiator (D) may be used independently and may use 2 or more types together.
  • the content of the component (D) is such that the total amount of the component (B) and the component (C) is 100 parts by mass. ) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, from the viewpoint of making the composition capable of sufficiently progressing the polymerization reaction of the component and forming an adhesive layer with improved storage stability.
  • the cationic polymerization initiator (D) used in one aspect of the present invention may be a thermal cationic polymerization initiator or a photocationic polymerization initiator, and the polymerization can be carried out in a simple process. From this point of view, a thermal cationic polymerization initiator is preferred.
  • the thermal cationic polymerization initiator used in one aspect of the present invention is a compound capable of generating a cationic species that initiates polymerization by heating. is mentioned. These thermal cationic polymerization initiators may be used alone or in combination of two or more.
  • Sulfonium salts include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris(4-methoxyphenyl)sulfonium hexafluoroalcinate, diphenyl(4-phenylthiophenyl ) sulfonium hexafluoroalcinate and the like.
  • commercially available sulfonium salts can also be used.
  • SI-80L, San-Aid SI-100L, San-Aid SI-B2A, San-Aid SI-B3 manufactured by Sanshin Chemical Industry Co., Ltd.
  • CYRACURE UVI-6974 CYRACURE UVI-6990 (manufactured by Union Carbide)
  • UVI -508, UVI-509 manufactured by General Electric Co.
  • FC-508, FC-509 manufactured by Minnesota Mining and Manufacturing Co.
  • CD-1010, CD-1011 manufactured by Thurstomer (manufactured by Nippon Soda Co., Ltd.), CI series products (manufactured by Nippon Soda Co., Ltd.), and the like.
  • 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-benzyltrifluoro romethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
  • Phosphonium salts include, for example, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.
  • diazonium salts examples include AMERICURE (manufactured by American Can) and ULTRASET (manufactured by ADEKA).
  • iodonium salts examples include diphenyliodonium hexafluoroarcinate, bis(4-chlorophenyl)iodonium hexafluoroarcinate, bis(4-bromophenyl)iodonium hexafluoroarcinate, phenyl(4-methoxyphenyl)iodonium hexafluoroalkinate, and the like.
  • Commercially available iodonium salts can also be used, such as UV-9310C (manufactured by Toshiba Silicone Co., Ltd.), Photoinitiator 2074 (manufactured by Rhone-Poulenc), UVE series products (manufactured by General Electric), FC series. (manufactured by Minnesota Mining and Manufacturing Co.).
  • the curable adhesive composition of one aspect of the present invention contains the cationic polymerization initiator (D), at least part of the cationic polymerization initiator (D) is subjected to differential scanning calorimetry under the following conditions.
  • It may be a high-temperature reactive thermal cationic polymerization initiator that gives a peak top temperature of an exothermic peak 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.
  • 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 curable adhesive composition of one aspect of the present invention includes a cationic polymerization initiator instead of the cationic polymerization initiator (D) or together with the cationic polymerization initiator (D), as long as the effects of the present invention are not impaired.
  • Other reactive curing agents than (D) may be contained.
  • the curable adhesive composition of one aspect of the present invention contains the cationic polymerization initiator (D)
  • the content of the other reactive curing agent is 0 with respect to 100 parts by mass of the total amount of component (D).
  • the content of the other reactive curing agent is the total of component (B) and component (C) 0.01 parts by mass or more, 0.05 parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more with respect to the amount of 100 parts by mass, Alternatively, it may be 0.30 parts by mass or more, and 6.0 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.5 parts by mass or less, 1. It may be 0 parts by mass or less, or 0.70 parts by mass or less.
  • Examples of reactive curing agents (D) other than cationic polymerization initiators include amine compounds such as benzylmethylamine and 2,4,6-trisdimethylaminomethylphenol; 2-methylimidazole, 2-ethyl-4-methyl imidazole compounds such as imidazole and 2-heptadecyl imidazole; Lewis acids such as boron trifluoride/monoethylamine complex and boron trifluoride/piperazine complex; peroxides such as di(t-butylperoxy)diisopropylbenzene; is mentioned.
