WO2023090215A1 - 樹脂組成物、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及びプリント配線板 - Google Patents

樹脂組成物、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及びプリント配線板 Download PDF

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WO2023090215A1
WO2023090215A1 PCT/JP2022/041663 JP2022041663W WO2023090215A1 WO 2023090215 A1 WO2023090215 A1 WO 2023090215A1 JP 2022041663 W JP2022041663 W JP 2022041663W WO 2023090215 A1 WO2023090215 A1 WO 2023090215A1
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Prior art keywords
resin composition
resin
group
polyphenylene ether
compound
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PCT/JP2022/041663
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English (en)
French (fr)
Japanese (ja)
Inventor
紘介 奥野
雅也 小山
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202280069540.8A priority Critical patent/CN118103421A/zh
Priority to JP2023561546A priority patent/JPWO2023090215A1/ja
Publication of WO2023090215A1 publication Critical patent/WO2023090215A1/ja
Priority to US18/646,300 priority patent/US12344738B2/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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • 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
    • C08L63/08—Epoxidised polymerised polyenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present disclosure generally relates to resin compositions, resin-coated films, resin-coated metal foils, metal-clad laminates, and printed wiring boards. More specifically, the present disclosure relates to a resin composition, a resin-coated film made from the resin composition, a resin-coated metal foil made from the resin composition, and a metal-clad laminate made from the resin composition. , and a printed wiring board made from the resin composition.
  • Patent Document 1 discloses a resin composition containing a modified polyphenylene ether compound and triallyl isocyanurate (hereinafter also referred to as TAIC) as a cross-linking curing agent having a carbon-carbon unsaturated double bond. Patent Document 1 describes that this resin composition can provide a cured product having excellent low dielectric properties.
  • TAIC triallyl isocyanurate
  • An object of the present disclosure is to provide a resin composition that provides a cured product having low dielectric properties, flexibility, and good adhesion to metal foil or the like, and a resin layer produced from the resin composition.
  • a resin-coated film comprising, a resin-coated metal foil comprising a resin layer made from the resin composition, a metal-clad laminate comprising an insulating layer made from the resin composition, and an insulation made from the resin composition.
  • the object is to provide a printed wiring board comprising a layer.
  • a resin composition according to one aspect of the present disclosure contains a polyphenylene ether compound (A), a styrene block copolymer (B), a polybutadiene compound (C), and a curing agent (D).
  • the polyphenylene ether compound (A) has at least one of the group represented by formula (1) and the group represented by formula (2) in the molecule.
  • the polybutadiene compound (C) has an epoxy group in its molecule.
  • the curing agent (D) contains an allyl compound (d1) represented by formula (3).
  • p represents an integer of 0 to 10
  • Z represents an arylene group
  • R 1 to R 3 each independently represent a hydrogen atom or an alkyl group.
  • R4 represents a hydrogen atom or an alkyl group.
  • R A represents an alkyl or alkenyl group having 8 to 22 carbon atoms.
  • a resin-coated film according to an aspect of the present disclosure includes a resin layer containing at least one of an uncured product of the resin composition and a semi-cured product of the resin composition, and a support film overlapping the resin layer. .
  • a resin-coated metal foil according to an aspect of the present disclosure includes a resin layer containing at least one of an uncured product of the resin composition and a semi-cured product of the resin composition, and a metal foil overlapping the resin layer. Prepare.
  • a metal-clad laminate according to one aspect of the present disclosure includes an insulating layer containing a cured product of the resin composition, and a metal foil overlapping the insulating layer.
  • a printed wiring board includes an insulating layer containing a cured product of the resin composition, and wiring overlapping the insulating layer.
  • FIG. 1 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the present disclosure.
  • FIG. 3 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present disclosure.
  • 4A to 4D are schematic cross-sectional views showing an example of a method for manufacturing a printed wiring board according to an embodiment of the present disclosure.
  • wiring boards used in various electronic devices are required to be high-frequency-compatible wiring boards, such as millimeter-wave radar boards for in-vehicle applications.
  • Substrate materials for composing insulating layers of wiring boards used in various electronic devices are required to have a low dielectric constant and dielectric loss tangent in order to increase signal transmission speed and reduce loss during signal transmission. .
  • Polyphenylene ether is known to have excellent low dielectric properties in the high frequency band from the MHz band to the GHz band. For this reason, polyphenylene ethers are used, for example, as high-frequency molding materials. More specifically, it is preferably used as a substrate material for forming an insulating layer of a printed wiring board provided in an electronic device using a high frequency band.
  • Patent Document 1 discloses a resin composition containing a modified polyphenylene ether compound and triallyl isocyanurate (hereinafter also referred to as TAIC) as a cross-linking curing agent having a carbon-carbon unsaturated double bond. Patent Document 1 describes that this resin composition can provide a cured product having excellent low dielectric properties.
  • TAIC triallyl isocyanurate
  • the resin composition according to the present embodiment (hereinafter also simply referred to as the resin composition) comprises a polyphenylene ether compound (A), a styrene block copolymer (B), a polybutadiene compound (C), and a curing agent (D ) and
  • the polyphenylene ether compound (A) has at least one of a group represented by the following formula (1) and a group represented by the following formula (2) in the molecule.
  • the polybutadiene compound (C) has an epoxy group in its molecule.
  • the curing agent (D) contains an allyl compound (d1) represented by the following formula (3).
  • p represents an integer of 0-10.
  • Z represents an arylene group.
  • R 1 to R 3 each independently represent a hydrogen atom or an alkyl group.
  • R4 represents a hydrogen atom or an alkyl group.
  • R A represents an alkyl or alkenyl group having 8 to 22 carbon atoms.
  • the resin composition contains a styrene-based block copolymer (B) and a polybutadiene compound (C) having an epoxy group in the molecule, so that the adhesiveness to metal foil or the like is improved. can get things.
  • the resin composition contains a curing agent (D) containing the allyl compound (d1) described above, thereby maintaining low dielectric properties and good adhesion to metal foils and the like while maintaining flexibility. It is possible to obtain a cured product with good.
  • the resin composition according to the present embodiment can obtain a cured product that has low dielectric properties, flexibility, and good adhesion to metal foil and the like.
  • composition contained in the resin composition according to this embodiment will be described in detail below.
  • the resin composition according to this embodiment contains the polyphenylene ether compound (A) as described above.
  • This polyphenylene ether compound (A) has at least one of the groups represented by the above formulas (1) and (2) in the molecule.
  • the polyphenylene ether compound (A) preferably has at least one of the group represented by the above formula (1) and the group represented by the above formula (2) at the molecular terminal. That is, the resin composition according to the present embodiment preferably contains a polyphenylene ether compound (A) terminally modified with at least one of the groups represented by the above formulas (1) and (2).
  • p represents an integer of 0 to 10 in the above formula (1).
  • Z represents an arylene group.
  • R 1 to R 3 are each independent. That is, R 1 to R 3 may each be the same group or different groups. Additionally, R 1 to R 3 represent hydrogen atoms or alkyl groups.
  • R 1 to R 3 are alkyl groups
  • R 1 to R 3 are preferably alkyl groups having 1 to 18 carbon atoms, such as alkyl groups having 1 to 10 carbon atoms. is more preferably an alkyl group of Specific examples of such alkyl groups include methyl, ethyl, propyl, hexyl, and decyl groups.
  • the arylene group includes, for example, a monocyclic aromatic group such as a phenylene group, or a polycyclic aromatic group such as a naphthalene ring.
  • a hydrogen atom directly bonded to the aromatic ring may be substituted with a substituent other than a hydrogen atom.
  • substituents include alkenyl groups, alkynyl groups, formyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, and the like.
  • the alkyl group bonded to the aromatic ring is, for example, preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. More specifically, the alkyl group includes, for example, methyl group, ethyl group, propyl group, hexyl group, or decyl group.
  • Specific examples of the group represented by the above formula (1) include, for example, a vinylbenzyl group or a vinylphenyl group represented by the following formula (4). Further, more specific examples of the vinylbenzyl group include o-ethenylbenzyl group, m-ethenylbenzyl group, p-ethenylbenzyl group, and the like.
  • R4 is a hydrogen atom or an alkyl group.
  • R 4 is, for example, preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
  • Specific examples of such alkyl groups include methyl, ethyl, propyl, hexyl, and decyl groups.
  • specific groups represented by the above formula (2) include, for example, an acryloyl group, a methacryloyl group, and the like.
  • the polyphenylene ether compound (A) has at least one of the group represented by the above formula (1) and the group represented by the above formula (2) in the molecule. That is, the polyphenylene ether compound (A) may have, for example, only one of the groups represented by the above formula (1) and the groups represented by the above formula (2), and may have two or more types. may be More specifically, the polyphenylene ether compound (A) has, for example, any one of an o-ethenylbenzyl group, an m-ethenylbenzyl group, and a p-ethenylbenzyl group. Well, you may have two or more types of these.
