WO2014148155A1 - Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition - Google Patents

Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition Download PDF

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Publication number
WO2014148155A1
WO2014148155A1 PCT/JP2014/053290 JP2014053290W WO2014148155A1 WO 2014148155 A1 WO2014148155 A1 WO 2014148155A1 JP 2014053290 W JP2014053290 W JP 2014053290W WO 2014148155 A1 WO2014148155 A1 WO 2014148155A1
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WIPO (PCT)
Prior art keywords
resin composition
component
alkyl group
halogen atom
carbon atoms
Prior art date
Application number
PCT/JP2014/053290
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French (fr)
Japanese (ja)
Inventor
慎 寺木
宗俊 日馬
吉田　真樹
Original Assignee
ナミックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ナミックス株式会社 filed Critical ナミックス株式会社
Priority to CN201480015746.8A priority Critical patent/CN105051111B/en
Priority to JP2015506649A priority patent/JP6188788B2/en
Priority to KR1020157026205A priority patent/KR102138174B1/en
Publication of WO2014148155A1 publication Critical patent/WO2014148155A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • 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
    • B32B2274/00—Thermoplastic elastomer material
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer

Definitions

  • the present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for an adhesive film for electric / electronic use or a coverlay film for a printed wiring board. Moreover, this invention relates to the adhesive film produced using this resin composition, and a coverlay film. The present invention also relates to the use of the resin composition for interlayer adhesion of multilayer printed wiring.
  • Patent Document 1 provides a curable resin composition that has a low dielectric constant, a low dielectric loss tangent, and has excellent heat resistance, mechanical properties, chemical resistance, and flame retardancy, and can be cured at low temperature. Curable films, cured products obtained by curing these films, and films are disclosed.
  • Patent Document 2 discloses a metal foil that forms a wiring of a flexible printed wiring board and an electrical material in a high frequency region having a frequency of 1 GHz or more that has excellent adhesive strength to the substrate material of the flexible printed wiring board.
  • a coverlay film that exhibits characteristics, specifically, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 GHz or higher has been proposed.
  • thermosetting it is possible to apply equipment / conditions generally used for substrate production at the time of interlayer adhesion of multilayer printed wiring boards and thermosetting of an adhesive film used as an FPC coverlay film.
  • equipment / conditions generally used for substrate production at the time of interlayer adhesion of multilayer printed wiring boards and thermosetting of an adhesive film used as an FPC coverlay film.
  • thermosetting it is desirable to carry out thermosetting at a lower temperature, for example, because warpage during cooling increases. Specifically, it is desirable to carry out thermosetting at 180 ° C. or lower.
  • the present invention provides organic substrate materials such as epoxy resins, phenol resins, bismaleimide triazine resins, inorganic substrate materials such as ceramic substrates and silicon substrates, and FPCs such as polyimide films.
  • organic substrate materials such as epoxy resins, phenol resins, bismaleimide triazine resins, inorganic substrate materials such as ceramic substrates and silicon substrates, and FPCs such as polyimide films.
  • ⁇ dielectric constant
  • a resin composition that has a low shrinkage stress during thermosetting and can be thermoset at 180 ° C. or less, and an adhesive film created using the resin composition, and
  • An object is to provide a coverlay film.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group.
  • — (O—X—O) — is represented by the following structural formula (2).
  • R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • -(YO)- is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
  • R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom.
  • a and b each represents an integer of 0 to 300, at least one of which is not 0.
  • c and d represent an integer of 0 or 1.
  • the component (D) is contained in an amount of 1 to 10% by mass based on the total mass of the components (A) to (F), Provided is a resin composition containing 0.1 to 10% by mass of the component (F) in terms of mass percent based on the content of the component (A).
  • — (O—X—O) — of the component (A) is represented by the following structural formula (4)
  • — (YO) — of the component (A) is Structural formula (5), or a structure represented by the following structural formula (6), or a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) are randomly arranged. It is preferable.
  • the organic peroxide as the component (F) is preferably a peroxyester or a dialkyl peroxide.
  • the epoxy resin as the component (D) is at least selected from the group consisting of a biphenyl type epoxy resin, a fluorene type epoxy resin, and a naphthalene type epoxy resin having no hydroxyl group in the molecule.
  • a biphenyl type epoxy resin a fluorene type epoxy resin
  • a naphthalene type epoxy resin having no hydroxyl group in the molecule.
  • One is preferred.
  • the present invention also provides an adhesive film comprising the resin composition of the present invention.
  • the present invention also provides a multilayer printed wiring board using the resin composition of the present invention or the adhesive film of the present invention for interlayer adhesion.
  • substrate which comprises the multilayer printed wiring board of this invention is a resin substrate which has as a main component the vinyl compound represented by the said General formula (1), and rubber
  • the present invention also provides a coverlay film comprising the resin composition of the present invention.
  • the present invention also provides a flexible printed wiring board having the cover lay film of the present invention.
  • the cover lay film of the present invention is used on the wiring pattern side of the resin substrate with wiring in which the wiring pattern is formed on the main surface of the resin substrate mainly composed of liquid crystal polymer, polyimide, or polyethylene naphthalate.
  • a flexible printed wiring board is provided.
  • the present invention provides a resin substrate with wiring in which a wiring pattern is formed on a main surface of a resin substrate mainly composed of the vinyl compound represented by the general formula (1) and rubber and / or thermoplastic elastomer.
  • a flexible printed wiring board is provided in which the coverlay film of the present invention is used on the wiring pattern side.
  • the resin composition of the present invention has excellent adhesive strength to FPC substrate materials such as metal foils and polyimide films that form FPC wiring, and has excellent electrical characteristics in the high frequency region, specifically Shows a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 GHz or more, and is suitable as a coverlay film for FPC.
  • the resin composition of the present invention has excellent adhesion strength to organic substrate materials such as epoxy resins, phenol resins, bismaleimide triazine resins, and inorganic substrate materials such as ceramic substrates and silicon substrates. Therefore, it is also suitable as an interlayer adhesive for multilayer printed wiring boards using these substrates.
  • the resin composition of the present invention is suitable for fluidity and dimensional stability when bonded on a substrate, so it is used as a coverlay film or as an interlayer adhesive for multilayer printed wiring boards. In this case, the workability is excellent, and the embedding property of the circuit is not impaired.
  • the resin composition of the present invention has a small shrinkage stress at the time of thermosetting, when it is used as an interlayer adhesive of a multilayer printed wiring board, the stress remaining in the interlayer adhesive portion is reduced. As a result, the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved.
  • the resin composition of the present invention is used as an FPC coverlay film, the occurrence of warpage during thermosetting is suppressed. Therefore, the flexibility of the FPC is not impaired.
  • the resin composition of the present invention can be cured at 180 ° C. or lower, it is generally used when used as an interlayer adhesive for multilayer printed wiring boards or as a coverlay film for FPC.
  • Equipment and conditions used for substrate manufacture are applicable, and there are further advantages such as reduction in warpage, dimensional stability, improved heat resistance such as solder heat resistance, and improved peel strength.
  • the resin composition of the present invention contains the following components (A) to (F) as essential components.
  • R 1, R 2, R 3, R 4, R 5, R 6, R 7 are the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or It is a phenyl group.
  • R 1, R 2, R 3, R 4, R 5, is preferably R 6, R 7 is a hydrogen atom.
  • — (O—X—O) — is represented by the following structural formula (2).
  • R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • R 8 , R 9 , R 10 , R 14 , and R 15 are preferably alkyl groups having 6 or less carbon atoms.
  • R 11 , R 12 and R 13 are preferably a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms.
  • -(YO)- is a random arrangement of one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) It is a thing.
  • R 16 and R 17 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • R 16 and R 17 are preferably alkyl groups having 6 or less carbon atoms.
  • R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
  • R 18 and R 19 are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms.
  • Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Among these, it is preferable that Z is a methylene group.
  • a and b each represents an integer of 0 to 300, at least one of which is not 0.
  • c and d represent an integer of 0 or 1.
  • c and d are preferably 1.
  • R 8, R 9, R 10, R 14, R 15 is alkyl group having 3 or less carbon atoms
  • R 11, R 12, R 13 is a hydrogen atom or alkyl group having 3 or less carbon atoms
  • R 16 and R 17 are alkyl groups having 3 or less carbon atoms
  • R 18 and R 19 are hydrogen atoms.
  • — (O—X—O) — in the general formula (1) is preferably represented by the following structural formula (4).
  • — (Y—O) — represents the structure represented by the following structural formula (5), the following structural formula (6), the structure represented by the following structural formula (5), and It is preferable to have a structure in which the structure represented by the following structural formula (6) is randomly arranged.
  • -(YO)- preferably has a structure in which structures defined by the following structural formula (6) are arranged.
  • the component (A) is an adhesive film and coverlay film prepared using the resin composition, or thermosetting, heat resistance of an interlayer adhesive using the resin composition, In addition, it contributes to excellent electrical characteristics at high frequencies, that is, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 GHz or higher.
  • the component (A) among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 500 to 4000 are used as follows.
  • Mw mass average molecular weight
  • the mass average molecular weight (Mw) is less than 500, the flexibility of the adhesive film and coverlay film prepared using the resin composition is lost, and the film becomes brittle and easily broken.
  • the melt viscosity is too low during thermocompression bonding or heat curing, the film thickness uniformity of the adhesive film and coverlay film created using the resin composition may be impaired, and the resin composition When used as an interlayer adhesive, the uniformity of the thickness of the interlayer adhesive may be impaired.
  • the component (A) among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 800 to 3500 are more preferable, and those having a mass average molecular weight (Mw) of 1000 to 3000 are more preferable.
  • the method for producing the vinyl compound represented by the general formula (1) is not particularly limited, and may be produced by any method.
  • chloromethylstyrene is added to a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like, if necessary, benzyltri n-butylammonium bromide, 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.
  • an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like
  • benzyltri n-butylammonium bromide 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.
  • — (O—X—O) and — (Y—O) — are as described above for formula (1).
  • Component (B) Polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35%
  • Component (C) Polystyrene-poly (ethylene-ethylene / propylene) having a styrene content of 25 to 40% Block Copolymer
  • the components (B) and (C) are particularly excellent electrical properties (frequency of 1 GHz or more) at high frequencies of adhesive films and coverlay films prepared using the resin composition. This contributes to low dielectric constant ( ⁇ ) and low dielectric loss tangent (tan ⁇ ), film properties, and heat resistance.
  • the component (C) is superior in the dielectric characteristics compared to the component (B), and has excellent electrical characteristics at high frequencies (low dielectric constant ( ⁇ ) in a frequency region of 1 GHz or more, and low dielectric constant). Tangent (tan ⁇ )).
  • component (C) has a higher elastic modulus (tensile elastic modulus) of the thermoset than component (B), if component (C) is used alone, the shrinkage stress during thermosetting increases. It is necessary to use the component (B) in combination. For this reason, in the resin composition of this invention, component (B) and (C) are used with the specific compounding ratio described below.
  • components (B) and (C) having a styrene content in the specific range described above.
  • the styrene content of the component (B) is less than 15%, there is a problem that the compatibility with other components of the resin composition is poor.
  • the styrene content of the component (B) is more than 35%, it becomes difficult to form a film such as a crack occurs in an uncured film when an adhesive film or a coverlay film is formed using the resin composition. There's a problem.
  • the styrene content of the component (C) is less than 25%, there is a problem that the compatibility with other components of the resin composition is poor.
  • the styrene content of the component (C) is more than 40%, when forming an adhesive film or a coverlay film using the resin composition, it becomes difficult to form a film such as a crack occurs in an uncured film. There's a problem.
  • Component (D) Epoxy resin
  • the component (D) used an adhesive film and a coverlay film prepared using the resin composition, and the resin composition was used as an interlayer adhesive. This contributes to thermosetting and adhesiveness.
  • the solubility of the component (E) with respect to low boiling-point solvents, such as toluene, methyl ethyl ketone, and methyl isobutyl ketone improves by using a component (D).
  • the content of the component (D) is 1 to 10% by mass with respect to the total mass of the components (A) to (E).
  • the resin composition of the present invention more preferably contains 1 to 5% by mass of the component (D) with respect to the total mass of the components (A) to (E).
  • the epoxy resin used as the component (D) is not particularly limited, and various epoxies such as novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, naphthalene type epoxy resin and the like. Resin can be used.
  • an epoxy resin having a hydroxyl group in the molecule is used as the epoxy resin of component (D)
  • the dielectric constant of the resin composition increases due to the influence of the polarity of the hydroxyl group when the content of the epoxy resin increases. .
  • epoxy resins this corresponds to biphenyl type epoxy resins, fluorene type epoxy resins, and naphthalene type epoxy resins that do not have a hydroxyl group in the molecule.
  • an epoxy resin in which no hydroxyl group exists in these molecules an increase in dielectric constant can be suppressed.
  • any 1 type may be used and 2 or more types may be used together.
  • the epoxy resin used as component (D) preferably has a number average molecular weight (Mn) of 150 to 2500 for reasons of thermosetting, adhesiveness, and mechanical properties after curing.
  • Component (E) Bismaleimide
  • the bismaleimide of component (E) acts with the vinyl compound of component (A) to advance the heat curing of the adhesive layer of the cover lay film at a lower temperature.
  • bismaleimide is used because it is preferable from the viewpoints of maintaining dielectric properties, imparting adhesive strength, and increasing Tg (glass transition point).
  • the blending amount of the component (E) bismaleimide is preferably determined by the equivalent ratio of the vinyl compound of the component (A) to the vinyl group. Specifically, the bismaleimide of the component (E) is 0.1 to 3 equivalents and 0.5 to 1.5 equivalents relative to 1 equivalent of the vinyl group of the vinyl compound of the component (A). Preferably, it is 0.8 to 1.3 equivalent.
  • components (A) and (E) are thermosetting resin materials
  • components (B) and (C) are thermoplastic resin materials.
  • the blending ratio of these thermosetting resin material and thermoplastic resin material affects the physical properties of the resin composition. Therefore, (components (A), (E)) and (components (B), (C)) are used in the specific blending ratio described below.
  • the epoxy resin of component (D) is also a thermosetting resin material. However, as described above, the content of component (D) is 1% by mass with respect to the total mass of components (A) to (E).
  • the component (D) can be obtained by using (components (A), (E)) and (components (B), (C)) and the specific blending ratio described below.
  • the influence on the physical properties of the resin composition of the present invention is negligible.
  • Component (F) Organic peroxide having an exothermic peak of 100 ° C. or higher and 180 ° C. or lower as measured by differential scanning calorimetry (DSC)
  • component (F) is a vinyl compound used as component (A). Accelerates the reaction and enables low temperature curing below 180 ° C. In addition, it exerts actions such as warpage reduction, dimensional stability, improved heat resistance such as solder heat resistance, and improved peel strength.
  • the exothermic peak by DSC measurement in the present invention refers to that measured by the following procedure. The exothermic peak is read from the DSC curve obtained with a differential scanning calorimeter at a temperature increase of 5 ° C./min. In the present invention, the temperature at the peak top is the exothermic peak of the object.
  • the exothermic peak by DSC measurement is less than 100 ° C.
  • the reaction proceeds and cures due to the heat history. For this reason, the bonding function is lost.
  • the resin composition of the present invention is used as an interlayer adhesive for multilayer printed wiring boards, it is necessary to volatilize the solvent and dry it after applying the varnish containing the resin composition. As in the film formation, the adhesive function is lost by curing due to thermal history. If the exothermic peak by DSC measurement is higher than 180 ° C, the heat curing time at 180 ° C or lower becomes longer. In the present invention, the exothermic peak by DSC measurement is more preferably 120 to 180 ° C.
  • the organic peroxide of component (F) includes isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide.
  • Diacyl peroxides such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane and the like; di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate
  • Peroxydicarbonates such as tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl Luziper adipate, cumyl perneodecanoate, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5 di Peroxyesters such as (benzoylperoxy) hexane; ketone peroxides such
  • peroxyesters and dialkyl peroxides are preferable, and tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and di (2- tert-Butylperoxyisopropyl) benzene is particularly preferred since the exothermic peak by DSC measurement is 120 to 180 ° C. and the storage stability of the composition is good.
  • the content of the component (F) is 0.1 to 10% by mass in terms of mass percent with respect to the content of the component (A).
  • the content of the component (F) is less than 0.1% by mass, the effect of promoting the reaction of the vinyl compound used as the component (A) becomes insufficient. For this reason, thermosetting at 180 degrees C or less cannot be achieved.
  • the content of the component (F) is more than 10% by mass, the electrical characteristics at high frequencies are deteriorated.
  • the content of the component (F) is more preferably 1 to 10% by mass with respect to the content of the component (A).
  • the resin composition of the present invention may contain a curing catalyst as the component (G) in addition to the components (A) to (F).
  • This curing catalyst acts as a curing catalyst for the epoxy resin of component (D).
  • the curing catalyst used as the component (G) is not particularly limited as long as it is an epoxy resin curing catalyst, and a known one can be used.
  • an imidazole-based curing catalyst, an amine-based curing catalyst, a phosphorus-based curing catalyst, and the like can be given.
  • imidazole curing catalysts examples include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl.
  • imidazole compounds such as -4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Of these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-imidazole are preferable.
  • amine-based curing catalysts include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene. And tertiary amine compounds such as -7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Of these, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine is preferable.
  • triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine is preferable.
  • Examples of phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and the like.
  • any 1 type may be used among said curing catalyst, and 2 or more types may be used together.
  • the effective amount of the curing catalyst varies depending on the type of the curing catalyst. The effective amount for each type of curing catalyst is shown below. In the case of an imidazole-based curing catalyst or an amine-based curing catalyst, the effective amount is 0.01 to 5% by mass and 0.05 to 3% by mass with respect to the total mass of all components of the resin composition. Is more preferable. In the case of a phosphorus-based curing catalyst, the effective amount is 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of all components of the resin composition.
  • the resin composition of the present invention may further contain other components as necessary.
  • specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, and the like.
  • the resin composition of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above components (A) to (F) (if the resin composition contains the above component (G) or other optional components, these optional components are further heated). Mix with a vacuum mixing kneader. A predetermined solvent so that the components (A) to (F) have a desired content ratio (if the resin composition contains the component (G) or other optional components, these optional components); Dissolve to a concentration, put them into a reaction kettle warmed to 10 to 80 ° C., perform normal pressure mixing for 3 hours while rotating at a rotational speed of 100 to 1000 rpm, and then under vacuum (maximum 1 Torr) The mixture can be further stirred for 30 to 60 minutes.
  • the resin composition of the present invention has suitable characteristics shown below.
  • the thermosetting material is excellent in the electrical property in a high frequency.
  • the thermosetting product of the resin composition preferably has a dielectric constant ( ⁇ ) of 3.0 or less, more preferably 2.5 or less in a region having a frequency of 1 GHz or more.
  • the dielectric loss tangent (tan ⁇ ) in the region of the frequency of 1 GHz or more is more preferably 0.01 or less, and more preferably 0.005 or less.
