WO2024101362A1 - Composition de résine, préimprégné, stratifié revêtu de métal, carte de câblage, feuille métallique avec résine, et film avec résine - Google Patents

Composition de résine, préimprégné, stratifié revêtu de métal, carte de câblage, feuille métallique avec résine, et film avec résine Download PDF

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WO2024101362A1
WO2024101362A1 PCT/JP2023/040084 JP2023040084W WO2024101362A1 WO 2024101362 A1 WO2024101362 A1 WO 2024101362A1 JP 2023040084 W JP2023040084 W JP 2023040084W WO 2024101362 A1 WO2024101362 A1 WO 2024101362A1
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group
composition
resin
compound
resin composition
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PCT/JP2023/040084
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Japanese (ja)
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祐司 山田
徹 中芝
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パナソニックＩｐマネジメント株式会社
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    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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

Definitions

  • This disclosure relates to a resin composition, a prepreg, a metal-clad laminate, a wiring board, a metal foil with resin, and a film with resin, and more specifically to a resin composition containing a thermosetting resin, and a prepreg, a metal-clad laminate, a wiring board, a metal foil with resin, and a film with resin made from the resin composition.
  • the polyphenylene ether resin composition described in Patent Document 1 has a low dielectric constant and low dielectric loss, and can stably maintain the dielectric constant and dielectric loss of the substrate over long-term use.
  • the objective of this disclosure is to provide a resin composition that has improved moldability and improved adhesion of the cured product to metal, as well as a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film made from the resin composition.
  • the resin composition according to one embodiment of the present disclosure contains a polyphenylene ether compound (A), a maleimide compound (B), a curing agent (C), and an inorganic filler (D).
  • the inorganic filler (D) includes an inorganic filler (D1) surface-treated with a hydrophobic silane coupling agent, and an inorganic filler (D2) surface-treated with a hydrophilic silane coupling agent.
  • the curing agent (C) includes a phenol compound (C1) having at least one of a group represented by formula (1) and a group represented by formula (2).
  • the content of the inorganic filler (D1) is 20% by mass or more and 80% by mass or less with respect to the total amount of the inorganic filler (D1) and the inorganic filler (D2).
  • the prepreg according to one embodiment of the present disclosure includes a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition.
  • the resin layer further includes a fibrous base material.
  • the metal-clad laminate according to one embodiment of the present disclosure comprises an insulating layer containing at least one of the cured product of the resin composition and the cured product of the prepreg, and a metal foil.
  • the wiring board according to one embodiment of the present disclosure comprises an insulating layer containing at least one of the cured product of the resin composition and the cured product of the prepreg, and wiring.
  • the resin-coated metal foil according to one embodiment of the present disclosure comprises a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition, and a metal foil.
  • the resin-coated film according to one embodiment of the present disclosure comprises a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition, and a support film.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present disclosure.
  • FIG. 3 is a schematic cross-sectional view illustrating an example of a wiring board according to an embodiment of the present disclosure.
  • FIG. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the present disclosure.
  • FIG. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present disclosure.
  • wiring boards used in various electronic devices are required to be compatible with high frequencies, such as millimeter wave radar boards for in-vehicle applications.
  • the substrate material used to configure the insulating layer of wiring boards used in various electronic devices is required to have low dielectric constant and dielectric tangent values in order to increase the signal transmission speed and reduce loss during signal transmission.
  • Polyphenylene ether is known to have excellent dielectric constant and dielectric dissipation factor in the high frequency range from the MHz to GHz range. For this reason, polyphenylene ether is used, for example, as a high frequency molding material. More specifically, it is preferably used as a substrate material for constituting the insulating layer of a printed wiring board installed in electronic devices that use high frequencies.
  • Patent Document 1 discloses a polyphenylene ether resin composition that has a low dielectric constant and low dielectric loss, and in which the dielectric constant and dielectric loss of the substrate are unlikely to change even after long-term use.