  • the polyphenylene ether compound (A) is a compound having a polyphenylene ether chain in its molecule.
  • the polyphenylene ether compound (A) preferably has, for example, a structural repeating unit represented by the following formula (5) in its molecule.
  • t represents 1-50.
  • R 5 to R 8 are each independent. That is, R 5 to R 8 may each be the same group or different groups.
  • R 5 to R 8 in formula (5) examples include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • R 5 to R 8 are preferably hydrogen atoms or alkyl groups.
  • the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of such alkyl groups include methyl, ethyl, propyl, hexyl, and decyl groups.
  • the alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms.
  • alkenyl groups include vinyl groups, allyl groups, 3-butenyl groups, and the like.
  • the alkynyl group is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms.
  • Specific examples of such alkynyl groups include ethynyl groups, propargyl groups (prop-2-yn-1-yl groups), and the like.
  • alkylcarbonyl group is a carbonyl group substituted with an alkyl group.
  • the alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 18 carbon atoms, more preferably an alkylcarbonyl group having 2 to 10 carbon atoms.
  • Specific examples of such alkylcarbonyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl groups.
  • alkenylcarbonyl group is a carbonyl group substituted with an alkenyl group.
  • the alkenylcarbonyl group is preferably an alkenylcarbonyl group having 3 to 18 carbon atoms, more preferably an alkenylcarbonyl group having 3 to 10 carbon atoms.
  • Specific examples of such alkenylcarbonyl groups include an acryloyl group, a methacryloyl group, a crotonoyl group, and the like.
  • alkynylcarbonyl group is a carbonyl group substituted with an alkynyl group.
  • the alkynylcarbonyl group is preferably an alkynylcarbonyl group having 3 to 18 carbon atoms, more preferably an alkynylcarbonyl group having 3 to 10 carbon atoms. Specific examples of such alkynylcarbonyl groups include propioloyl groups and the like.
  • the weight average molecular weight (Mw) of the polyphenylene ether compound (A) is preferably 500 or more, more preferably 800 or more, even more preferably 1000 or more. Also, the weight average molecular weight (Mw) of the polyphenylene ether compound (A) is preferably 5000 or less, more preferably 4000 or less, even more preferably 3000 or less. When the weight average molecular weight (Mw) of the polyphenylene ether compound (A) satisfies the above numerical range of 500 or more and 5000 or less, the resin composition has low dielectric properties, flexibility, and compatibility with metal foil and the like. It becomes possible to obtain a cured product having good adhesiveness.
  • the weight average molecular weight is not particularly limited as long as it is measured by a general molecular weight measuring method. Specifically, the weight average molecular weight is preferably measured using, for example, gel permeation chromatography (GPC). Further, when the polyphenylene ether compound (A) has a structural repeating unit represented by the above formula (5) in the molecule, t in the above formula (5) is the weight of the polyphenylene ether compound (A) It is preferable that the average molecular weight is a numerical value that falls within the above range. That is, the value of t at this time is preferably 1 to 50, for example.
  • the polyphenylene ether compound (A) according to the present embodiment has at least one of the group represented by the above formula (1) and the group represented by the above formula (2) in the molecule. . Therefore, even when the weight average molecular weight of the polyphenylene ether compound (A) is within the numerical range of 500 or more and 5000 or less, which is a relatively low molecular weight, the resin composition according to the present embodiment has a low dielectric It is possible to obtain a cured product that has excellent flexibility and adhesion to metal foil or the like while having the desired properties.
  • a group represented by at least one of the groups represented by the above formula (1) and the groups represented by the above formula (2), which each molecule of the polyphenylene ether compound (A) has is, for example, preferably 1 to 5, more preferably 1 to 3, even more preferably 1.5 to 3.
  • the resin composition according to the present embodiment has low dielectric properties and flexibility. , it is possible to obtain a cured product having good adhesion to metal foil or the like.
  • each molecule of the polyphenylene ether compound (A) has at least one of the groups represented by the above formula (1) and the groups represented by the above formula (2) that each molecule of the polyphenylene ether compound (A) has
  • the average number of groups represented by the above formula (1) per molecule of all polyphenylene ether compounds (A) present in 1 mol of the polyphenylene ether compound (A) and the groups represented by the above formula (2) A numerical value representing the average value of at least one of the groups represented by is mentioned.
  • the number of hydroxyl groups remaining in the obtained polyphenylene ether compound (A) is measured, and the groups represented by the above formula (1) and the groups represented by the above formula (2) are It can be measured by calculating the decrease from the number of hydroxyl groups of the polyphenylene ether before having, that is, before terminal modification with the group represented by the above formula (1) and the group represented by the above formula (2) .
  • a method for measuring the number of hydroxyl groups remaining in the polyphenylene ether compound (A) includes, for example, adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of the polyphenylene ether compound (A), and mixing the It can be determined by measuring the UV absorbance of the solution.
  • a quaternary ammonium salt tetraethylammonium hydroxide
  • the intrinsic viscosity of the polyphenylene ether compound (A) according to the present embodiment is preferably 0.03 dl/g or more, more preferably 0.04 dl/g or more, and 0.06 dl/g or more. is more preferred.
  • the intrinsic viscosity of the polyphenylene ether compound (A) according to the present embodiment is preferably 0.12 dl/g or less, more preferably 0.11 dl/g or less, and 0.095 dl/g or less. is more preferred.
  • the resin composition When the intrinsic viscosity of the polyphenylene ether compound (A) satisfies the numerical range of 0.03 dl/g or more and 0.12 dl/g or less, the resin composition has low dielectric properties and flexibility and metal It is possible to obtain a cured product having good adhesion to foil or the like.
  • the intrinsic viscosity of the polyphenylene ether compound (A) here is the intrinsic viscosity measured in methylene chloride at 25°C. More specifically, the intrinsic viscosity of the polyphenylene ether compound (A) is, for example, by dissolving the polyphenylene ether compound (A) in methylene chloride to prepare a 0.18 g/45 mL methylene chloride solution, and It is a value measured with a viscometer after adjusting the liquid temperature to 25°C. Viscometers that can be used to measure the intrinsic viscosity include, for example, Schott's AVS500 Visco System.
  • the polyphenylene ether compound (A) includes a polyphenylene ether compound (a1) having a structure represented by the following formula (6), a polyphenylene ether compound (a2) having a structure represented by the following formula (7), and the following formula ( It preferably contains at least one selected from the group consisting of polyphenylene ether compounds (a3) having the structure represented by 8).
  • the polyphenylene ether compound (A) includes a polyphenylene ether compound (a1) having a structure represented by the following formula (6), a polyphenylene ether compound (a2) having a structure represented by the following formula (7), and the following Only one of the polyphenylene ether compounds (a3) having the structure represented by formula (8) may be contained, or two or more of these may be contained.
  • R 9 to R 16 , R 17 to R 24 and R 25 to R 28 are each independent. That is, R 9 to R 16 , R 17 to R 24 and R 25 to R 28 may each be the same group or different groups.
  • R 9 to R 16 , R 17 to R 24 and R 25 to R 28 are, for example, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, A formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group can be mentioned.
  • R 9 to R 16 , R 17 to R 24 and R 25 to R 28 are preferably hydrogen atoms or alkyl groups.
  • X 1 to X 3 are each independent. That is, X 1 to X 3 may be the same group or different groups. X 1 to X 3 are preferably groups represented by the above formula (1) or groups represented by the above formula (2).
  • s is an integer of 1 to 100, for example.
  • a and B in the above formulas (6) and (7) each contain a constituent repeating unit represented by at least one of the following formulas (9) and (10).
  • n each represent 0 to 20.
  • R 29 to R 32 and R 33 to R 36 are each independent. That is, R 29 to R 32 and R 33 to R 36 may each be the same group or different groups.
  • R 29 to R 32 and R 33 to R 36 are, for example, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group. , an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • R 29 to R 32 and R 33 to R 36 are preferably hydrogen atoms or alkyl groups.
  • m and n represent numerical values in which the total value of m and n is 1-30. That is, m represents 0-20, n represents 0-20, and the sum of m and n preferably represents 1-30.
  • R 29 to R 36 may be the same as R 5 to R 8 in the above formula (5).
  • Y is preferably a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms.
  • Examples of specific structures of Y include groups represented by the following formula (11).
  • R 37 to R 38 are each independent. That is, R 37 to R 38 may each be the same group or different groups.
  • R 37 to R 38 are, for example, hydrogen atoms or alkyl groups.
  • this alkyl group include, for example, a methyl group.
  • specific examples of the group represented by formula (11) include a methylene group, a methylmethylene group, a dimethylmethylene group, and the like. Among these, a dimethylmethylene group is preferable as the group represented by the formula (11).