  • the thermosetting product has a tensile elastic modulus of 150 to 450 MPa since the adhesive strength is high and the shrinkage stress during thermosetting is reduced. If the tensile modulus is 450 MPa or less, the shrinkage stress at the time of thermosetting is reduced, and the following effects are obtained.
  • the stress remaining in the interlayer adhesive portion is reduced. As a result, the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved.
  • the curvature amount of the thermosetting material of a 100 mm square film is 15 mm or less, and is 10 mm or less. Is more preferable.
  • the tensile elastic modulus of the thermoset is too low, the adhesive strength of the resin composition is lowered, so it is necessary to set it to 150 MPa or more.
  • the resin composition of the present invention more preferably has a tensile elastic modulus of the thermoset of 200 to 400 MPa.
  • the resin composition of the present invention preferably has a minimum melt viscosity of 1000 to 50000 Pa ⁇ s in the temperature range of 100 to 180 ° C., when it is thermally cured. If the minimum melt viscosity at the time of thermosetting is in the above range, it is preferable because the fluidity at the time of thermosetting becomes an appropriate state. Specifically, the fluidity is good at the time of thermocompression bonding of an adhesive film or coverlay film produced using the resin composition, or at the time of thermocompression bonding when the resin composition is used as an interlayer adhesive. Therefore, the embedding property to the fine pitch wiring pattern is improved.
  • the minimum melt viscosity is the minimum value of the viscosity when the adhesive film is melted when the resin composition is heated.
  • the minimum melt viscosity in the temperature range of 100 to 180 ° C is less than 1000 Pa ⁇ s, the fluidity at the time of thermosetting is too high, so the film thickness of the adhesive film or coverlay film before or after thermosetting, or the interlayer adhesion part There is a possibility that the thickness of the material changes. If the minimum melt viscosity in the temperature range of 100 to 180 ° C. is more than 50000 Pa ⁇ s, the embedding property in the fine pitch wiring pattern may be insufficient, and it is necessary to increase the press pressure applied during thermocompression bonding.
  • the resin composition of the present invention preferably has a minimum melt viscosity of 2000 to 20000 Pa ⁇ s in a temperature range of 100 to 180 ° C.
  • the resin composition of the present invention preferably has a glass transition temperature of 160 ° C. or higher from the viewpoint of heat resistance and long-term reliability of the thermoset.
  • the thermosetting material has sufficient adhesive strength.
  • the thermosetting product of the resin-resin composition preferably has a peel strength (180 degree peel) with respect to the roughened copper foil surface measured in accordance with JIS C6471 of 5 N / cm or more, more preferably 6 N. / Cm or more.
  • times peel) with respect to the polyimide film measured based on JISC6471 is 5 N / cm or more, More preferably, it is 6 N / cm or more.
  • the adhesive film and coverlay film of the present invention can be obtained from the resin composition of the present invention by a known method.
  • the resin composition of the present invention is diluted with a solvent to obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.
  • the solvent that can be used as the varnish examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high-boiling solvents such as dioctyl phthalate and dibutyl phthalate.
  • the amount of the solvent used is not particularly limited and may be a conventionally used amount, but is preferably 20 to 90% by mass with respect to the solid content.
  • the support is appropriately selected depending on the desired form in the film production method, and is not particularly limited. Examples thereof include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When providing the adhesive film of this invention as a form of the film peeled from the support body, it is preferable that the support body is mold-release-processed with the silicone compound etc.
  • the method for applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, which are appropriately selected according to a desired film thickness and the like. This is preferable because it can be designed to be thin.
  • coating is performed so that the thickness of the film formed after drying may turn into desired thickness. Such a thickness can be derived from the solvent content by those skilled in the art.
  • the thickness of the adhesive film and cover lay film of the present invention is appropriately designed based on characteristics such as mechanical strength required according to the application, but is generally 1 to 100 ⁇ m, and when thinning is required, It is preferably 1 to 30 ⁇ m.
  • the drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used and the thickness of the coating, and are not particularly limited.
  • the drying conditions are 60 to 100 ° C., It can be performed under atmospheric pressure.
  • the procedure for using the adhesive film of the present invention is as follows.
  • the adhesive film of the present invention is placed on the surface to be bonded of one object, the other surface is exposed to the adhesive film. Place it in contact with the surface.
  • the adhesive film is placed so that the exposed surface of the adhesive film is in contact with the adherend surface of one object, and the adhesive film is transferred onto the adherend surface.
  • the temperature at the time of transfer can be set to 130 ° C., for example.
  • the other object is placed on the surface of the adhesive film exposed by peeling the support during transfer so that the surface to be bonded is in contact with the exposed surface of the adhesive film.
  • thermocompression bonding is performed for a predetermined temperature and for a predetermined time, and then heat-cured.
  • the temperature during thermocompression bonding is preferably 100 to 180 ° C.
  • the time for thermocompression bonding is preferably 0.5 to 10 minutes.
  • the temperature for heat curing is preferably 150 to 180 ° C.
  • the heat curing time is preferably 30 to 120 minutes.
  • the varnish obtained by diluting the resin composition of the present invention with a solvent is applied to the adherend surface of one object to be bonded and dried, and then the one object described above is used. You may implement the procedure which mounts an object.
  • the adhesive film of the present invention can also be used for interlayer adhesion of multilayer printed wiring boards.
  • the above-described object to be bonded becomes a substrate constituting each layer of the multilayer printed wiring board.
  • a varnish obtained by diluting the resin composition of the present invention with a solvent may be used instead of using a film formed in advance.
  • the stress remaining in the interlayer bonded portion is reduced.
  • the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved.
  • the dimensional stability of the interlayer adhesive portion is excellent.
  • the substrate constituting each layer of the multilayer printed wiring board is not particularly limited, and any of an organic substrate such as an epoxy resin, a phenol resin, and a bismaleimide triazine resin, and an inorganic substrate such as a ceramic substrate and a silicon substrate can be used.
  • a resin substrate suitable for the FPC of the present invention described later can also be used.
  • the cover lay film of the present invention is placed at a predetermined position on the resin substrate with wiring on which the wiring pattern is formed on the main surface, that is, on the side where the wiring pattern is formed, with the cover lay film.
  • the thermocompression bonding may be performed for a predetermined temperature and a predetermined time.
  • the temperature at the time of provisional pressure bonding is preferably 100 to 180 ° C.
  • the pre-bonding time is preferably 0.5 to 10 minutes.
  • the temperature for heat curing is preferably 150 to 180 ° C.
  • the heat curing time is preferably 30 to 120 minutes.
  • production of the curvature at the time of thermosetting is suppressed.
  • the flexible printed wiring board (FPC) of the present invention is heat-cured for a predetermined temperature and for a predetermined time after the coverlay film of the present invention is disposed on the wiring pattern side of the resin substrate with wiring having a wiring pattern formed on the main surface.
  • the resin substrate with wiring and the coverlay film are integrated.
  • the resin substrate used in the FPC of the present invention also has excellent electrical characteristics in a high frequency region, that is, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency region of 1 GHz or higher. preferable.
  • Specific examples of such a resin substrate include a resin substrate mainly composed of any one of liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimide (PI), and polyethylene naphthalate (PEN). Is mentioned.
  • the resin substrate suitable for the FPC of the present invention (A) a vinyl compound represented by the following general formula (1), and (B) rubber and / or thermoplastic elastomer, And a resin substrate containing as a main component.
  • a vinyl compound represented by the said Formula (1) of a component (a) it is as having mentioned above about the resin composition of this invention.
  • the vinyl compound represented by the general formula (1), and (b) a resin substrate mainly composed of rubber and / or thermoplastic elastomer have the same configuration as the resin composition of the present invention. It has a low dielectric constant and low dielectric loss tangent.
  • the interlayer adhesive and coverlay film which used the resin composition of this invention for example, it can be set as the printed circuit board excellent in the high frequency characteristic. Moreover, since it is the same structure as the resin composition of this invention, the adhesive strength with the interlayer adhesive and coverlay film using the resin composition of this invention is high.
  • Component (b) rubber and / or thermoplastic elastomer
  • the specific example of the resin substrate suitable for the FPC of the present invention described above contains at least one of rubber and thermoplastic elastomer as the component (b).
  • the resin substrate may contain both rubber and a thermoplastic elastomer.
  • component (b) rubber examples include rubbers such as styrene-butadiene rubber, butyl rubber, butadiene rubber, and acrylic rubber. These rubbers may be used alone or in combination of two or more.
  • examples of the thermoplastic elastomer include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, and a polyester thermoplastic elastomer. A thermoplastic elastomer may be used individually by 1 type, and may use 2 or more types together.
  • thermoplastic elastomer As the component (b), a thermoplastic elastomer is preferable, and a styrene-based thermoplastic elastomer is particularly preferable because the resin substrate is excellent in flexibility.
  • styrenic thermoplastic elastomer include a styrene-butadiene block copolymer, a styrene-isoprene-styrene block copolymer, or a copolymer obtained by hydrogenating a part of these double bonds.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SEEPS styrene-ethylene.
  • SEEPS styrene-Propylene-styrene block copolymer
  • the mass average molecular weight is preferably 20,000 to 250,000. Further, the compatibility with the component (a) is good, and the styrene content in the styrenic thermoplastic elastomer is preferably 15 to 60% by mass, more preferably 20 to 50% by mass.
  • the mass average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.
  • the styrene thermoplastic elastomer examples include a styrene-butadiene block copolymer “JSR TR” series and a styrene-isoprene block copolymer “JSR SIS” series manufactured by JSR Corporation.
  • the component (D) of the resin composition of the present invention described above when added, the thermosetting property and the adhesiveness with the copper constituting the wiring pattern are improved, and the component of the resin composition of the present invention described above. Addition of (E) leads to retention of dielectric properties, provision of adhesive strength, and high Tg (glass transition point). Moreover, you may add the component (F) of the resin composition of this invention mentioned above. By adding the component (F), the resin substrate using the component (a) can be cured at a low temperature. This makes it possible to apply facilities and conditions generally used for substrate manufacture. Furthermore, it leads to improvement of heat resistance such as warpage reduction, dimensional stability, solder heat resistance, and peel strength.
  • heat resistance such as warpage reduction, dimensional stability, solder heat resistance, and peel strength.
  • the resin substrate suitable for the FPC of the present invention described above preferably contain a silane coupling agent as the component (c) in addition to the components (a) and (b) described above.
  • the component (c) silane coupling agent contributes to adhesion between the resin substrate and the wiring pattern when the wiring pattern is transferred to the resin substrate.
  • the mass ratio of the component (a) and the component (b) is preferably 3: 7 to 7: 3, and preferably 4: 6 to 6: 4 is more preferable.
  • the resin substrate suitable for the FPC of the present invention described above may include any component other than the components (a) to (c) described above.
  • optional components include fillers used for the purpose of improving the mechanical strength of the resin substrate.
  • specific examples of such a filler include inorganic compounds such as silica, alumina, titania, boron nitride, and iron oxide, and organic fillers such as carbon.
  • the mass ratio of the filler to the total amount of components (a) to (c) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2 : 8, and more preferably 7: 3 to 3: 7.
  • the resin substrate suitable for the FPC of the present invention described above is an inorganic fiber such as glass fiber or carbon fiber, or an organic fiber such as aramid fiber, instead of the filler described above or instead of the filler described above. May be included for the purpose of improving the mechanical strength of the resin substrate.
  • Examples 1 to 9, Comparative Examples 1 to 12 Sample preparation and measurement method Each component was weighed and blended so as to have the blending ratio (mass%) shown in the following table, and then charged into a reaction kettle heated to 70 ° C and rotated at a rotation speed of 300 rpm. Normal pressure mixing was performed for 3 hours. When adding a curing agent, the curing agent was added after cooling. An adhesive film with a support was obtained by applying the varnish containing the resin composition thus obtained to one side of a support (PET film subjected to a release treatment) and drying at 100 ° C. .
  • surface represents the following, respectively.
  • Ingredient (A) OPE2200: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Ingredient (BC ') TR2003: Polystyrene-polybutadiene block copolymer (styrene / butadiene 43/57), manufactured by JSR Corporation
  • HP4032D Naphthalene type epoxy resin
  • DIC Corporation 828EL Bisphenol A type epoxy resin
  • Perbutyl Z tert-butyl peroxybenzoate, manufactured by NOF Corporation, exothermic peak 140-170 ° C
  • Perbutyl P Di (2-tert-butylperoxyisopropyl) benzene, NOF Corporation, exothermic peak 160 to 180 ° C.
  • Perocta O 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by NOF Corporation, exothermic peak 120 to 130 ° C.
  • Dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ ) After the adhesive film was cured by heating at 180 ° C. and peeled off from the support, a test piece (40 ⁇ 0.5 mm ⁇ 100 ⁇ 2 mm) was cut out from the adhesive film The thickness was measured. The test piece was rolled into a cylindrical shape having a length of 100 mm and a diameter of 2 mm or less, and a dielectric constant ( ⁇ ) and a dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method (10 GHz).
  • Tensile modulus After heat-curing the adhesive film at 180 ° C.
  • test pieces 25 ⁇ 0.5 mm ⁇ 220 ⁇ 2 mm
  • Warpage amount Copper foil with a thickness of 18 ⁇ m (copper foil CF-T8 manufactured by Fukuda Metal Foil Powder Co., Ltd.) cut into 100 ⁇ 0.5 mm square, and an adhesive film cut into the same size was pressed on one side of the copper foil.
  • peel strength (PI) The dried adhesive film is thermocompression bonded to a polyimide film (K100EN, manufactured by Toray DuPont Co., Ltd., 25 ⁇ m), and then heat-cured (thermocompression: 130 ° C. for 3 minutes, heat-curing: 180 The peel strength (180 degree peel) was measured according to JIS C6471.
  • the adhesive film was cut with a width of 10 mm from the film surface of the polyimide film, peeled off by an autograph, and peel strength (180 degree peel) was measured.
  • Dimensional stability JISC6471 compliant: A copper foil was bonded to both surfaces of the adhesive film obtained by the above-described method by thermocompression bonding (180 ° C., 60 minutes, 1 MPa) to obtain a 200 mm ⁇ 250 mm sample. Holes with a diameter of 2 mm were drilled at the four corners of the sample, and first, the vertical and horizontal distances between adjacent holes were measured. Next, the entire surface of the copper foil was etched and then dried at 80 ° C. for 30 minutes.
  • solder heat resistance solder float test: A copper foil was bonded to both surfaces of the adhesive film obtained by the above method by thermocompression bonding (180 ° C., 60 minutes, 1 MPa) to prepare a 50 mm ⁇ 50 mm sample. This was evaluated for the presence or absence of blistering for 30 seconds in a solder bath whose temperature was increased from 290 ° C to 10 ° C.
  • Examples 1 to 9 were all excellent in warpage, high frequency electrical characteristics (dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ )), tensile modulus, peel strength, dimensional stability, and solder heat resistance.
  • ⁇ dielectric constant
  • tan ⁇ dielectric loss tangent
  • the above components were dry-mixed at a peripheral speed of 400 rpm using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., BLW1200) to prepare a resin composition.
  • the resin composition was added to a solvent toluene and heated and stirred to prepare a varnish (solid content concentration of about 30% by mass).
  • the varnish was applied to a PET film (thickness 50 ⁇ m) as a support with a gravure coater, dried at 100 ° C. for 10 minutes, allowed to cool, and peeled from the PET film to obtain a resin substrate for FPC.
  • the thickness of the resin substrate was 30 ⁇ m.
  • the copper foil was bonded to both surfaces of the resin substrate obtained by the above procedure with the roughened surface inside, and thermocompression bonded with a press machine (200 ° C. 60 min, 1 MPa).
  • One side or both sides of the thermocompressed copper foil was etched to draw a wiring pattern, and a resin substrate with wiring was prepared.
  • the cover lay film obtained by the above procedure is arranged on the wiring pattern side of the resin substrate with wiring so that the adhesive layer faces, and is heat-cured while being thermocompressed with a press machine (180 ° C., 60 min, 1 MPa). ), A printed wiring board was produced.
  • Insertion loss A microstrip line designed to have an impedance of 50 ⁇ is produced on the resin substrate, and the adhesive film is vacuum-pressed as a coverlay film (180 ° C. 1 hr, 1 MPa, vacuum ⁇ 10 kPa)
  • a test piece was prepared by pasting.
  • the insertion loss (db) was measured under the following conditions using the prepared test piece.
  • Measuring instrument E8363B (manufactured by Agilent Technologies) Measurement frequency: 10MHz-60GHz Measurement point: 4000 Measuring probe: GSG250 Wiring length: 30mm, 50mm, 70mm Wiring width: 130 ⁇ 10 ⁇ m The results are shown in the table below.

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Abstract

Provided are: a resin composition that can be thermally cured at 180°C or lower, the resin composition having excellent adhesive strength to substrate materials, electrical properties in the high-frequency region of a frequency of 1 GHz or higher, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in the region of a frequency of 1 GHz or higher, as well as little shrinkage stress during thermal curing; and an adhesive film and a coverlay film produced using this resin composition. This resin composition includes (A) a vinyl compound indicated by general formula (1), (B) a polystyrene-poly(ethylene/butylene) block copolymer having a styrene content of 25-40%, (D) an epoxy resin, (E) bismaleimide, and (F) an organic peroxide having an exothermic peak measured by differential scanning calorimetry (DSC) of 100-180°C, the mass ratio of each component being (A + E)/(B + C) = 0.81-1.00, (B)/(C) = 1.00-4.00, and the resin composition containing 1-10 mass% of component (D) by mass percent in relation to the total mass of components (A)-(F) and 0.1-10 mass% of component (F) by mass percent in relation to the content of component (A).

Description

樹脂組成物、ならびに、それによる接着フィルム、カバーレイフィルム、層間接着剤Resin composition, and adhesive film, coverlay film, and interlayer adhesive formed thereby
　本発明は、樹脂組成物に関する。より具体的には、電気・電子用途の接着フィルムやプリント配線板のカバーレイフィルムに適した樹脂組成物に関する。
　また、本発明は、該樹脂組成物を用いて作成される接着フィルム、および、カバーレイフィルムに関する。
　また、本発明は、多層プリント配線の層間接着への該樹脂組成物の使用に関する。 The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for an adhesive film for electric / electronic use or a coverlay film for a printed wiring board.
Moreover, this invention relates to the adhesive film produced using this resin composition, and a coverlay film.
The present invention also relates to the use of the resin composition for interlayer adhesion of multilayer printed wiring.
　近年、電気・電子機器に使用されるプリント配線板は、機器の小型化、軽量化、および、高性能化が進んでおり、特に多層プリント配線板に対し、さらなる高多層化、高密度化、薄型化、軽量化、高信頼性、および、成形加工性等が要求されている。
　また、最近のプリント配線板における伝送信号の高速化要求に伴い、伝送信号の高周波化が顕著に進んでいる。これにより、プリント配線板に使用する材料に対して、高周波領域、具体的には、周波数１ＧＨｚ以上の領域での電気信号損失を低減できることが求められる。
　多層プリント配線板に使用される層間接着剤や、プリント配線板の表面保護膜（すなわち、カバーレイフィルム）として用いる接着フィルムについても、高周波領域で優れた電気特性（低誘電率（ε）、低誘電正接（ｔａｎδ））を示すことが求められる。 In recent years, printed wiring boards used in electrical and electronic equipment have been reduced in size, weight, and performance, especially for multilayer printed wiring boards. Thinning, lightening, high reliability, moldability, etc. are required.