  • insulating materials for printed wiring boards and the like are required to have both high moldability of the resin composition and high adhesion to metal of the cured resin composition.
  • composition (X) The components contained in the resin composition of the present disclosure (hereinafter also referred to as composition (X)) will be described.
  • Composition (X) contains a polyphenylene ether compound (A), a maleimide compound (B), a curing agent (C), and an inorganic filler (D).
  • the inorganic filler (D) contains an inorganic filler (D1) (hereinafter, also simply referred to as inorganic filler (D1)) that has been surface-treated with a hydrophobic silane coupling agent, and an inorganic filler (D2) (hereinafter, also simply referred to as inorganic filler (D2)) that has been surface-treated with a hydrophilic silane coupling agent.
  • the composition (X) contains the polyphenylene ether compound (A), which can reduce the dielectric constant and the dielectric tangent of a cured product of the composition (X) and can enhance the heat resistance of the cured product of the composition (X).
  • the polyphenylene ether compound (A) preferably contains a modified polyphenylene ether compound (A1) (hereinafter also simply referred to as modified polyphenylene ether compound (A1)) that is terminally modified with a substituent having a carbon-carbon unsaturated double bond.
  • modified polyphenylene ether compound (A1) hereinafter also simply referred to as modified polyphenylene ether compound (A1)
  • the dielectric constant and dielectric tangent of the cured product of the composition (X) can be further reduced, and the heat resistance of the cured product of the composition (X) can be further improved.
  • examples of the substituent having a carbon-carbon unsaturated double bond include the substituent represented by the following formula (3).
  • p represents an integer of 0 to 10.
  • Z represents an arylene group.
  • R 1 to R 3 are each independent. That is, R 1 to R 3 may be the same group or different groups.
  • R 1 to R 3 represent a hydrogen atom or an alkyl group.
  • Specific examples of the arylene group include monocyclic aromatic groups such as a phenylene group, and polycyclic aromatic groups such as a naphthalene ring.
  • the arylene group may also include a derivative in which a hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • examples of the substituent having a carbon-carbon unsaturated double bond include the substituent represented by the following formula (4).
  • R4 represents a hydrogen atom or an alkyl group.
  • the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • Examples of the substituent represented by the above formula (4) include an acrylate group or a methacrylate group.
  • the group represented by the above formula (3) include, for example, a vinylbenzyl group (ethenylbenzyl group) represented by the following formula (5), or a vinylphenyl group. More specific examples of the vinylbenzyl group include, for example, an o-ethenylbenzyl group, an m-ethenylbenzyl group, or a p-ethenylbenzyl group.
  • the modified polyphenylene ether compound (A1) that is terminally modified with a substituent having a carbon-carbon unsaturated double bond has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (6) in the molecule.
  • t represents an integer of 1 or more and 50 or less.
  • R 5 to R 8 are each independent. That is, R 5 to R 8 may be the same group or different groups.
  • R 5 to R 8 represent 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. Among these, a hydrogen atom and an alkyl group are preferred.
  • R 5 to R 8 Specific examples of the functional groups mentioned for R 5 to R 8 include the following.
  • the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • the alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms.
  • Specific examples of the alkenyl group include a vinyl group, an allyl group, and a 3-butenyl group.
  • the alkynyl group is not particularly limited, but is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms.
  • Specific examples of alkynyl groups include an ethynyl group, a prop-2-yn-1-yl group (propargyl group), and the like.
  • the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but is preferably an alkylcarbonyl group having 2 to 18 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 10 carbon atoms.
  • Specific examples of alkylcarbonyl groups include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, or a cyclohexylcarbonyl group.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, it is preferably an alkenylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkenylcarbonyl group having 3 to 10 carbon atoms.
  • Specific examples of the alkenylcarbonyl group include an acryloyl group, a methacryloyl group, and a crotonoyl group.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, it is preferably an alkynylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkynylcarbonyl group having 3 to 10 carbon atoms. Specific examples of alkynylcarbonyl groups include a propioloyl group.