  • amine compounds such as benzylmethylamine and 2,4,6-trisdimethylaminomethylphenol
  • 2-methylimidazole, 2-ethyl-4-methyl imidazole compounds such as imidazole and 2-heptadecyl imidazole
  • Lewis acids such as boron trifluoride/monoethylamine complex and boron trifluoride/piperazine
  • the curable adhesive composition of one aspect of the present invention preferably further contains a cross-linking agent (E) capable of reacting with the reactive functional group of component (A).
  • a composition that further contains the cross-linking agent (E) together with the component (A) it is possible to form an adhesive layer that is highly effective in suppressing the exudation of the adhesive component. That is, in the process of forming an adhesive layer from a coating film formed from a curable adhesive composition, by reacting with the reactive functional groups possessed by the crosslinking agent (E) and the binder resin (A), A crosslinked structure is formed, and an adhesive layer that is difficult to fluidize even when heated can be formed.
  • the formed adhesive layer is more likely to seep out of the adhesive component from the edges in the bonding step of sticking it to an adherend such as a circuit board, curing it, and adhering it to the adherend. it gets harder.
  • the cross-linking agent (E) may be used alone or in combination of two or more.
  • the content of the component (E) is such that the adhesive layer has a higher effect of suppressing the bleeding of the adhesive component with respect to the total amount of the component (A) of 100 parts by mass.
  • it is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, and more preferably 6.0 parts by mass.
  • parts or less more preferably 5.0 parts by mass or less, still more preferably 4.0 parts by mass or less, still more preferably 3.0 parts by mass or less, still more preferably 2.5 parts by mass or less, still more preferably 2.0 parts by mass or less It is not more than 1.5 parts by mass, particularly preferably not more than 1.5 parts by mass.
  • the molecular weight of the cross-linking agent (E) used in one aspect of the present invention increases the probability of reaction with the component (A), facilitates the formation of a cross-linked structure, and has a higher effect of suppressing the bleeding of the adhesive component into the adhesive layer.
  • the cross-linking agent (E) is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, even more preferably 600 or less, particularly preferably 500 or less, and forms an adhesive layer
  • it is preferable It is 100 or more, more preferably 150 or more, still more preferably 200 or more, even more preferably 250 or more, and particularly preferably 300 or more.
  • the cross-linking agent (E) used in one aspect of the present invention is appropriately selected according to the type of reactive functional group possessed by the component (A). , aziridine-based cross-linking agents, and the like.
  • the cross-linking agent (E) used in one embodiment of the present invention is preferably at least one selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents.
  • the cross-linking agent (E) used in one embodiment of the present invention is preferably a cross-linking agent having an isocyanurate skeleton.
  • the isocyanate-based cross-linking agent is preferably a compound having two or more isocyanate groups in the molecule.
  • Examples include triphenylmethane triisocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and the like.
  • the epoxy-based cross-linking agent is preferably a compound having two or more epoxy groups in the molecule. -m-xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
  • Metal chelate-based cross-linking agents include chelate compounds having metal ions functioning as cross-linking points. Examples of such metal ions include aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, and tin ions. Among these, the metal chelate-based cross-linking agent is preferably an aluminum chelate compound. aluminum bisoleyl acetoacetate and the like.
  • the cross-linking agent (E) used in one aspect of the invention is preferably an isocyanate-based cross-linking agent, more preferably an isocyanurate of a polyisocyanate compound, an isocyanurate of 1,5-pentamethylene diisocyanate [1,3,5-tris (5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione] and the isocyanurate of 1,6-hexamethylene diisocyanate [1,3,5-tris(6-isocyanatohexyl) -1,3,5-triazine-2,4,6-trione] is more preferable.
  • the curable adhesive composition of one aspect of the present invention preferably further contains a silane coupling agent (F).
  • a silane coupling agent (F) By using a composition containing a silane coupling agent, a cured product with improved adhesive strength can be formed.
  • the silane coupling agent (F) may be used alone or in combination of two or more.
  • the content of the component (F) is such that the content of the component (F) is a cured product having excellent adhesive strength even in a high-temperature and high-humidity environment with respect to the total amount of the component (A) of 100 parts by mass.