  • polyphenylene ether compound (a1) represented by the above formula (6) include, for example, the polyphenylene ether compound (a11) represented by the following formula (12).
  • polyphenylene ether compound (a2) represented by the formula (7) include, for example, a polyphenylene ether compound (a21) represented by the following formula (13), or a polyphenylene ether compound (a21) represented by the following formula (14). polyphenylene ether compound (a22) and the like.
  • m and n are the same as m and n in formulas (9) and (10) above, for example.
  • R 1 to R 3 , p and Z are, for example, the same as R 1 to R 3 , p and Z in formula (1) above.
  • Y is, for example, the same as Y in the above formula (7).
  • R 4 is, for example, the same as R 4 in formula (2) above.
  • a method for synthesizing the polyphenylene ether compound (A) according to this embodiment will now be described.
  • a method for synthesizing a modified polyphenylene ether compound (A) terminally modified with at least one of the group represented by the above formula (1) and the group represented by the above formula (2) is described.
  • the method for producing the polyphenylene ether compound (A) according to the present embodiment has at least one of the group represented by the above formula (1) and the group represented by the above formula (2) in the molecule.
  • the polyphenylene ether compound (A) can be synthesized.
  • a method for synthesizing a modified polyphenylene ether compound (A) terminally modified with at least one of the group represented by the above formula (1) and the group represented by the above formula (2) is, for example, polyphenylene ether as a raw material , a method of reacting at least one of the group represented by the above formula (1) and the group represented by the above formula (2) with a compound having a halogen atom.
  • a halogen atom includes, for example, a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom.
  • the halogen atom is preferably a chlorine atom.
  • specific examples of the compound having at least one of the group represented by the above formula (1) and the group represented by the above formula (2) and a halogen atom include, for example, o-chloro Examples include methylstyrene, p-chloromethylstyrene, m-chloromethylstyrene, and the like.
  • the raw material polyphenylene ether is not particularly limited as long as it can finally synthesize the desired polyphenylene ether compound (A).
  • Specific examples of polyphenylene ether as a raw material include, for example, 2,6-dimethylphenol, polyphenylene ether composed of at least one of bifunctional phenol and trifunctional phenol, or poly(2,6-dimethyl-1 , 4-phenylene oxide) and other polyphenylene ethers.
  • a bifunctional phenol is a phenol compound that has two phenolic hydroxyl groups in its molecule.
  • bifunctional phenols include tetramethylbisphenol A and the like.
  • a trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.
  • the method for synthesizing the polyphenylene ether compound (A) comprises: polyphenylene ether as a raw material, and at least one of the group represented by the above formula (1) and the group represented by the above formula (2) , and a halogen atom are dissolved in a solvent and stirred with heating to react them.
  • the reaction step is preferably carried out in the presence of an alkali metal hydroxide.
  • the reaction between the polyphenylene ether, at least one of the group represented by the above formula (1) and the group represented by the above formula (2), and the halogen atom proceeds favorably.
  • alkali metal hydroxides include sodium hydroxide and the like.
  • the alkali metal hydroxide is preferably used, for example, in the form of an aqueous solution. That is, in the method for producing the polyphenylene ether compound (A) according to the present embodiment, it is preferable that an aqueous sodium hydroxide solution is used in the reaction step.
  • the reaction step in the method for producing the polyphenylene ether compound (A) according to the present embodiment at least the polyphenylene ether as a raw material and the group represented by the above formula (1) and the group represented by the above formula (2) It is preferable that the reaction conditions are set so that the compound having one and the halogen atom reacts favorably.
  • the reaction temperature in the above reaction step is, for example, preferably 20°C or higher and 100°C or lower, more preferably 30°C or higher and 100°C or lower. Further, the reaction time in the above reaction step is preferably, for example, 0.5 hours or more and 20 hours or less, and more preferably 0.5 hours or more and 10 hours or less.
  • the solvent used in the reaction step includes, for example, the raw material polyphenylene ether and the group represented by the above formula (1) and the above formula (2). It is preferable that the compound having at least one of the represented groups and a halogen atom can be dissolved and the reaction thereof is not inhibited. Specific examples of such solvents include toluene and the like.
  • an alkali metal hydroxide and a phase transfer catalyst are preferably used in combination. . That is, in the presence of an alkali hydroxide and a phase transfer catalyst, polyphenylene ether as a raw material and at least one of the groups represented by the above formula (1) and the above formula (2) , and a halogen atom.
  • phase transfer catalysts include quaternary ammonium salts such as tetra-n-butylammonium bromide.
  • the resin composition according to the present embodiment contains the styrene block copolymer (B) as described above.
  • the styrene-based block copolymer (B) is preferably a resin contained in a resin composition or the like used for producing an insulating layer included in metal-clad laminates, printed wiring boards, and the like.
  • Such styrenic block copolymers (B) include, for example, methylstyrene (ethylene/butylene) methylstyrene copolymers, methylstyrene (ethylene-ethylene/propylene) methylstyrene copolymers, styrene isoprene copolymers, Styrene isoprene styrene copolymer, styrene (ethylene/butylene) styrene copolymer, styrene (ethylene-ethylene/propylene) styrene copolymer, styrene butadiene styrene copolymer, styrene (butadiene/buty
  • the styrene-based block copolymer (B) includes a styrene-butadiene-styrene copolymer, a styrene (ethylene/butylene) styrene copolymer, a methylstyrene (ethylene/butylene) methylstyrene copolymer, and More preferably, it contains at least one selected from the group consisting of these hydrogenated products.
  • styrene-based block copolymer (B) may be used alone, or two or more of them may be used in combination.
  • the weight average molecular weight of the styrenic block copolymer (B) according to this embodiment is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 60,000 or more. Moreover, the weight average molecular weight of the styrenic block copolymer (B) according to the present embodiment is preferably 300,000 or less, more preferably 250,000 or less, and even more preferably 200,000 or less. When the weight average molecular weight of the styrenic block copolymer (B) satisfies the numerical range of 10000 or more and 300000 or less, the resin composition according to the present embodiment has low dielectric properties and flexibility, It is possible to obtain a cured product having good adhesion to metal foil or the like.
  • the resin composition according to this embodiment contains the polybutadiene compound (C) as described above. And the polybutadiene compound (C) has an epoxy group in the molecule.
  • a specific example of such a polybutadiene compound (C) is, for example, a compound in which an epoxy group is introduced into the molecule by epoxidizing at least part of the carbon-carbon double bonds contained in the polybutadiene. , or compounds in which both ends of polybutadiene are glycidyl-etherified.
  • a compound in which an epoxy group is introduced into the molecule by epoxidizing at least a portion of the carbon-carbon double bonds contained in polybutadiene is, for example, a carbon-carbon double bond contained in non-epoxidized polybutadiene. It can be obtained by adding one oxygen atom to the heavy bond with an epoxidizing agent to introduce a three-membered ring epoxy group.
  • a compound in which both ends of polybutadiene are glycidyl-etherified can be obtained, for example, by adding epichlorohydrin to polybutadiene having hydroxyl groups at both ends.
  • the above-mentioned non-epoxidized polybutadiene has, for example, any of cis-1,4, trans-1,4, cis-1,2, and trans-1,2 stereostructures of carbon-carbon double bonds.
  • the ratio of these steric structures allows the resin composition according to the present embodiment to obtain a cured product having low dielectric properties, flexibility, and good adhesion to metal foil and the like. It is preferable that the ratio is as high as possible.
  • the above-mentioned epoxidizing agent is preferably capable of epoxidizing the carbon-carbon double bonds contained in polybutadiene.
  • epoxidizing agents include percarboxylic acids such as peracetic acid, performic acid, perbenzoic acid, trifluoroperacetic acid and perpropionic acid, t-butyl hydroperoxide and cumene.
  • organic hydroperoxides such as hydroperoxides, hydrogen peroxide, and the like.
  • the percentage of oxirane oxygen in the polybutadiene compound (C) is preferably 1% by mass or more, more preferably 5% by mass or more. Also, the percentage of oxirane oxygen in the polybutadiene compound (C) is preferably 10% by mass or less, more preferably 9% by mass or less. When the percentage of oxirane oxygen satisfies the above numerical range of 1% by mass or more and 10% by mass or less, the resin composition according to the present embodiment has low dielectric properties, and flexibility and resistance to metal foil and the like. It becomes possible to obtain a cured product having good adhesiveness.
  • the resin composition according to this embodiment contains a curing agent (D) as described above.
  • the curing agent (D) contained in the resin composition according to this embodiment contains an allyl compound (d1) represented by the following formula (3).
  • the curing agent (D) can cure the resin composition containing the polyphenylene ether compound (A), for example, by reacting with the polyphenylene ether compound (A).
