WO2021075367A1 - Composition adhésive à base de polyoléfine - Google Patents

Composition adhésive à base de polyoléfine Download PDF

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Publication number
WO2021075367A1
WO2021075367A1 PCT/JP2020/038267 JP2020038267W WO2021075367A1 WO 2021075367 A1 WO2021075367 A1 WO 2021075367A1 JP 2020038267 W JP2020038267 W JP 2020038267W WO 2021075367 A1 WO2021075367 A1 WO 2021075367A1
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group
adhesive composition
less
mass
resin
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PCT/JP2020/038267
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English (en)
Japanese (ja)
Inventor
遼 薗田
哲生 川楠
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020227011419A priority Critical patent/KR20220084038A/ko
Priority to CN202080061312.7A priority patent/CN114341300A/zh
Priority to JP2021519670A priority patent/JPWO2021075367A1/ja
Publication of WO2021075367A1 publication Critical patent/WO2021075367A1/fr

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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
    • 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
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a polyolefin-based adhesive composition. More specifically, the present invention relates to a polyolefin-based 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 a cover film, a laminated board, a copper foil with a resin, and a bonding sheet 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 relative permittivity, low dielectric loss tangent
  • measures have been taken to reduce the dielectric loss of the FPC base material and the adhesive.
  • As an adhesive a combination of polyimide and epoxy resin using dimer diamine has been developed (Patent Document 1).
  • the present invention provides an adhesive composition containing an acid-modified polyolefin (a) and an epoxy resin (b) with excellent adhesion between a resin base material and a metal base material.
  • the present invention has been completed by finding that it exhibits properties, solder heat resistance, and low dielectric properties (relative permittivity, dielectric loss tangent) and is excellent in dielectric loss tangent after moisture absorption (saturated water absorption).
  • the present invention has good adhesiveness to both various resin substrates such as liquid crystal polymers (LCP) and metal substrates as well as polyimide (PI), and has solder heat resistance, dielectric properties, and moisture absorption. It is an object of the present invention to provide an adhesive composition having excellent dielectric loss tangent after (saturated water absorption).
  • LCP liquid crystal polymers
  • PI polyimide
  • the relative permittivity ( ⁇ c 1) at 1 GHz immediately after curing of the cured product of the adhesive composition is 3.0 or less, and the dielectric loss tangent (tan ⁇ 1) is 0.02 or less.
  • Adhesive composition The amount of change between the dielectric loss tangent (tan ⁇ 1) at 1 GHz immediately after curing of the cured product and the dielectric loss tangent (tan ⁇ 2) at 1 GHz after being immersed in water at 25 ° C. for 24 hours is 0.01 or less.
  • the acid value of the acid-modified polyolefin (a) is preferably 5 to 40 mgKOH / g.
  • the epoxy resin (b) is preferably contained in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (a), and more preferably the oligophenylene ether (c) and / or the carbodiimide compound (d) is contained. ..
  • An adhesive sheet or laminate having a layer containing the above-mentioned adhesive composition.
  • a printed wiring board containing the laminate as a component.
  • 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 metal substrates, and has solder heat resistance, low dielectric properties and moisture absorption (saturation). There is little change in dielectric loss tangent after (water absorption), and it is stable.
  • 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 compatibility with the epoxy resin (b) becomes good, and excellent adhesive strength can be exhibited.
  • the crosslink density is high and the heat resistance is good. Further, the dielectric loss tangent after moisture absorption (saturated water absorption) hardly increases.
  • the upper limit is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, and even more preferably 30 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.
  • 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 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 value is set to the lower limit or more, the cohesive force derived from the crystal becomes good, and excellent adhesiveness and heat resistance can be exhibited. Further, when 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 generate an unsaturated carboxylic acid and (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 generate an unsaturated carboxylic acid and (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 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.
  • Epoxy resin (b) used in the present invention (hereinafter, also simply referred to as the component (b)) 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 a glycidyl 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 or an epoxy-modified polybutadiene. More preferably, it is a dicyclopentadiene type epoxy resin.