  • 0.001 parts by mass or more is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, More preferably 0.05 parts by mass or more, more preferably 0.07 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.12 parts by mass or more, particularly preferably 0.15 parts by mass or more
  • it is preferably 6.0 mass from the viewpoint of making it a composition that can suppress the amount of outgassing that can occur in a high-temperature and high-humidity environment and form a cured product that maintains good adhesive strength.
  • parts or less more preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.0 parts by mass or less, still more preferably 1.5 parts by mass parts or less, more preferably 1.0 parts by mass or less, even more preferably 0.80 parts by mass or less, and particularly preferably 0.60 parts by mass or less.
  • the silane coupling agent (E) used in one aspect of the present invention is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule.
  • Specific silane coupling agents include, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 - Silane coupling agents having a (meth)acryloyl group such as acryloxypropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy) Silane coupling agents having a vinyl group such as silane; 2-(3,4-epoxycyclohexyl)ethy
  • the curable adhesive composition of one aspect of the present invention may further be a composition containing a cyclic ether compound or a composition containing no cyclic ether compound.
  • Any compound having a cyclic ether group can be used as the cyclic ether compound.
  • the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, a tetrahydropyranyl group and the like.
  • the oxirane group includes groups having an oxirane structure such as glycidyl group, glycidyl ether group and epoxycyclohexyl group.
  • a cyclic ether compound may be used independently and may use 2 or more types together.
  • a composition containing a cyclic ether compound has the property of being able to form a cured product with excellent adhesive strength, but the cured product tends to have a large relative dielectric constant and dielectric loss tangent value and poor low dielectric properties.
  • the curable adhesive composition of one aspect of the present invention contains the above-described components (A) to (C), it forms a cured product with improved adhesive strength and low dielectric properties in a well-balanced manner. It has the property of obtaining Therefore, the curable adhesive composition of one aspect of the present invention does not need to contain a cyclic ether compound that causes deterioration of low dielectric properties.
  • the content of the cyclic ether compound is less than 5.0% by mass with respect to the total amount (100% by mass) of the active ingredients of the curable adhesive composition, less than 3.0% by weight, less than 1.0% by weight, less than 0.50% by weight, less than 0.10% by weight, less than 0.010% by weight, less than 0.0010% by weight, less than 0.00010% by weight, or It may be less than 0.000010% by mass.
  • the content of the cyclic ether compound is less than 5.0 parts by mass, less than 3.0 parts by mass, less than 1.0 parts by mass, less than 0.50 parts by mass, less than 0.10 parts by mass, less than 0.010 parts by mass, less than 0.0010 parts by mass , less than 0.00010 parts by mass, or less than 0.000010 parts by mass.
  • the curable adhesive composition of one aspect of the present invention may further be a composition containing an inorganic filler or a composition containing no inorganic filler.
  • inorganic fillers include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide, calcium carbonate, and the like. is mentioned. These inorganic fillers may be used alone or in combination of two or more.
  • the content of the inorganic filler is preferably as low as possible.
  • the content of the inorganic filler is 0 to 30 mass%, 0 ⁇ 20% by mass, 0-10% by mass, 0-5.0% by mass, 0-2.0% by mass, 0-1.0% by mass, 0-0.1% by mass, 0-0.01% by mass , or 0 to 0.001% by mass.
  • the content of the inorganic filler is , less than 50 parts by weight, less than 30 parts by weight, less than 10 parts by weight, less than 5.0 parts by weight, less than 1.0 parts by weight, less than 0.1 parts by weight, less than 0.01 parts by weight, 0.001 parts by weight It may be less than or less than 0.0001 part by mass.
  • the curable adhesive composition of one aspect of the present invention may contain additives other than the above-described components within a range that does not impair the effects of the present invention.
  • additives include, for example, ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, pigments, extenders, softeners, and the like. These additives may be used alone or in combination of two or more.
  • the content of these additives can be appropriately set according to the type of additive. For example, the content of each additive is 0.001 to 30 parts by mass, 0.005 to 20 parts by mass, 0.005 to 20 parts by mass, and 0 0.01 to 10 parts by mass, or 0.03 to 5 parts by mass.
  • the curable adhesive composition of one aspect of the present invention preferably contains an active ingredient that is liquid at 25°C.