  • R A represents an alkyl or alkenyl group having 8 to 22 carbon atoms. Since the resin composition according to the present embodiment contains the allyl compound (d1) having the alkyl group or alkenyl group with the number of carbon atoms described above, it has low dielectric properties, flexibility, and compatibility with metal foils and the like. A cured product having good adhesiveness can be obtained.
  • the number of carbon atoms in RA is more preferably 12 or more and 18 or less from the viewpoint of improving handling properties.
  • the fluidity of the resin composition is improved, and molding of the resin composition is facilitated.
  • the resin composition according to the present embodiment can obtain a cured product having low dielectric properties, flexibility, and good adhesion to metal foil or the like.
  • the double bond equivalent (reactive group equivalent) of the allyl compound (d1) according to this embodiment is preferably 1000 or less.
  • the resin composition according to the present embodiment can obtain a high Tg, have low dielectric properties, and is flexible. It is possible to obtain a cured product having excellent properties and adhesion to metal foil or the like.
  • examples of alkyl groups having 8 to 22 carbon atoms in R 1 A include linear or branched alkyl groups. More specific examples of such alkyl groups include octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and docosyl groups. Examples of alkenyl groups having 8 to 22 carbon atoms include decenyl groups.
  • Examples of the allyl compound (d1) according to the present embodiment include 5-octyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5-hexadecyl-1,3-diallyl isocyanurate, 5-octadecyl-1,3-diallyl isocyanurate, 5-eicosyl-1,3-diallyl isocyanurate, 5-docosyl-1,3-diallyl isocyanurate, and 5 -decenyl-1,3-diallyl isocyanurate.
  • the allyl compound (d1) according to the present embodiment can be prepared, for example, by adding diallyl isocyanurate and an alkyl halide in an aprotic polar solvent such as N,N'-dimethylformamide (DMF) to form a basic substance. It can be synthesized by reacting diallyl isocyanurate with an alkyl halide while stirring in the presence of heat.
  • Basic substances include, for example, sodium hydroxide, potassium carbonate, triethylamine, and the like.
  • the reaction temperature is, for example, 60° C. or higher and 150° C. or lower.
  • the curing agent (D) includes, in addition to the above allyl compound (d1), for example, styrene, styrene derivatives, compounds having an acryloyl group in the molecule, compounds having a methacryloyl group in the molecule, may contain at least one selected from the group consisting of compounds having a vinyl group in the molecule, compounds having an acenaphthylene structure in the molecule, and compounds having a maleimide group in the molecule.
  • allyl compound (d1) for example, styrene, styrene derivatives, compounds having an acryloyl group in the molecule, compounds having a methacryloyl group in the molecule, may contain at least one selected from the group consisting of compounds having a vinyl group in the molecule, compounds having an acenaphthylene structure in the molecule, and compounds having a maleimide group in the molecule.
  • Examples of the compound having a maleimide group in the molecule include a monofunctional maleimide compound having one maleimide group in the molecule, a polyfunctional maleimide compound having two or more maleimide groups in the molecule, or a modified maleimide compound. etc.
  • Examples of the modified maleimide compound include a modified maleimide compound in which a portion of the molecule is modified with an amine compound, a modified maleimide compound in which a portion of the molecule is modified with a silicone compound, and a modified maleimide compound in which a portion of the molecule is modified with an amine compound. , or a modified maleimide compound modified with a silicone compound.
  • the resin composition according to this embodiment contains, for example, a silane coupling agent (E) having a triazine ring.
  • a silane coupling agent (E) having a triazine ring When the resin composition according to the present embodiment contains a silane coupling agent (E) having a triazine ring, the resin composition according to the present embodiment has low dielectric properties and adhesion to metal foil etc. It becomes possible to obtain a cured product having good properties.
  • Silane coupling agents (E) having such a triazine ring include, for example, triazine derivatives having a trimethoxysilyl group or a triethoxysilyl group at the end.
  • the resin composition according to the present embodiment includes, for example, a polyphenylene ether compound (A), a styrene-based block copolymer (B), a polybutadiene compound (C), Components other than the curing agent (D) and the triazine ring-containing silane coupling agent (E) may be contained.
  • Other components contained in the resin composition according to the present embodiment include, for example, a flame retardant, an initiator, a curing accelerator, an antifoaming agent, an antioxidant, a polymerization inhibitor, a polymerization retarder, a dispersant, and a leveling agent. agents, heat stabilizers, antistatic agents, UV absorbers, dyes, pigments, lubricants, additives such as fillers, and the like.
  • the resin composition according to the present embodiment may contain a thermosetting resin other than the polyphenylene ether compound (A) in addition to the polyphenylene ether compound (A).
  • thermosetting resins include, for example, at least one selected from the group consisting of epoxy resins, unsaturated polyester resins, and thermosetting polyimide resins.
  • the resin composition according to this embodiment may contain a flame retardant as described above.
  • the resin composition according to the present embodiment contains a flame retardant
  • the cured product of the resin composition has good flame retardancy.
  • flame retardants in the field using halogen-based flame retardants such as brominated flame retardants include, for example, ethylene dipentabromobenzene, ethylenebistetrabromoimide, and decabromodiphenyl oxide, which have a melting point of 300° C. or higher. , or tetradecabromodiphenoxybenzene.
  • Specific examples of flame retardants in fields requiring halogen-free include phosphate ester flame retardants, phosphazene flame retardants, bisdiphenylphosphine oxide flame retardants, and phosphinate flame retardants. is mentioned.
  • the resin composition according to this embodiment may contain an initiator (reaction initiator) as described above.
  • the reaction initiator is preferably one capable of promoting the curing reaction between the polyphenylene ether compound (A) and the curing agent (D).
  • Specific examples of the reaction initiator include ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy) -3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl mono Oxidizing agents such as carbonates or azobisisobutyronitrile can be used.
  • reaction initiator ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene is preferably used as the reaction initiator.
  • carboxylic acid metal salt etc. may be used as needed. That is, it is preferable to use the reaction initiator and the metal carboxylate together. In this case, the curing reaction of the resin composition according to this embodiment is facilitated.
  • the reaction initiator may be used alone, or two or more of them may be used in combination.
  • the resin composition according to this embodiment may contain a curing accelerator as described above.
  • the curing accelerator is preferably one that can accelerate the curing reaction of the resin composition according to this embodiment.
  • Specific examples of curing accelerators include imidazoles and derivatives thereof, organic phosphorus compounds, amines such as secondary amines and tertiary amines, quaternary ammonium salts, and organic boron compounds. , or metal soaps.
  • Imidazoles and derivatives thereof include, for example, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, and the like. including at least one selected from
  • the organophosphorus compound includes, for example, at least one selected from the group consisting of triphenylphosphine, diphenylphosphine, phenylphosphine, tributylphosphine, trimethylphosphine, and the like.
  • Amines include, for example, at least one selected from the group consisting of dimethylbenzylamine, triethylenediamine, triethanolamine, and 1,8-diazabicyclo[5,4,0]-7-undecene (DBU).
  • DBU 1,8-diazabicyclo[5,4,0]-7-undecene
  • quaternary ammonium salts examples include tetrabutylammonium bromide and the like.
  • the organoboron compound is, for example, from the group consisting of tetraphenylboron salts such as 2-ethyl-4-methylimidazole/tetraphenylborate, and tetrasubstituted phosphonium/tetrasubstituted borates such as tetraphenylphosphonium/ethyltriphenylborate. At least one selected is included.
  • tetraphenylboron salts such as 2-ethyl-4-methylimidazole/tetraphenylborate
  • tetrasubstituted phosphonium/tetrasubstituted borates such as tetraphenylphosphonium/ethyltriphenylborate. At least one selected is included.
  • a metal soap refers to a fatty acid metal salt, and may be a linear fatty acid metal salt or a cyclic fatty acid metal salt.
  • metal soaps include linear aliphatic metal salts and cyclic aliphatic metal salts having 6 to 10 carbon atoms. More specifically, metal soaps include, for example, linear fatty acids such as stearic acid, lauric acid, ricinoleic acid, and octylic acid, cyclic fatty acids such as naphthenic acid, and lithium, magnesium, calcium, barium, and copper. and metals such as zinc, and at least one selected from the group consisting of aliphatic metal salts and the like.
  • a hardening accelerator may be used independently and may be used in combination of 2 or more type.
  • the resin composition according to the present embodiment may contain fillers such as inorganic fillers.
  • the filler is preferably one capable of enhancing the heat resistance and flame retardancy of the cured product of the resin composition.
  • Fillers include, for example, silica such as spherical silica, metal oxides such as alumina, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and carbonate. It contains at least one selected from the group consisting of calcium and the like.
  • the filler is preferably silica such as spherical silica, mica, or talc, or more preferably spherical silica.
  • filler Only one filler may be used alone, or two or more fillers may be used in combination. Moreover, the filler surface-treated with a silane coupling agent, for example, may be used as the filler.