In addition, with the recent demand for higher speed transmission signals in printed wiring boards, the frequency of transmission signals has increased significantly. Thereby, it is required that the material used for the printed wiring board can reduce electric signal loss in a high frequency region, specifically, in a region having a frequency of 1 GHz or more.
Excellent electrical properties in the high frequency range (low dielectric constant (ε), low) are also used for interlayer adhesives used in multilayer printed wiring boards and adhesive films used as surface protective films (ie, coverlay films) for printed wiring boards. It is required to show a dielectric loss tangent (tan δ)).
　特許文献１には、低誘電率、低誘電正接で、耐熱性、機械特性、耐薬品性、難燃性に優れた硬化物を与え、低温で硬化できる硬化性樹脂組成物、およびこれを用いた硬化性フィルム、およびこれらを硬化してなる硬化物、フィルムが開示されている。
　一方、特許文献２には、フレキシブルプリント配線板の配線をなす金属箔や、該フレキシブルプリント配線板の基板材料に対して優れた接着強度を有し、かつ、周波数１ＧＨｚ以上の高周波領域での電気特性、具体的には、周波数１ＧＨｚ以上の領域で低誘電率（ε）、および、低誘電正接（ｔａｎδ）を示すカバーレイフィルムが提案されている。 Patent Document 1 provides a curable resin composition that has a low dielectric constant, a low dielectric loss tangent, and has excellent heat resistance, mechanical properties, chemical resistance, and flame retardancy, and can be cured at low temperature. Curable films, cured products obtained by curing these films, and films are disclosed.
On the other hand, Patent Document 2 discloses a metal foil that forms a wiring of a flexible printed wiring board and an electrical material in a high frequency region having a frequency of 1 GHz or more that has excellent adhesive strength to the substrate material of the flexible printed wiring board. A coverlay film that exhibits characteristics, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 GHz or higher has been proposed.
特開２００９－１６１７２５号公報JP 2009-161725 A 特開２０１１－６８７１３号公報JP 2011-68713 A
　多層プリント配線板の層間接着時において、熱硬化時の収縮応力により、層間接着部に応力が残留する場合がある。層間接着部における応力歪が大きくなると、反りが生じてビア接続の信頼性が低下する。
　また、フレキシブルプリント配線板（ＦＰＣ）のカバーレイフィルムとして用いる接着フィルムにおいても、熱硬化時の収縮応力により反りが発生する場合がある。このような反りが発生すると、本来求められるべきＦＰＣの柔軟性が損なわれてしまい、例えば、ＦＰＣケーブルとしての使用が困難となる。なお、このような反りは、薄板化が進むリジット基板のカバーレイフィルムとして使用した場合も問題となる。 At the time of interlayer adhesion of a multilayer printed wiring board, stress may remain in the interlayer adhesion portion due to shrinkage stress during thermosetting. When the stress strain at the interlayer adhesion portion increases, warpage occurs and the reliability of via connection decreases.
Further, even in an adhesive film used as a cover lay film of a flexible printed wiring board (FPC), warping may occur due to shrinkage stress during thermosetting. When such warpage occurs, the flexibility of the FPC that should be originally required is impaired, and for example, it becomes difficult to use the FPC cable. Such warpage also becomes a problem when used as a cover lay film of a rigid substrate that is becoming thinner.
　また、多層プリント配線板の層間接着時や、ＦＰＣのカバーレイフィルムとして用いる接着フィルムの熱硬化時において、一般的に基板製造に使用される設備・条件が適用可能であること、２００℃以上の高温から冷却すると、冷却時の反りが大きくなる等の理由から、より低温での熱硬化を実施することが望ましい。具体的には、１８０℃以下で熱硬化を実施することが望ましい。 In addition, it is possible to apply equipment / conditions generally used for substrate production at the time of interlayer adhesion of multilayer printed wiring boards and thermosetting of an adhesive film used as an FPC coverlay film. When cooling from a high temperature, it is desirable to carry out thermosetting at a lower temperature, for example, because warpage during cooling increases. Specifically, it is desirable to carry out thermosetting at 180 ° C. or lower.
　本発明は上記した従来技術の問題点を解決するため、エポキシ樹脂、フェノール樹脂、ビスマレイミドトリアジン樹脂等の有機基板材料や、セラミック基板やシリコン基板等の無機基板材料、および、ポリイミドフィルム等のＦＰＣの基板材料に対して優れた接着強度を有し、かつ、周波数１ＧＨｚ以上の高周波領域での電気特性、具体的には、周波数１ＧＨｚ以上の領域で低誘電率（ε）、および、低誘電正接（ｔａｎδ）を示すことに加えて、熱硬化時の収縮応力が少なく、１８０℃以下で熱硬化することができる樹脂組成物、および、該樹脂組成物を用いて作成される接着フィルム、および、カバーレイフィルムを提供することを目的とする。 In order to solve the above-mentioned problems of the prior art, the present invention provides organic substrate materials such as epoxy resins, phenol resins, bismaleimide triazine resins, inorganic substrate materials such as ceramic substrates and silicon substrates, and FPCs such as polyimide films. Have excellent adhesive strength with respect to the substrate material, and electrical characteristics in a high frequency region having a frequency of 1 GHz or more, specifically, a low dielectric constant (ε) and a low dielectric loss tangent in a region having a frequency of 1 GHz or more. In addition to exhibiting (tan δ), a resin composition that has a low shrinkage stress during thermosetting and can be thermoset at 180 ° C. or less, and an adhesive film created using the resin composition, and An object is to provide a coverlay film.
　上記の目的を達成するため、本発明は、
（Ａ）下記一般式（１）で示される、質量平均分子量（Ｍｗ）が５００～４０００のビニル化合物、
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7は、同一または異なってもよく、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基またはフェニル基である。－（Ｏ－Ｘ－Ｏ）－は下記構造式（２）で示される。
Figure JPOXMLDOC01-appb-C000013
Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ11，Ｒ12，Ｒ13は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。－（Ｙ－Ｏ）－は下記構造式（３）で定義される１種類の構造、または下記構造式（３）で定義される２種類以上の構造がランダムに配列したものである。
Figure JPOXMLDOC01-appb-C000014
Ｒ16，Ｒ17は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ18，Ｒ19は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｚは、炭素数１以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。ａ，ｂは、少なくともいずれか一方が０でない、０～３００の整数を示す。ｃ，ｄは、０または１の整数を示す。）
（Ｂ）スチレン含有量が１５～３５％のポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体、
（Ｃ）スチレン含有量が２５～４０％のポリスチレン－ポリ（エチレン－エチレン／プロピレン）ブロック共重合体、
（Ｄ）エポキシ樹脂、
（Ｅ）ビスマレイミド、
（Ｆ）示差走査熱量（ＤＳＣ）測定による発熱ピークが１００℃以上１８０℃以下の有機過酸化物を含み、各成分の質量比が、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝０．８１以上１．００以下、（Ｂ）／（Ｃ）＝１．００以上４．００以下であり、
　前記成分（Ａ）～（Ｆ）の合計質量に対する質量パーセントで、前記成分（Ｄ）を１～１０質量％含有し、
　前記（Ａ）成分の含有量に対する質量パーセントで、前記成分（Ｆ）を０．１～１０質量％含有する樹脂組成物を提供する。 In order to achieve the above object, the present invention provides:
(A) A vinyl compound having a mass average molecular weight (Mw) of 500 to 4000 represented by the following general formula (1):
Figure JPOXMLDOC01-appb-C000012
 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).
Figure JPOXMLDOC01-appb-C000013
R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
Figure JPOXMLDOC01-appb-C000014
R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
(B) a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35%,
(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer having a styrene content of 25 to 40%,
(D) epoxy resin,
(E) bismaleimide,
(F) An organic peroxide having an exothermic peak of 100 ° C. or more and 180 ° C. or less by differential scanning calorimetry (DSC) measurement, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 Hereinafter, (B) / (C) = 1.00 to 4.00,
The component (D) is contained in an amount of 1 to 10% by mass based on the total mass of the components (A) to (F),
Provided is a resin composition containing 0.1 to 10% by mass of the component (F) in terms of mass percent based on the content of the component (A).
　本発明の樹脂組成物において、前記成分（Ａ）の－（Ｏ－Ｘ－Ｏ）－が、下記構造式（４）で示され、前記成分（Ａ）の－（Ｙ－Ｏ）－が下記構造式（５）、若しくは、下記構造式（６）で示される構造、または、下記構造式（５）で示される構造および下記構造式（６）で示される構造がランダムに配列した構造を有することが好ましい。
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 In the resin composition of the present invention, — (O—X—O) — of the component (A) is represented by the following structural formula (4), and — (YO) — of the component (A) is Structural formula (5), or a structure represented by the following structural formula (6), or a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) are randomly arranged. It is preferable.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
　本発明の樹脂組成物において、前記（Ｆ）成分の有機過酸化物が、パーオキシエステル類又はジアルキルパーオキサイド類であることが好ましい。 In the resin composition of the present invention, the organic peroxide as the component (F) is preferably a peroxyester or a dialkyl peroxide.
　本発明の樹脂組成物において、前記（Ｄ）成分のエポキシ樹脂が、分子中に水酸基が存在しない、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、および、ナフタレン型エポキシ樹脂からなる群から選択される少なくとも１つであることが好ましい。 In the resin composition of the present invention, the epoxy resin as the component (D) is at least selected from the group consisting of a biphenyl type epoxy resin, a fluorene type epoxy resin, and a naphthalene type epoxy resin having no hydroxyl group in the molecule. One is preferred.
　また、本発明は、本発明の樹脂組成物よりなる接着フィルムを提供する。 The present invention also provides an adhesive film comprising the resin composition of the present invention.
　また、本発明は、層間接着に、本発明の樹脂組成物、または、本発明の接着フィルムを用いた、多層プリント配線板を提供する。 The present invention also provides a multilayer printed wiring board using the resin composition of the present invention or the adhesive film of the present invention for interlayer adhesion.
　また、本発明の多層プリント配線板を構成する基板が、上記一般式（１）で表されるビニル化合物、ならびに、ゴムおよび／または熱可塑性エラストマー、を主成分とする樹脂基板であることが好ましい。 Moreover, it is preferable that the board | substrate which comprises the multilayer printed wiring board of this invention is a resin substrate which has as a main component the vinyl compound represented by the said General formula (1), and rubber | gum and / or a thermoplastic elastomer. .
　また、本発明は、本発明の樹脂組成物よりなるカバーレイフィルムを提供する。 The present invention also provides a coverlay film comprising the resin composition of the present invention.
　また、本発明は、本発明のカバーレイフィルムを有するフレキシブルプリント配線板を提供する。 The present invention also provides a flexible printed wiring board having the cover lay film of the present invention.
　液晶ポリマー、ポリイミド、および、ポリエチレンナフタレ－トのいずれかを主成分とする樹脂基板の主面に配線パターンが形成された配線付樹脂基板の配線パターン側に、本発明のカバーレイフィルムが用いられていることを特徴とするフレキシブルプリント配線板を提供する。
　また、本発明は、上記一般式（１）で表されるビニル化合物、ならびに、ゴムおよび／または熱可塑性エラストマー、を主成分とする樹脂基板の主面に配線パターンが形成された配線付樹脂基板の配線パターン側に、本発明のカバーレイフィルムが用いられていることを特徴とするフレキシブルプリント配線板を提供する。 The cover lay film of the present invention is used on the wiring pattern side of the resin substrate with wiring in which the wiring pattern is formed on the main surface of the resin substrate mainly composed of liquid crystal polymer, polyimide, or polyethylene naphthalate. A flexible printed wiring board is provided.
In addition, the present invention provides a resin substrate with wiring in which a wiring pattern is formed on a main surface of a resin substrate mainly composed of the vinyl compound represented by the general formula (1) and rubber and / or thermoplastic elastomer. A flexible printed wiring board is provided in which the coverlay film of the present invention is used on the wiring pattern side.
　本発明の樹脂組成物は、ＦＰＣの配線をなす金属箔や、ポリイミドフィルム等のＦＰＣの基板材料、に対して優れた接着強度を有し、かつ、高周波領域で優れた電気特性、具体的には、周波数１ＧＨｚ以上の領域で低誘電率（ε）、および、低誘電正接（ｔａｎδ））を示すので、ＦＰＣ用のカバーレイフィルムとして好適である。 The resin composition of the present invention has excellent adhesive strength to FPC substrate materials such as metal foils and polyimide films that form FPC wiring, and has excellent electrical characteristics in the high frequency region, specifically Shows a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 GHz or more, and is suitable as a coverlay film for FPC.
　また、本発明の樹脂組成物は、エポキシ樹脂、フェノール樹脂、ビスマレイミドトリアジン樹脂等の有機基板材料や、セラミック基板やシリコン基板等の無機基板材料に対しても優れた接着強度を有しているため、これらの基板を用いた多層プリント配線板の層間接着剤としても好適である。 In addition, the resin composition of the present invention has excellent adhesion strength to organic substrate materials such as epoxy resins, phenol resins, bismaleimide triazine resins, and inorganic substrate materials such as ceramic substrates and silicon substrates. Therefore, it is also suitable as an interlayer adhesive for multilayer printed wiring boards using these substrates.
　また、本発明の樹脂組成物は、基板上に接着する際の流動性、寸法安定性が適切であることから、カバーレイフィルムとして使用する際、あるいは、多層プリント配線板の層間接着剤として使用する際の作業性に優れ、かつ、回路の埋込み性が損なわれることがない。 In addition, the resin composition of the present invention is suitable for fluidity and dimensional stability when bonded on a substrate, so it is used as a coverlay film or as an interlayer adhesive for multilayer printed wiring boards. In this case, the workability is excellent, and the embedding property of the circuit is not impaired.
　また、本発明の樹脂組成物は、熱硬化時の収縮応力が少ないため、多層プリント配線板の層間接着剤として使用した場合に、層間接着部に残留する応力が軽減される。これにより、層間接着部での反りの発生が抑制されるため、多層プリント配線板のビア接続の信頼性が向上する。 In addition, since the resin composition of the present invention has a small shrinkage stress at the time of thermosetting, when it is used as an interlayer adhesive of a multilayer printed wiring board, the stress remaining in the interlayer adhesive portion is reduced. As a result, the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved.
　また、本発明の樹脂組成物をＦＰＣのカバーレイフィルムとして使用した場合に、熱硬化時の反りの発生が抑制される。そのため、ＦＰＣの柔軟性が損なわれることがない。 Also, when the resin composition of the present invention is used as an FPC coverlay film, the occurrence of warpage during thermosetting is suppressed. Therefore, the flexibility of the FPC is not impaired.
　また、本発明の樹脂組成物は、１８０℃以下で熱硬化が可能であるため、多層プリント配線板の層間接着剤として使用した際、あるいは、ＦＰＣのカバーレイフィルムとして使用した際、一般的に基板製造に使用される設備・条件が適用可能であり、さらに反り低減、寸法安定性、半田耐熱性などの耐熱性向上、ピール強度の向上等の利点がある。 In addition, since the resin composition of the present invention can be cured at 180 ° C. or lower, it is generally used when used as an interlayer adhesive for multilayer printed wiring boards or as a coverlay film for FPC. Equipment and conditions used for substrate manufacture are applicable, and there are further advantages such as reduction in warpage, dimensional stability, improved heat resistance such as solder heat resistance, and improved peel strength.
　以下、本発明の樹脂組成物について詳細に説明する。
　本発明の樹脂組成物は、以下に示す（Ａ）～（Ｆ）成分を必須成分として含有する。 Hereinafter, the resin composition of the present invention will be described in detail.
The resin composition of the present invention contains the following components (A) to (F) as essential components.
（Ａ）下記一般式（１）で示される、質量平均分子量（Ｍｗ）が５００～４０００のビニル化合物
Figure JPOXMLDOC01-appb-C000017
 (A) A vinyl compound represented by the following general formula (1) and having a mass average molecular weight (Mw) of 500 to 4000
Figure JPOXMLDOC01-appb-C000017
　一般式（１）中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7は、同一または異なってもよく、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基またはフェニル基である。これらの中でも、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7が水素原子であることが好ましい。
　式中、－（Ｏ－Ｘ－Ｏ）－は下記構造式（２）で示される。
Figure JPOXMLDOC01-appb-C000018
　構造式（２）中、Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。これらの中でも、Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15が炭素数６以下のアルキル基であることが好ましい。これらの中でも、Ｒ11，Ｒ12，Ｒ13は、水素原子、ハロゲン原子または炭素数６以下のアルキル基であることが好ましい。
　一般式（１）中、－（Ｙ－Ｏ）－は下記構造式（３）で定義される１種類の構造、または下記構造式（３）で定義される２種類以上の構造がランダムに配列したものである。
Figure JPOXMLDOC01-appb-C000019
　構造式（３）中Ｒ16，Ｒ17は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。これらの中でも、Ｒ16，Ｒ17が炭素数６以下のアルキル基であることが好ましい。
　Ｒ18，Ｒ19は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。これらの中でも、Ｒ18，Ｒ19が水素原子または炭素数３以下のアルキル基であることが好ましい。
　一般式（１）中、Ｚは、炭素数１以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。これらの中でも、Ｚがメチレン基であることが好ましい。
　ａ，ｂは、少なくともいずれか一方が０でない、０～３００の整数を示す。
　ｃ，ｄは、０または１の整数を示す。これらの中でも、ｃ，ｄが１であることが好ましい。
　これらのなかでも好ましくは、Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は炭素数３以下のアルキル基、Ｒ11，Ｒ12，Ｒ13は水素原子または炭素数３以下のアルキル基、Ｒ16，Ｒ17は炭素数３以下のアルキル基、Ｒ18，Ｒ19は水素原子である。 In the general formula (1), R 1, R 2, R 3, R 4, R 5, R 6, R 7 are the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or It is a phenyl group. Among these, R 1, R 2, R 3, R 4, R 5, is preferably R 6, R 7 is a hydrogen atom.
In the formula, — (O—X—O) — is represented by the following structural formula (2).
Figure JPOXMLDOC01-appb-C000018
In the structural formula (2), R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R 8 , R 9 , R 10 , R 14 , and R 15 are preferably alkyl groups having 6 or less carbon atoms. Among these, R 11 , R 12 and R 13 are preferably a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms.
In the general formula (1),-(YO)-is a random arrangement of one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) It is a thing.
Figure JPOXMLDOC01-appb-C000019
In the structural formula (3), R 16 and R 17 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R 16 and R 17 are preferably alkyl groups having 6 or less carbon atoms.
R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R 18 and R 19 are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms.