  • the weight average molecular weight (Mw) of the modified polyphenylene ether compound (A1) is not particularly limited, but is preferably 500 or more and 5,000 or less, more preferably 800 or more and 4,000 or less, and even more preferably 1,000 or more and 3,000 or less.
  • the weight average molecular weight of the modified polyphenylene ether compound (A1) may be measured by a general molecular weight measurement method, and specifically, may be a value measured using gel permeation chromatography (GPC) and converted into polystyrene.
  • t is preferably a value such that the weight average molecular weight of the polyphenylene ether compound (A) is in the range of 500 to 5,000. Specifically, t is preferably 1 to 50.
  • the weight average molecular weight of the modified polyphenylene ether compound (A1) is within the range of 500 or more and 5,000 or less, the heat resistance of the cured product of the composition (X) is increased, and the moldability of the composition (X) is also increased.
  • the moldability of the composition (X) refers to the amount of voids that are generated when the composition (X) is cured, and the generation of voids in the cured product of the composition (X) can be suppressed by increasing the moldability of the composition (X).
  • composition (X) contains a modified polyphenylene ether compound (A1) having a weight-average molecular weight in the range of 500 to 5,000, the heat resistance of the cured product of composition (X) is increased, and the moldability of composition (X) is also increased. This is believed to be due to the following reasons.
  • Normal polyphenylene ether that is not modified at the terminals has a weight average molecular weight in the range of 500 to 5,000, and is therefore relatively low molecular weight, so that the heat resistance of the cured product produced from the resin composition containing the polyphenylene ether tends to decrease.
  • the modified polyphenylene ether compound (A1) has an unsaturated double bond at the terminal, and therefore the heat resistance of the cured product produced from the composition (X) containing the modified polyphenylene ether compound (A1) is high.
  • the weight average molecular weight of the modified polyphenylene ether compound (A1) is in the range of 500 to 5,000, and is therefore relatively low molecular weight, so that the moldability of the composition (X) is improved.
  • the weight average molecular weight of the modified polyphenylene ether compound (A1) is in the range of 500 to 5,000, the heat resistance of the cured product of the composition (X) is improved, and the moldability of the composition (X) is also improved.
  • the average number of substituents having a carbon-carbon unsaturated double bond (number of terminal functional groups) per molecule of the modified polyphenylene ether compound (A1) is not particularly limited, but specifically, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3.
  • the number of terminal functional groups is 1 or more, the heat resistance of the cured product of the composition (X) can be further improved.
  • the number of terminal functional groups is 5 or less, the reactivity of the composition (X) is easily adjusted, and as a result, the fluidity of the composition (X) is increased and the storage stability of the composition (X) can be increased.
  • the fluidity of the composition (X) is sufficiently increased, so that the occurrence of voids in the cured product of the composition (X) during the preparation of a multilayer printed wiring board is easily suppressed.
  • This can increase the reliability of the wiring board containing the cured product of the composition (X).
  • the "reliability of the wiring board” means insulation reliability.
  • a wiring board containing a cured product of a resin composition with many voids can absorb water, which tends to impair the insulation reliability of the wiring board.
  • a wiring board containing a cured product of the composition (X) of the present disclosure has reduced generation of voids in the cured product, and therefore tends to absorb less water. This can increase the insulation reliability of a wiring board containing a cured product of the composition (X).
  • the number of terminal functional groups of the modified polyphenylene ether compound (A1) may be a numerical value representing the average number of substituents per molecule of all modified polyphenylene ether compounds (A1) present in 1 mole of the modified polyphenylene ether compound (A1).
  • the number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound (A1) and calculating the reduction from the number of hydroxyl groups of the polyphenylene ether before modification.
  • the reduction from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups.
