WO2021106848A1 - Composition adhésive, feuille adhésive, stratifié et carte de circuit imprimé - Google Patents

Composition adhésive, feuille adhésive, stratifié et carte de circuit imprimé Download PDF

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Publication number
WO2021106848A1
WO2021106848A1 PCT/JP2020/043610 JP2020043610W WO2021106848A1 WO 2021106848 A1 WO2021106848 A1 WO 2021106848A1 JP 2020043610 W JP2020043610 W JP 2020043610W WO 2021106848 A1 WO2021106848 A1 WO 2021106848A1
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Prior art keywords
adhesive composition
mass
resin
less
parts
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Ceased
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PCT/JP2020/043610
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English (en)
Japanese (ja)
Inventor
遼 薗田
哲生 川楠
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2021517739A priority Critical patent/JP6919777B1/ja
Priority to CN202080069116.4A priority patent/CN114514300B/zh
Priority to KR1020227002553A priority patent/KR102884272B1/ko
Publication of WO2021106848A1 publication Critical patent/WO2021106848A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/02—Condensation polymers of aldehydes or ketones only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/02—Condensation polymers of aldehydes or ketones only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types

Definitions

  • the present invention relates to an adhesive composition. More specifically, the present invention relates to an adhesive composition used for adhering a resin base material to a resin base material or a metal base material. In particular, the present invention relates to an adhesive composition for a flexible printed wiring board (hereinafter abbreviated as FPC), and an adhesive sheet, a laminate and a printed wiring board containing the same.
  • FPC flexible printed wiring board
  • the flexible printed wiring board has excellent flexibility, it can be used for multi-functionality and miniaturization of personal computers (PCs) and smartphones, and therefore, an electronic circuit board is incorporated in a narrow and complicated interior. It is often used for.
  • electronic devices have become smaller, lighter, higher in density, and have higher output, and due to these trends, the demand for the performance of wiring boards (electronic circuit boards) has become more and more sophisticated.
  • the frequency of signals is increasing.
  • FPCs having low dielectric properties (low dielectric constant, low dielectric loss tangent) in the high frequency region.
  • the base material used for FPC not only the conventional polyimide (PI) and polyethylene terephthalate (PET), but also the base film such as liquid crystal polymer (LCP) and syndiotactic polystyrene (SPS) having low dielectric properties.
  • PI polyimide
  • PET polyethylene terephthalate
  • SPS syndiotactic polystyrene
  • measures have been taken to reduce the dielectric loss of the FPC base material and the adhesive.
  • As an adhesive development is underway with a combination of polyolefin and epoxy (Patent Document 1) and a combination of elastomer and epoxy (Patent Document 2).
  • Patent Document 1 it cannot be said that the heat resistance of the reinforcing plate and the adhesive used between the layers is excellent. Further, in Patent Document 2, the storage stability after compounding, which is important at the time of use, was not sufficient.
  • the present invention contains not only a conventional polyimide film but also a resin base material such as a liquid crystal polymer or syndiotactic polystyrene and copper as an adhesive composition having a specific composition.
  • a resin base material such as a liquid crystal polymer or syndiotactic polystyrene and copper
  • the present invention has good adhesiveness not only to polyimide but also to various resin substrates such as liquid crystal polymers and syndiotactic polystyrene and metal substrates, and has low dielectric properties (electrical properties) and solder.
  • An object of the present invention is to provide an adhesive composition having excellent heat resistance and pot life.
  • the phenol resin (b) having a polycyclic structure is preferably a phenol resin having a tricyclodecane skeleton, and more preferably has a carbonate skeleton.
  • the acid value of the acid-modified polyolefin (a) is preferably 5 to 40 mgKOH / g.
  • polycarbodiimide (d) it is preferable to further contain polycarbodiimide (d). Further, with respect to 100 parts by mass of the acid-modified polyolefin (a), 0.05 to 120 parts by mass of the phenol resin (b) having a polycyclic structure, 0.1 to 60 parts by mass of the epoxy resin (c), and It is preferable to contain 0.1 to 30 parts by mass of polycarbodiimide (d).
  • the adhesive composition preferably has a relative permittivity ( ⁇ c ) of 3.0 or less and a dielectric loss tangent (tan ⁇ ) of 0.02 or less at 1 GHz.
  • An adhesive sheet or laminate containing the adhesive composition An adhesive sheet or laminate containing the adhesive composition.
  • the adhesive composition according to the present invention has good adhesiveness not only to polyimide but also to various resin substrates such as liquid crystal polymers and syndiotactic polystyrene and metal substrates, and has low dielectric properties (electricity). (Characteristics), excellent in solder heat resistance and pot life.