In general formula (1), Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Among these, it is preferable that Z is a methylene group.
a and b each represents an integer of 0 to 300, at least one of which is not 0.
c and d represent an integer of 0 or 1. Among these, c and d are preferably 1.
Preferably Among these, R 8, R 9, R 10, R 14, R 15 is alkyl group having 3 or less carbon atoms, R 11, R 12, R 13 is a hydrogen atom or alkyl group having 3 or less carbon atoms, R 16 and R 17 are alkyl groups having 3 or less carbon atoms, and R 18 and R 19 are hydrogen atoms.
　また、上記一般式（１）中の－（Ｏ－Ｘ－Ｏ）－は、下記構造式（４）で示されることが好ましい。
Figure JPOXMLDOC01-appb-C000020
　また、一般式（１）中の－（Ｙ－Ｏ）－が下記構造式（５）、若しくは、下記構造式（６）で示される構造、または、下記構造式（５）で示される構造および下記構造式（６）で示される構造がランダムに配列した構造を有することが好ましい。これらの中でも、－（Ｙ－Ｏ）－は下記構造式（６）で定義される構造が配列した構造を有することが好ましい。
Figure JPOXMLDOC01-appb-C000021
 In addition, — (O—X—O) — in the general formula (1) is preferably represented by the following structural formula (4).
Figure JPOXMLDOC01-appb-C000020
In the general formula (1), — (Y—O) — represents the structure represented by the following structural formula (5), the following structural formula (6), the structure represented by the following structural formula (5), and It is preferable to have a structure in which the structure represented by the following structural formula (6) is randomly arranged. Among these,-(YO)-preferably has a structure in which structures defined by the following structural formula (6) are arranged.
Figure JPOXMLDOC01-appb-C000021
　本発明の樹脂組成物において、成分（Ａ）は該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルム、あるいは、該樹脂組成物を用いた層間接着剤の熱硬化性、耐熱性、および、高周波での優れた電気特性、すなわち、周波数１ＧＨｚ以上の領域での低誘電率（ε）、および、低誘電正接（ｔａｎδ）に寄与する。 In the resin composition of the present invention, the component (A) is an adhesive film and coverlay film prepared using the resin composition, or thermosetting, heat resistance of an interlayer adhesive using the resin composition, In addition, it contributes to excellent electrical characteristics at high frequencies, that is, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 GHz or higher.
　本発明の樹脂組成物において、成分（Ａ）として、一般式（１）で示されるビニル化合物のうち、質量平均分子量（Ｍｗ）が５００～４０００のものを用いる理由は以下の通り。
　質量平均分子量（Ｍｗ）が５００未満だと、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムの柔軟性がなくなり、もろく割れやすいフィルムになる。また、熱圧着時や加熱硬化時に溶融粘度が低下しすぎるため、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムの膜厚の均一性が損なわれるおそれや、該樹脂組成物を層間接着剤として使用した際に、層間接着部の厚さの均一性が損なわれるおそれがある。
　一方、質量平均分子量（Ｍｗ）が４０００超だと、溶解性が低下するため、樹脂組成物の調製時に問題となる。具体的には、樹脂組成物を溶剤で希釈したワニスの調製時に熱トルエン中での長時間の混合溶解が必要となる。また、フィルムを作成するためにワニスを室温に戻すと再結晶し始め、ワニスの保存安定性が悪くなる。また、フィルム化後に結晶化するため、フィルムとしての形状の維持が難しくなる。このため、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムが割れやすくなる。また、薄膜のフィルムを作成することができなくなる。さらにまた、フィルム表面の平滑性が悪化する。
　成分（Ａ）として、一般式（１）で示されるビニル化合物のうち、質量平均分子量（Ｍｗ）が８００～３５００のものを用いることがより好ましく、１０００～３０００のものを用いることがさらに好ましい。 In the resin composition of the present invention, as the component (A), among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 500 to 4000 are used as follows.
When the mass average molecular weight (Mw) is less than 500, the flexibility of the adhesive film and coverlay film prepared using the resin composition is lost, and the film becomes brittle and easily broken. In addition, since the melt viscosity is too low during thermocompression bonding or heat curing, the film thickness uniformity of the adhesive film and coverlay film created using the resin composition may be impaired, and the resin composition When used as an interlayer adhesive, the uniformity of the thickness of the interlayer adhesive may be impaired.
On the other hand, when the mass average molecular weight (Mw) exceeds 4000, the solubility is lowered, which causes a problem when preparing the resin composition. Specifically, long-time mixing and dissolution in hot toluene is required when preparing a varnish obtained by diluting a resin composition with a solvent. Further, when the varnish is returned to room temperature to form a film, recrystallization starts and the storage stability of the varnish is deteriorated. Moreover, since it crystallizes after film formation, it becomes difficult to maintain the shape as a film. For this reason, the adhesive film and coverlay film created using this resin composition are easily broken. Moreover, it becomes impossible to produce a thin film. Furthermore, the smoothness of the film surface is deteriorated.
As the component (A), among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 800 to 3500 are more preferable, and those having a mass average molecular weight (Mw) of 1000 to 3000 are more preferable.
　上記一般式（１）で表されるビニル化合物の製法は、特に限定されず、いかなる方法で製造してもよい。例えば、下記一般式（７）で示される化合物に対してクロロメチルスチレンを水酸化ナトリウム、炭酸カリウム、ナトリウムエトキサイド等のアルカリ触媒存在下で、必要に応じてベンジルトリｎ－ブチルアンモニウムブロマイド、１８－クラウン－６－エーテル等の相間移動触媒を用いて反応させることにより得ることができる。
Figure JPOXMLDOC01-appb-C000022
　一般式（７）中の－（Ｏ－Ｘ－Ｏ）、および、－（Ｙ－Ｏ）－については、一般式（１）について上述した通りである。 The method for producing the vinyl compound represented by the general formula (1) is not particularly limited, and may be produced by any method. For example, chloromethylstyrene is added to a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like, if necessary, benzyltri n-butylammonium bromide, 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.
Figure JPOXMLDOC01-appb-C000022
In formula (7), — (O—X—O) and — (Y—O) — are as described above for formula (1).
成分（Ｂ）：スチレン含有量が１５～３５％のポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体
成分（Ｃ）：スチレン含有量が２５～４０％のポリスチレン－ポリ（エチレン－エチレン／プロピレン）ブロック共重合体
　本発明の樹脂組成物において、成分（Ｂ），（Ｃ）は特に該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムの高周波での優れた電気特性（周波数１ＧＨｚ以上の領域での低誘電率（ε）、および、低誘電正接（ｔａｎδ））、フィルム性状、および、耐熱性に寄与する。また、本発明の樹脂組成物を層間接着剤として使用した際に、高周波での優れた電気特性（１ＧＨｚ以上の領域での低誘電率（ε）、および、低誘電正接（ｔａｎδ））、および、耐熱性に寄与する。
　これらのうち、成分（Ｃ）は、成分（Ｂ）に比べて誘電特性に優れており、高周波での優れた電気特性（周波数１ＧＨｚ以上の領域での低誘電率（ε）、および、低誘電正接（ｔａｎδ））に寄与する。
　しかしながら、成分（Ｃ）は、成分（Ｂ）に比べて熱硬化物の弾性率（引張弾性率）が高いため、成分（Ｃ）を単独で使用すると、熱硬化時の収縮応力が高くなるため、成分（Ｂ）を組み合わせて使用する必要がある。
　このため、本発明の樹脂組成物では、成分（Ｂ），（Ｃ）を以下に述べる特定の配合割合で用いる。 Component (B): Polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35% Component (C): Polystyrene-poly (ethylene-ethylene / propylene) having a styrene content of 25 to 40% Block Copolymer In the resin composition of the present invention, the components (B) and (C) are particularly excellent electrical properties (frequency of 1 GHz or more) at high frequencies of adhesive films and coverlay films prepared using the resin composition. This contributes to low dielectric constant (ε) and low dielectric loss tangent (tan δ), film properties, and heat resistance. Further, when the resin composition of the present invention is used as an interlayer adhesive, excellent electrical characteristics at high frequencies (low dielectric constant (ε) and low dielectric loss tangent (tan δ) in a region of 1 GHz or higher), and Contributes to heat resistance.
Among these, the component (C) is superior in the dielectric characteristics compared to the component (B), and has excellent electrical characteristics at high frequencies (low dielectric constant (ε) in a frequency region of 1 GHz or more, and low dielectric constant). Tangent (tan δ)).
However, since component (C) has a higher elastic modulus (tensile elastic modulus) of the thermoset than component (B), if component (C) is used alone, the shrinkage stress during thermosetting increases. It is necessary to use the component (B) in combination.
For this reason, in the resin composition of this invention, component (B) and (C) are used with the specific compounding ratio described below.
　本発明では、樹脂組成物における成分（Ｂ），（Ｃ）の質量比を、（Ｂ）／（Ｃ）＝１．００以上４．００以下とする。
　（Ｂ）／（Ｃ）＝１．００未満であると、所望の接着強度は得られるが、熱硬化物の弾性率が高くなるため、樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムの熱硬化時の収縮応力が高くなり、反りが発生しやすくなる。また、樹脂組成物を層間接着剤として使用した場合に、層間接着部における応力歪が大きくなると、反りが生じてビア接続の信頼性が低下する。
　一方、（Ｂ）／（Ｃ）＝４．００を超えると、熱硬化物の弾性率が低くなるため、樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムでの反りの発生や、樹脂組成物による層間接着部における反りの発生を抑制できるが、所望の接着強度が得られない。
　（Ｂ）／（Ｃ）＝１．００以上４．００以下であると、熱硬化物の弾性率が高くならず、かつ、所望の接着強度が得られる。
　成分（Ｂ），（Ｃ）の質量比は、（Ｂ）／（Ｃ）＝１．５以上３．５以下であることがより好ましい。 In the present invention, the mass ratio of the components (B) and (C) in the resin composition is (B) / (C) = 1.00 or more and 4.00 or less.
If (B) / (C) = less than 1.00, the desired adhesive strength can be obtained, but the elastic modulus of the thermoset is increased, so that an adhesive film and a coverlay produced using the resin composition are used. The shrinkage stress at the time of heat curing of the film becomes high, and warping is likely to occur. Further, when the resin composition is used as an interlayer adhesive, if the stress strain at the interlayer adhesive portion becomes large, warpage occurs and the reliability of via connection decreases.
On the other hand, when (B) / (C) = 4.00 is exceeded, the elastic modulus of the thermoset is lowered, and thus the occurrence of warpage in the adhesive film and the coverlay film created using the resin composition, Although generation | occurrence | production of the curvature in the interlayer adhesion part by a resin composition can be suppressed, desired adhesive strength is not obtained.
When (B) / (C) = 1.00 or more and 4.00 or less, the elastic modulus of the thermoset does not increase, and desired adhesive strength is obtained.
The mass ratio of the components (B) and (C) is more preferably (B) / (C) = 1.5 or more and 3.5 or less.
　但し、成分（Ｂ），（Ｃ）は、スチレン含有量が上記した特定の範囲のものを用いる必要がある。
　成分（Ｂ）のスチレン含有量が１５％未満だと、樹脂組成物の他の成分との相溶性が劣る問題がある。
　一方、成分（Ｂ）のスチレン含有量が３５％超だと、樹脂組成物を用いて接着フィルムやカバーレイフィルムを作成する際に、未硬化フィルムにクラックが発生するなどフィルム形成が困難となる問題がある。
　成分（Ｃ）のスチレン含有量が２５％未満だと、樹脂組成物の他の成分との相溶性が劣る問題がある。
　一方、成分（Ｃ）のスチレン含有量が４０％超だと、樹脂組成物を用いて接着フィルムやカバーレイフィルムを作成する際に、未硬化フィルムにクラックが発生するなどフィルム形成が困難となる問題がある。 However, it is necessary to use components (B) and (C) having a styrene content in the specific range described above.
When the styrene content of the component (B) is less than 15%, there is a problem that the compatibility with other components of the resin composition is poor.
On the other hand, when the styrene content of the component (B) is more than 35%, it becomes difficult to form a film such as a crack occurs in an uncured film when an adhesive film or a coverlay film is formed using the resin composition. There's a problem.
When the styrene content of the component (C) is less than 25%, there is a problem that the compatibility with other components of the resin composition is poor.
On the other hand, when the styrene content of the component (C) is more than 40%, when forming an adhesive film or a coverlay film using the resin composition, it becomes difficult to form a film such as a crack occurs in an uncured film. There's a problem.
成分（Ｄ）：エポキシ樹脂
　本発明の樹脂組成物において、成分（Ｄ）は該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルム、ならびに、該樹脂組成物を層間接着剤として使用した際の熱硬化性、および、接着性に寄与する。
　また、成分（Ｄ）を用いることで、トルエン、メチルエチルケトン、メチルイソブチルケトン等の低沸点溶媒に対する成分（Ｅ）の溶解性が向上する。
　本発明の樹脂組成物において、成分（Ｄ）の含有量は、成分（Ａ）～（Ｅ）の合計質量に対する質量パーセントで１～１０質量％である。
　成分（Ｄ）の含有量が１質量％未満だと、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルム、ならびに、該樹脂組成物を層間接着剤として使用した際の接着性が不十分となる等の問題がある。
　成分（Ｄ）の含有量が１０質量％超だと、相溶性が悪化し、また、所望する誘電正接（ｔａｎδ）値を得られなくなる。また、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムの熱硬化時の流れ出しが過剰に大きくなる。さらに、全成分中に占める成分（Ｄ）の割合が多くなるため、耐熱性に劣る成分（Ｄ）の特性が該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルム、ならびに、該樹脂組成物を用いた層間接着部全体に影響する。そのため、該樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルム、ならびに、該樹脂組成物を用いた層間接着部の耐熱性や硬化性が低下するおそれがある。
　本発明の樹脂組成物は、成分（Ａ）～（Ｅ）の合計質量に対して、成分（Ｄ）を１～５質量％含有することがより好ましい。 Component (D): Epoxy resin In the resin composition of the present invention, the component (D) used an adhesive film and a coverlay film prepared using the resin composition, and the resin composition was used as an interlayer adhesive. This contributes to thermosetting and adhesiveness.
Moreover, the solubility of the component (E) with respect to low boiling-point solvents, such as toluene, methyl ethyl ketone, and methyl isobutyl ketone, improves by using a component (D).
In the resin composition of the present invention, the content of the component (D) is 1 to 10% by mass with respect to the total mass of the components (A) to (E).
When the content of the component (D) is less than 1% by mass, an adhesive film and a coverlay film prepared using the resin composition, and adhesiveness when the resin composition is used as an interlayer adhesive There are problems such as being insufficient.
When the content of the component (D) exceeds 10% by mass, the compatibility is deteriorated and a desired dielectric loss tangent (tan δ) value cannot be obtained. Moreover, the outflow at the time of thermosetting of the adhesive film and coverlay film produced using this resin composition becomes excessively large. Furthermore, since the ratio of the component (D) in all the components increases, the adhesive film and the coverlay film in which the properties of the component (D) inferior in heat resistance are produced using the resin composition, and the resin Affects the entire interlayer adhesion using the composition. Therefore, the heat resistance and curability of the adhesive film and cover lay film created using the resin composition, and the interlayer adhesive portion using the resin composition may be reduced.
The resin composition of the present invention more preferably contains 1 to 5% by mass of the component (D) with respect to the total mass of the components (A) to (E).
　成分（Ｄ）として使用するエポキシ樹脂は特に限定されず、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、ナフタレン型エポキシ樹脂等の各種エポキシ樹脂を用いることができる。
　但し、成分（Ｄ）のエポキシ樹脂として、分子中に水酸基が存在するものを使用した場合は、エポキシ樹脂の含有量が増加すると、水酸基の極性による影響で、樹脂組成物の誘電率が上昇する。
　このため、成分（Ｄ）のエポキシ樹脂は分子中に水酸基が存在しないものを用いることが好ましい。上記のエポキシ樹脂のうち、これに該当するのは、分子中に水酸基が存在しない、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、ナフタレン型エポキシ樹脂である。
　これら分子中に水酸基が存在しないエポキシ樹脂を用いることで、誘電率の上昇を抑制できる。
　なお、上記のエポキシ樹脂のうち、いずれか１種を使用してもよく、２種以上を併用してもよい。 The epoxy resin used as the component (D) is not particularly limited, and various epoxies such as novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, naphthalene type epoxy resin and the like. Resin can be used.
However, when an epoxy resin having a hydroxyl group in the molecule is used as the epoxy resin of component (D), the dielectric constant of the resin composition increases due to the influence of the polarity of the hydroxyl group when the content of the epoxy resin increases. .
For this reason, it is preferable to use the component (D) epoxy resin having no hydroxyl group in the molecule. Among the above-described epoxy resins, this corresponds to biphenyl type epoxy resins, fluorene type epoxy resins, and naphthalene type epoxy resins that do not have a hydroxyl group in the molecule.
By using an epoxy resin in which no hydroxyl group exists in these molecules, an increase in dielectric constant can be suppressed.
In addition, among said epoxy resins, any 1 type may be used and 2 or more types may be used together.
　成分（Ｄ）として使用するエポキシ樹脂は、数平均分子量（Ｍｎ）が１５０～２５００であることが熱硬化性、接着性、硬化後の機械的特性の理由から好ましい。 The epoxy resin used as component (D) preferably has a number average molecular weight (Mn) of 150 to 2500 for reasons of thermosetting, adhesiveness, and mechanical properties after curing.
成分（Ｅ）：ビスマレイミド
　本発明のカバーレイフィルムにおいて、成分（Ｅ）のビスマレイミドは、成分（Ａ）のビニル化合物と作用し、カバーレイフィルムの接着層の加熱硬化をより低い温度で進行させることができる。
　本発明において、ビスマレイミドを使用するのは、誘電特性の保持、接着強度の付与及び高Ｔｇ（ガラス転移点）化の観点から好ましいからである。 Component (E): Bismaleimide In the cover lay film of the present invention, the bismaleimide of component (E) acts with the vinyl compound of component (A) to advance the heat curing of the adhesive layer of the cover lay film at a lower temperature. Can be made.
In the present invention, bismaleimide is used because it is preferable from the viewpoints of maintaining dielectric properties, imparting adhesive strength, and increasing Tg (glass transition point).
　成分（Ｅ）のビスマレイミドの配合量は、成分（Ａ）のビニル化合物のビニル基に対する当量比で決めることが好ましい。具体的には、成分（Ａ）のビニル化合物のビニル基１当量に対して、成分（Ｅ）のビスマレイミドが０．１～３当量であり、０．５～１．５当量であることが好ましく、０．８～１．３当量であることがより好ましい。 The blending amount of the component (E) bismaleimide is preferably determined by the equivalent ratio of the vinyl compound of the component (A) to the vinyl group. Specifically, the bismaleimide of the component (E) is 0.1 to 3 equivalents and 0.5 to 1.5 equivalents relative to 1 equivalent of the vinyl group of the vinyl compound of the component (A). Preferably, it is 0.8 to 1.3 equivalent.