  • an active ingredient that is liquid at 25°C.
  • the content of the active ingredient that is liquid at 25° C. is Preferably 5.0% by mass or more, more preferably 7.0% by mass or more, still more preferably 10% by mass or more, and even more preferably 12% by mass, relative to the total amount (100% by mass) of the active ingredients of the composition Above, particularly preferably 14% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, particularly preferably 25% by mass % by mass or less.
  • At least one active ingredient that is liquid at 25° C. contained in the curable adhesive composition is preferably a polyfunctional compound (C).
  • the content of the polyfunctional compound (C) with respect to the total amount (100% by mass) of the active ingredients that are liquid at 25°C is preferably 70% by mass or more, and more Preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and 100% by mass or less, 99.9% by mass or less, 99.9% by mass or less. It may be 5% by mass or less, 99.0% by mass or less, 98.5% by mass or less, or 98.0% by mass or less.
  • the curable adhesive composition of one aspect of the present invention may be in the form of a solution by further adding a diluent solvent.
  • diluent solvents used in one aspect of the present invention 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 n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like.
  • These diluent solvents may be used alone or in combination of two or more. These diluent solvents may be the solvents used during the synthesis of the components (A) and (B) as they are, or the solvents other than the solvents used during the synthesis of the components (A) and (B). More than one solvent may be added.
  • the concentration of the active ingredient in the curable adhesive composition is appropriately set so as to achieve a desired viscosity in consideration of applicability and the like.
  • the total amount (100% by mass) of the curable adhesive composition 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.50% by mass or more, 1 0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, or 10% by mass or more, and 80% by mass or less, 70% by mass or less, 60% by mass or less, and 50% by mass or less , 40% by mass or less, or 30% by mass or less.
  • a curable adhesive sheet of one aspect of the present invention has an adhesive layer formed from the curable adhesive composition of one aspect of the present invention described above.
  • the said adhesive bond layer can become hardened
  • the curable adhesive sheet of one aspect of the present invention is not particularly limited as long as it has the adhesive layer.
  • it may be a curable adhesive sheet having an adhesive layer on at least one side of a substrate, A curable adhesive sheet having a configuration in which an adhesive layer is sandwiched between two release sheets may also be used.
  • FIG. 1 is a schematic cross-sectional view in the thickness direction of the adhesive sheet, showing an example of the configuration of the curable adhesive sheet of one embodiment of the present invention.
  • the curable adhesive sheet 1 of for example, as shown in FIG.
  • the curable adhesive sheet 1 of may be used as a specific configuration of the curable adhesive sheet of one embodiment of the present invention.
  • a curable adhesive sheet with a substrate having a first adhesive layer 11 and a second adhesive layer 12 on both surface sides of the substrate 20. 2 may be used.
  • the substrate 20 and the adhesive layer 10 may be directly laminated like the curable adhesive sheet 1 shown in FIG.
  • a configuration having another layer between the substrate 20 and the adhesive layer 10 may be employed. The same applies to the substrate 20 and the first adhesive layer 11 and the substrate 20 and the second adhesive layer 12 in the curable adhesive sheet 2 shown in FIG. 1(b).
  • the curable adhesive sheet of one embodiment of the present invention has a release sheet 30 on the adhesive surface of the adhesive layer 10 in addition to the configuration of the curable adhesive sheet 1.
  • a configuration such as a laminated curable adhesive sheet 3 with a substrate may be used.
  • the curable adhesive sheet 2 shown in FIG. It may be configured as an adhesive sheet.
  • the two release sheets are preferably made of materials adjusted to have different release forces.
  • the curable adhesive sheet of one aspect of the present invention is formed by combining the adhesive layer 10 with the first release sheet 31 and the second release sheet 31 without using a base material, as shown in FIG. 1(d). It may be configured like the curable adhesive sheet 4 without a substrate, which is sandwiched by the release sheets 32 of the substrate.
  • the materials of the first release sheet 31 and the second release sheet 32 of the curable adhesive sheet 4 may be the same or different. It is preferable that the material is adjusted to Other examples include a curable adhesive sheet having a configuration in which a release sheet having a release-treated surface and an adhesive layer provided on one side thereof is wound into a roll.