  • the acid-modified polyolefin (a) used in the present invention (hereinafter, also simply referred to as the component (a)) is not limited, but at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride is added to the polyolefin resin. It is preferably obtained by grafting.
  • the polyolefin resin is a hydrocarbon such as homopolymerization of an olefin monomer exemplified by ethylene, propylene, butene, butadiene, isoprene, or copolymerization with other monomers, and hydrides and halides of the obtained polymer.
  • the acid-modified polyolefin is obtained by grafting at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride to at least one of polyethylene, polypropylene and a propylene- ⁇ -olefin copolymer. Is preferred.
  • the propylene- ⁇ -olefin copolymer is a copolymer of propylene as a main component and ⁇ -olefin.
  • ⁇ -olefin for example, one or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these ⁇ -olefins, ethylene and 1-butene are preferable.
  • the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and their acid anhydrides.
  • acid anhydride is preferable, and maleic anhydride is more preferable.
  • Specific examples thereof include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer and the like.
  • These acid-modified polyolefins can be used alone or in combination of two or more.
  • the lower limit of the acid value of the acid-modified polyolefin (a) is preferably 5 mgKOH / g or more, more preferably 6 mgKOH / g or more, from the viewpoint of heat resistance and adhesion to a resin base material or a metal base material. , More preferably 7 mgKOH / g or more.
  • the upper limit is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, and further preferably 20 mgKOH / g or less.
  • the number average molecular weight (Mn) of the acid-modified polyolefin (a) is preferably in the range of 10,000 to 50,000. It is more preferably in the range of 15,000 to 45,000, further preferably in the range of 20,000 to 40,000, and particularly preferably in the range of 22,000 to 38,000.
  • Mn number average molecular weight
  • the acid-modified polyolefin (a) is preferably a crystalline acid-modified polyolefin.
  • Crystallinity as used in the present invention means that the temperature is raised from ⁇ 100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and a clear melting peak is shown in the heating process. Point to.
  • DSC differential scanning calorimeter
  • the melting point (Tm) of the acid-modified polyolefin (a) is preferably in the range of 50 ° C. to 120 ° C. It is more preferably in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C.
  • Tm melting point
  • the cohesive force derived from the crystal becomes good, and excellent adhesiveness and solder heat resistance can be exhibited.
  • the value is not more than the upper limit, the solution stability and fluidity are excellent, and the operability at the time of adhesion is improved.
  • the heat of fusion ( ⁇ H) of the acid-modified polyolefin (a) is preferably in the range of 5 J / g to 60 J / g. It is more preferably in the range of 10 J / g to 50 J / g, and most preferably in the range of 20 J / g to 40 J / g.
  • the cohesive force derived from the crystal becomes good, and excellent adhesiveness and solder heat resistance can be exhibited.
  • the value is not more than the upper limit, the solution stability and fluidity are excellent, and the operability at the time of adhesion is improved.
  • the method for producing the acid-modified polyolefin (a) is not particularly limited, and for example, a radical graft reaction (that is, a radical species is generated for a polymer serving as a main chain, and the radical species is used as a polymerization initiation point to form an unsaturated carboxylic acid (Reaction of graft polymerization of acid anhydride), and the like.
  • a radical graft reaction that is, a radical species is generated for a polymer serving as a main chain, and the radical species is used as a polymerization initiation point to form an unsaturated carboxylic acid (Reaction of graft polymerization of acid anhydride), and the like.
  • the radical generator is not particularly limited, but it is preferable to use an organic peroxide.
  • the organic peroxide is not particularly limited, but is di-tert-butylperoxyphthalate, tert-butylhydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-.
  • Peroxides such as 2-ethylhexanoate, tert-butylperoxypivalate, methylethylketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples include azonitriles.
  • the phenol resin (b) having a polycyclic structure used in the present invention (hereinafter, also simply referred to as the component (b)) is not limited as long as it is a phenol resin having one or more polycyclic structures in one molecule.
  • the polycyclic structure refers to a structure in which a plurality of ring structures mainly composed of carbon are bonded, for example, an aromatic skeleton such as naphthalene, anthracene, indane, and tetralin, and an alicyclic structure such as decalin, norbornane, and tricyclodecane. Examples include structures having a skeleton.
  • the number of polycyclic structures contained in one molecule is preferably 2 or more, and more preferably 3 or more. Further, it is preferably 10 or less, more preferably 8 or less, and further preferably 5 or less. Within the above range, excellent dielectric properties can be exhibited.