　本発明の樹脂組成物において、成分（Ａ），（Ｅ）は熱硬化性の樹脂材料であり、成分（Ｂ），（Ｃ）は熱可塑性の樹脂材料である。
　本発明において、これら熱硬化性の樹脂材料と、熱可塑性の樹脂材料と、の配合割合は、樹脂組成物の物性に影響を及ぼす。そのため、（成分（Ａ），（Ｅ））、および、（成分（Ｂ），（Ｃ））を以下に述べる特定の配合割合で用いる。
　なお、成分（Ｄ）のエポキシ樹脂も熱硬化性の樹脂材料であるが、上述したように、成分（Ｄ）の含有量は、成分（Ａ）～（Ｅ）の合計質量に対する質量パーセントで１～１０質量％と少ないため、（成分（Ａ），（Ｅ））、および、（成分（Ｂ），（Ｃ））と、以下に述べる特定の配合割合で使用すれば、成分（Ｄ）が、本発明の樹脂組成物の物性に及ぼす影響は無視できる。 In the resin composition of the present invention, components (A) and (E) are thermosetting resin materials, and components (B) and (C) are thermoplastic resin materials.
In the present invention, the blending ratio of these thermosetting resin material and thermoplastic resin material affects the physical properties of the resin composition. Therefore, (components (A), (E)) and (components (B), (C)) are used in the specific blending ratio described below.
The epoxy resin of component (D) is also a thermosetting resin material. However, as described above, the content of component (D) is 1% by mass with respect to the total mass of components (A) to (E). Since it is as small as ˜10% by mass, the component (D) can be obtained by using (components (A), (E)) and (components (B), (C)) and the specific blending ratio described below. The influence on the physical properties of the resin composition of the present invention is negligible.
　本発明の樹脂組成物では、成分（Ａ），（Ｅ）の合量と、成分（Ｂ），（Ｃ）の合量と、の質量比を、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝０．８１以上１．００以下とする。
　各成分の質量比が、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝０．８１未満であると所望の接着強度が得られない。
　一方、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝１．００を超えると、熱硬化物の弾性率が高くなるため、樹脂組成物を用いて作成される接着フィルムおよびカバーレイフィルムでの反りや、樹脂組成物による層間接着部における反りを発生させやすくなる。 In the resin composition of the present invention, the mass ratio of the total amount of components (A) and (E) and the total amount of components (B) and (C) is (A + E) / (B + C) = 0.81. More than 1.00.
If the mass ratio of each component is less than (A + E) / (B + C) = 0.81, desired adhesive strength cannot be obtained.
On the other hand, when (A + E) / (B + C) = 1.00 is exceeded, the elastic modulus of the thermoset increases, so warpage in the adhesive film and coverlay film produced using the resin composition, and the resin composition It becomes easy to generate the curvature in the interlayer adhesion part by a thing.
成分（Ｆ）：示差走査熱量（ＤＳＣ）測定による発熱ピークが１００℃以上１８０℃以下の有機過酸化物
　本発明の樹脂組成物において、成分（Ｆ）は、成分（Ａ）として用いるビニル化合物の反応を促進して、１８０℃以下での低温硬化を可能にする。また、反り低減、寸法安定性、半田耐熱性などの耐熱性向上、ピール強度の向上等の作用を発揮する。
　本発明におけるＤＳＣ測定による発熱ピークは、下記手順で測定されるものを指す。
　示差走査熱量計にて５℃／ｍｉｎの昇温で得られたＤＳＣ曲線より発熱ピークを読み取る。本発明ではピークトップの温度を対象物の発熱ピークとする。 Component (F): Organic peroxide having an exothermic peak of 100 ° C. or higher and 180 ° C. or lower as measured by differential scanning calorimetry (DSC) In the resin composition of the present invention, component (F) is a vinyl compound used as component (A). Accelerates the reaction and enables low temperature curing below 180 ° C. In addition, it exerts actions such as warpage reduction, dimensional stability, improved heat resistance such as solder heat resistance, and improved peel strength.
The exothermic peak by DSC measurement in the present invention refers to that measured by the following procedure.
The exothermic peak is read from the DSC curve obtained with a differential scanning calorimeter at a temperature increase of 5 ° C./min. In the present invention, the temperature at the peak top is the exothermic peak of the object.
　ＤＳＣ測定による発熱ピークが１００℃未満だと、樹脂組成物から接着フィルムやカバーレイフィルムを形成する際に、熱履歴により反応が進行し硬化する。このため接着機能が失われる。また、本発明の樹脂組成物を多層プリント配線板の層間接着剤として使用する場合も、樹脂組成物を含むワニスを塗布後、溶剤を揮発させ、乾燥する必要があるので、接着フィルムやカバーレイフィルムの形成時と同様に、熱履歴による硬化で接着機能が失われる。
　ＤＳＣ測定による発熱ピークが１８０℃超だと、１８０℃以下での熱硬化時間が長くなる。
　本発明において、ＤＳＣ測定による発熱ピークが、１２０～１８０℃であることがより好ましい。 When the exothermic peak by DSC measurement is less than 100 ° C., when the adhesive film or the coverlay film is formed from the resin composition, the reaction proceeds and cures due to the heat history. For this reason, the bonding function is lost. In addition, when the resin composition of the present invention is used as an interlayer adhesive for multilayer printed wiring boards, it is necessary to volatilize the solvent and dry it after applying the varnish containing the resin composition. As in the film formation, the adhesive function is lost by curing due to thermal history.
If the exothermic peak by DSC measurement is higher than 180 ° C, the heat curing time at 180 ° C or lower becomes longer.
In the present invention, the exothermic peak by DSC measurement is more preferably 120 to 180 ° C.
　本発明において、成分（Ｆ）の有機過酸化物としては、イソノナノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキシドなどのジアシルパーオキサイド類；２，２－ジ（４，４－ジ－（ジ－ｔｅｒｔ－ブチルパーオキシ）シクロヘキシル）プロパンなどのパーオキシケタール類；ジ－３－メトキシブチルパージカーボネート、ジシクロヘキシルパージカーボネートなどのパーオキシジカーボネート類；ｔｅｒｔ－ブチルパーベンゾエート、ｔｅｒｔ－ブチルパーアセテート、ｔｅｒｔ－ブチルパー－２－エチルへキサノエート、ｔｅｒｔ－ブチルパーイソブチレート、ｔｅｒｔ－ブチルパーピバレート、ｔｅｒｔ－ブチルジパーアジペート、キュミルパーネオデカノエート、ｔｅｒｔ－ブチルパーオキシベンゾエート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、２，５－ジメチル－２，５ジ（ベンゾイルパーオキシ）ヘキサンなどのパーオキシエステル類；メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイドなどのケトンパーオキサイド類；ジ－ｔｅｒｔ－ブチルパーオキサイド、ジキュミルパーオキサイド、ｔｅｒｔ－ブチルキュミルパーオキサイド、１，１－ジ（ｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ジ－ｔｅｒｔ－ヘキシルパーオキサイド、ジ（２－ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、などのジアルキルパーオキサイド類；キュメンヒドロキシパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド、ｐ－メンタハイドロパーオキサイドなどのハイドロパーオキサイド類等を使用することができる。
　これらの中でも、パーオキシエステル類およびジアルキルパーオキサイド類が好ましく、ｔｅｒｔ－ブチルパーオキシベンゾエート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、および、ジ（２－ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、が、ＤＳＣ測定による発熱ピークが１２０～１８０℃であること及び組成物の保存安定性が良好なことから特に好ましい。 In the present invention, the organic peroxide of component (F) includes isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide. Diacyl peroxides such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane and the like; di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate Peroxydicarbonates such as tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl Luziper adipate, cumyl perneodecanoate, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5 di Peroxyesters such as (benzoylperoxy) hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1 , 1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, and the like dialkyl peroxides; cumene hydro Shi peroxide, tert- butyl hydroperoxide, may be used hydroperoxide, and the like such as p- mentha hydroperoxide.
Among these, peroxyesters and dialkyl peroxides are preferable, and tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and di (2- tert-Butylperoxyisopropyl) benzene is particularly preferred since the exothermic peak by DSC measurement is 120 to 180 ° C. and the storage stability of the composition is good.
　本発明の樹脂組成物において、成分（Ｆ）の含有量は、成分（Ａ）の含有量に対する質量パーセントで、０．１～１０質量％である。
　成分（Ｆ）の含有量が０．１質量％未満だと、成分（Ａ）として用いるビニル化合物の反応を促進する作用が不十分となる。このため、１８０℃以下での熱硬化を達成できない。
　一方、成分（Ｆ）の含有量が１０質量％超だと、高周波での電気特性が悪化する。
　成分（Ｆ）の含有量は、成分（Ａ）の含有量に対する質量パーセントで、１～１０質量％であることがより好ましい。 In the resin composition of the present invention, the content of the component (F) is 0.1 to 10% by mass in terms of mass percent with respect to the content of the component (A).
When the content of the component (F) is less than 0.1% by mass, the effect of promoting the reaction of the vinyl compound used as the component (A) becomes insufficient. For this reason, thermosetting at 180 degrees C or less cannot be achieved.
On the other hand, if the content of the component (F) is more than 10% by mass, the electrical characteristics at high frequencies are deteriorated.
The content of the component (F) is more preferably 1 to 10% by mass with respect to the content of the component (A).
　本発明の樹脂組成物は、上記成分（Ａ）～（Ｆ）に加えて、成分（Ｇ）として、硬化触媒を含有してもよい。この硬化触媒は、成分（Ｄ）のエポキシ樹脂の硬化触媒として作用する。 The resin composition of the present invention may contain a curing catalyst as the component (G) in addition to the components (A) to (F). This curing catalyst acts as a curing catalyst for the epoxy resin of component (D).
　成分（Ｇ）として使用する硬化触媒は、エポキシ樹脂の硬化触媒であれば、特に限定されず、公知のものを使用することができる。例えば、イミダゾール系硬化触媒、アミン系硬化触媒、リン系硬化触媒等が挙げられる。 The curing catalyst used as the component (G) is not particularly limited as long as it is an epoxy resin curing catalyst, and a known one can be used. For example, an imidazole-based curing catalyst, an amine-based curing catalyst, a phosphorus-based curing catalyst, and the like can be given.
　イミダゾール系硬化触媒としては、２－メチルイミダゾール、２－ウンデシルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－エチル－４－イミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール等のイミダゾール化合物が挙げられる。中でも、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、および、１－シアノエチル－２－エチル－４－イミダゾールが好ましい。
　アミン系硬化触媒としては、２，４－ジアミノ－６－〔２’―メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジン等のトリアジン化合物、１，８－ジアザビシクロ［５，４，０］ウンデセン－７（ＤＢＵ）、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン等の第三級アミン化合物が挙げられる。中でも、２，４－ジアミノ－６－〔２’―メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジンが好ましい。
　また、リン系硬化触媒としては、トリフェニルホスフィン、トリブチルホスフィン、トリ（ｐ－メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィン等が挙げられる。 Examples of imidazole curing catalysts include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl. Examples thereof include imidazole compounds such as -4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Of these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-imidazole are preferable.
Examples of amine-based curing catalysts include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene. And tertiary amine compounds such as -7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Of these, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine is preferable.
Examples of phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and the like.
　なお、上記の硬化触媒のうち、いずれか１種を使用してもよく、２種以上を併用してもよい。硬化触媒の有効量は硬化触媒の種類によって異なる。硬化触媒の種類ごとに、その有効量を以下に示す。
　イミダゾール系硬化触媒、アミン系硬化触媒の場合、その有効量は、樹脂組成物の全成分の合計質量に対する質量パーセントで０．０１～５質量％であり、０．０５～３質量％であることがより好ましい。
　リン系硬化触媒の場合、その有効量は、樹脂組成物の全成分の合計質量に対する質量パーセントで０．０１～１０質量％であり、０．０５～５質量％であることがより好ましい。 In addition, any 1 type may be used among said curing catalyst, and 2 or more types may be used together. The effective amount of the curing catalyst varies depending on the type of the curing catalyst. The effective amount for each type of curing catalyst is shown below.
In the case of an imidazole-based curing catalyst or an amine-based curing catalyst, the effective amount is 0.01 to 5% by mass and 0.05 to 3% by mass with respect to the total mass of all components of the resin composition. Is more preferable.
In the case of a phosphorus-based curing catalyst, the effective amount is 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of all components of the resin composition.
　本発明の樹脂組成物は、さらに他の成分を必要に応じて含有してもよい。このような成分の具体例としては、シランカップリング剤、消泡剤、流動調整剤、成膜補助剤、分散剤等が挙げられる。 The resin composition of the present invention may further contain other components as necessary. Specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, and the like.
　本発明の樹脂組成物は、慣用の方法により製造することができる。例えば、溶剤の存在下または非存在下で、上記成分（Ａ）～成分（Ｆ）（樹脂組成物が上記成分（Ｇ）や他の任意成分を含有する場合はさらにこれらの任意成分）を加熱真空混合ニーダーにより混合する。
　上記成分（Ａ）～成分（Ｆ）が所望の含有割合となるように、（樹脂組成物が上記成分（Ｇ）や他の任意成分を含有する場合はさらにこれらの任意成分）、所定の溶剤濃度に溶解し、それらを１０～８０℃に加温された反応釜に所定量投入し、回転数１００～１０００ｒｐｍで回転させながら、常圧混合を３時間行った後、真空下（最大１Ｔｏｒｒ）でさらに３０～６０分混合攪拌することができる。 The resin composition of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above components (A) to (F) (if the resin composition contains the above component (G) or other optional components, these optional components are further heated). Mix with a vacuum mixing kneader.
A predetermined solvent so that the components (A) to (F) have a desired content ratio (if the resin composition contains the component (G) or other optional components, these optional components); Dissolve to a concentration, put them into a reaction kettle warmed to 10 to 80 ° C., perform normal pressure mixing for 3 hours while rotating at a rotational speed of 100 to 1000 rpm, and then under vacuum (maximum 1 Torr) The mixture can be further stirred for 30 to 60 minutes.
　本発明の樹脂組成物は、以下に示す好適な特性を有している。 The resin composition of the present invention has suitable characteristics shown below.
　本発明の樹脂組成物は、その熱硬化物が高周波での電気特性に優れている。具体的には、樹脂組成物の熱硬化物は、周波数１ＧＨｚ以上の領域での誘電率（ε）が３．０以下であることが好ましく、２．５以下であることがより好ましい。また、周波数１ＧＨｚ以上の領域での誘電正接（ｔａｎδ）が０．０１以下であることがより好ましく、０．００５以下であることがより好ましい。
　周波数１ＧＨｚ以上の領域での誘電率（ε）および誘電正接（ｔａｎδ）が上記の範囲であることにより、周波数１ＧＨｚ以上の領域での電気信号損失を低減することができる。 As for the resin composition of this invention, the thermosetting material is excellent in the electrical property in a high frequency. Specifically, the thermosetting product of the resin composition preferably has a dielectric constant (ε) of 3.0 or less, more preferably 2.5 or less in a region having a frequency of 1 GHz or more. Further, the dielectric loss tangent (tan δ) in the region of the frequency of 1 GHz or more is more preferably 0.01 or less, and more preferably 0.005 or less.
When the dielectric constant (ε) and the dielectric loss tangent (tan δ) in the frequency region of 1 GHz or higher are in the above range, the electric signal loss in the frequency region of 1 GHz or higher can be reduced.
　本発明の樹脂組成物は、その熱硬化物の引張弾性率が１５０～４５０ＭＰａであることが、接着強度が高く、かつ、熱硬化時の収縮応力が軽減されることから好ましい。
　引張弾性率が４５０ＭＰａ以下であれば、熱硬化時の収縮応力が軽減されるため、以下の効果を奏する。
　多層プリント配線板の層間接着剤として使用した際に、層間接着部に残留する応力が軽減される。これにより、層間接着部での反りの発生が抑制されるため、多層プリント配線板のビア接続の信頼性が向上する。
　また、本発明の樹脂組成物をＦＰＣのカバーレイフィルムとして使用した場合に、熱硬化時の反りの発生が抑制される。そのため、ＦＰＣの柔軟性が損なわれることがない。
　なお、本発明の樹脂組成物は、後述する実施例に記載の手順で測定されるように、１００ｍｍ角のフィルムの熱硬化物の反り量が１５ｍｍ以下であることが好ましく、１０ｍｍ以下であることがより好ましい。
　但し、熱硬化物の引張弾性率が低すぎると、樹脂組成物の接着強度が低下するので、１５０ＭＰａ以上とする必要がある。
　本発明の樹脂組成物は、その熱硬化物の引張弾性率が２００～４００ＭＰａであることがより好ましい。 In the resin composition of the present invention, it is preferable that the thermosetting product has a tensile elastic modulus of 150 to 450 MPa since the adhesive strength is high and the shrinkage stress during thermosetting is reduced.
If the tensile modulus is 450 MPa or less, the shrinkage stress at the time of thermosetting is reduced, and the following effects are obtained.
When used as an interlayer adhesive of a multilayer printed wiring board, the stress remaining in the interlayer adhesive portion is reduced. As a result, the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved.
Moreover, generation | occurrence | production of the curvature at the time of thermosetting is suppressed when the resin composition of this invention is used as a coverlay film of FPC. Therefore, the flexibility of the FPC is not impaired.
In addition, as for the resin composition of this invention, as measured in the procedure as described in the Example mentioned later, it is preferable that the curvature amount of the thermosetting material of a 100 mm square film is 15 mm or less, and is 10 mm or less. Is more preferable.
However, if the tensile elastic modulus of the thermoset is too low, the adhesive strength of the resin composition is lowered, so it is necessary to set it to 150 MPa or more.
The resin composition of the present invention more preferably has a tensile elastic modulus of the thermoset of 200 to 400 MPa.
　本発明の樹脂組成物は、その熱硬化時、具体的には、１００～１８０℃の温度域における最低溶融粘度が１０００～５００００Ｐａ・ｓであることが好ましい。
　熱硬化時の最低溶融粘度が上記範囲であれば、熱硬化時の流動性が適切な状態となるため好ましい。具体的には、樹脂組成物を用いて作製した接着フィルムやカバーレイフィルムの熱圧着時において、あるいは、樹脂組成物を層間接着剤として使用した際の熱圧着時において、流動性が良好であるため、ファインピッチ配線パターンへの埋め込み性が良好になる。
　ここで、最低溶融粘度とは、樹脂組成物を加熱した際に、該接着フィルムが溶融した際の粘度の最低値である。
　１００～１８０℃の温度域における最低溶融粘度が１０００Ｐａ・ｓ未満だと、熱硬化時の流動性が高すぎるため、熱硬化の前後で接着フィルムやカバーレイフィルムの膜厚、あるいは、層間接着部の厚さが変化するおそれがある。
　１００～１８０℃の温度域における最低溶融粘度が５００００Ｐａ・ｓ超だと、ファインピッチ配線パターンへの埋め込み性が不十分になるおそれがあり、熱圧着時に印加するプレス圧を大きくする必要がある。
　本発明の樹脂組成物は、１００～１８０℃の温度域における最低溶融粘度が２０００～２００００Ｐａ・ｓであることがより好ましい。 The resin composition of the present invention preferably has a minimum melt viscosity of 1000 to 50000 Pa · s in the temperature range of 100 to 180 ° C., when it is thermally cured.