  • the number of hydroxyl groups remaining in the modified polyphenylene ether compound (A1) can be determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of the modified polyphenylene ether compound (A1) and measuring the UV absorbance of the mixed solution.
  • a quaternary ammonium salt tetraethylammonium hydroxide
  • the intrinsic viscosity of the modified polyphenylene ether compound (A1) is not particularly limited, but specifically, it is preferably 0.03 dl/g or more and 0.12 dl/g or less, more preferably 0.04 dl/g or more and 0.11 dl/g or less, and even more preferably 0.06 dl/g or more and 0.095 dl/g or less.
  • the intrinsic viscosity is 0.03 dl/g or more, the weight average molecular weight of the modified polyphenylene ether compound (A1) is easily increased, and the dielectric constant and dielectric tangent of the cured product of the composition (X) can be particularly reduced.
  • the viscosity of the composition (X) can be easily adjusted, and the fluidity of the composition (X) can be ensured. This can improve the moldability of the composition (X). That is, when the intrinsic viscosity of the modified polyphenylene ether compound (A1) is within the range of 0.03 dl/g or more and 0.12 dl/g or less, the dielectric constant and dielectric tangent of the cured product of the composition (X) can be reduced, while the moldability of the composition (X) can be improved.
  • the intrinsic viscosity of the modified polyphenylene ether compound (A1) is the intrinsic viscosity measured in methylene chloride at 25°C, and more specifically, is the value measured, for example, with a viscometer for a 0.18 g/45 ml methylene chloride solution (liquid temperature 25°C).
  • a viscometer for example, the AVS500 Visco System manufactured by Schott Corporation, etc. is used.
  • the modified polyphenylene ether compound (A1) may contain, for example, at least one of the modified polyphenylene ether compound (A1-1) represented by the following formula (7) and the modified polyphenylene ether compound (A1-2) represented by the following formula (8).
  • the polyphenylene ether compound (A) may contain either one of the modified polyphenylene ether compound (A1-1) represented by the following formula (7) and the modified polyphenylene ether compound (A1-2) represented by the following formula (8), or may contain both the modified polyphenylene ether compound (A1-1) represented by the following formula (7) and the modified polyphenylene ether compound (A1-2) represented by the following formula (8).
  • R 9 to R 16 and R 17 to R 24 each independently represent 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.
  • X 1 and X 2 each independently represent a substituent having a carbon-carbon unsaturated double bond.
  • a and B each represent a repeating unit represented by the following formula (9) and formula (10), respectively.
  • Y represents a linear, branched, or cyclic hydrocarbon group having 20 or less carbon atoms.
  • R 25 to R 28 and R 29 to R 32 each independently represent 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 25 to R 28 and R 29 to R 32 are each independent as described above. That is, R 25 to R 28 and R 29 to R 32 may be the same group or different groups. Furthermore, R 25 to R 28 and R 29 to R 32 represent 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. Among these, a hydrogen atom and an alkyl group are preferred. Furthermore, R 25 to R 32 may be the same as R 5 to R 8 in the above formula (6).
  • m and n each represent 0 or more and 20 or less, as described above. It is also preferable that m and n represent a numerical value such that the sum of m and n is 1 or more and 30 or less. Therefore, it is more preferable that m represents 0 or more and 20 or less, n represents 0 or more and 20 or less, and the sum of m and n represents 1 or more and 30 or less.
  • Y is, as described above, a linear, branched, or cyclic hydrocarbon group having 20 or less carbon atoms.
  • Examples of Y include a group represented by the following formula (11).
  • R 33 and R 34 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group include a methyl group.
  • the group represented by the above formula (11) include a methylene group, a methylmethylene group, and a dimethylmethylene group, and among these, a dimethylmethylene group is preferred.
  • X1 and X2 are each independent.
  • X1 and X2 are, for example, a substituent having a carbon-carbon unsaturated double bond.
  • Each of X1 and X2 is, for example, a substituent represented by the above formula (3) or a substituent represented by the above formula (4).