  • the polycyclic structure is not particularly limited, but is preferably an alicyclic skeleton having 4 to 30 carbon atoms, more preferably an alicyclic skeleton having 5 to 25 carbon atoms, and further preferably 8 to 20 carbon atoms.
  • the alicyclic skeleton of the above particularly preferably an alicyclic skeleton having 10 to 15 carbon atoms.
  • Specific examples of the polycyclic structure include bicyclic alicyclic compounds such as bicyclobutane, bicyclopentane, bicyclohexane, bicycloheptan (norbornan), bicyclooctane, bicyclononane, and bicyclodecane, which may have optionally substituents.
  • Ring structure such as tricyclooctane, tricyclononane, tricyclodecane, tricycloundecane, tricyclododecane, etc., which may have a substituent arbitrarily; Good alicyclic structures of tetracyclic or higher such as tetracyclodecane, tetracycloundecane, tetracyclododecane; aromatic structures such as naphthalene, anthracene, indane, tetralin which may optionally have substituents can be mentioned.
  • the alicyclic structure may have an unsaturated bond, and examples thereof include bicyclohexene, bicyclohexene, bicyclohexene, bicyclooctene, bicyclononene, and bicyclodecene, which may have an optionally substituent.
  • These polycyclic structures may have one type or two or more types in one molecule of the phenol resin.
  • the substituent is not particularly limited, but is an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkoxy group such as a methoxy group or an ethoxy group; a thioalkoxy group such as a thiomethoxy group or a thioethoxy group; a hydroxyl group, an amino group or the like. Can be mentioned.
  • a tricyclic alicyclic structure such as tricyclooctane, tricyclononane, tricyclodecane, tricycloundecane, and tricyclododecane, which may have a substituent, is preferable. It is preferably a tricyclodecane which may have a substituent.
  • tricyclo [5.2.1.0 2,6 ] decane, tricyclo [6.1.1.0 2,6 ] decane, tricyclo [6.1.1.0 2, ] which may have a substituent may be present.
  • the phenol resin (b) having a polycyclic structure preferably further has a carbonate skeleton.
  • the carbonate skeleton By having the carbonate skeleton, it is possible to further impart flexibility to the adhesive composition while maintaining adhesiveness and electrical properties.
  • the amount of the carbonate skeleton contained in the phenol resin (b) having a polycyclic structure is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more in one molecule. Further, it is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less.
  • the phenol resin (b) having a polycyclic structure preferably has a structure represented by the general formula (1).
  • m and n are each independently preferably an integer of 1 or more and 10 or less, more preferably 8 or less, further preferably 5 or less, and particularly preferably 2 or less. ..
  • the phenol resin (b) having a polycyclic structure is more preferably the general formula (2).
  • m and n have the same meanings as described above.
  • p is preferably an integer of 1 or more and 10 or less, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 4 or more. Further, it is preferably 8 or less, and more preferably 5 or less.
  • R 1 and R 2 are aromatic hydrocarbons that may independently have a substituent, and as the substituent, an aliphatic hydrocarbon that may further have a substituent and further having a substituent. It is preferably an alicyclic hydrocarbon which may have a substituent, or an aromatic hydrocarbon which may further have a substituent.
  • R 1 and R 2 independently have the structure of the formula (11) or the formula (12), respectively.
  • R 3 and R 4 are independently alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or substitutions. It is preferably a phenyl group which may have a group. It is more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.
  • x and y are independently integers of 0 to 4, preferably integers of 0 to 3, more preferably 0 or 1, and particularly preferably 1.
  • Z 1 is preferably an integer of 0 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
  • Z 2 is preferably an integer of 0 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
  • the hydroxyl group or ether group may be in the ortho-position, meta-position or para-position with respect to the benzyl group, but is preferably in the para-position. * Indicates a bond with the oxygen atom of the general formula (2).
  • the number average molecular weight of the component (b) is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3500 or less.
  • the number average molecular weight of the component (b) is preferably 500 or more, and more preferably 700 or more.
  • the content of the component (b) is preferably 0.05 parts by mass or more, more preferably 1 part by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the component (a). is there.
  • the value to the lower limit or more excellent solder heat resistance can be exhibited.
  • it is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, further preferably 90 parts by mass or less, and particularly preferably 80 parts by mass or less.
  • By setting the value to the upper limit or less excellent adhesiveness and solder heat resistance can be exhibited.
  • Epoxy resin (c) used in the present invention (hereinafter, also simply referred to as the component (c)) is not particularly limited as long as it has an epoxy group in the molecule, but preferably two or more in the molecule. It has an epoxy group.