  • the percentage ratio of the polyphenylene ether compound (A) to the resin component (organic component) in the resin composition according to this embodiment is preferably 10% by mass or more, more preferably 20% by mass or more. Also, the percentage ratio of the polyphenylene ether compound (A) to the resin component (organic component) in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less.
  • the resin components in the resin composition according to the present embodiment include, for example, a polyphenylene ether compound (A), a styrene-based block copolymer (B), a polybutadiene compound (C), and a curing agent (D). It is an organic component containing
  • the percentage of the styrene block copolymer (B) to the total of the polyphenylene ether compound (A), the styrene block copolymer (B), and the allyl compound (d1) is preferably 5% by mass or more. , more preferably 10% by mass or more. Also, the percentage of the styrene block copolymer (B) to the total of the polyphenylene ether compound (A), the styrene block copolymer (B), and the allyl compound (d1) is 50% by mass or less. is preferred, and 40% by mass or less is more preferred.
  • the percentage of the polybutadiene compound (C) with respect to the total of the polyphenylene ether compound (A), the polybutadiene compound (C), and the allyl compound (d1) is preferably at least 5% by mass, and at least 6% by mass. is more preferred. Further, the percentage of the polybutadiene compound (C) with respect to the total of the polyphenylene ether compound (A), the polybutadiene compound (C), and the allyl compound (d1) is preferably 40% by mass or less, and 25% by mass or less. It is more preferable to have
  • the percentage ratio of the curing agent (D) to the resin component in the resin composition according to this embodiment is preferably 5% by mass or more, more preferably 10% by mass or more. Moreover, the percentage ratio of the curing agent (D) to the resin component in the resin composition is preferably 60% by mass or less, more preferably 50% by mass or less.
  • the percentage ratio of the silane coupling agent (E) having a triazine ring to the filler is preferably 0.1% by mass or more, more preferably 1% by mass or more. Also, the percentage ratio of the silane coupling agent (E) having a triazine ring to the filler is preferably 7% by mass or less, more preferably 5% by mass or less.
  • the mass ratio of the styrenic block copolymer (B) to the total of the polyphenylene ether compound (A) and the allyl compound (d1) is preferably from 50:50 to 95:5.
  • the resin composition according to the present embodiment has a low dielectric It is possible to obtain a cured product that has excellent flexibility and adhesion to metal foil or the like while having the desired properties.
  • the mass ratio of the styrene block copolymer (B) to the total of the polyphenylene ether compound (A) and the allyl compound (d1) is more preferably 50:50 to 90:10, more preferably 50:50. to 85:15 is more preferred.
  • the content of the polybutadiene compound (C) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to a total of 100 parts by mass of the polyphenylene ether compound (A) and the allyl compound (d1).
  • the resin composition according to the present embodiment makes it possible to obtain a cured product which has low dielectric properties and which has good flexibility and good adhesion to metal foil or the like.
  • the content of the polybutadiene compound (C) with respect to the total of the polyphenylene ether compound (A) and the allyl compound (d1) is more preferably 6 parts by mass or more.
  • the content of the polybutadiene compound (C) with respect to the total of the polyphenylene ether compound (A) and the allyl compound (d1) is more preferably 35 parts by mass or less.
  • the percentage of the compound having a maleimide group in the molecule relative to the resin composition according to the present embodiment is less than 10% by mass. is preferred. If the percentage of the compound having a maleimide group in the molecule with respect to the resin composition according to the present embodiment is less than 10% by mass, the resin composition according to the present embodiment has low dielectric properties and flexibility. With this, it becomes possible to obtain a cured product having good adhesion to metal foil or the like.
  • the percentage of the filler to the resin composition is preferably 50% by mass or more and 300% by mass or less, and is 70% by mass or more and 300% by mass or less. is more preferable, and more preferably 100% by mass or more and 300% by mass or less.
  • a polyphenylene ether compound (A), a styrene-based block copolymer (B), a polybutadiene compound (C), and a curing agent (D) are added to a predetermined The method of mixing so that it may become content, etc. are mentioned.
  • the resin composition according to this embodiment may contain an organic solvent. That is, the resin composition according to this embodiment is preferably used as a varnish-like resin composition containing an organic solvent.
  • the varnish-like resin composition containing an organic solvent is obtained by adding an organic solvent to the composition contained in the resin composition according to the present embodiment described above.
  • Such a varnish-like resin composition can be produced as follows. First, a component that can be dissolved in an organic solvent is put into the organic solvent and dissolved with stirring to prepare a mixture. The mixture may also be made by stirring while heating. Subsequently, a component that does not dissolve in an organic solvent is added to the mixture, and dispersed using a ball mill, bead mill, planetary mixer, roll mill, or the like until a desired dispersion state is obtained, thereby obtaining a varnish-like resin. Manufacture the composition.
  • organic solvent used here is capable of dissolving, for example, polyphenylene ether (A), styrenic block copolymer (B), polybutadiene compound (C), and curing agent (D), and resin It is preferable that it does not inhibit the curing reaction of the composition.
  • organic solvents include toluene, methyl ethyl ketone (MEK), and the like.
  • the resin composition according to the present embodiment is used for producing the resin layer of the resin-coated film, the resin layer of the resin-coated metal foil, the insulating layer of the metal-clad laminate, and the insulating layer of the printed wiring board. be done. More specifically, the resin layer included in the resin-coated film includes at least one of an uncured product of the resin composition according to the present embodiment and a semi-cured product of the resin composition. The resin layer included in the resin-coated metal foil includes at least one of an uncured product of the resin composition according to the present embodiment and a semi-cured product of the resin composition. The insulating layer included in the metal-clad laminate contains a cured product of the resin composition according to the present embodiment. The insulating layer included in the printed wiring board contains a cured product of the resin composition according to the present embodiment.
  • the semi-cured product is a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a state in which the resin composition is semi-cured, that is, the so-called B-staged resin composition.
  • the resin composition according to the present embodiment is heated, the viscosity gradually decreases at the beginning of heating, but then the solvent contained in the resin composition volatilizes, and the resin curing starts. This causes a gradual increase in viscosity.
  • semi-curing means, for example, the state from when the viscosity starts to rise to before it is completely cured.
  • the polyphenylene ether compound (A) contained in the resin composition according to the present embodiment and the unsaturated bonds of the curing agent (D) and the like do not react, and curing has not started.
  • the resin composition is considered to be in a semi-cured state.
  • the varnish-like resin composition is used to produce the resin layer 12 of the resin-coated film 11 or the resin layer 22 of the resin-coated metal foil 21 described later, it is contained in the resin layers 12 and 22.
  • the solvent content is preferably 1.5% by mass or less, more preferably 1% by mass or less.
  • the semi-cured product of the resin composition according to this embodiment preferably has a minimum bending radius of 2 mm or less.
  • the resin composition according to the present embodiment can obtain a cured product having excellent flexibility and adhesion to metal foil or the like.
  • the minimum bending radius of the semi-cured product in this embodiment is, for example, the semi-cured product produced from the resin composition according to this embodiment by the MIT test based on JIS P8115 with a load of 0.5 kgf and a bending angle of It shows the value of R of a bending clamp that can be bent once or more under the measurement conditions of 135 degrees and a test speed of 175 cpm.
  • a test piece used for measurement is, for example, a test piece having a circuit pattern cut into a width of 15 mm and a length of 130 mm. Furthermore, in order to conduct the minimum bending test, for example, an MIT testing device (manufactured by Toyo Seiki Seisakusho, model number: MIT-DA) is used.
  • the semi-cured product of the resin composition according to the present embodiment preferably has a minimum bending radius of 1 mm or less, more preferably 0.5 mm or less.
  • the cured product of the resin composition according to this embodiment preferably has a minimum bending radius of 2 mm or less. Also in this case, the resin composition according to the present embodiment enables obtaining a cured product having excellent flexibility and adhesion to metal foil or the like.
  • the minimum bending radius of the cured product of the resin composition is measured, for example, by the same method as for the minimum bending radius of the semi-cured product in the present embodiment.
  • the cured product of the resin composition according to the present embodiment preferably has a minimum bending radius of 1 mm or less, more preferably 0.5 mm or less.
  • FIG. 1 is a schematic cross-sectional view showing an example of a resin-coated film 11 according to this embodiment.
  • the resin-coated film 11 according to the present embodiment includes a resin layer 12 containing at least one of the resin composition according to the present embodiment and a semi-cured product of the resin composition, and a support film 13.
  • the resin-coated film 11 includes a resin layer 12 containing at least one of an uncured product of the resin composition according to the present embodiment and a semi-cured product of the resin composition, and a support film 13 overlapping the resin layer 12.
  • the resin-coated film 11 may have another layer between the resin layer 12 and the support film 13, for example.