If the minimum melt viscosity at the time of thermosetting is in the above range, it is preferable because the fluidity at the time of thermosetting becomes an appropriate state. Specifically, the fluidity is good at the time of thermocompression bonding of an adhesive film or coverlay film produced using the resin composition, or at the time of thermocompression bonding when the resin composition is used as an interlayer adhesive. Therefore, the embedding property to the fine pitch wiring pattern is improved.
Here, the minimum melt viscosity is the minimum value of the viscosity when the adhesive film is melted when the resin composition is heated.
If the minimum melt viscosity in the temperature range of 100 to 180 ° C is less than 1000 Pa · s, the fluidity at the time of thermosetting is too high, so the film thickness of the adhesive film or coverlay film before or after thermosetting, or the interlayer adhesion part There is a possibility that the thickness of the material changes.
If the minimum melt viscosity in the temperature range of 100 to 180 ° C. is more than 50000 Pa · s, the embedding property in the fine pitch wiring pattern may be insufficient, and it is necessary to increase the press pressure applied during thermocompression bonding.
The resin composition of the present invention preferably has a minimum melt viscosity of 2000 to 20000 Pa · s in a temperature range of 100 to 180 ° C.
　本発明の樹脂組成物は、熱硬化物のガラス転移温度が１６０℃以上であることが、熱硬化物の耐熱性や長期信頼性の観点から好ましい。 The resin composition of the present invention preferably has a glass transition temperature of 160 ° C. or higher from the viewpoint of heat resistance and long-term reliability of the thermoset.
　本発明の樹脂組成物は、その熱硬化物が十分な接着強度を有している。具体的には、加樹脂組成物の熱硬化物は、ＪＩＳ Ｃ６４７１に準拠して測定した銅箔粗化面に対するピール強度（１８０度ピール）が５Ｎ／ｃｍ以上あることが好ましく、より好ましくは６Ｎ／ｃｍ以上である。
　また、ＪＩＳ　Ｃ６４７１に準拠して測定したポリイミドフィルムに対するピール強度（１８０度ピール）が５Ｎ／ｃｍ以上あることが好ましく、より好ましくは６Ｎ／ｃｍ以上である。 As for the resin composition of this invention, the thermosetting material has sufficient adhesive strength. Specifically, the thermosetting product of the resin-resin composition preferably has a peel strength (180 degree peel) with respect to the roughened copper foil surface measured in accordance with JIS C6471 of 5 N / cm or more, more preferably 6 N. / Cm or more.
Moreover, it is preferable that the peel strength (180 degree | times peel) with respect to the polyimide film measured based on JISC6471 is 5 N / cm or more, More preferably, it is 6 N / cm or more.
　本発明の接着フィルムおよびカバーレイフィルムは、本発明の樹脂組成物から公知の方法により得ることができる。例えば、本発明の樹脂組成物を溶剤で希釈してワニスとし、これを支持体の少なくとも片面に塗布し、乾燥させた後、支持体付のフィルム、または、支持体から剥離したフィルムとして提供することができる。 The adhesive film and coverlay film of the present invention can be obtained from the resin composition of the present invention by a known method. For example, the resin composition of the present invention is diluted with a solvent to obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.
　ワニスとして使用可能な溶剤としては、メチルエチルケトン、メチルイソブチルケトン等のケトン類；トルエン、キシレン等の芳香族溶剤；ジオクチルフタレート、ジブチルフタレート等の高沸点溶剤等が挙げられる。溶剤の使用量は特に限定されず、従来から使用されている量とすることができるが、好ましくは、固形分に対して２０～９０質量％である。 Examples of the solvent that can be used as the varnish include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high-boiling solvents such as dioctyl phthalate and dibutyl phthalate. The amount of the solvent used is not particularly limited and may be a conventionally used amount, but is preferably 20 to 90% by mass with respect to the solid content.
　支持体は、フィルムの製造方法における所望の形態により適宜選択され、特に限定されないが、例えば、銅、アルミニウム等の金属箔、ポリエステル、ポリエチレン等の樹脂のキャリアフィルム等が挙げられる。本発明の接着フィルムを、支持体から剥離したフィルムの形態として提供する場合、支持体は、シリコーン化合物等で離型処理されていることが好ましい。 The support is appropriately selected depending on the desired form in the film production method, and is not particularly limited. Examples thereof include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When providing the adhesive film of this invention as a form of the film peeled from the support body, it is preferable that the support body is mold-release-processed with the silicone compound etc.
　ワニスを塗布する方法は、特に限定されないが、例えば、スロットダイ方式、グラビア方式、ドクターコーター方式等が挙げられ、所望のフィルムの厚みなどに応じて適宜選択されるが、特に、グラビア方式がフィルムの厚みを薄く設計しうることから好ましい。塗布は、乾燥後に形成されるフィルムの厚みが、所望の厚みになるように行われる。このような厚みは、当業者であれば、溶剤含有量から導くことができる。 The method for applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, which are appropriately selected according to a desired film thickness and the like. This is preferable because it can be designed to be thin. Application | coating is performed so that the thickness of the film formed after drying may turn into desired thickness. Such a thickness can be derived from the solvent content by those skilled in the art.
　本発明の接着フィルムおよびカバーレイフィルムの厚みは、用途に応じて要求される機械的強度などの特性に基づいて適宜設計されるが、一般に１～１００μｍであり、薄膜化が要求される場合、１～３０μｍであることが好ましい。 The thickness of the adhesive film and cover lay film of the present invention is appropriately designed based on characteristics such as mechanical strength required according to the application, but is generally 1 to 100 μm, and when thinning is required, It is preferably 1 to 30 μm.
　乾燥の条件は、ワニスに使用される溶剤の種類や量、ワニスの使用量や塗布の厚みなどに応じて適宜設計され、特に限定されるものではないが、例えば、６０～１００℃であり、大気圧下で行うことができる。 The drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used and the thickness of the coating, and are not particularly limited. For example, the drying conditions are 60 to 100 ° C., It can be performed under atmospheric pressure.
　本発明の接着フィルムの使用手順は以下の通り。
　本発明の接着フィルムを用いて接着する対象物のうち、一方の対象物の被接着面に本発明の接着フィルムを載置した後、もう一方の対象物をその被接着面が接着フィルムの露出面と接するように載置する。ここで、支持体付の接着フィルムを用いる場合、接着フィルムの露出面が一方の対象物の被接着面に接するように接着フィルムを載置して、被着面上に該接着フィルムを転写する。ここで、転写時の温度は例えば１３０℃とすることができる。
　次に、転写時に支持体を剥離することによって露出した接着フィルムの面上にもう一方の対象物をその被接着面が接着フィルムの露出面と接するように載置する。これらの手順を実施した後、所定温度及び所定時間熱圧着させ、その後、加熱硬化させる。
　熱圧着時の温度は好ましくは１００～１８０℃である。熱圧着の時間は好ましくは０．５～１０分である。
　加熱硬化の温度は、好ましくは１５０～１８０℃である。加熱硬化時間は、好ましくは３０～１２０分である。
　なお、予めフィルム化したものを使用する代わりに、本発明の樹脂組成物を溶剤で希釈したワニスを、一方の接着対象物の被接着面に塗布し、乾燥させた後に、上記した一方の対象物を載置する手順を実施してもよい。 The procedure for using the adhesive film of the present invention is as follows.
Among objects to be bonded using the adhesive film of the present invention, after the adhesive film of the present invention is placed on the surface to be bonded of one object, the other surface is exposed to the adhesive film. Place it in contact with the surface. Here, when using an adhesive film with a support, the adhesive film is placed so that the exposed surface of the adhesive film is in contact with the adherend surface of one object, and the adhesive film is transferred onto the adherend surface. . Here, the temperature at the time of transfer can be set to 130 ° C., for example.
Next, the other object is placed on the surface of the adhesive film exposed by peeling the support during transfer so that the surface to be bonded is in contact with the exposed surface of the adhesive film. After performing these procedures, thermocompression bonding is performed for a predetermined temperature and for a predetermined time, and then heat-cured.
The temperature during thermocompression bonding is preferably 100 to 180 ° C. The time for thermocompression bonding is preferably 0.5 to 10 minutes.
The temperature for heat curing is preferably 150 to 180 ° C. The heat curing time is preferably 30 to 120 minutes.
Instead of using a pre-filmed one, the varnish obtained by diluting the resin composition of the present invention with a solvent is applied to the adherend surface of one object to be bonded and dried, and then the one object described above is used. You may implement the procedure which mounts an object.
　本発明の接着フィルムは、多層プリント配線板の層間接着にも使用できる。この場合、上記した接着する対象物が、多層プリント配線板の各層を構成する基板となる。なお、多層プリント配線板の層間接着についても、予めフィルム化したものを使用する代わりに、本発明の樹脂組成物を溶剤で希釈したワニスを使用してもよい。
　本発明の接着フィルムもしくはワニスを用いて層間接着された多層プリント配線板は、層間接着部に残留する応力が軽減される。これにより、層間接着部での反りの発生が抑制されるため、多層プリント配線板のビア接続の信頼性が向上する。また、層間接着部の寸法安定性が優れている。 The adhesive film of the present invention can also be used for interlayer adhesion of multilayer printed wiring boards. In this case, the above-described object to be bonded becomes a substrate constituting each layer of the multilayer printed wiring board. For interlayer adhesion of the multilayer printed wiring board, a varnish obtained by diluting the resin composition of the present invention with a solvent may be used instead of using a film formed in advance.
In the multilayer printed wiring board bonded with the interlayer using the adhesive film or varnish of the present invention, the stress remaining in the interlayer bonded portion is reduced. As a result, the occurrence of warpage at the interlayer adhesion portion is suppressed, and the reliability of via connection of the multilayer printed wiring board is improved. Further, the dimensional stability of the interlayer adhesive portion is excellent.
　多層プリント配線板の各層を構成する基板は特に限定されず、エポキシ樹脂、フェノール樹脂、ビスマレイミドトリアジン樹脂等の有機基板や、セラミック基板やシリコン基板等の無機基板のいずれも使用できる。また、後述する本発明のＦＰＣに好適な樹脂基板も使用できる。 The substrate constituting each layer of the multilayer printed wiring board is not particularly limited, and any of an organic substrate such as an epoxy resin, a phenol resin, and a bismaleimide triazine resin, and an inorganic substrate such as a ceramic substrate and a silicon substrate can be used. A resin substrate suitable for the FPC of the present invention described later can also be used.
　次に、本発明のカバーレイフィルムの使用手順を示す。
　本発明のカバーレイフィルムを、主面に配線パターンが形成された配線付樹脂基板の所定の位置、すなわち、配線パターンが形成された側の、カバーレイフィルムで被覆する位置に、該カバーレイフィルムを配置した後、所定温度及び所定時間熱圧着させればよい。
　熱圧着のうち仮圧着時の温度は好ましくは１００～１８０℃である。仮圧着の時間は好ましくは０．５～１０分である。
　加熱硬化の温度は、好ましくは１５０～１８０℃である。加熱硬化時間は、好ましくは３０～１２０分である。
　本発明のカバーレイフィルムでは、熱硬化時の反りの発生が抑制されている。 Next, the procedure for using the coverlay film of the present invention will be shown.
The cover lay film of the present invention is placed at a predetermined position on the resin substrate with wiring on which the wiring pattern is formed on the main surface, that is, on the side where the wiring pattern is formed, with the cover lay film. After the arrangement, the thermocompression bonding may be performed for a predetermined temperature and a predetermined time.
Of thermocompression bonding, the temperature at the time of provisional pressure bonding is preferably 100 to 180 ° C. The pre-bonding time is preferably 0.5 to 10 minutes.
The temperature for heat curing is preferably 150 to 180 ° C. The heat curing time is preferably 30 to 120 minutes.
In the coverlay film of this invention, generation | occurrence | production of the curvature at the time of thermosetting is suppressed.
　本発明のフレキシブルプリント配線板（ＦＰＣ）は、主面に配線パターンが形成された配線付樹脂基板の配線パターン側に、本発明のカバーレイフィルムを配置した後、所定温度及び所定時間加熱硬化して、配線付樹脂基板とカバーレイフィルムとを一体化したものである。
　本発明のＦＰＣに使用する樹脂基板も、高周波領域の電気特性が優れていること、すなわち、周波数１ＧＨｚ以上の領域において、低誘電率（ε）、および、低誘電正接（ｔａｎδ）であることが好ましい。このような樹脂基板の具体例としては、液晶ポリマー（ＬＣＰ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリイミド（ＰＩ）、および、ポリエチレンナフタレ－ト（ＰＥＮ）のいずれかを主成分とする樹脂基板が挙げられる。 The flexible printed wiring board (FPC) of the present invention is heat-cured for a predetermined temperature and for a predetermined time after the coverlay film of the present invention is disposed on the wiring pattern side of the resin substrate with wiring having a wiring pattern formed on the main surface. The resin substrate with wiring and the coverlay film are integrated.
The resin substrate used in the FPC of the present invention also has excellent electrical characteristics in a high frequency region, that is, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency region of 1 GHz or higher. preferable. Specific examples of such a resin substrate include a resin substrate mainly composed of any one of liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimide (PI), and polyethylene naphthalate (PEN). Is mentioned.
　また、本発明のＦＰＣに好適な樹脂基板の別の具体例としては、
（ａ）下記一般式（１）で表されるビニル化合物、ならびに、
（ｂ）ゴムおよび／または熱可塑性エラストマー、
を主成分とする樹脂基板が挙げられる。
Figure JPOXMLDOC01-appb-C000023
 　成分（ａ）の上記式（１）で表されるビニル化合物については、本発明の樹脂組成物について上述した通りである。
　（ａ）上記一般式（１）で表されるビニル化合物、ならびに、（ｂ）ゴムおよび／または熱可塑性エラストマーを主成分とする樹脂基板は、本発明の樹脂組成物と同様の構成をしており、低誘電率・低誘電正接である。このため、例えば本発明の樹脂組成物を用いた層間接着剤やカバーレイフィルムと組み合わせれば、高周波特性に優れたプリント基板とすることができる。
　また、本発明の樹脂組成物と同様の構成をしているため、本発明の樹脂組成物を用いた層間接着剤やカバーレイフィルムとの接着強度が高い。 As another specific example of the resin substrate suitable for the FPC of the present invention,
(A) a vinyl compound represented by the following general formula (1), and
(B) rubber and / or thermoplastic elastomer,
And a resin substrate containing as a main component.
Figure JPOXMLDOC01-appb-C000023
 About the vinyl compound represented by the said Formula (1) of a component (a), it is as having mentioned above about the resin composition of this invention.
(A) The vinyl compound represented by the general formula (1), and (b) a resin substrate mainly composed of rubber and / or thermoplastic elastomer have the same configuration as the resin composition of the present invention. It has a low dielectric constant and low dielectric loss tangent. For this reason, if it combines with the interlayer adhesive and coverlay film which used the resin composition of this invention, for example, it can be set as the printed circuit board excellent in the high frequency characteristic.
Moreover, since it is the same structure as the resin composition of this invention, the adhesive strength with the interlayer adhesive and coverlay film using the resin composition of this invention is high.
成分（ｂ）：ゴムおよび／または熱可塑性エラストマー、
　上記した本発明のＦＰＣに好適な樹脂基板の具体例は、成分（ｂ）として、ゴムと熱可塑性エラストマーのうち、少なくとも一方を含有する。樹脂基板はゴムと熱可塑性エラストマーの両方を含有してもよい。 Component (b): rubber and / or thermoplastic elastomer,
The specific example of the resin substrate suitable for the FPC of the present invention described above contains at least one of rubber and thermoplastic elastomer as the component (b). The resin substrate may contain both rubber and a thermoplastic elastomer.
　成分（ｂ）のゴムとしては、スチレン－ブタジエンゴム、ブチルゴム、ブタジエンゴム、アクリルゴム等のゴム類が挙げられる。これらのゴム類は１種単独で用いてもよく、２種以上を併用してもよい。
　一方、熱可塑性エラストマーとしては、スチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー等が挙げられる。熱可塑性エラストマーは１種単独で用いてもよく、２種以上を併用してもよい。 Examples of the component (b) rubber include rubbers such as styrene-butadiene rubber, butyl rubber, butadiene rubber, and acrylic rubber. These rubbers may be used alone or in combination of two or more.
On the other hand, examples of the thermoplastic elastomer include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, and a polyester thermoplastic elastomer. A thermoplastic elastomer may be used individually by 1 type, and may use 2 or more types together.
　成分（ｂ）としては、樹脂基板が柔軟性に優れること等の理由から、熱可塑性エラストマーが好ましく、スチレン系熱可塑性エラストマーが特に好ましい。
　スチレン系熱可塑性エラストマーの具体例としては、スチレン－ブタジエンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、または、それらの二重結合の一部を水添した共重合体が挙げられ、より具体的には、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＥＰＳ）等が挙げられる。これらの中でも、ＳＢＳ、ＳＥＢＳが好ましい。 As the component (b), a thermoplastic elastomer is preferable, and a styrene-based thermoplastic elastomer is particularly preferable because the resin substrate is excellent in flexibility.
Specific examples of the styrenic thermoplastic elastomer include a styrene-butadiene block copolymer, a styrene-isoprene-styrene block copolymer, or a copolymer obtained by hydrogenating a part of these double bonds. More specifically, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene. -Propylene-styrene block copolymer (SEEPS) and the like. Among these, SBS and SEBS are preferable.
　成分（ｂ）として、スチレン系熱可塑性エラストマーを用いる場合、質量平均分子量が２０，０００～２５０，０００であるのが好ましい。また、成分（ａ）との相溶性が良好で、スチレン系熱可塑性エラストマーにおけるスチレン含有量は１５～６０質量％であることが好ましく、より好ましくは２０～５０質量％である。なお、質量平均分子量はＧＰＣにより、標準ポリスチレンによる検量線を用いて求めた値である。
　スチレン系熱可塑性エラストマーの具体例としては、ＪＳＲ株式会社製のスチレン－ブタジエンブロック共重合体「ＪＳＲ　ＴＲ」シリーズ、スチレン－イソプレンブロック共重合体「ＪＳＲ　ＳＩＳ」シリーズなどが挙げられる。
　さらに、成分（ｂ）として、上述した本発明の樹脂組成物の成分（Ｂ）、（Ｃ）を用い、成分（Ｂ）、（Ｃ）の質量比を（Ｂ）／（Ｃ）＝１．００以上４．００以下とすると、高周波での優れた電気特性に寄与しながらも熱硬化物の弾性率が高くならず、また、配線パターンを構成する銅との接着性に優れる。
　さらにまた、上述した本発明の樹脂組成物の成分（Ｄ）を添加すると熱硬化性の向上や配線パターンを構成する銅との接着性の向上につながり、上述した本発明の樹脂組成物の成分（Ｅ）を添加すると誘電特性の保持、接着強度の付与及び高Ｔｇ（ガラス転移点）化につながる。
　また、上述した本発明の樹脂組成物の成分（Ｆ）を添加してもよい。成分（Ｆ）を添加することで、成分（ａ）を使用する樹脂基板の低温硬化が可能となる。これにより、一般的に基板製造に使用される設備・条件が適用可能となる。さらに反り低減、寸法安定性、半田耐熱性などの耐熱性向上、ピール強度の向上につながる。 When a styrene thermoplastic elastomer is used as the component (b), the mass average molecular weight is preferably 20,000 to 250,000. Further, the compatibility with the component (a) is good, and the styrene content in the styrenic thermoplastic elastomer is preferably 15 to 60% by mass, more preferably 20 to 50% by mass. The mass average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.