  • the epoxy equivalent of the epoxy resin (b) is preferably 50 g / eq or more, more preferably 100 g / eq or more, and further preferably 150 g / eq or more. Further, it is preferably 400 g / eq or less, more preferably 350 g / eq or less, and further preferably 300 g / eq or less. Within the above range, excellent solder heat resistance can be exhibited.
  • the content of the epoxy resin (b) is preferably 0.5 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the acid-modified polyolefin (a).
  • the above is more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more.
  • it 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 dielectric property of the adhesive composition becomes good. That is, within the above range, an adhesive composition having excellent adhesiveness, solder heat resistance, low dielectric properties, and dielectric loss tangent after saturated water absorption can be obtained.
  • the adhesive composition of the present invention is a composition containing at least an acid-modified polyolefin (a) and an epoxy resin (b), and may further contain an oligophenylene ether (c) and / or a carbodiimide compound (d). preferable.
  • the adhesive composition of the present invention has excellent adhesiveness not only to polyimide but also to low-polarity resin substrates such as liquid crystal polymers and metal substrates, and further has solder heat resistance, electrical properties (low dielectric properties), and moisture absorption. Excellent dielectric loss tangent after (saturated water absorption). That is, the adhesive coating film (adhesive layer) after the adhesive composition is applied to the base material and cured can exhibit excellent electrical characteristics.
  • the adhesive composition according to the present invention has a relative permittivity ( ⁇ c 1) of 3.0 or less at a frequency of 1 GHz immediately after curing. It is preferably 2.6 or less, and more preferably 2.3 or less. The lower limit is not particularly limited, but is 2.0 in practice. Further, the relative permittivity ( ⁇ c 1) in the entire region of frequencies 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 has a dielectric loss tangent (tan ⁇ 1) of 0.02 or less at a frequency of 1 GHz immediately after curing. It is preferably 0.01 or less, 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 ⁇ 1) 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 0.008 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 the adhesive composition is dried at about 130 ° C. for about 3 minutes. Then, it is cured by heat treatment at about 140 ° C. for about 4 hours, and the cured adhesive composition layer (adhesive layer) is peeled off from the release film. The relative permittivity ( ⁇ c 1) of the adhesive composition layer after peeling at a frequency of 1 GHz is measured.
  • the relative permittivity ( ⁇ c 1) and the dielectric loss tangent (tan ⁇ 1) can be calculated from the measurement by the cavity resonator perturbation method.
  • "immediately after curing” means within 30 minutes after heat treatment curing.
  • the amount of change between the dielectric loss tangent (tan ⁇ 1) at 1 GHz immediately after curing and the dielectric loss tangent (tan ⁇ 2) at 1 GHz of the cured product after being immersed in water at 25 ° C. for 24 hours after curing is 0.01 or less. Is. It is preferably 0.008 or less, and more preferably 0.005 or less. Industrially, the lower limit may be 0.0001 or more, and may be 0.001 or more.
  • the adhesive composition according to the present invention hardly shows an increase in the relative permittivity even after the cured product of the adhesive composition is absorbed with moisture (saturated water absorption).
  • the relative permittivity ( ⁇ c 2) at a frequency of 1 GHz after moisture absorption (saturated water absorption) of the cured product of the adhesive composition is preferably 3.0 or less. 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.
  • the relative permittivity ( ⁇ c 2) in the entire region of frequencies 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 total amount of maleic acid and maleic anhydride contained in the adhesive composition is preferably 1% by mass or less. It is more preferably 0.8% by mass or less, further preferably 0.6% by mass or less, and particularly preferably 0.4% by mass, because the adhesiveness, solder heat resistance and pot life property are improved. It is as follows. The smaller the total amount of maleic anhydride and maleic acid is, the more preferable it is, but industrially, it may be 0.01% by mass or more, and 0.1% by mass or more may be used.
  • oligophenylene ether (c) By incorporating the oligophenylene ether (c) in the adhesive composition of the present invention, further excellent solder heat resistance can be exhibited. Further, by containing the oligophenylene ether (c), it is possible to suppress an increase in the dielectric loss tangent after moisture absorption.