  • X1 and X2 may be the same or different substituents.
  • polyphenylene ether compound (A1-1) represented by the above formula (7) is the modified polyphenylene ether compound (A1-11) represented by the following formula (12).
  • polyphenylene ether compound (A1-2) represented by the above formula (8) include the modified polyphenylene ether compound (A1-21) represented by the following formula (13) and the modified polyphenylene ether compound (A1-22) represented by the following formula (14).
  • m and n are the same as m and n in the above formulas (9) and (10).
  • R 1 to R 3 , p and Z are the same as R 1 to R 3 , p and Z in the above formula (3).
  • Y is the same as Y in the above formula (8).
  • R 4 is the same as R 4 in the above formula (4).
  • the following describes a method for synthesizing the modified polyphenylene ether compound (A1). Specifically, one example of such a method is to react a polyphenylene ether with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded to the polyphenylene ether.
  • the raw material polyphenylene ether is not particularly limited as long as it can ultimately synthesize a specified modified polyphenylene ether compound (A1).
  • Specific examples include polyphenylene ethers composed of 2,6-dimethylphenol and at least one of a difunctional phenol and a trifunctional phenol, and those containing polyphenylene ether as the main component, such as poly(2,6-dimethyl-1,4-phenylene oxide).
  • a bifunctional phenol is a phenolic compound having two phenolic hydroxyl groups in the molecule, such as tetramethylbisphenol A.
  • a trifunctional phenol is a phenolic compound having three phenolic hydroxyl groups in one molecule.
  • the modified polyphenylene ether compound (A1) can be synthesized by the method described above. Specifically, the polyphenylene ether described above and a compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded are dissolved in a solvent and stirred. By doing so, the polyphenylene ether reacts with the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and the modified polyphenylene ether compound (A1) used in this embodiment is obtained.
  • the alkali metal hydroxide removes hydrogen halide from the phenol group of the polyphenylene ether and the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and as a result, the substituent having a carbon-carbon unsaturated double bond bonds to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of the polyphenylene ether.
  • the alkali metal hydroxide is not particularly limited as long as it can act as a dehalogenating agent, but examples include sodium hydroxide. Furthermore, the alkali metal hydroxide is usually used in the form of an aqueous solution, specifically, as an aqueous sodium hydroxide solution.
  • Reaction conditions such as reaction time and reaction temperature vary depending on the type of substituent having a carbon-carbon unsaturated double bond and the compound to which a halogen atom is bonded, and are not particularly limited as long as the above-mentioned reaction proceeds favorably.
  • the reaction temperature is preferably from room temperature (20°C) to 100°C, and more preferably from 30°C to 100°C.
  • the reaction time is preferably from 0.5 hours to 20 hours, and more preferably from 0.5 hours to 10 hours.
  • the solvent used in the reaction of polyphenylene ether with a compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom is not particularly limited, so long as it can dissolve polyphenylene ether and a compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom and does not inhibit the reaction of polyphenylene ether with a compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom.
  • Specific examples include toluene, etc.
  • the reaction between polyphenylene ether and a compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded is preferably carried out in the presence of not only an alkali metal hydroxide but also a phase transfer catalyst.
  • the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. It is believed that the above reaction proceeds more smoothly by doing so. This is believed to be due to the following.
  • the phase transfer catalyst is a catalyst that has the function of incorporating an alkali metal hydroxide, is soluble in both a polar solvent phase such as water and a non-polar solvent phase such as an organic solvent, and can move between these phases.
  • phase transfer catalyst is not particularly limited, but examples include quaternary ammonium salts such as tetra-n-butylammonium bromide.
  • composition (X) contains the modified polyphenylene ether compound (A1) obtained as described above.
  • the composition (X) contains the maleimide compound (B) having a maleimide group in the molecule, which can increase the glass transition temperature of a cured product of the composition (X).
  • the maleimide compound (B) may contain only a single compound, or may contain two or more types of compounds.