  • biphenyl type epoxy resin naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, At least one selected from the group consisting of tetraglycidyl diaminodiphenylmethane, triglycidyl paraaminophenol, tetraglycidyl bisaminomethylcyclohexanone, N, N, N', N'-tetraglycidyl-m-xylene diamine, and epoxy-modified polybutadiene.
  • tetraglycidyl diaminodiphenylmethane triglycidyl paraaminophenol
  • tetraglycidyl bisaminomethylcyclohexanone N, N, N', N'-tetraglycidyl-m-xylene diamine
  • epoxy-modified polybutadiene can be used.
  • it is a biphenyl type epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, triglycidyl paraaminophenol or an epoxy-modified polybutadiene. More preferably, it is a dicyclopentadiene type epoxy resin, a novolac type epoxy resin or triglycidyl paraaminophenol.
  • the content of the epoxy resin (c) is preferably 0.1 part by mass or more, more preferably 0.5 parts by mass, based on 100 parts by mass of the acid-modified polyolefin (a). It is by mass or more, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more.
  • the value is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less.
  • the pot life property and the low dielectric property are improved. That is, within the above range, an adhesive composition having excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life property can be obtained.
  • the polycarbodiimide (d) used in the present invention (hereinafter, also simply referred to as the component (d)) is not particularly limited as long as it has a carbodiimide group in the molecule. It is preferably a polycarbodiimide having two or more carbodiimide groups in the molecule.
  • the carboxyl group of the acid-modified polyolefin (a) reacts with the carbodiimide group, the interaction between the adhesive composition and the substrate can be enhanced, and the adhesiveness can be improved.
  • the content of the polycarbodiimide (d) is preferably 0.1 part by mass or more, more preferably 0.5 parts by mass, based on 100 parts by mass of the acid-modified polyolefin (a). It is by mass or more, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. When it is set to the above lower limit value or more, the interaction with the base material is exhibited and the adhesiveness is improved. Further, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. Is.
  • the content of polycarbodiimide (d) with respect to the epoxy resin (c) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more with respect to 100 parts by mass of the epoxy resin (c). Is. Further, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less. Within the above range, an adhesive composition having a good balance of solder heat resistance and low dielectric properties can be obtained.
  • the adhesive composition of the present invention contains the three types of resins (a) to (c), and thus contains a low-polarity resin base material such as a liquid crystal polymer (LCP) or syndiotactic polystyrene (SPS). It can exhibit excellent adhesiveness to a metal substrate, pot life, electrical properties (low dielectric properties), and heat resistance. That is, the adhesive coating film (adhesive layer) after the adhesive composition is applied to the base material and cured can exhibit excellent low dielectric constant characteristics.
  • a low-polarity resin base material such as a liquid crystal polymer (LCP) or syndiotactic polystyrene (SPS).
  • the adhesive composition of the present invention can further contain an organic solvent.
  • the organic solvent used in the present invention is not particularly limited as long as it dissolves the acid-modified polyolefin (a), the phenol resin (b) having a polycyclic structure, the epoxy resin (c), and the polycarbodiimide (d). ..
  • aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
  • Halogenized hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene and chloroform
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methylisobutylketone, Ketone solvents such as methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone
  • cell solves such as methyl cellsolve and ethyl cell solve
  • ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate
  • Ethylene glycol mono n-butyl ether ethylene glycol mono iso-butyl ether, ethylene glycol mono t e r t-butyl ether, diethylene glyco
  • the organic solvent is preferably in the range of 100 to 1000 parts by mass, more preferably in the range of 200 to 900 parts by mass, and 300 to 800 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (a). Most preferably it is in the range. When it is at least the above lower limit value, the liquid and pot life properties are improved. Further, setting the value to the upper limit or less is advantageous in terms of manufacturing cost and transportation cost.
  • the adhesive composition according to the present invention preferably has a relative permittivity ( ⁇ c ) of 3.0 or less at a frequency of 1 GHz. It is more preferably 2.6 or less, and even more preferably 2.3 or less. The lower limit is not particularly limited, but is 2.0 in practice. Further, the relative permittivity ( ⁇ ) in the entire region of the frequency 1 GHz to 60 GHz is preferably 3.0 or less, more preferably 2.6 or less, and further preferably 2.3 or less.