  • the oligophenylene ether (c) used in the present invention (hereinafter, also simply referred to as the component (c)) is not particularly limited, but is a structural unit represented by the following general formula (c1) and / or a structure of the general formula (c2). It is preferably a compound having a unit.
  • R 1 , R 2 , R 3 , and R 4 are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted alkoxy groups, and optionally substituted, respectively. It is preferably a good alkynyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or an optionally optionally substituted alkoxy group.
  • the "alkyl group” of the alkyl group which may be substituted is, for example, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, preferably 1 or more and 3 or less carbon atoms.
  • a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like can be mentioned, and a methyl group or an ethyl group can be used. More preferably.
  • alkenyl group examples include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group and the like, and an ethenyl group or 1 -It is more preferably a propenyl group.
  • alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl (propargyl) group, 3-butynyl group, pentynyl group, hexynyl group and the like.
  • aryl group of the aryl group which may be substituted include a phenyl group, a naphthyl group and the like, and a phenyl group is more preferable.
  • aralkyl group of the optionally substituted aralkyl group include a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, an ⁇ -methylbenzyl group, a 2-vinylphenethyl group and a 4-.
  • alkoxy group of the optionally substituted alkoxy group is, for example, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, preferably 1 or more and 3 or less carbon atoms.
  • a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and the like can be mentioned, and the group may be a methoxy group or an ethoxy group. preferable.
  • alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group When the above alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group are substituted, it may have one or more substituents.
  • substituents include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom) and an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group).
  • R 1 and R 4 are methyl groups
  • R 2 and R 3 are hydrogen.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are independently hydrogen atoms, optionally substituted alkyl groups, and substituted, respectively. It is preferably an alkenyl group which may be substituted, an alkynyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, or an alkoxy group which may be substituted.
  • the definition of each substituent is as described above.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like, and a methyl group is preferable. .. Of these, it is preferable that R 13 , R 14 , R 17 and R 18 are methyl groups, and R 11 , R 12 , R 15 and R 16 are hydrogen. Further, —A— is preferably a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms, or oxygen.
  • the carbon number of A is more preferably 1 or more and 15 or less, and further preferably 2 or more and 10 or less.
  • Examples of the divalent hydrocarbon group of A include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a cyclohexylene group, a phenylene group and the like, and a phenylene group is preferable. Particularly preferred is oxygen.
  • the oligophenylene ether (c) was partially or wholly functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxyl group, a silyl group and the like. It may be a modified polyphenylene ether. Further, it is preferable that both ends have a hydroxy group, an epoxy group, or an ethylenically unsaturated group.
  • an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxyl group, a silyl group and the like. It may be a modified polyphenylene ether. Further, it is preferable that both ends have a hydroxy group, an epoxy group, or an ethylenically unsaturated group.
  • Examples of the ethylenically unsaturated group include an alkenyl group such as an ethenyl group, an allyl group, a methacrylic group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and a vinylbenzyl group.
  • Alkenylaryl groups such as vinylnaphthyl groups can be mentioned.
  • both ends may be the same functional group or different functional groups. From the viewpoint of highly controlling the balance between low dielectric loss tangent and reduction of resin residue, it is preferable that both ends are hydroxy groups or vinylbenzyl groups, and both ends are hydroxy groups or vinylbenzyl groups. More preferably.
  • n is preferably 3 or more, more preferably 5 or more, preferably 23 or less, more preferably 21 or less, and further preferably 19 or less.
  • n is preferably 2 or more, more preferably 4 or more, preferably 23 or less, more preferably 20 or less, still more preferably 18 or less.
  • the number average molecular weight of the oligophenylene ether (c) is preferably 3000 or less, more preferably 2700 or less, and even more preferably 2500 or less.
  • the number average molecular weight of the oligophenylene ether (c) is preferably 500 or more, and more preferably 700 or more.
  • the content thereof is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (a). Since excellent solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, and further preferably 5 parts by mass or more. Further, it is preferably 200 parts by mass or less. It is more preferably 150 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less because it can exhibit excellent adhesiveness and solder heat resistance.