  • Examples of the maleimide compound (B) include monofunctional maleimide compounds having one maleimide group in the molecule, and polyfunctional maleimide compounds having two or more maleimide groups in the molecule.
  • Examples of monofunctional maleimide compounds having one maleimide group in the molecule include chlorophenylmaleimides such as o-chlorophenylmaleimide, methylphenylmaleimide such as o-methylphenylmaleimide, hydroxyphenylmaleimide such as p-hydroxyphenylmaleimide, carboxyphenylmaleimide such as p-carboxyphenylmaleimide, N-dodecylmaleimide, and phenylmethanemaleimide.
  • chlorophenylmaleimides such as o-chlorophenylmaleimide
  • methylphenylmaleimide such as o-methylphenylmaleimide
  • hydroxyphenylmaleimide such as p-hydroxyphenylmaleimide
  • carboxyphenylmaleimide such as p-carboxyphenylmaleimide
  • N-dodecylmaleimide N-dodecylmaleimide
  • polyfunctional maleimide compounds having two or more maleimide groups in the molecule include 4,4'-diphenylmethane bismaleimide, bisphenol A bis(4-maleimidophenyl ether), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and polyphenylmethane maleimide.
  • the maleimide compound (B) contains polyphenylmethane maleimide.
  • the dielectric constant and dielectric loss tangent of the composition (X) are easily reduced, and the glass transition temperature of the cured product of the composition (X) can be increased.
  • the maleimide compound (B) contains a maleimide compound (B1) (hereinafter simply referred to as maleimide compound (B1)) represented by the following formula (15).
  • maleimide compound (B1) represented by the following formula (15).
  • the dielectric constant and dielectric tangent of the composition (X) are easily reduced, and the glass transition temperature of the cured product of the composition (X) can be increased.
  • s indicates the number of repeating units, which is the average value of the degree of polymerization, and is 1 or more and 5 or less.
  • the maleimide compound (B1) contains a plurality of maleimide compounds represented by the above formula (15), and in these plurality of maleimide compounds, the average value of the number of repeating units in the above formula (15) may be 1 or more and 5 or less.
  • the maleimide compound (B1) may contain a monofunctional maleimide compound represented by a formula in which s is 0 in the above formula (15), or may contain a maleimide compound represented by a formula in which s is 6 or more in the above formula (15).
  • R 35 to R 38 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • a hydrogen atom is preferable.
  • the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a neopentyl group.
  • R 35 to R 38 represent groups possessed by an aromatic ring directly bonded to the maleimide ring. More specifically, R 35 and R 36 are each bonded to any of the carbon atoms possessed by an aromatic ring directly bonded to the maleimide ring that is not included in the repeating unit in the above formula (15). And, R 37 and R 38 are each bonded to any of the carbon atoms possessed by an aromatic ring directly bonded to the maleimide ring that is included in the repeating unit in the above formula (15).
  • each of R 37 and R 38 contained in the repeating unit in the above formula (15) is independent for each repeating unit. Therefore, each of R 37 and R 38 contained in the repeating unit in the above formula (15) may be the same or different for each repeating unit.
  • the number average molecular weight of the maleimide compound (B1) is preferably 150 or more and 2,000 or less. In this case, the glass transition temperature of the cured product of the composition (X) can be further increased.
  • the number average molecular weight of the maleimide compound (B1) is more preferably 400 or more and 1,300 or less. In addition, the weight average molecular weight of the maleimide compound (B1) is preferably 150 or more and 2,500 or less. In this case, the glass transition temperature of the cured product of the composition (X) can be further increased.
  • the weight average molecular weight of the maleimide compound (B1) is more preferably 400 or more and 1,500 or less.
  • the number average molecular weight and weight average molecular weight of the maleimide compound (B1) may be measured by a general molecular weight measurement method, and specifically, the value measured by gel permeation chromatography (GPC) and converted into polystyrene may be mentioned.