  • the adhesive composition according to the present invention preferably has a dielectric loss tangent (tan ⁇ ) at a frequency of 1 GHz or less. It is more preferably 0.01 or less, and even more preferably 0.008 or less. The lower limit is not particularly limited, but is 0.0001 in practice. Further, the dielectric loss tangent (tan ⁇ ) in the entire region of the frequency 1 GHz to 60 GHz is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.005 or less.
  • the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) can be measured as follows. That is, the adhesive composition is applied to the release base material so that the thickness after drying is 25 ⁇ m, and dried at about 130 ° C. for about 3 minutes. Then, it is heat-treated at about 140 ° C. for about 4 hours to be cured, and the cured adhesive composition layer (adhesive layer) is peeled off from the release film. The relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) of the adhesive composition layer after peeling at a frequency of 1 GHz are measured. Specifically, the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) can be calculated from the measurement by the cavity resonator perturbation method.
  • the adhesive composition of the present invention may further contain other components as required.
  • specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
  • a flame retardant may be added to the adhesive composition of the present invention, if necessary.
  • the flame retardant include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds.
  • a phosphorus-based flame retardant is preferable, and a known phosphorus-based flame retardant such as a phosphate ester such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate or the like, a phosphate such as aluminum phosphite, or phosphazene can be used. .. These may be used alone or in any combination of two or more.
  • the flame retardant is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, based on 100 parts by mass of the total of the components (a) to (d).
  • the range of 10 to 100 parts by mass is most preferable. Within the above range, flame retardancy can be exhibited while maintaining adhesiveness, solder heat resistance and electrical characteristics.
  • a tackifier may be added to the adhesive composition of the present invention, if necessary.
  • the tackifier include polyterpene resin, rosin resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, styrene resin, hydrogenated petroleum resin, and the like for the purpose of improving adhesive strength. Used in. These may be used alone or in any combination of two or more.
  • the tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, based on 100 parts by mass of the total of the components (a) to (d). The range of ⁇ 100 parts by mass is most preferable. Within the above range, the effect of the tackifier can be exhibited while maintaining the adhesiveness, solder heat resistance and electrical characteristics.
  • a filler such as silica may be added to the adhesive composition of the present invention. It is very preferable to add silica because the heat resistance property is improved. Hydrophobic silica and hydrophilic silica are generally known as silica, but here, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. in order to impart moisture absorption resistance is used. Is good. When silica is blended, the blending amount is preferably 0.05 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d). Further heat resistance can be exhibited by setting it to the above lower limit value or more. Further, by setting the value to the upper limit or less, it is possible to prevent poor dispersion of silica and excessively high solution viscosity, and workability is improved.
  • a silane coupling agent may be added to the adhesive composition of the present invention, if necessary. It is very preferable to add a silane coupling agent because the properties of adhesion to metal and heat resistance are improved.
  • the silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amino group.
  • glycidyls such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane from the viewpoint of heat resistance.
  • a silane coupling agent having a group is more preferable.
  • the blending amount thereof is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (a) to (d). Within the above range, solder heat resistance and adhesiveness can be improved.
  • the laminate of the present invention is one in which an adhesive composition is laminated on a base material (two-layer laminate of a base material / adhesive layer), or one in which a base material is further bonded (base material / adhesive layer / It is a three-layer laminate of a base material).
  • the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present invention is applied to a base material and dried.
  • the laminate of the present invention can be obtained by applying and drying the adhesive composition of the present invention to various substrates according to a conventional method, and further laminating other substrates.
  • the base material is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, but the base material is a resin base material such as a film-like resin, or a metal. Examples include metal substrates such as plates and metal foils, papers, and the like.
  • the resin base material examples include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
  • a film-like resin hereinafter, also referred to as a base film layer is preferable.
  • any conventionally known conductive material that can be used for the circuit board can be used.
  • the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, as well as alloys, plated products, and metals treated with other metals such as zinc and chromium compounds.
  • a metal leaf is preferable, and a copper foil is more preferable.
  • the thickness of the metal foil is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less.
  • the metal leaf is usually provided in roll form.
  • the form of the metal foil used in manufacturing the printed wiring board of the present invention is not particularly limited. When a ribbon-shaped metal foil is used, its length is not particularly limited. The width thereof is also not particularly limited, but is preferably about 250 to 500 cm.
  • the surface roughness of the base material is not particularly limited, but is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
  • it is practically preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.7 ⁇ m or more. Further, it is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
  • Examples of papers include high-quality paper, kraft paper, roll paper, glassine paper, and the like. Further, as the composite material, glass epoxy or the like can be exemplified.
  • polyester resin polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluorine resin, etc.
  • SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferable.