  • the thicknesses of the adhesive layer, the substrate, and the release sheet are values measured in accordance with JIS K7130 (1999), and can be measured using a known thickness meter. .
  • the adhesive layer of the curable adhesive sheet of one aspect of the present invention is a layer formed from the curable adhesive composition of one aspect of the present invention described above.
  • the thickness of the adhesive layer is preferably 1.0 ⁇ m or more, more preferably 1.0 ⁇ m or more, from the viewpoint of forming a cured product having a thickness that can protect the circuit board.
  • 3.0 ⁇ m or more more preferably 5.0 ⁇ m or more, more preferably 7.0 ⁇ m or more, still more preferably 10 ⁇ m or more, still more preferably 12 ⁇ m or more, still more preferably 15 ⁇ m or more, even more preferably 17 ⁇ m or more, particularly preferably 20 ⁇ m It is preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 45 ⁇ m or less, still more preferably 40 ⁇ m or less, and particularly preferably 35 ⁇ m or less.
  • the adhesive layer included in the curable adhesive sheet of one embodiment of the present invention has curability, it can be a cured product.
  • the method of curing the adhesive layer can be adjusted depending on the type of the reactive curing agent such as component (D), etc., and may be a heat curing method or a photocuring method, and is appropriately selected according to the application. be able to.
  • a thermosetting method is preferable.
  • the curable adhesive sheet of one aspect of the present invention may have a base material.
  • the base material of the curable adhesive sheet of one embodiment of the present invention is not particularly limited and may be appropriately selected depending on the application, but a resin film is preferable.
  • resin components constituting the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, and acrylic. based resins, cycloolefin-based polymers, aromatic polymers, polyurethane-based polymers, liquid crystal polymer films, and the like.
  • the thickness of the substrate is not particularly limited and is appropriately selected depending on the application, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 12 ⁇ m or more, even more preferably 15 ⁇ m or more, and particularly preferably 17 ⁇ m or more. and is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, still more preferably 300 ⁇ m or less, even more preferably 200 ⁇ m or less, and particularly preferably 150 ⁇ m or less.
  • the curable adhesive sheet of one aspect of the present invention may have a release sheet.
  • the release sheet functions as a protective film for the adhesive layer until the curable adhesive sheet is used.
  • the release sheet functions as a support in the manufacturing process of the curable adhesive sheet. Note that when using the curable adhesive sheet of one embodiment of the present invention, the release sheet is usually peeled off and removed.
  • Examples of the release sheet included in the curable adhesive sheet of one embodiment of the present invention include those having a release layer formed by coating a release agent on the surface of a release film substrate.
  • substrates for release films include paper substrates such as glassine paper, coated paper, and woodfree paper; laminated paper obtained by laminating thermoplastic resins such as polyethylene on these paper substrates; polyethylene terephthalate resins and polybutylene terephthalate resins.
  • plastic films such as polyethylene naphthalate resin, polypropylene resin, and polyethylene resin
  • release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and the like.
  • the thickness of the release sheet is not particularly limited, but is usually 20 to 250 ⁇ m.
  • the method for producing the curable adhesive sheet of one aspect of the present invention is not particularly limited, and the curable adhesive composition of one aspect of the present invention is applied onto the substrate or release sheet described above by a known coating method. can be manufactured by From the viewpoint of improving the applicability to the substrate or the release sheet, the curable adhesive composition of one embodiment of the present invention is preferably diluted with a diluting solvent to form a solution.
  • Examples of methods for applying the curable adhesive composition onto a substrate or release sheet include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure. A coat method and the like can be mentioned.
  • drying treatment After coating the curable adhesive composition on a substrate or release sheet to form a coating film, it is preferable to carry out a drying treatment.
  • the drying treatment method include hot air drying, hot roll drying, and infrared irradiation.
  • the drying conditions for the formed coating film are preferably 80° C. to 150° C. and heating for 30 seconds to 5 minutes (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes) to dry. Through this drying process, an adhesive layer can be formed on the substrate or the release sheet.
  • the curable adhesive composition used for forming the adhesive layer contains the cross-linking agent (E), a certain period of time (for example, about 1 to 14 days) is required to complete the cross-linking reaction. It is preferable to pass through a seasoning step to hold.