  • GPC gel permeation chromatography
  • the composition (X) contains the curing agent (C).
  • the curing agent (C) also contains a phenol compound (C1) (hereinafter, also simply referred to as the phenol compound (C1)) having at least one of a group represented by the following formula (1) and a group represented by the following formula (2) in one molecule.
  • the curing agent (C) preferably further contains a methacrylate compound (C2).
  • the curing agent (C) contains the phenol compound (C1).
  • the composition (X) contains the phenol compound (C1)
  • the heat resistance of the cured product of the composition (X) is improved, and the adhesion of the cured product of the composition (X) to metals is also improved.
  • the composition (X) contains such a phenol compound (C1)
  • the water absorption of the cured product of the composition (X) is easily reduced, and this can suppress deterioration of the dielectric constant and dielectric loss tangent of the cured product of the composition (X).
  • composition (X) containing a polyphenylene ether compound (A) and a maleimide compound (B) and a phenol compound (C1) when cured, the phenol compound (C1) can promote the formation of a complex between the polyphenylene ether compound (A) and the maleimide compound (B), so that a complex between the polyphenylene ether compound (A) and the maleimide compound (B) is easily formed. It is presumed that this improves the heat resistance and adhesion to metals of the cured product of the composition (X).
  • the ease of forming a complex between the polyphenylene ether compound (A) and the maleimide compound (B) can be confirmed by measuring the loss tangent (tan ⁇ ) of the cured product of the resin composition using a dynamic viscoelasticity measuring device (DMA). Specifically, in the case of a resin composition that is unlikely to form a complex between the polyphenylene ether compound (A) and the maleimide compound (B) when cured, a graph of the loss tangent obtained by dynamic viscoelasticity measurement of the cured product shows a broad maximum peak or multiple peaks.
  • DMA dynamic viscoelasticity measuring device
  • composition (X) of the present disclosure that is likely to form a complex between the polyphenylene ether compound (A) and the maleimide compound (B) when cured, a graph of the loss tangent obtained by dynamic viscoelasticity measurement of the cured product shows a sharp single maximum peak.
  • the phenol compound (C1) has at least one of the substituents represented by the above formula (1) and the substituents represented by the above formula (2) in one molecule.
  • the phenol compound (C1) has at least one of an allyl group and a 1-propenyl group in one molecule.
  • the phenol compound (C1) may have both an allyl group and a 1-propenyl group in one molecule.
  • the total number of allyl groups and 1-propenyl groups contained in the phenolic compound (C1) is preferably 2 or more per molecule on average.
  • the phenolic compound (C1) preferably has at least two groups selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) in one molecule.
  • the phenolic compound (C1) preferably contains a phenolic compound (C1-0) having at least two groups selected from the group consisting of the groups represented by the above formula (1) and the above formula (2) in one molecule.
  • the heat resistance of the cured product of the composition (X) is further improved, and the adhesion of the cured product of the composition (X) to metals is further improved.
  • the phenol compound (C1) preferably includes a phenol compound (C1-1) (hereinafter, sometimes simply referred to as phenol compound (C1-1)) having a chemical structure represented by the following formula (16):
  • R 39 to R 41 in the above formula (16) are each independent of one another.
  • R 39 is bonded to the oxygen atom in the above formula (16) and represents an allyl group, a 1-propenyl group, or a hydrogen atom.
  • R 40 is bonded to any of the carbon atoms of the aromatic ring in the above formula (16) and represents an allyl group, a 1-propenyl group, or a hydrogen atom. At least one of R 39 and R 40 represents an allyl group or a 1-propenyl group. That is, the phenol compound (C1-1) has at least one of an allyl group and a 1-propenyl group in one molecule.
  • R 41 is bonded to a carbon atom of the aromatic ring in the above formula (16) and represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, or a phenyl group.
  • the phenol compound (C1-1) may have other substituents in addition to the allyl group or 1-propenyl group in one molecule.