  • the adhesive sheet is a laminate of the laminate and a release base material via an adhesive composition.
  • Specific configuration embodiments include a laminate / adhesive layer / release base material, or a release base material / adhesive layer / laminate / adhesive layer / release base material.
  • the release base material By laminating the release base material, it functions as a protective layer of the base material. Further, by using the release base material, the release base material can be released from the adhesive sheet and the adhesive layer can be transferred to another base material.
  • the adhesive sheet of the present invention can be obtained by applying the adhesive composition of the present invention to various laminates and drying them according to a conventional method.
  • a release base material is attached to the adhesive layer after drying, it can be wound up without causing set-off to the base material, which is excellent in operability and protects the adhesive layer for storage stability. It is excellent and easy to use.
  • the release base material is coated and dried, and then another release base material is attached as needed, the adhesive layer itself can be transferred to another base material.
  • the release base material is not particularly limited, but for example, a coating layer of a sealant such as clay, polyethylene, or polypropylene is applied to both sides of paper such as high-quality paper, kraft paper, roll paper, and glassine paper. Examples thereof include those in which a silicone-based, fluorine-based, or alkyd-based mold release agent is coated on each of the coating layers.
  • various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, and propylene- ⁇ -olefin copolymer alone, and films such as polyethylene terephthalate coated with the above-mentioned release agent can also be mentioned.
  • polypropylene sealing treatment is applied to both sides of high-quality paper, and an alkyd-based release agent is used on top of it.
  • an alkyd-based mold release agent on polyethylene terephthalate.
  • the method for coating the adhesive composition on the substrate in the present invention is not particularly limited, and examples thereof include a comma coater and a reverse roll coater.
  • the adhesive layer may be provided directly or by a transfer method on the rolled copper foil or the polyimide film which is the constituent material of the printed wiring board.
  • the thickness of the adhesive layer after drying is appropriately changed as needed, but is preferably in the range of 5 to 200 ⁇ m. Sufficient adhesive strength can be obtained by setting the adhesive film thickness to 5 ⁇ m or more. Further, when the thickness is 200 ⁇ m or less, it becomes easy to control the amount of residual solvent in the drying process, and blister is less likely to occur during pressing for manufacturing a printed wiring board.
  • the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% by mass or less. By setting the content to 1% by mass or less, foaming of the residual solvent during pressing of the printed wiring board is suppressed, and blistering is less likely to occur.
  • the "printed wiring board” in the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin base material as a constituent element.
  • the printed wiring board is manufactured by a conventionally known method such as a subtractive method using a metal-clad laminate, for example.
  • the printed wiring board of the present invention can have an arbitrary laminated structure that can be adopted as a printed wiring board.
  • it can be a printed wiring board composed of four layers, a base film layer, a metal foil layer, an adhesive layer, and a cover film layer.
  • it can be a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.
  • two or three or more of the above printed wiring boards may be laminated.
  • the adhesive composition of the present invention can be suitably used for each adhesive layer of the printed wiring board.
  • the adhesive composition of the present invention when used as an adhesive, it has high adhesiveness not only to the conventional polyimide, polyester film, and copper foil constituting the printed wiring board, but also to a low-polarity resin base material such as LCP. , Solder reflow resistance can be obtained, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition used for coverlay films, laminated boards, copper foils with resins, and bonding sheets.
  • any resin film conventionally used as the base material of the printed wiring board can be used as the base film.
  • the resin of the base film include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
  • it has excellent adhesiveness to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfides, syndiotactic polystyrenes, and polyolefin resins.
  • any conventionally known insulating film as an insulating film for a printed wiring board can be used.
  • films made from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyamideimide, liquid crystal polymer, syndiotactic polystyrene, and polyolefin resin are used. It is possible. More preferably, it is a polyimide film or a liquid crystal polymer film.
  • the printed wiring board of the present invention can be manufactured by any conventionally known process other than using the above-mentioned materials for each layer.
  • a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter, referred to as "cover film side semi-finished product”) is manufactured.
  • a semi-finished product (hereinafter referred to as “base film side two-layer semi-finished product”) in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern, or an adhesive layer is laminated on a base film layer.
  • a semi-finished product (hereinafter referred to as “base film side 3-layer semi-finished product") in which a metal foil layer is laminated on the metal foil layer to form a desired circuit pattern (hereinafter referred to as a base film-side 2-layer semi-finished product) Together with the base film side three-layer semi-finished product, it is called “base film side semi-finished product”).
  • base film side semi-finished product By laminating the cover film side semi-finished product thus obtained and the base film side semi-finished product, a four-layer or five-layer printed wiring board can be obtained.