  • the carbodiimide compound (d) used in the present invention (hereinafter, also simply referred to as the component (d)) is preferably a polyfunctional carbodiimide compound having two or more carbodiimide groups in one molecule.
  • the carboxylic acid anhydride group of the acid-modified polyolefin reacts with the carbodiimide to enhance the interaction between the adhesive composition and the substrate, and improve the adhesiveness and solder heat resistance. be able to.
  • the content thereof is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (a). Since a sufficient curing effect can be obtained and excellent adhesiveness and solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, further preferably 1.5 part by mass or more, and particularly preferably 2 parts. It is more than a mass part. Further, since it has excellent low dielectric properties in addition to adhesiveness and solder heat resistance, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. , Especially preferably 5 parts by mass or less.
  • the carbodiimide compound (d) may be any of an aromatic carbodiimide compound, an alicyclic carbodiimide compound or an aliphatic carbodiimide compound, and these can be used alone or in combination of two or more.
  • the aromatic carbodiimide compound include poly-m-phenylene carbodiimide, poly-p-phenylene carbodiimide, polytrilencarbodiimide, poly (diisopropylphenylene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), and poly (4,4'-diphenylmethanecarbodiimide). ) And so on.
  • Examples of the alicyclic carbodiimide compound include poly-m-cyclohexylcarbodiimide, poly-p-cyclohexylcarbodiimide, poly (4,4'-dicyclohexylmethanecarbodiimide, poly (3,3′-dicyclohexylmethanecarbodiimide, etc.) and the like.
  • the carbodiimide compound may be either a linear or branched aliphatic carbodiimide compound.
  • a linear aliphatic carbodiimide compound is preferable, and specifically, polymethylene carbodiimide, polyethylene carbodiimide, etc.
  • Examples thereof include polypropylene carbodiimide, polybutylene carbodiimide, polypentamethylene carbodiimide, polyhexamethylene carbodiimide, etc. These can be used alone or in combination of two or more, among which aromatic carbodiimide compounds or alicyclic carbodiimides. It is preferably a compound.
  • 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 epoxy resin (b), the oligophenylene ether (c) and the carbodiimide compound (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, etc.
  • Ethylene glycol mono n-butyl ether ethylene glycol mono iso-butyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, triethylene glycol mono n-butyl ether, tetraethylene glycol mono n-butylate, etc.
  • a glycol ether solvent or the like can be used, and one or more of these can be used in combination.
  • Methylcyclohexane and toluene are particularly preferable because of their work environment and dryness.
  • 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 olefin (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 organic solvent is one or more selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons from the viewpoint of the solution state and pot life of the adhesive composition.
  • a mixed solution of one or more solvents (e2) selected from the group consisting of a solvent (e1), an alcohol solvent, a ketone solvent, an ester solvent and a glycol ether solvent is preferable.
  • the solvent (e1) is an aromatic hydrocarbon or an alicyclic hydrocarbon
  • the solvent (e2) is a ketone solvent.
  • the adhesive composition of the present invention may further contain other components as necessary, as long as the effects of the present invention are not impaired.
  • 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, as long as the effects of the present invention are not impaired.
  • 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 When the flame retardant 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, with respect to the total of 100 parts by mass of the components (a) to (d). The range of 100 parts by mass is most preferable. When it is set to the lower limit value or more, the flame retardancy becomes good. Further, when the value is not more than the above upper limit value, the adhesiveness, solder heat resistance, electrical characteristics and the like are not deteriorated.
  • a tackifier may be added to the adhesive composition of the present invention as long as the effects of the present invention are not impaired.
  • 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.
  • the value By setting the value to the lower limit or more, the effect of the tackifier can be exhibited. Further, when the value is not more than the above upper limit value, the adhesiveness, solder heat resistance, electrical characteristics and the like are not deteriorated.
  • the adhesive composition of the present invention may contain a filler such as silica, if necessary, as long as the effects of the present invention are not impaired. It is very preferable to add silica because the properties of solder heat resistance are 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 contained, the content thereof is preferably in the range of 0.05 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d).