  • the resin layer 12 may contain a semi-cured material of the resin composition according to the present embodiment, or may contain an uncured resin composition. That is, the resin-coated film 11 may be a resin-coated film 11 including a resin layer 12 containing a semi-cured product of a resin composition (B-stage resin composition) and a support film 13. It may be a resin-coated film 11 comprising a resin layer 12 containing a composition and a support film 13 .
  • the resin layer 12 may contain a fibrous base material. That is, a prepreg including the resin composition according to the present embodiment and a fibrous base material may be used for the resin layer 12 of the resin-coated film 11 according to the present embodiment.
  • a fibrous base material is used for the resin layer 12
  • the fibrous base material is selected from the group consisting of, for example, glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. At least one selected is included.
  • the fibrous base material is preferably glass cloth. The use of glass cloth makes it possible to obtain the resin layer 12 having excellent mechanical strength. Further, the glass cloth is more preferably flattened.
  • the fibrous base material is more preferably flattened glass cloth.
  • the flattening process there is a method in which the glass cloth is continuously pressed with a press roll at an appropriate pressure to flatten the yarn.
  • the thickness of the generally used fibrous base material is, for example, 0.01 mm or more and 0.3 mm or less.
  • the support film 13 is, for example, a group consisting of polyester film, polyethylene terephthalate (PET) film, polyimide film, polyparabanic acid film, polyetheretherketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, polyarylate film, and the like. at least one electrically insulating film selected from
  • the resin-coated film 11 may include, for example, a cover film or the like.
  • a cover film By providing the cover film, it is possible to prevent foreign matter from entering.
  • Specific examples of the cover film include polyolefin film, polyester film, polymethylpentene film, and the like.
  • the support film 13 and the cover film may be subjected to surface treatments such as matte treatment, corona treatment, release treatment, and roughening treatment.
  • the resin composition according to the present embodiment is mixed with a solvent to prepare a varnish-like resin composition, and the varnish-like resin is produced.
  • examples include a method of manufacturing resin-coated film 11 by applying a composition onto support film 13 and heating to form resin layer 12 overlapping support film 13 .
  • Examples of the method of applying the varnish-like resin composition to the support film 13 include a method using a bar coater.
  • the applied varnish-like resin composition is heated to volatilize the organic solvent from the varnish-like resin composition and remove the organic solvent. do.
  • the temperature when heating the applied varnish-like resin composition is preferably 80° C. or higher and 180° C. or lower, for example.
  • the time for heating the applied varnish-like resin composition is preferably 1 minute or more and 10 minutes or less.
  • the resin composition according to the present embodiment is formed as the uncured or semi-cured resin layer 12 on the support film 13, thereby manufacturing the resin-coated film 11 according to the present embodiment. .
  • the resin-coated film 11 has a resin layer 12 that provides an insulating layer that has low dielectric properties, flexibility, and good adhesion to metal foil or the like.
  • This resin-coated film 11 is suitably used for producing a printed wiring board provided with an insulating layer having low dielectric properties, flexibility, and good adhesion to metal foil or the like. sell.
  • This resin-coated film 11 is formed by, for example, laminating on a printed wiring board and then peeling off the support film 13, or peeling off the support film 13 and then laminating on the printed wiring board. A printed wiring board can be manufactured.
  • the method of manufacturing the resin-coated film 11 including the resin layer 12 made from the resin composition according to the present embodiment and the support film 13 overlapping the resin layer 12 is not limited to the above method. That is, the resin-coated film 11 manufactured using the resin composition according to this embodiment can be manufactured by an appropriate method. Furthermore, the resin-coated film 11 according to the present embodiment is not limited to use only for manufacturing printed wiring boards. That is, the resin-coated film 11 according to this embodiment is applied to various uses.
  • FIG. 2 is a schematic cross-sectional view showing an example of the resin-coated metal foil 21 according to this embodiment.
  • the resin-coated metal foil 21 according to the present embodiment includes a resin layer 22 containing at least one of the resin composition according to the present embodiment and a semi-cured product of the resin composition, and the resin layer and a metal foil 23 that overlaps 22 . That is, the resin-coated metal foil 21 according to this embodiment includes a resin layer 22 containing at least one of an uncured product of the resin composition according to this embodiment and a semi-cured product of the resin composition, and the resin layer 22 and a metal foil 23 that overlaps the Moreover, the resin-coated metal foil 21 may have another layer between the resin layer 22 and the metal foil 23 .
  • the resin layer 22 may contain a semi-cured resin composition according to the present embodiment, or may contain an uncured resin composition. That is, the resin-coated metal foil 21 may be a resin-coated metal foil 21 including a resin layer 22 containing a semi-cured resin composition (B-stage resin composition) and a metal foil 23. and a metal foil 23 with resin.
  • B-stage resin composition a semi-cured resin composition
  • the resin layer 22 may contain, for example, a fibrous base material.
  • a fibrous base material for example, the same fibrous base material as used for manufacturing the above-described resin-coated film 11 may be used.
  • the metal foil 23 for example, an appropriate metal foil is used.
  • the metal foil 23 include copper foil, aluminum foil, and the like.
  • the resin-coated metal foil 21 may be provided with a cover film or the like, for example.
  • a cover film for example, the same cover film as used for manufacturing the resin-coated film 11 can be used.
  • the resin composition according to the present embodiment is mixed with a solvent to prepare a varnish-like resin composition, and the varnish-like resin composition is prepared.
  • a method of manufacturing the resin-coated metal foil 21 by forming the resin layer 22 overlying the metal foil 23 by applying a substance onto the metal foil 23 and heating the same.
  • Examples of the method of applying the varnish-like resin composition to the metal foil 23 include a method using a bar coater.
  • the applied varnish-like resin composition is heated to volatilize the organic solvent from the varnish-like resin composition and remove the organic solvent. do.
  • the temperature when heating the applied varnish-like resin composition is preferably 80° C. or higher and 180° C. or lower.
  • the time for heating the applied varnish-like resin composition is preferably 1 minute or more and 10 minutes or less.
  • the resin composition according to the present embodiment provides a cured product that has low dielectric properties, flexibility, and good adhesion to metal foil and the like. Therefore, the resin-coated metal foil 21 has a resin layer 22 that provides an insulating layer that has low dielectric properties, flexibility, and good adhesion to the metal foil or the like.
  • This resin-coated metal foil 21 is suitably used for manufacturing a printed wiring board provided with an insulating layer that has low dielectric properties, flexibility, and good adhesion to metal foil and the like. can be
  • the method of manufacturing the resin-coated metal foil 21 including the resin layer 22 made from the resin composition according to this embodiment and the metal foil 23 overlapping the resin layer 22 is not limited to the above method. That is, the resin-coated metal foil 21 produced using the resin composition according to this embodiment can be produced by an appropriate method. Furthermore, the use of the resin-coated metal foil 21 according to this embodiment is not limited to the manufacture of printed wiring boards. That is, the resin-coated metal foil 21 according to this embodiment is applied to various uses.
  • FIG. 3 is a schematic cross-sectional view showing an example of the metal-clad laminate 31 according to this embodiment.
  • the metal-clad laminate 31 includes an insulating layer 32 made from the resin composition according to this embodiment and a metal foil 33 overlapping the insulating layer 32 . That is, the metal-clad laminate 31 has an insulating layer 32 containing a cured product of the resin composition according to this embodiment, and a metal foil 33 overlapping the insulating layer 32 .
  • this insulating layer 32 is preferably a cured product of the resin composition according to this embodiment.
  • the insulating layer 32 may be, for example, a cured product of a prepreg including the resin composition according to the present embodiment and a fibrous base material.
  • the fibrous base material may be the same as the fibrous base material used when producing the resin-coated film 11 and the resin-coated metal foil 21 .
  • the thickness of the metal foil 33 can be appropriately set according to the purpose. Further, specific examples of the metal foil 33 include copper foil, aluminum foil, and the like.
  • the insulating layer 32 is prepared from the cured resin composition according to the present embodiment, and the metal foil 33 is superimposed on the insulating layer 32 and heated and pressurized to form a metal.
  • a method for producing the tension laminate 31 can be mentioned. More specifically, the method for manufacturing the metal-clad laminate 31 includes forming metal foils 33 such as copper foils on both upper and lower sides or on one side of the insulating layer 32 containing the cured product of the resin composition according to the present embodiment. , and the metal foil 33 and the insulating layer 32 are heat-pressed and laminated to form a metal-clad laminate 31 with the metal foil 33 attached to one or both sides thereof.
  • the insulating layer 32 may be produced using the resin-coated film 11 described above. More specifically, the insulating layer 32 of the metal-clad laminate 31 according to this embodiment can be produced by heating and curing the resin layer 12 of the resin-coated film 11 .