Specific examples of the styrene thermoplastic elastomer include a styrene-butadiene block copolymer “JSR TR” series and a styrene-isoprene block copolymer “JSR SIS” series manufactured by JSR Corporation.
Furthermore, the components (B) and (C) of the resin composition of the present invention described above are used as the component (b), and the mass ratio of the components (B) and (C) is (B) / (C) = 1. If it is 00 or more and 4.00 or less, while contributing to excellent electrical characteristics at high frequencies, the elastic modulus of the thermoset does not increase, and the adhesiveness with copper constituting the wiring pattern is excellent.
Furthermore, when the component (D) of the resin composition of the present invention described above is added, the thermosetting property and the adhesiveness with the copper constituting the wiring pattern are improved, and the component of the resin composition of the present invention described above. Addition of (E) leads to retention of dielectric properties, provision of adhesive strength, and high Tg (glass transition point).
Moreover, you may add the component (F) of the resin composition of this invention mentioned above. By adding the component (F), the resin substrate using the component (a) can be cured at a low temperature. This makes it possible to apply facilities and conditions generally used for substrate manufacture. Furthermore, it leads to improvement of heat resistance such as warpage reduction, dimensional stability, solder heat resistance, and peel strength.
　上記した本発明のＦＰＣに好適な樹脂基板の具体例は、上記した成分（ａ）、（ｂ）に加えて、成分（ｃ）として、シランカップリング剤を含有することが好ましい。成分（ｃ）のシランカップリング剤は、樹脂基板に配線パターンを転写する際に、樹脂基板と配線パターンとの密着性に寄与する。 Specific examples of the resin substrate suitable for the FPC of the present invention described above preferably contain a silane coupling agent as the component (c) in addition to the components (a) and (b) described above. The component (c) silane coupling agent contributes to adhesion between the resin substrate and the wiring pattern when the wiring pattern is transferred to the resin substrate.
　上記した本発明のＦＰＣに好適な樹脂基板の具体例において、成分（ａ）と、成分（ｂ）と、の質量割合は、３：７～７：３であることが好ましく、４：６～６：４であることがより好ましい。 In the specific example of the resin substrate suitable for the FPC of the present invention described above, the mass ratio of the component (a) and the component (b) is preferably 3: 7 to 7: 3, and preferably 4: 6 to 6: 4 is more preferable.
　上記した本発明のＦＰＣに好適な樹脂基板の具体例は、上記した成分（ａ）～（ｃ）以外の任意の成分を含んでいてもよい。このような任意の成分の具体例としては、樹脂基板の機械的強度を向上させる目的で使用される充填剤が挙げられる。このような充填剤の具体例としては、シリカ、アルミナ、チタニア、窒化ホウ素、酸化鉄等の無機化合物、あるいは、カーボン等の有機充填剤が挙げられる。
　任意成分として、充填剤を含有させる場合、成分（ａ）～（ｃ）の総量に対する充填剤の質量割合が、９：１～１：９であることが好ましく、より好ましくは８：２～２：８であり、さらに好ましくは７：３～３：７である。
　また、上記した本発明のＦＰＣに好適な樹脂基板は、上記した充填剤とともに、または、上記した充填剤の代わりに、ガラス繊維や炭素繊維のような無機繊維や、アラミド繊維のような有機繊維を、樹脂基板の機械的強度を向上させる目的で含んでいてもよい。 Specific examples of the resin substrate suitable for the FPC of the present invention described above may include any component other than the components (a) to (c) described above. Specific examples of such optional components include fillers used for the purpose of improving the mechanical strength of the resin substrate. Specific examples of such a filler include inorganic compounds such as silica, alumina, titania, boron nitride, and iron oxide, and organic fillers such as carbon.
When a filler is included as an optional component, the mass ratio of the filler to the total amount of components (a) to (c) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2 : 8, and more preferably 7: 3 to 3: 7.
In addition, the resin substrate suitable for the FPC of the present invention described above is an inorganic fiber such as glass fiber or carbon fiber, or an organic fiber such as aramid fiber, instead of the filler described above or instead of the filler described above. May be included for the purpose of improving the mechanical strength of the resin substrate.
　以下、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
（実施例１～９、比較例１～１２）
サンプル作成と測定方法
　各成分を下記表に示す配合割合（質量％）になるように、計量配合した後、それらを７０℃に加温された反応釜に投入し、回転数３００ｒｐｍで回転させながら、常圧混合を３時間行った。硬化剤を加える場合には、冷却後に硬化剤を加えた。
　このようにして得られた樹脂組成物を含むワニスを支持体（離型処理をほどこしたＰＥＴフィルム）の片面に塗布し、１００℃で乾燥させることにより、支持体付の接着性フィルムを得た。
　なお、表中の略号はそれぞれ以下を表わす。
成分（Ａ）
ＯＰＥ２２００：オリゴフェニレンエーテル（上記一般式（１）で示されるビニル化合物）（Ｍｎ＝２２００）、三菱ガス化学株式会社製
成分（Ｂ）
タフテックＨ１０５２：ポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体（スチレン量２０％）、旭化成株式会社製
タフテックＨ１０３１：ポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体（スチレン量３０％）、旭化成株式会社製
成分（Ｂ´）
タフテックＨ１２２１：ポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体（スチレン量１２％）、旭化成株式会社製
セプトン８１０４：ポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体（スチレン量６０％）、株式会社クラレ製
成分（Ｃ）
セプトン４０４４：ポリスチレン－ポリ（エチレン－エチレン／プロピレン）ブロック共重合体（スチレン量３２％）、株式会社クラレ製
成分（ＢＣ´）
ＴＲ２００３：ポリスチレン－ポリブタジエンブロック共重合体（スチレン／ブタジエン＝４３／５７）、ＪＳＲ株式会社製
成分（Ｄ）
ＮＣ３０００Ｈ：ビフェニル型エポキシ樹脂、日本化薬株式会社製
ＨＰ４０３２Ｄ：ナフタレン型エポキシ樹脂、ＤＩＣ株式会社製
８２８ＥＬ：ビスフェノールＡ型エポキシ樹脂、三菱化学株式会社製
成分（Ｅ）
ＢＭＩ－７０：ビスマレイミド、ケイ・アイ化成株式会社製
成分（Ｆ）
パーブチルＺ：ｔｅｒｔ－ブチルパーオキシベンゾエート、日油株式会社製、発熱ピーク１４０～１７０℃
パーブチルＰ：ジ（２－ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、日油株式会社、発熱ピーク１６０～１８０℃
パーオクタＯ：１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、日油株式会社製、発熱ピーク１２０～１３０℃
成分（Ｆ´）
パーロイルＯＰＰ：ジ（２－エチルヘキシル）パーオキシジカーボネート、日油株式会社、発熱ピーク８０～１００℃
ノフマーＢＣ－９０：２，３－ジメチル－２，３－ジフェニルブタン、日油株式会社、発熱ピーク２００℃以上
成分（Ｇ）
Ｃ１１ＺＣＮ：１－シアノエチル－２－ウンデシルイミダゾール、四国化成工業株式会社製
２Ｅ４ＭＺ：２－エチル－４－メチルイミダゾール、四国化成工業株式会社製
１Ｂ２ＰＺ：１－ベンジル－２－フェニルイミダゾール、四国化成工業株式会社製
ＴＰＰ－ＭＫ：テトラフェニルホスホニウムテトラ－ｐ－トリルボレート、北興化学工業株式会社製 (Examples 1 to 9, Comparative Examples 1 to 12)
Sample preparation and measurement method Each component was weighed and blended so as to have the blending ratio (mass%) shown in the following table, and then charged into a reaction kettle heated to 70 ° C and rotated at a rotation speed of 300 rpm. Normal pressure mixing was performed for 3 hours. When adding a curing agent, the curing agent was added after cooling.
An adhesive film with a support was obtained by applying the varnish containing the resin composition thus obtained to one side of a support (PET film subjected to a release treatment) and drying at 100 ° C. .
In addition, the symbol in a table | surface represents the following, respectively.
Ingredient (A)
OPE2200: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd.
Ingredient (B)
Tuftec H1052: Polystyrene-poly (ethylene / butylene) block copolymer (styrene amount 20%), Asahi Kasei Corporation Tuftec H1031: Polystyrene-poly (ethylene / butylene) block copolymer (styrene amount 30%), Asahi Kasei Corporation Made by company
Ingredient (B ')
Tuftec H1221: Polystyrene-poly (ethylene / butylene) block copolymer (styrene content 12%), Asahi Kasei Corporation Septon 8104: Polystyrene-poly (ethylene / butylene) block copolymer (styrene content 60%), Co., Ltd. Kuraray
Ingredient (C)
Septon 4044: Polystyrene-poly (ethylene-ethylene / propylene) block copolymer (styrene content 32%), manufactured by Kuraray Co., Ltd.
Ingredient (BC ')
TR2003: Polystyrene-polybutadiene block copolymer (styrene / butadiene = 43/57), manufactured by JSR Corporation
Ingredient (D)
NC3000H: Biphenyl type epoxy resin, Nippon Kayaku Co., Ltd. HP4032D: Naphthalene type epoxy resin, DIC Corporation 828EL: Bisphenol A type epoxy resin, Mitsubishi Chemical Corporation
Ingredient (E)
BMI-70: Bismaleimide, manufactured by Kay Kasei Co., Ltd.
Ingredient (F)
Perbutyl Z: tert-butyl peroxybenzoate, manufactured by NOF Corporation, exothermic peak 140-170 ° C
Perbutyl P: Di (2-tert-butylperoxyisopropyl) benzene, NOF Corporation, exothermic peak 160 to 180 ° C.
Perocta O: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by NOF Corporation, exothermic peak 120 to 130 ° C.
Ingredient (F ')
Parroyl OPP: Di (2-ethylhexyl) peroxydicarbonate, NOF Corporation, exothermic peak 80-100 ° C
NOFMER BC-90: 2,3-dimethyl-2,3-diphenylbutane, NOF Corporation, exothermic peak over 200 ° C
Ingredient (G)
C11ZCN: 1-cyanoethyl-2-undecylimidazole, 2E4MZ manufactured by Shikoku Chemicals Co., Ltd .: 2-ethyl-4-methylimidazole, 1B2PZ manufactured by Shikoku Chemicals Co., Ltd .: 1-benzyl-2-phenylimidazole, Shikoku Chemicals Co., Ltd. Company TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate, manufactured by Hokuko Chemical Co., Ltd.
誘電率（ε）、誘電正接（ｔａｎδ）：接着性フィルムを１８０℃で加熱硬化させ、支持体から剥離した後、該接着性フィルムから試験片（４０±０．５ｍｍ×１００±２ｍｍ）を切り出し、厚みを測定した。試験片を長さ１００ｍｍ、直径２ｍｍ以下の筒状に丸めて、空洞共振器摂動法（１０ＧＨｚ）にて、誘電率（ε）および誘電正接（ｔａｎδ）を測定した。
引張弾性率：接着性フィルムを１８０℃で加熱硬化させ、支持体から剥離した後、該接着性フィルムから試験片（２５±０．５ｍｍ×２２０±２ｍｍ）をＭＤ方向に５枚切り出し、厚みを測定した。この試験片をオートグラフに掴み治具幅１７０ｍｍでセットし、引張速度１ｍｍ/ｍｉｎでストローク５ｍｍまで測定した。Ｎ＝５の平均値を測定値とした。
反り量：厚さ１８μｍの銅箔（福田金属箔粉工業株式会社製の銅箔ＣＦ－Ｔ８）１００±０．５ｍｍ角に切り出し、同サイズに切り出した接着性フィルムを、銅箔片面にプレス機で圧着させつつ加熱硬化させた（１８０℃、６０ｍｉｎ、１ＭＰａ）。支持体を剥離し、接着性フィルムを貼り付けた面を下にして平らな机の水平面上に載置し、硬化収縮による反り量を測定した。すなわち、反り量とは、机の水平面からフィルム中央浮き上がり箇所までの高さの最大値である。
ピール強度（Ｃｕ）：銅箔（ＣＦ－Ｔ８、福田金属箔粉工業株式会社製、厚さ１８μｍ）の粗化面に、乾燥させた接着性フィルムを、熱圧着し、その後加熱硬化（熱圧着：１３０℃ ３分，加熱硬化：１８０℃×１ｈｒ）させた後、ＪＩＳ Ｃ６４７１に準拠してピール強度（１８０度ピール）を測定した。銅箔面から、１０ｍｍ幅で接着性フィルムをカットし、オートグラフで引きはがして、ピール強度（１８０度ピール）を測定した。
ピール強度（ＰＩ）：ポリイミドフィルム（Ｋ１００ＥＮ、東レ・デュポン株式会社製、２５μｍ）に、乾燥させた接着性フィルムを、熱圧着し、その後加熱硬化（熱圧着：１３０℃ ３分，加熱硬化：１８０℃×１ｈｒ）させた後、ＪＩＳ Ｃ６４７１に準拠してピール強度（１８０度ピール）を測定した。ポリイミドフィルムのフィルム面から、１０ｍｍ幅で接着性フィルムをカットし、オートグラフで引きはがして、ピール強度（１８０度ピール）を測定した。
寸法安定性（ＪＩＳＣ６４７１準拠）：上述の方法により得られた接着性フィルムの両面に銅箔を熱圧着（１８０℃、６０分、１ＭＰa）にて貼り合わせ、２００ｍｍ×２５０ｍｍの試料とした。試料の４隅に直径２ｍｍの孔をあけ、まず隣り合う孔の縦及び横の間隔を測定し、次に表面の銅箔を全面エッチングした後に８０℃で３０分乾燥処理をおこない、この後、再び隣り合う孔の縦及び横の間隔を測定し、そして処理前後の孔の間隔の変化より縦と横の寸法変化率を求めた。更に１５０℃で３０分の熱処理を行い前述と同様な測定をして縦と横の寸法変化率を求めた。表には縦と横の寸法変化率の平均値を記載した。
半田耐熱性（半田フロート試験）：上述の方法により得られた接着フィルムの両面に銅箔を熱圧着（１８０℃、６０分、１ＭＰa）にて貼り合わせ５０ｍｍ×５０ｍｍの試料を作製した。これを２９０℃から１０℃ずつ温度を上げた半田浴に３０秒浮かべ膨れの有無を評価した。表には、膨れが発生した温度より１０℃低い温度の数値を記載した。
　なお、反り量１５ｍｍ以下、及びピール強度５Ｎ／ｃｍ以上の結果を得られなかった組成については、寸法安定性と半田耐熱性の評価を行わなかった。 Dielectric constant (ε), dielectric loss tangent (tan δ): After the adhesive film was cured by heating at 180 ° C. and peeled off from the support, a test piece (40 ± 0.5 mm × 100 ± 2 mm) was cut out from the adhesive film The thickness was measured. The test piece was rolled into a cylindrical shape having a length of 100 mm and a diameter of 2 mm or less, and a dielectric constant (ε) and a dielectric loss tangent (tan δ) were measured by a cavity resonator perturbation method (10 GHz).
Tensile modulus: After heat-curing the adhesive film at 180 ° C. and peeling from the support, 5 test pieces (25 ± 0.5 mm × 220 ± 2 mm) were cut out in the MD direction from the adhesive film, and the thickness was increased. It was measured. The test piece was gripped on an autograph, set at a jig width of 170 mm, and measured up to a stroke of 5 mm at a tensile speed of 1 mm / min. The average value of N = 5 was taken as the measured value.
Warpage amount: Copper foil with a thickness of 18 μm (copper foil CF-T8 manufactured by Fukuda Metal Foil Powder Co., Ltd.) cut into 100 ± 0.5 mm square, and an adhesive film cut into the same size was pressed on one side of the copper foil. And heat-cured while being pressure-bonded at 180 ° C. (60 ° C., 60 min, 1 MPa). The support was peeled off and placed on a horizontal surface of a flat desk with the surface to which the adhesive film was attached facing down, and the amount of warpage due to curing shrinkage was measured. That is, the amount of warpage is the maximum value of the height from the horizontal plane of the desk to the location where the center of the film is lifted.
Peel strength (Cu): The dried adhesive film is thermocompression bonded to the roughened surface of copper foil (CF-T8, manufactured by Fukuda Metal Foil Powder Co., Ltd., thickness 18 μm), and then heat-cured (thermocompression bonding). : 130 ° C. for 3 minutes, heat curing: 180 ° C. × 1 hr), and then peel strength (180 degree peel) was measured according to JIS C6471. The adhesive film was cut with a width of 10 mm from the copper foil surface, peeled off with an autograph, and peel strength (180 degree peel) was measured.
Peel strength (PI): The dried adhesive film is thermocompression bonded to a polyimide film (K100EN, manufactured by Toray DuPont Co., Ltd., 25 μm), and then heat-cured (thermocompression: 130 ° C. for 3 minutes, heat-curing: 180 The peel strength (180 degree peel) was measured according to JIS C6471. The adhesive film was cut with a width of 10 mm from the film surface of the polyimide film, peeled off by an autograph, and peel strength (180 degree peel) was measured.
Dimensional stability (JISC6471 compliant): A copper foil was bonded to both surfaces of the adhesive film obtained by the above-described method by thermocompression bonding (180 ° C., 60 minutes, 1 MPa) to obtain a 200 mm × 250 mm sample. Holes with a diameter of 2 mm were drilled at the four corners of the sample, and first, the vertical and horizontal distances between adjacent holes were measured. Next, the entire surface of the copper foil was etched and then dried at 80 ° C. for 30 minutes. The vertical and horizontal intervals between adjacent holes were measured again, and the vertical and horizontal dimensional change rates were determined from the change in the interval between the holes before and after the treatment. Further, heat treatment was performed at 150 ° C. for 30 minutes, and the same measurement as described above was performed to obtain the vertical and horizontal dimensional change rates. The table lists the average values of the vertical and horizontal dimensional change rates.
Solder heat resistance (solder float test): A copper foil was bonded to both surfaces of the adhesive film obtained by the above method by thermocompression bonding (180 ° C., 60 minutes, 1 MPa) to prepare a 50 mm × 50 mm sample. This was evaluated for the presence or absence of blistering for 30 seconds in a solder bath whose temperature was increased from 290 ° C to 10 ° C. In the table, numerical values of temperatures 10 ° C. lower than the temperature at which blistering occurred are described.