  • the value By setting the value to the lower limit or more, the effect of improving the solder heat resistance can be obtained. Further, when the value is not more than the upper limit value, poor dispersion of silica does not occur, the solution viscosity is good, and the workability is good. Moreover, the adhesiveness does not decrease.
  • a silane coupling agent may be added to the adhesive composition of the present invention, if necessary, as long as the effects of the present invention are not impaired. It is highly preferable to add a silane coupling agent because the properties of adhesion to metal and solder 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.
  • a silane coupling agent having a glycidyl group is more preferable.
  • the silane coupling agent is contained, the content thereof is preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (a) to (d).
  • the amount is 0.5 parts by mass or more, excellent solder heat resistance becomes good.
  • the amount is 20 parts by mass or less, the solder heat resistance and the adhesiveness are improved.
  • the laminate of the present invention is one in which an adhesive composition is laminated on a base material (a 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.
  • 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 glassin 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. If the adhesive film thickness is less than 5 ⁇ m, the adhesive strength is insufficient. If the thickness is 200 ⁇ m or more, drying is insufficient, the amount of residual solvent increases, and there is a problem that blister is generated 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. If it exceeds 1% by mass, there is a problem that the residual solvent foams when the printed wiring board is pressed, causing blisters.
  • 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 a cover film, a laminated board, a copper foil with a resin, and a bonding sheet.
  • 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 sulfide, syndiotactic polystyrene, 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 produced by using any conventionally known process other than using the materials of the above-mentioned layers.
  • 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).
  • 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 (mgKOH / g) The acid value (mgKOH / g) in the present invention was determined by dissolving an acid-modified polyolefin in toluene and titrating with a methanol solution of sodium methoxide 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 calorific value of melting in the present invention are 20 ° C. 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 temperature is raised and thawed at a rate of / minute, and the resin is converted into a cooling resin and then heated and melted again.
  • DSC differential scanning calorimeter
  • peeling strength (adhesiveness)
  • the adhesive composition described later is applied to a 12.5 ⁇ m-thick polyimide film (Kaneka Corporation, Apical (registered trademark)) or a 25 ⁇ m-thick LCP film (Kurare Co., Ltd., Vecstar (registered trademark)).
  • the film was applied so that the thickness after drying was 25 ⁇ m, 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. for 30 seconds so that the glossy surface of the rolled copper foil was in contact with the adhesive layer. Then, it was heat-treated at 140 ° C. for 4 hours to be cured to obtain a sample for evaluation of peel strength.
  • the peel strength was measured by performing a 90 ° peel test at a film pulling rate of 50 mm / min at 25 ° C. This test shows the adhesive strength at room temperature.
  • the relative permittivity ( ⁇ c 1) and the dielectric loss tangent (tan ⁇ 1) 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. The measurement was performed within 1 hour after the heat treatment and curing.
  • the obtained relative permittivity and dielectric loss tangent were evaluated as follows.
  • Teflon registered trademark
  • the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing.
  • the test adhesive resin sheet was immersed in water at 25 ° C. and left for 24 hours. Then, the water on the surface was wiped off, and the obtained test adhesive resin sheet was cut into strips of 8 cm ⁇ 3 mm to obtain a test sample.
  • the relative permittivity ( ⁇ c 2) and the dielectric loss tangent (tan ⁇ 2) 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.
  • the amount of change between the dielectric loss tangent (tan ⁇ 1) immediately after curing and the dielectric loss tangent (tan ⁇ 2) after saturated water absorption was calculated and evaluated by the following formula.
  • Amount of change
  • Table 1 shows the blending amount, adhesive strength, solder heat resistance, electrical characteristics immediately after curing, and the rate of change in dielectric loss tangent after saturated water absorption.
  • Examples 2 to 16 The blending amounts of the components (a) to (d) were changed as shown in Table 1, and Examples 2 to 16 were carried out in the same manner as in Example 1.