  • the base film side semi-finished product is, for example, (A) a step of applying a resin solution to be a base film to the metal foil and initially drying the coating film, and (B) the metal foil obtained in (A). It is obtained by a production method including a step of heat-treating and drying the laminate with the initial dry coating film (hereinafter, referred to as "heat treatment / solvent removal step").
  • a conventionally known method can be used for forming the circuit in the metal foil layer.
  • the active method may be used, or the subtractive method may be used.
  • the subtractive method is preferable.
  • the obtained base film side semi-finished product may be used as it is for bonding with the cover film side semi-finished product, or for bonding with the cover film side semi-finished product after the release film is bonded and stored. You may use it.
  • the cover film side semi-finished product is manufactured by applying an adhesive to the cover film, for example. If necessary, a cross-linking reaction can be carried out on the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.
  • the obtained cover film side semi-finished product may be used as it is for bonding with the base film side semi-finished product, or may be bonded to the base film side semi-finished product after the release film is bonded and stored. May be used for.
  • the base film side semi-finished product and the cover film side semi-finished product are, for example, stored in the form of rolls and then bonded together to manufacture a printed wiring board. Any method can be used as the bonding method, and for example, the bonding can be performed using a press or a roll. It is also possible to bond the two together while heating by a method such as using a heating press or a heating roll device.
  • the reinforcing material side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material.
  • an adhesive to the reinforcing material.
  • the adhesive previously applied to the release base material is transferred and applied. It is preferable to be manufactured. Further, if necessary, a cross-linking reaction can be carried out in the applied adhesive.
  • the adhesive layer is semi-cured.
  • the obtained reinforcing material side semi-finished product may be used as it is for bonding with the back surface of the printed wiring board, or may be used for bonding with the base film side semi-finished product after the release film is bonded and stored. You may.
  • the base film side semi-finished product, the cover film side semi-finished product, and the reinforcing material side semi-finished product are all laminates for the printed wiring board in the present invention.
  • Acid value (a) component Acid-modified polyolefin
  • the acid value (mgKOH / g) in the present invention was obtained by dissolving the acid-modified polyolefin in toluene and titrating with a methanol solution of sodium methoxydo using phenolphthalein as an indicator.
  • the number average molecular weight in the present invention is gel permeation chromatography manufactured by Shimadzu Corporation (hereinafter, GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 + KF-804L + KF-806L, column. Temperature: 30 ° C., flow velocity: 1.0 ml / min, detector: RI detector).
  • the melting point and heat of melting in the present invention are increased at a rate of 20 ° C./min using a differential scanning calorimeter (hereinafter, DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when the melting point is heated and melted again by hot melting and cooling resin conversion.
  • DSC differential scanning calorimeter
  • peeling strength (adhesiveness)
  • the adhesive composition described below was applied to a polyimide film having a thickness of 12.5 ⁇ m (manufactured by Kaneka Corporation, Apical (registered trademark)) so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes.
  • the adhesive film (B stage product) thus obtained was bonded to a rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., BHY series) having a thickness of 18 ⁇ m.
  • the bonding was performed by pressing the rolled copper foil under a pressure of 40 kgf / cm 2 at 160 ° C.
  • ⁇ Evaluation criteria (PI film and LCP film)> ⁇ : 1.0 N / mm or more ⁇ : 0.8 N / mm or more and less than 1.0 N / mm ⁇ : 0.5 N / mm or more and less than 0.8 N / mm ⁇ : 0.5 N / mm or less ⁇ Evaluation standard (SPS film) )> ⁇ : 0.7 N / mm or more ⁇ : 0.5 N / mm or more and less than 0.7 N / mm ⁇ : 0.3 N / mm or more and less than 0.5 N / mm ⁇ : 0.3 N / mm or less
  • the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu) under the conditions of a temperature of 23 ° C. and a frequency of 1 GHz.
  • a resin solution (varnish) is prepared by blending so as to be%, and refers to the stability of the varnish immediately after blending or after a certain period of time has passed after blending. If the pot life is good, it means that the viscosity of the varnish does not increase so much that it can be stored for a long time.
  • the varnish prepared according to the ratio shown in Table 1 was prepared using a Brookfield type viscometer to obtain a spindle type rotor No. 2. The viscosity of the dispersion liquid at 25 ° C. was measured at a rotation speed of 30 rpm to determine the initial dispersion liquid viscosity ⁇ B0. Then, the varnish was stored at 25 ° C.