In addition, about the composition which was not able to obtain the result of the curvature amount of 15 mm or less and the peel strength of 5 N / cm or more, dimensional stability and solder heat resistance were not evaluated.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　実施例１～９は、反り量、高周波の電気特性（誘電率（ε）、誘電正接（ｔａｎδ））、引張弾性率、ピール強度、寸法安定性、半田耐熱性のいずれも優れていた。実施例１に比べてＢ／Ｃを大きくした実施例５では、引張弾性率を低くすることできた。実施例５に比べてＢ／Ｃをさらに大きくした実施例６では、引張弾性率をさらに低くすることできた。
　また、実施例１に比べて（Ｄ）成分のエポキシ樹脂の含有量を少なくした実施例８では、誘電正接（ｔａｎδ）をより低くすることができた。
　成分（Ｂ），（Ｃ）の代わりに、熱可塑性エラストマーとして、ポリスチレン・ポリブタジエンブロック共重合体を使用した比較例１では反り量が大きかった。また、寸法安定性および半田耐熱性が劣っていた。
　成分（Ｂ）を含まない比較例２では引張弾性率が高くなり、反り量も大きかった。また、寸法安定性および半田耐熱性が劣っていた。
　成分（Ｃ）を含まない比較例３は、ピール強度が低かった。
　各成分の質量比が、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝０．８１未満の比較例４は、ピール強度が低かった。
　各成分の質量比が、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝１．００超の比較例５は、反り量が大きかった。
　成分（Ｂ），（Ｃ）の質量比（Ｂ）／（Ｃ）＝１．００未満の比較例６は、反り量が大きかった。
　成分（Ｂ），（Ｃ）の質量比（Ｂ）／（Ｃ）＝４．００超の比較例７は、ピール強度が低かった。
　成分（Ｆ）を含まない比較例８は、寸法安定性が劣っていた。
　成分（Ｂ）の代わりにスチレン含有量が１５％未満のポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体を使用した比較例９は、ピール強度（ＰＩ）が低かった。また、寸法安定性および半田耐熱性が劣っていた。
　成分（Ｂ）の代わりにスチレン含有量が３５％超満のポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体を使用した比較例１０は、反り量が大きかった。また、寸法安定性が劣っていた。
　成分（Ｆ）の発熱ピークが１８０℃超の比較例１１は、寸法安定性が劣っていた。
　成分（Ｆ）の発熱ピークが１００℃未満の比較例１２は、ピール強度が測定できなかった。 Examples 1 to 9 were all excellent in warpage, high frequency electrical characteristics (dielectric constant (ε), dielectric loss tangent (tan δ)), tensile modulus, peel strength, dimensional stability, and solder heat resistance. In Example 5 in which B / C was increased compared to Example 1, the tensile modulus could be lowered. In Example 6 in which B / C was further increased as compared with Example 5, the tensile elastic modulus could be further reduced.
Further, in Example 8 in which the content of the epoxy resin as the component (D) was reduced as compared with Example 1, the dielectric loss tangent (tan δ) could be further reduced.
In Comparative Example 1 in which a polystyrene / polybutadiene block copolymer was used as the thermoplastic elastomer instead of the components (B) and (C), the amount of warpage was large. Moreover, the dimensional stability and solder heat resistance were inferior.
In the comparative example 2 which does not contain a component (B), the tensile elasticity modulus became high and the curvature amount was also large. Moreover, the dimensional stability and solder heat resistance were inferior.
The comparative example 3 which does not contain a component (C) had low peel strength.
In Comparative Example 4 in which the mass ratio of each component was less than (A + E) / (B + C) = 0.81, the peel strength was low.
In Comparative Example 5 in which the mass ratio of each component exceeded (A + E) / (B + C) = 1.00, the amount of warpage was large.
In Comparative Example 6 in which the mass ratio (B) / (C) of the components (B) and (C) was less than 1.00, the amount of warpage was large.
In Comparative Example 7 in which the mass ratio (B) / (C) = 4.00 of the components (B) and (C), the peel strength was low.
The comparative example 8 which does not contain a component (F) was inferior in dimensional stability.
Comparative Example 9 using a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of less than 15% instead of component (B) had a low peel strength (PI). Moreover, the dimensional stability and solder heat resistance were inferior.
In Comparative Example 10 in which a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content exceeding 35% was used instead of the component (B), the amount of warpage was large. Moreover, the dimensional stability was inferior.
The comparative example 11 in which the exothermic peak of the component (F) exceeds 180 ° C. was inferior in dimensional stability.
In Comparative Example 12 in which the exothermic peak of the component (F) was less than 100 ° C., the peel strength could not be measured.
成分（ａ），（ｂ）を主成分とするＦＰＣをベースにしたプリント配線板の作製方法
　ＦＰＣ用の樹脂基板の作成には、下記成分を含有する樹脂組成物を用いた。
成分（ａ）：ＯＰＥ２ｓｔ：オリゴフェニレンエーテル（上記一般式（１）で示されるビニル化合物）（Ｍｎ＝２２００）、三菱ガス化学株式会社製　　５０．０部
成分（ｂ）：ポリスチレン－ポリブタジエンブロック共重合体（ＪＳＲ株式会社製：「ＴＲ２００３」：質量平均分子量約１０万、スチレン含有量４３質量％）　　　５０．０部
成分（ｃ）シランカップリング剤
γ－アクリロキシプロピルトリメトキシシラン（「ＫＢＭ－５１０３」、信越化学工業株式会社製）　　　　　　　　　　　　　　　　　　　０．５部 Method for Producing Printed Wiring Board Based on FPC Containing Components (a) and (b) as Main Components For producing a resin substrate for FPC, a resin composition containing the following components was used.
Component (a): OPE2st: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd. 50.0 parts
Component (b): Polystyrene-polybutadiene block copolymer (manufactured by JSR Corporation: “TR2003”: mass average molecular weight of about 100,000, styrene content of 43% by mass) 50.0 parts
Component (c) Silane coupling agent γ-acryloxypropyltrimethoxysilane (“KBM-5103”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part
　上記各成分をスリーワンモーター（新東科学株式会社製、ＢＬＷ１２００）を用いて周速度４００ｒｐｍで乾式混合し樹脂組成物を調製した。該樹脂組成物を溶媒トルエンに加えて加熱攪拌してワニス（固形分濃度約３０質量％）を調製した。該ワニスを支持体であるＰＥＴフィルム（厚さ５０μｍ）にグラビアコーターで塗布した後、１００℃で１０分間乾燥し、放置冷却し、ＰＥＴフィルムから剥離してＦＰＣ用の樹脂基板を得た。樹脂基板の厚さは３０μｍであった。 The above components were dry-mixed at a peripheral speed of 400 rpm using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., BLW1200) to prepare a resin composition. The resin composition was added to a solvent toluene and heated and stirred to prepare a varnish (solid content concentration of about 30% by mass). The varnish was applied to a PET film (thickness 50 μm) as a support with a gravure coater, dried at 100 ° C. for 10 minutes, allowed to cool, and peeled from the PET film to obtain a resin substrate for FPC. The thickness of the resin substrate was 30 μm.
　上記の手順で得られた樹脂基板の両面に、粗化面を内側にして銅箔を貼りあわせ、プレス機で熱圧着させた（２００℃６０ｍｉｎ、１ＭＰａ）。熱圧着させた銅箔の片面もしくは両面をエッチングして、配線パターンを描き、配線付樹脂基板を作製した。この配線付樹脂基板の配線パターン側に、上記の手順で得られたカバーレイフィルムを接着層が対向するように配置し、プレス機で熱圧着させつつ加熱硬化させて（１８０℃、６０ｍｉｎ、１ＭＰａ）、プリント配線板を作製した。 The copper foil was bonded to both surfaces of the resin substrate obtained by the above procedure with the roughened surface inside, and thermocompression bonded with a press machine (200 ° C. 60 min, 1 MPa). One side or both sides of the thermocompressed copper foil was etched to draw a wiring pattern, and a resin substrate with wiring was prepared. The cover lay film obtained by the above procedure is arranged on the wiring pattern side of the resin substrate with wiring so that the adhesive layer faces, and is heat-cured while being thermocompressed with a press machine (180 ° C., 60 min, 1 MPa). ), A printed wiring board was produced.
挿入損失：上記の樹脂基板上にインピーダンスが５０Ωになるよう設計されたマイクロストリップラインを作製し、カバーレイフィルムとして、上記の接着性フィルムを真空プレス（１８０℃１ｈｒ、１ＭＰａ、真空度　＜１０ｋＰａ）にて貼り付けて、試験片を作成した。作製した試験片を用いて下記条件で挿入損失（ｄｂ）を測定した。
測定機器：Ｅ８３６３Ｂ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）
測定周波数：１０ＭＨｚ～６０ＧＨｚ
測定ポイント：４０００
測定プローブ：ＧＳＧ２５０
配線長：３０ｍｍ、５０ｍｍ、７０ｍｍ
配線幅：１３０±１０μｍ
　結果を下記表に示す。
Figure JPOXMLDOC01-appb-T000028
 Insertion loss: A microstrip line designed to have an impedance of 50Ω is produced on the resin substrate, and the adhesive film is vacuum-pressed as a coverlay film (180 ° C. 1 hr, 1 MPa, vacuum <10 kPa) A test piece was prepared by pasting. The insertion loss (db) was measured under the following conditions using the prepared test piece.
Measuring instrument: E8363B (manufactured by Agilent Technologies)
Measurement frequency: 10MHz-60GHz
Measurement point: 4000
Measuring probe: GSG250
Wiring length: 30mm, 50mm, 70mm
Wiring width: 130 ± 10 μm
The results are shown in the table below.
Figure JPOXMLDOC01-appb-T000028
　表５の結果より、本発明の樹脂組成物を用いて作製したカバーレイフィルムつき樹脂基板は、挿入損失が＜５ｄｂのため、高速伝送に優れていることがわかる。 From the results in Table 5, it can be seen that the resin substrate with a coverlay film produced using the resin composition of the present invention is excellent in high-speed transmission because the insertion loss is <5 db.

Claims (12)

  1. （Ａ）下記一般式（１）で示される、質量平均分子量（Ｍｗ）が５００～４０００のビニル化合物、
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7は、同一または異なってもよく、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基またはフェニル基である。－（Ｏ－Ｘ－Ｏ）－は下記構造式（２）で示される。
    Figure JPOXMLDOC01-appb-C000002
    Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ11，Ｒ12，Ｒ13は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。－（Ｙ－Ｏ）－は下記構造式（３）で定義される１種類の構造、または下記構造式（３）で定義される２種類以上の構造がランダムに配列したものである。
    Figure JPOXMLDOC01-appb-C000003
    Ｒ16，Ｒ17は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ18，Ｒ19は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｚは、炭素数１以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。ａ，ｂは、少なくともいずれか一方が０でない、０～３００の整数を示す。ｃ，ｄは、０または１の整数を示す。）
    （Ｂ）スチレン含有量が１５～３５％のポリスチレン－ポリ（エチレン／ブチレン）ブロック共重合体、
    （Ｃ）スチレン含有量が２５～４０％のポリスチレン－ポリ（エチレン－エチレン／プロピレン）ブロック共重合体、
    （Ｄ）エポキシ樹脂、
    （Ｅ）ビスマレイミド
    （Ｆ）示差走査熱量（ＤＳＣ）測定による発熱ピークが１００℃以上１８０℃以下の有機過酸化物を含み、各成分の質量比が、（Ａ＋Ｅ）／（Ｂ＋Ｃ）＝０．８１以上１．００以下、（Ｂ）／（Ｃ）＝１．００以上４．００以下であり、
    　前記成分（Ａ）～（Ｆ）の合計質量に対する質量パーセントで、前記成分（Ｄ）を１～１０質量％含有し、
    　前記（Ａ）成分の含有量に対する質量パーセントで、前記成分（Ｆ）を０．１～１０質量％含有する樹脂組成物。     (A) A vinyl compound having a mass average molecular weight (Mw) of 500 to 4000 represented by the following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).
    Figure JPOXMLDOC01-appb-C000002
    R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
    Figure JPOXMLDOC01-appb-C000003
    R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
    (B) a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35%,
    (C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer having a styrene content of 25 to 40%,
    (D) epoxy resin,
    (E) The bismaleimide (F) includes an organic peroxide having an exothermic peak of 100 ° C. or higher and 180 ° C. or lower as measured by differential scanning calorimetry (DSC), and the mass ratio of each component is (A + E) / (B + C) = 0. 81 to 1.00, (B) / (C) = 1.00 to 4.00,
    The component (D) is contained in an amount of 1 to 10% by mass based on the total mass of the components (A) to (F),
    A resin composition containing 0.1 to 10% by mass of the component (F) in terms of mass percent based on the content of the component (A).
  2. 　前記成分（Ａ）の－（Ｏ－Ｘ－Ｏ）－が、下記構造式（４）で示され、前記成分（Ａ）の－（Ｙ－Ｏ）－が下記構造式（５）、若しくは、下記構造式（６）で示される構造、または、下記構造式（５）で示される構造および下記構造式（６）で示される構造がランダムに配列した構造を有する、請求項１に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
         In the component (A), — (O—X—O) — is represented by the following structural formula (4), and — (YO) — in the component (A) is represented by the following structural formula (5), or The resin according to claim 1, having a structure represented by the following structural formula (6), or a structure in which the structure represented by the following structural formula (5) and the structure represented by the following structural formula (6) are randomly arranged. Composition.
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
  3. 　前記（Ｆ）成分の有機過酸化物が、パーオキシエステル類又はジアルキルパーオキサイド類である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the organic peroxide as the component (F) is a peroxyester or a dialkyl peroxide.
  4. 　前記（Ｄ）成分のエポキシ樹脂が、分子中に水酸基が存在しない、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、および、ナフタレン型エポキシ樹脂からなる群から選択される少なくとも１つである、請求項１～３のいずれかに記載の樹脂組成物。 The epoxy resin as the component (D) is at least one selected from the group consisting of a biphenyl type epoxy resin, a fluorene type epoxy resin, and a naphthalene type epoxy resin having no hydroxyl group in the molecule. 4. The resin composition according to any one of to 3.
  5. 　請求項１～４のいずれかに記載の樹脂組成物よりなる接着フィルム。 An adhesive film comprising the resin composition according to any one of claims 1 to 4.
  6. 　層間接着に、請求項１～４のいずれかに記載の樹脂組成物を用いた多層プリント配線板。 A multilayer printed wiring board using the resin composition according to any one of claims 1 to 4 for interlayer adhesion.
  7. 　層間接着に、請求項５に記載の接着フィルムを用いた多層プリント配線板。 A multilayer printed wiring board using the adhesive film according to claim 5 for interlayer adhesion.
  8. 　多層プリント配線板を構成する基板が、下記一般式（１）で表されるビニル化合物、ならびに、ゴムおよび／または熱可塑性エラストマー、を主成分とする樹脂基板である、
    請求項７に記載の多層プリント配線板。
    （Ａ）下記一般式（１）で示されるビニル化合物、
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7は、同一または異なってもよく、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基またはフェニル基である。－（Ｏ－Ｘ－Ｏ）－は下記構造式（２）で示される。
    Figure JPOXMLDOC01-appb-C000007
    Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ11，Ｒ12，Ｒ13は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。－（Ｙ－Ｏ）－は下記構造式（３）で定義される１種類の構造、または下記構造式（３）で定義される２種類以上の構造がランダムに配列したものである。
    Figure JPOXMLDOC01-appb-C000008
    Ｒ16，Ｒ17は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ18，Ｒ19は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｚは、炭素数１以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。ａ，ｂは、少なくともいずれか一方が０でない、０～３００の整数を示す。ｃ，ｄは、０または１の整数を示す。）     The substrate constituting the multilayer printed wiring board is a resin substrate mainly composed of a vinyl compound represented by the following general formula (1), and rubber and / or a thermoplastic elastomer.
    The multilayer printed wiring board according to claim 7.
    (A) a vinyl compound represented by the following general formula (1),
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).
    Figure JPOXMLDOC01-appb-C000007
    R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
    Figure JPOXMLDOC01-appb-C000008
    R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
  9. 　請求項１～４のいずれかに記載の樹脂組成物よりなるカバーレイフィルム。 A coverlay film comprising the resin composition according to any one of claims 1 to 4.
  10. 　請求項９に記載のカバーレイフィルムを有するフレキシブルプリント配線板。 A flexible printed wiring board having the coverlay film according to claim 9.
  11. 　液晶ポリマー、ポリイミド、および、ポリエチレンナフタレ－トのいずれかを主成分とする樹脂基板の主面に配線パターンが形成された配線付樹脂基板の配線パターン側に、請求項９に記載のカバーレイフィルムが用いられていることを特徴とするフレキシブルプリント配線板。 The coverlay according to claim 9 is provided on a wiring pattern side of a resin substrate with wiring in which a wiring pattern is formed on a main surface of a resin substrate mainly composed of any of liquid crystal polymer, polyimide, and polyethylene naphthalate. A flexible printed wiring board using a film.
  12. 　下記一般式（１）で表されるビニル化合物、ならびに、ゴムおよび／または熱可塑性エラストマー、を主成分とする樹脂基板の主面に配線パターンが形成された配線付樹脂基板の配線パターン側に、請求項９に記載のカバーレイフィルムが用いられていることを特徴とするフレキシブルプリント配線板。
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，Ｒ5，Ｒ6，Ｒ7は、同一または異なってもよく、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基またはフェニル基である。－（Ｏ－Ｘ－Ｏ）－は下記構造式（２）で示される。
    Figure JPOXMLDOC01-appb-C000010
    Ｒ8，Ｒ9，Ｒ10，Ｒ14，Ｒ15は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ11，Ｒ12，Ｒ13は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。－（Ｙ－Ｏ）－は下記構造式（３）で定義される１種類の構造、または下記構造式（３）で定義される２種類以上の構造がランダムに配列したものである。
    Figure JPOXMLDOC01-appb-C000011
    Ｒ16，Ｒ17は、同一または異なってもよく、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｒ18，Ｒ19は、同一または異なってもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基またはフェニル基である。Ｚは、炭素数１以上の有機基であり、酸素原子、窒素原子、硫黄原子、ハロゲン原子を含むこともある。ａ，ｂは、少なくともいずれか一方が０でない、０～３００の整数を示す。ｃ，ｄは、０または１の整数を示す。）     On the wiring pattern side of the resin substrate with wiring, in which the wiring pattern is formed on the main surface of the resin substrate mainly composed of the vinyl compound represented by the following general formula (1), and rubber and / or thermoplastic elastomer, A flexible printed wiring board, wherein the coverlay film according to claim 9 is used.
    Figure JPOXMLDOC01-appb-C000009
     (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).
    Figure JPOXMLDOC01-appb-C000010
    R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
    Figure JPOXMLDOC01-appb-C000011
    R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
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