  • the insulating layer 32 may be produced using the resin-coated metal foil 21 described above. More specifically, the insulating layer 32 of the metal-clad laminate 31 according to this embodiment can be produced by heating and curing the resin layer 22 of the resin-coated metal foil 21 . In this case, the metal foil 23 of the resin-coated metal foil 21 becomes the metal foil 33 of the metal-clad laminate 31 .
  • the heating and pressurizing conditions when manufacturing the metal-clad laminate 31 are preferably appropriately set according to the thickness of the metal-clad laminate 31 to be manufactured, the type of composition of the insulating layer 32, and the like.
  • the heating temperature for manufacturing the metal-clad laminate 31 is preferably 170°C or higher and 230°C or lower. Moreover, the pressure when manufacturing the metal-clad laminate 31 is preferably 1.5 MPa or more and 5.0 MPa or less. Furthermore, the heating and pressurizing time for manufacturing the metal-clad laminate 31 is preferably 60 minutes or more and 150 minutes or less.
  • the thickness of the metal foil 33 can be appropriately set according to the desired purpose.
  • the metal foil 33 may have a thickness of 0.2 ⁇ m or more and 70 ⁇ m or less.
  • the thickness of the metal foil is, for example, 10 ⁇ m or less, it may be a copper foil with a carrier provided with a release layer and a carrier for improved handling.
  • the thickness of the metal foil 33 is preferably 0.2 ⁇ m or more and 35 ⁇ m or less, and more preferably 1 ⁇ m or more and 18 ⁇ m or less.
  • the peel strength between the insulating layer 32, which is a cured product of the resin composition, and the metal foil 33 is preferably 0.50 N/mm or more. It is more preferably 55 N/mm or more, and even more preferably 0.60 N/mm or more.
  • the resin composition according to the present embodiment provides a cured product that has low dielectric properties, flexibility, and good adhesion to metal foil and the like. Therefore, the metal-clad laminate 31 provided with the insulating layer 32 containing the cured product of this resin composition has low dielectric properties, and the insulating layer 32 has good flexibility and good adhesion to metal foil and the like. Prepare.
  • a metal-clad laminate 31 can be suitably used, for example, as a flexible copper-clad laminate (FCCL: Flexible Copper Clad Laminate).
  • FCCL Flexible Copper Clad Laminate
  • the metal-clad laminate 31 according to this embodiment is not limited to being used as a flexible copper-clad laminate. That is, the metal-clad laminate 31 according to this embodiment can be used for various purposes. Moreover, the method for manufacturing the metal-clad laminate 31 including the insulating layer 32 made from the resin composition according to the present embodiment and the metal foil 33 overlapping the insulating layer 32 is not limited to the above method. That is, the metal-clad laminate 31 produced using the resin composition according to this embodiment can be produced by an appropriate method.
  • 4C and 4D are schematic cross-sectional views of the printed wiring board 41 according to this embodiment.
  • a printed wiring board 41 according to the present embodiment includes an insulating layer 42 made from the resin composition according to the present embodiment and wiring 43 overlapping the insulating layer 42, as shown in FIG. 4C. That is, in the printed wiring board 41 according to the present embodiment, the resin composition according to the present embodiment is applied to the wiring 43 formed by partially removing the metal foil 45 superimposed on the base material layer 44. An insulating layer 42 containing a hardened material is overlaid. Moreover, as shown in FIG. 4D, the printed wiring board 41 according to the present embodiment may further have a metal foil 46 overlaid on the insulating layer 42 .
  • the base material layer 44 include polyimide, liquid crystal polymer (hereinafter also referred to as LCP), and the like. Moreover, among these, LCP is preferable for the base material layer 44 .
  • the peel strength between the insulating layer 42, which is a cured product of the resin composition, and the LCP is preferably 0.25 N/mm or more, more preferably 0.30 N/mm or more. and more preferably 0.40 N/mm or more.
  • the resin composition according to the present embodiment may be used for the base material layer 44 of the printed wiring board 41.
  • the base material layer 44 of the printed wiring board 41 is preferably a cured prepreg including the resin composition according to the present embodiment and a fibrous base material.
  • the metal foil 45 may be the same as that used when manufacturing the metal-clad laminate 31 .
  • the method for manufacturing the printed wiring board 41 according to this embodiment is as follows. First, as shown in FIG. 4A, a metal foil 45 is laminated on the base material layer 44 .
  • the wiring 43 which will be the circuit of the printed wiring board, is formed on the surface of the base material layer 44.
  • a method for forming a circuit for example, a semi-additive process (SAP: Semi-Additive Process) or a modified semi-additive process (MSAP: Modified Semi-Additive Process) is used.
  • SAP Semi-Additive Process
  • MSAP Modified Semi-Additive Process
  • the insulating layer 42 made of the resin composition according to the present embodiment is formed on the wiring 43 formed.
  • a varnish-like resin composition prepared by mixing the resin composition according to the present embodiment and a solvent is applied on the wiring 43, and a varnish-like resin composition is applied. can be formed by curing the resin composition.
  • the printed wiring board 41 is manufactured. Also, as described above, a metal foil 46 may be further overlaid on the fabricated insulating layer 42, as shown in FIG. 4D. By partially removing the metal foil 46 to form a wiring, and then by repeatedly stacking an insulating layer, a multi-layered structure may be formed.
  • a printed wiring board 41 according to the present embodiment includes an insulating layer 42 containing a cured product that has low dielectric properties, flexibility, and good adhesion to metal foil or the like.
  • the printed wiring board 41 according to the present embodiment includes the insulating layer 42 that has low dielectric properties, flexibility, and good adhesion to metal foil or the like.
  • Such a printed wiring board 41 can be suitably used, for example, as a flexible printed circuit board (FPC: Flexible Printed Circuits).
  • the method for manufacturing the printed wiring board 41 according to this embodiment is not limited to the above method. That is, the printed wiring board 41 manufactured using the resin composition according to this embodiment can be manufactured by an appropriate method.
  • the printed wiring board 41 according to the present embodiment is not limited to being used as a flexible printed circuit board. That is, the printed wiring board 41 according to this embodiment can be applied to various uses.
  • the resin composition according to the first aspect of the present disclosure includes a polyphenylene ether compound (A), a styrene-based block copolymer (B), a polybutadiene compound (C), and a curing agent (D).
  • the polyphenylene ether compound (A) has at least one of the group represented by the following formula (1) and the group represented by the following formula (2) in the molecule.
  • the polybutadiene compound (C) has an epoxy group in its molecule.
  • Curing agent (D) contains an allyl compound (d1) represented by formula (3).
  • p represents an integer of 0 to 10
  • Z represents an arylene group
  • R 1 to R 3 each independently represent a hydrogen atom or an alkyl group.
  • R4 represents a hydrogen atom or an alkyl group.
  • the resin composition can provide a cured product that has low dielectric properties and has good flexibility and good adhesion to metal foil and the like.
  • the semi-cured product of the resin composition has a minimum bending radius of 2 mm or less.
  • the resin composition makes it possible to obtain a cured product with good flexibility and good adhesion to metal foil and the like.
  • the cured product of the resin composition has a minimum bending radius of 2 mm or less.
  • the third aspect it is possible to obtain a cured product with good flexibility and good adhesion to metal foil and the like from the resin composition.
  • the resin composition according to the fourth aspect of the present disclosure in any one of the first to third aspects, further contains a silane coupling agent (E) having a triazine ring.
  • the fourth aspect it is possible to obtain a cured product of the resin composition that has low dielectric properties and good adhesion to metal foil and the like.
  • the resin composition according to the fifth aspect of the present disclosure is a polyphenylene ether compound (A) and a styrene block copolymer with respect to the total of the allyl compound (d1)
  • the mass ratio of (B) is from 50:50 to 95:5.
  • the fifth aspect it is possible to obtain a cured product of the resin composition that has low dielectric properties and has good flexibility and good adhesion to metal foil and the like.
  • the resin composition according to the sixth aspect of the present disclosure is a polybutadiene compound with respect to a total of 100 parts by mass of the polyphenylene ether compound (A) and the allyl compound (d1)
  • the content of (C) is 5 parts by mass or more and 40 parts by mass or less.
  • the sixth aspect it is possible to obtain a cured product of the resin composition that has low dielectric properties and has good flexibility and good adhesion to metal foil and the like.
  • a resin-coated film according to a seventh aspect of the present disclosure includes a resin layer containing at least one of an uncured product of the resin composition and a semi-cured product of the resin composition according to any one of the first to sixth aspects; and a support film overlying the resin layer.
  • a resin containing at least one of an uncured product and a semi-cured product of a resin composition that has low dielectric properties and has good flexibility and good adhesion to a metal foil or the like A resin-coated film comprising layers may be provided.
  • a resin-coated metal foil according to an eighth aspect of the present disclosure is a resin layer containing at least one of an uncured product of the resin composition and a semi-cured product of the resin composition of any one of the first to sixth aspects. and a metal foil overlapping the resin layer.