  • Solution viscosity ratio solution viscosity ⁇ B / solution viscosity ⁇ B0 ⁇ Evaluation criteria> ⁇ : 0.5 or more and less than 1.5 ⁇ : 1.5 or more and less than 2.0 ⁇ : 2.0 or more and less than 3.0 ⁇ : 3.0 or more or viscosity cannot be measured due to pudding
  • Table 1 shows the blending amount, adhesive strength, solder heat resistance, and electrical characteristics.
  • Examples 2-18 The types and ratios of the resins used were changed as shown in Table 1, and Examples 2 to 18 were carried out in the same manner as in Example 1.
  • Table 1 shows the adhesive strength, solder heat resistance, electrical properties and pot life properties.
  • Comparative Examples 1 to 4 The types and ratios of the resins used were changed as shown in Table 1, and Comparative Examples 1 to 4 were carried out in the same manner as in Example 1.
  • Table 1 shows the adhesive strength, solder heat resistance, electrical properties and pot life properties.
  • the acid-modified polyolefin (a), the phenol resin (b) having a polycyclic structure, and the epoxy resin (c) polycarbodiimide (d) used in Table 1 are as follows.
  • Phenol resin (b) having a polycyclic structure Phenol resin (b1): FTC-509 (manufactured by Gun Ei Chemical Industry Co., Ltd.), a phenol resin having the structures of the general formula (2) and the general formula (11). Both x and y are 0, Z 1 is 1, and the hydroxyl group is bonded to the para position of the benzyl group.
  • R 3 and R 4 are both 2-propenyl groups, x, y, and Z 1 are both 1, and the hydroxyl group is bonded to the para position of the benzyl group.
  • the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-butene copolymer graft-polymerized with maleic anhydride, (poly) maleic anhydride and a low molecular weight substance. Then, by drying under reduced pressure at 70 ° C. for 5 hours, a maleic anhydride-modified propylene-butene copolymer (CO-1, acid value 19 mgKOH / g, number average molecular weight 25,000, Tm80 ° C., ⁇ H35J / g) Got
  • the adhesive composition of the present invention has high adhesiveness not only to conventional polyimide and polyethylene terephthalate films but also to resin base materials such as LCP and SPS and metal base materials such as copper foil, and has high solder heat resistance. It is also excellent in pot life and low dielectric properties (electrical properties).
  • the adhesive composition of the present invention can obtain an adhesive sheet and a laminate bonded using the adhesive sheet. Due to the above characteristics, it is useful for flexible printed wiring board applications, especially for FPC applications where low dielectric properties (low dielectric constant, low dielectric loss tangent) in a high frequency region are required.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

Le problème décrit par la présente invention est de fournir une composition adhésive qui a une adhérence élevée à un substrat métallique et un substrat de résine tel qu'un polymère à cristaux liquides ou un polystyrène syndiotactique, ainsi qu'un film de polyimide ou de polyester classique, et a également d'excellentes caractéristiques diélectriques et une excellente durée de vie en pot, et à partir de laquelle une résistance à la chaleur de soudure élevée peut être obtenue. La solution selon l'invention porte sur une composition adhésive qui contient (a) une polyoléfine modifiée par un acide, (b) une résine phénolique ayant une structure polycyclique, et (c) une résine époxyde.
PCT/JP2020/043610 2019-11-29 2020-11-24 Composition adhésive, feuille adhésive, stratifié et carte de circuit imprimé Ceased WO2021106848A1 (fr)

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JP2021517739A JP6919777B1 (ja) 2019-11-29 2020-11-24 接着剤組成物、接着シート、積層体およびプリント配線板
CN202080069116.4A CN114514300B (zh) 2019-11-29 2020-11-24 粘接剂组合物、粘接片、层叠体以及印刷线路板
KR1020227002553A KR102884272B1 (ko) 2019-11-29 2020-11-24 접착제 조성물, 접착 시트, 적층체 및 프린트 배선판

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2022014531A1 (fr) * 2020-07-17 2022-01-20 東洋紡株式会社 Composition adhésive, feuille adhésive, corps multicouche et carte de circuit imprimé
JP2022108928A (ja) * 2021-01-14 2022-07-27 味の素株式会社 樹脂組成物
JP2022108927A (ja) * 2021-01-14 2022-07-27 味の素株式会社 樹脂組成物
JPWO2023282318A1 (fr) * 2021-07-09 2023-01-12
WO2026033761A1 (fr) * 2024-08-08 2026-02-12 株式会社レゾナック Composition de résine durcissable pour liaison hybride, et procédé de production de corps de connexion de circuit

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