  • the following methods are mentioned as a specific manufacturing method according to the structure of the curable adhesive sheet of one aspect of the present invention.
  • a method for producing the curable adhesive sheet 1 as shown in FIG. A method having steps is mentioned.
  • a method for producing the curable adhesive sheet 2 as shown in FIG. A method including the step of forming the adhesive layer 12 is mentioned.
  • a method including a step of bonding both sides and a step of removing the release sheet may be used.
  • a step of laminating a release sheet 30 on the surface of the adhesive layer 10 of the curable adhesive sheet 3 produced as described above is performed.
  • the adhesive layer included in the curable adhesive sheet of one embodiment of the present invention can be cured to form a cured product.
  • the cured product thus formed is excellent in adhesive strength and low dielectric properties.
  • the adhesive strength of the cured product obtained by curing the adhesive layer to the copper foil is preferably 0.75 kgf/cm or more, more preferably 0.78 kgf/cm or more, more preferably 0.80 kgf/cm or more, still more preferably 0.85 kgf/cm or more, and still more preferably It is 0.88 kgf/cm or more, more preferably 0.90 kgf/cm or more, particularly preferably 0.92 kgf/cm or more, and may be 0.95 kgf/cm or more or 0.97 kgf/cm or more.
  • the adhesive strength of the cured product means a value measured based on the method described in Examples below.
  • the cured product obtained by curing the adhesive layer of the curable adhesive sheet of one embodiment of the present invention has a relative dielectric constant at 23° C. and 1 GHz, preferably less than 2.36, more preferably 2.35 or less, and even more preferably. is 2.34 or less, more preferably 2.33 or less, and particularly preferably 2.32 or less.
  • the dielectric constant at 23° C. and 1 GHz of the cured product is not particularly limited to a lower limit, and is, for example, 1.50 or more, 1.60 or more, 1.70 or more, 1.80 or more, 1.90 or more, Alternatively, it may be 2.00 or more.
  • the dielectric loss tangent at 23° C. and 1 GHz of the cured product obtained by curing the adhesive layer of the curable adhesive sheet of one embodiment of the present invention is preferably less than 0.005, more preferably 0.004 or less, and more preferably It is 0.003 or less, more preferably less than 0.001, still more preferably 0.0009 or less, and particularly preferably 0.0008 or less.
  • the dielectric loss tangent at 23 ° C. and 1 GHz of the cured product has no particular lower limit, for example, 0.00001 or more, 0.00003 or more, 0.00005 or more, 0.00007 or more, or 0.0001 or more good too.
  • dielectric constant and dielectric loss tangent of the cured product mean values measured based on the method described in Examples below.
  • the curable adhesive sheet of one aspect of the present invention is such that, after bonding the adhesive layer to an adherend such as a circuit board, the adhesive layer is cured and adhered to the adherend in the adhesion process. It is possible to suppress the adhesive component of the adhesive layer from oozing out from the edge, and to prevent contamination of the adherend.
  • the exudation distance of the adhesive component measured based on the method described in Examples below is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and more preferably It is 100 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, still more preferably 25 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • a cured product obtained by curing the adhesive layer of the curable adhesive sheet of one embodiment of the present invention has high adhesive strength and excellent low dielectric properties in a high frequency region.
  • the curable adhesive sheet of one aspect of the present invention is suitably used when forming a member in a device that requires low dielectric properties, and is particularly used as a cover lay sheet for protecting a circuit board. is preferred.
  • circuit boards include flexible printed circuit boards (FPC).
  • the present invention can also provide the following [1] and [2].
  • [1] The adhesive layer of the curable adhesive sheet of one aspect of the present invention is laminated to a circuit board, the adhesive layer is cured to obtain a cured product, and the cured product is adhered to the circuit board.
  • a method of using a curable adhesive sheet, which has a bonding step of allowing [2] The adhesive layer of the curable adhesive sheet of one aspect of the present invention is laminated to a circuit board, the adhesive layer is cured to obtain a cured product, and the cured product is adhered to the circuit board.