  • a resin containing at least one of an uncured product and a semi-cured product of a resin composition that has low dielectric properties and has good flexibility and good adhesion to a metal foil or the like A resin-coated metal foil comprising layers may be provided.
  • a metal-clad laminate according to a ninth aspect of the present disclosure includes an insulating layer containing a cured product of the resin composition of any one of the first to sixth aspects, and a metal foil overlapping the insulating layer.
  • a metal-clad laminate including an insulating layer containing a cured product of a resin composition that has low dielectric properties, flexibility, and good adhesion to a metal foil or the like.
  • a printed wiring board includes an insulating layer containing a cured product of the resin composition of any one of the first to sixth aspects, and wiring overlapping the insulating layer.
  • a printed wiring board comprising an insulating layer containing a cured product of a resin composition that has low dielectric properties, flexibility, and good adhesion to a metal foil or the like. obtain.
  • Modified PPE1 polyphenylene ether compound having a methacryloyl group at the end (modified polyphenylene ether obtained by modifying the terminal hydroxyl group of polyphenylene ether with a methacryloyl group, represented by the above formula (14), where Y in formula (14) is a dimethylmethylene group (formula (11), wherein R 37 and R 38 in formula (11) are methyl groups) modified polyphenylene ether compound, SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw 2000, terminal functional group number 2 Individual) Modified PPE2: A polyphenylene ether compound (modified polyphenylene ether obtained by reacting polyphenylene ether with chloromethylsty
  • polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, 2 terminal hydroxyl groups, weight average molecular weight Mw 1700) was added to a 1-liter three-necked flask equipped with a temperature controller, a stirrer, a cooling device, and a dropping funnel.
  • 200 g a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene: CMS manufactured by Tokyo Chemical Industry Co., Ltd.) 30 g, tetra-n-butylammonium as a phase transfer catalyst 1.227 g of bromide and 400 g of toluene were charged and stirred.
  • the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were stirred until they were dissolved in toluene. At that time, it was gradually heated until the liquid temperature finally reached 75°C. Then, an aqueous sodium hydroxide solution (20 g of sodium hydroxide/20 g of water) was added dropwise to the solution as an alkali metal hydroxide over 20 minutes. After that, the mixture was further stirred at 75° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass hydrochloric acid, a large amount of methanol was added. By doing so, the liquid in the flask was caused to precipitate.
  • the solid obtained was analyzed by 1H-NMR (400 MHz, CDCl3, TMS). As a result of NMR measurement, a peak derived from a vinylbenzyl group (ethenylbenzyl group) was confirmed at 5 to 7 ppm. As a result, it was confirmed that the obtained solid was a modified polyphenylene ether having a vinylbenzyl group (ethenylbenzyl group) as the substituent at the molecular terminal in the molecule. Specifically, it was confirmed to be an ethenylbenzylated polyphenylene ether.
  • the resulting modified polyphenylene ether compound is represented by the above formula (13), Y is represented by a dimethylmethylene group (formula (11), and R 37 and R 38 in formula (11) are methyl groups. ), Z is a phenylene group, R 1 to R 3 are hydrogen atoms, and p is 1, which is a modified polyphenylene ether compound.
  • terminal functional group number of the modified polyphenylene ether was measured as follows.
  • TEAH tetraethylammonium hydroxide
  • Residual OH amount ( ⁇ mol/g) [(25 ⁇ Abs)/( ⁇ OPL ⁇ X)] ⁇ 10 6
  • ⁇ indicates the extinction coefficient and is 4700 L/mol ⁇ cm.
  • OPL is the cell optical path length and is 1 cm.
  • the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, it was found that the hydroxyl groups of the polyphenylene ether before modification were almost modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups was two.
  • the intrinsic viscosity (IV) of the modified polyphenylene ether was measured in methylene chloride at 25°C. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured using a 0.18 g/45 ml methylene chloride solution (liquid temperature: 25°C) of the modified polyphenylene ether with a viscometer (AVS500 Visco System manufactured by Schott). It was measured. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl/g. Also, the molecular weight distribution of the modified polyphenylene ether was measured using GPC. Then, the weight average molecular weight (Mw) was calculated from the obtained molecular weight distribution. As a result, Mw was 1,900.
  • Tuftec H1041 Hydrogenated styrenic thermoplastic elastomer (Tuftec H1041 from Asahi Kasei Corporation)
  • Tuftec H1221 Hydrogenated styrenic thermoplastic elastomer (Tuftec H1221 from Asahi Kasei Corporation)
  • JP-100 Polybutadiene compound having an epoxy group in the molecule (JP-100 manufactured by Nippon Soda Co., Ltd., oxirane concentration: 7.7% by mass)
  • L-DAIC long-chain alkyl-modified diallyl isocyanurate (L-DAIC manufactured by Shikoku Kasei Co., Ltd.)
  • TAIC triallyl isocyanurate (TAIC manufactured by Nippon Kasei Co., Ltd.) (Silane coupling agent having a triazine ring)
  • VD-5 silane coupling agent having a triazine ring
  • evaluation board production 1 an evaluation substrate used for measuring dielectric properties (relative permittivity and dielectric loss tangent), copper foil peel strength, minimum bending radius of semi-cured product, and minimum bending radius of cured product was obtained as follows. rice field.
  • the varnish-like resin composition obtained by the above method was applied to a copper foil (Mitsui Kinzoku Co., Ltd. product number: 3EC-VLP, thickness 18 ⁇ m) so that the thickness was 75 ⁇ m, and the thickness was 100 to 160 ⁇ m. C. for 2 to 5 minutes to form a semi-cured resin layer on the film, thereby obtaining a resin-coated metal foil.
  • a copper foil Mitsubishi Chemical Company, Ltd. product number: 3EC-VLP, thickness 18 ⁇ m
  • the evaluation substrate used for measuring the minimum bending radius of the semi-cured product was one in which the resin layer was not cured without heating and pressurizing for 2 hours under vacuum conditions of 200 ° C. and a pressure of 4 MPa, that is, the resin layer was in a semi-cured state.
  • the evaluation board produced as described above was evaluated by the method shown below.
  • the copper foil was peeled off from the evaluation board, and the peel strength (copper foil peel strength) at that time was measured according to JIS C 6481. Specifically, the copper foil is pulled from the evaluation board and peeled off at a speed of 50 mm / min with a tensile tester (manufactured by Imada Seisakusho Co., Ltd., model number: SV-52-E-5M), and the peel strength at that time (N / mm) was measured.
  • a tensile tester manufactured by Imada Seisakusho Co., Ltd., model number: SV-52-E-5M
  • the evaluation substrate used for measuring the LCP film peel strength is a film (LCP film, Kuraray Co., Ltd. product number: Vecstar CT-Q). Then, the semi-cured resin layer of the resin-coated metal foil was cured by heating and pressurizing it for 2 hours under a vacuum condition of 200° C. and a pressure of 4 MPa. This obtained laminate was used as an evaluation substrate. The thickness of the cured resin layer in this evaluation substrate was also 75 ⁇ m.
  • the evaluation board produced as described above was evaluated by the method shown below.
  • LCP film peel strength The film was peeled off from the evaluation substrate, and the peel strength at that time (LCP film peel strength) was measured according to JIS C 6481. Specifically, the LCP film was pulled from the evaluation substrate and peeled off at a speed of 50 mm / min with a tensile tester (manufactured by Imada Seisakusho Co., Ltd., model number: SV-52-E-5M), and the peel strength at that time (N / mm) was measured.
  • a tensile tester manufactured by Imada Seisakusho Co., Ltd., model number: SV-52-E-5M
  • Table 1 shows the results of each of the above evaluations.
  • Examples 1 to 3 and 5 to 9 had better results in the minimum bending test of the cured product compared to Comparative Example 1 in which L-DAIC was not used.
  • Examples 2 to 3 and 5 to 8 show better copper foil peel strength than Comparative Example 2, which contains polybutadiene having no epoxy group instead of the polybutadiene compound having an epoxy group in the molecule. was high.
  • Examples 1 to 9 had higher LCP film peel strength than Comparative Example 2, which contained polybutadiene having no epoxy group in place of the polybutadiene compound having an epoxy group in the molecule.
  • Examples 1-7 had higher LCP film peel strength than Examples 8-9, which did not contain a silane coupling agent having a triazine ring. From this, it can be said that the silane coupling agent is preferably a silane coupling agent having a triazine ring.
  • the resin composition according to the present embodiment can provide a cured product that has low dielectric properties, flexibility, and good adhesion to metal foil and the like.
  • a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a printed wiring board are provided, which contain a cured product produced from the resin composition.

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PCT/JP2022/041663 2021-11-19 2022-11-09 樹脂組成物、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及びプリント配線板 Ceased WO2023090215A1 (ja)

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TW202323372A (zh) 2023-06-16

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