  • Table 1 shows the adhesive strength, solder heat resistance, electrical characteristics immediately after curing, and the amount of change in dielectric loss tangent after saturated water absorption.
  • Comparative Examples 1 to 3 The blending amounts of the components (a) to (d) were changed as shown in Table 1, and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1.
  • Table 1 shows the adhesive strength, solder heat resistance, electrical characteristics immediately after curing, and the rate of change in dielectric loss tangent after saturated water absorption.
  • the acid-modified polyolefin (a), epoxy resin (b), oligophenylene ether (c) and carbodiimide compound (d) used in Table 1 are as follows.
  • Oligophenylene ether styrene modified product OPE-2St 1200 (Compound having the structure of the general formula (c4) of Mn1000 manufactured by Mitsubishi Gas Chemical Company, Inc.)
  • 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
  • Production example 5 By carrying out the same procedure as in Production Example 1 except that the amount of maleic anhydride charged was changed to 3 parts by mass, the maleic anhydride-modified propylene-butene copolymer (CO-5, acid value 4 mgKOH / g, number average molecular weight 37) was used. 000, Tm 84 ° C., ⁇ H25J / g) was obtained.
  • the adhesive composition of the present invention has excellent adhesiveness not only to polyimide but also to a non-polar resin base material such as a liquid crystal polymer and a metal base material such as copper foil. Furthermore, it has excellent solder heat resistance and low dielectric properties, and is also excellent in dielectric loss tangent after saturated water absorption.
  • 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 relative permittivity, low dielectric loss tangent) are required in a high frequency region.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention aborde le problème de la fourniture d'une composition adhésive qui a une adhérence élevée entre un substrat métallique et un substrat de résine non polaire tel qu'un substrat fait d'un polymère à cristaux liquides, présente également une résistance à la chaleur de soudure et de faibles propriétés diélectriques, et présente en outre une tangente diélectrique exceptionnelle après saturation par absorption d'eau.　La composition adhésive selon l'invention contient une polyoléfine modifiée par un acide (a) et une résine époxy (b) et satisfait les conditions (1) et (2). (1) La constante diélectrique relative (εc1) à 1 GHz immédiatement après le durcissement d'un produit durci de la composition adhésive est inférieure ou égale à 3,0 et la tangente diélectrique (tanδ1) est inférieure ou égale à 0,02. (2) La quantité de changement entre la tangente diélectrique (tanδ1) à 1 GHz immédiatement après le durcissement d'un produit durci de la composition adhésive et la tangente diélectrique (tanδ2) à 1 GHz après que le produit durci a été immergé dans de l'eau à 25 °C pendant 24 heures est de 0,01 ou moins.
PCT/JP2020/038267 2019-10-18 2020-10-09 Composition adhésive à base de polyoléfine WO2021075367A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016031342A1 (fr) * 2014-08-27 2016-03-03 東洋紡株式会社 Composition adhésive faiblement diélectrique
WO2016047289A1 (fr) * 2014-09-24 2016-03-31 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive l'utilisant
JP2019127501A (ja) * 2018-01-22 2019-08-01 藤森工業株式会社 熱硬化性接着剤組成物、接着フィルム、カバーレイフィルム及びフレキシブルプリント配線板

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JP6829200B2 (ja) * 2015-08-25 2021-02-10 三井金属鉱業株式会社 樹脂層付金属箔、金属張積層板、及びプリント配線板の製造方法
JP6759932B2 (ja) 2015-09-30 2020-09-23 荒川化学工業株式会社 変性ポリイミド、接着剤組成物、樹脂付銅箔、銅張積層板、プリント配線板及び多層基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016031342A1 (fr) * 2014-08-27 2016-03-03 東洋紡株式会社 Composition adhésive faiblement diélectrique
WO2016047289A1 (fr) * 2014-09-24 2016-03-31 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive l'utilisant
JP2019127501A (ja) * 2018-01-22 2019-08-01 藤森工業株式会社 熱硬化性接着剤組成物、接着フィルム、カバーレイフィルム及びフレキシブルプリント配線板

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