  • a method for producing a circuit board with a cured product which includes an adhesion step of
  • the curing method in the above [1] and [2] may be a heat curing method or a photo-curing method. Selected by type.
  • a thermosetting method is preferred.
  • the heating temperature for heat curing is preferably 80 to 200° C., more preferably 90 to 190° C., still more preferably 100 to 180° C.
  • the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 6 hours, more preferably 40 minutes to 3 hours.
  • the pressure for hot pressing is preferably 0.1 to 10 MPa, more preferably 0.5 to 8.0 MPa, still more preferably 1.0 to 5.0 MPa.
  • a cured product when the adhesive layer is cured by a photo-curing method, a cured product can be obtained by irradiating the adhesive layer with energy rays such as ultraviolet rays.
  • each physical property value is a value measured by the method shown below.
  • ⁇ Component (A): Binder resin> - "Modified polyolefin”: a solution containing a maleic anhydride-modified ⁇ -olefin polymer with Mn 47,000 (corresponding to the above-mentioned component (A1), solid at 25 ° C.) (manufactured by Mitsui Chemicals, Inc., product name) "Unistor H-200”).
  • Component (E): Crosslinking agent> ⁇ “Isocyanate-based cross-linking agent”: 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione (manufactured by Mitsui Chemicals, Inc., product name “Stabio D- 370N”), molecular weight 462, liquid at 25°C.
  • Silane coupling agent> Silane coupling agent
  • Silane coupling agent 8-glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM4803"), liquid at 25°C.
  • curable adhesive sheet The curable adhesive composition prepared in (1) above is applied onto the release-treated surface of the first release sheet (manufactured by Lintec Corporation, product name “SP-PET752150”). Then, the coating film was dried at 100° C. for 2 minutes to form an adhesive layer having a thickness of 25 ⁇ m. Furthermore, the exposed surface of the formed adhesive layer and the release-treated surface of the second release sheet (manufactured by Lintec Corporation, product name "SP-PET381130”) are pasted together, as shown in FIG. 1(d). A curable adhesive sheet having the same configuration as curable adhesive sheet 4 shown was obtained.
  • the other release sheet is also peeled off from the curable adhesive sheet with copper foil, and the surface of the exposed adhesive layer and a modified polyimide film having a thickness of 25 ⁇ m (manufactured by PI Advanced Materials, FG grade) are placed in a heat laminator. was used to laminate at a temperature of 100° C. to obtain a laminate in which copper foil/adhesive layer/modified polyimide film were laminated in this order. Next, this laminate was heat-pressed at 160° C. and 5 MPa for 1 hour to thermally cure the adhesive layer to obtain a cured product sample for measurement.
  • the laminate of copper foil and cured product possessed by the measurement sample is a modified polyimide film.
  • the "adhesive strength of the cured product” was measured when the adhesive was peeled off from the adhesive at a peeling angle of 90° and a peeling speed of 50 mm/min.
  • the area of the copper foil 100 is larger than the area of the adhesive layer 10 and the substrate 20, which is a polyimide film. It spreads from the outer edge of the base material 20 which is a polyimide film and adheres onto the copper foil 100 that is not bonded to the adhesive layer 10 .
  • the test sample after hot pressing is viewed from above, and the adhesive component that has exuded from the outer edge of the base material 20, which is a polyimide film, is observed, and the adhesive component farthest from the outer edge.
  • the distance to the point where the adhesive component oozes out was measured as "the oozing distance of the adhesive component". It can be said that the shorter the "extrusion distance of the adhesive component", the higher the effect of suppressing the exudation of the adhesive component.
  • the cured products formed from the curable adhesive compositions prepared in Examples 1 to 3 have high adhesive strength, low dielectric constant and dielectric loss tangent values, and excellent low dielectric properties. became. It was also confirmed that the adhesive layers formed from the curable adhesive compositions prepared in Examples 1 to 3 had a high effect of suppressing exudation of the adhesive component. On the other hand, the cured product formed from the curable adhesive composition prepared in Comparative Example 1 was inferior in adhesive strength to those of Examples 1-3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2022/027985 2021-07-20 2022-07-19 硬化性接着剤組成物、及び硬化性接着シート Ceased WO2023002970A1 (ja)

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