  • the heat resistance of the cured product of the composition (X) is more likely to be improved, and the adhesion of the cured product of the composition (X) to metal is more likely to be improved.
  • the phenolic compound (C1) contains the phenolic compound (C1-1)
  • the water absorption rate of the cured product of the composition (X) is more likely to be reduced, and deterioration of the dielectric constant and dielectric tangent of the cured product of the composition (X) can be suppressed.
  • the phenolic compound (C1-1) preferably contains a polyfunctional phenolic compound (C1-2) (hereinafter also simply referred to as phenolic compound (C1-2)) having two or more chemical structures represented by the above formula (16) in one molecule.
  • the phenolic compound (C1) preferably contains a phenolic compound (C1-2).
  • each of the chemical structures represented by the above formula (16) is independent of each other. That is, in the phenolic compound (C1-2), each of the chemical structures represented by the above formula (16) may be the same or different.
  • a linking group means a divalent organic group that links any one of the carbon atoms of an aromatic ring in one of the two chemical structures represented by the above formula (16) in the phenolic compound (C1-2) to any one of the carbon atoms of an aromatic ring in the other chemical structure represented by the above formula (16).
  • the phenol compound (C1-2) when the phenolic compound (C1-2) has a linking group in one molecule, any one of the carbon atoms of the aromatic ring in the chemical structure represented by the above formula (16) is bonded to the linking group.
  • the phenol compound (C1-2) also includes two chemical structures represented by the above formula (16) in which one of the carbon atoms in the aromatic ring in one of the chemical structures represented by the above formula (16) is directly bonded to one of the carbon atoms in the aromatic ring in the other chemical structure represented by the above formula (16) without a linking group.
  • the phenol compound (C1-2) having the chemical structure represented by the above formula (16) may, for example, have only one linking group in one molecule, or may have two or more linking groups. Furthermore, when the phenol compound (C1-2) has two or more linking groups, those linking groups are independent of each other. In other words, each of the two or more linking groups that the phenol compound (C1-2) has may have the same structure, or may have different structures.
  • linking group include the chemical structures represented by the following formulas (17) to (22).
  • R 42 and R 43 each independently represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a trifluoromethyl group.
  • u represents an integer of 0 to 35.
  • R 44 and R 46 are each independently a substituent containing a carbonate ester group.
  • R 44 and R 46 are particularly preferably a chemical structure represented by the following formula (23).
  • R 45 represents a cyclic aliphatic hydrocarbon group.
  • the cyclic aliphatic hydrocarbon group may be a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group.
  • the cyclic aliphatic hydrocarbon group preferably does not have an unsaturated bond.
  • the number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 6 to 20.
  • the cyclic aliphatic hydrocarbon group may have a substituent such as an allyl group, an alkyl group, or a halogen atom bonded thereto.
  • the cyclic aliphatic hydrocarbon group is particularly preferably a chemical structure represented by the following formula (24).
  • each of R 44 and R 45 contained in the repeating unit in the above formula (22) is independent for each repeating unit. That is, each of R 44 and R 45 contained in the repeating unit may be the same or different for each repeating unit.
  • R 47 and R 48 are each independent. Examples of R 47 and R 48 include a hydrogen atom, an allyl group, or a 1-propenyl group. It is preferable that R 47 and R 48 are the same group. It is preferable that when R 47 and R 48 are hydrogen atoms, R 39 is an allyl group or a 1-propenyl group, and R 40 is a hydrogen atom. It is preferable that when either one of R 47 and R 48 is an allyl group or a 1-propenyl group, R 39 is a hydrogen atom, and R 40 is an allyl group or a 1-propenyl group.
  • the phenol compound (C1-2) contains a phenol compound (C1-21) represented by the following formula (25) (hereinafter, simply referred to as the phenol compound (C1-21)).
  • the phenol compound (C1-21) has a chemical structure represented by the above formula (16) and a chemical structure represented by the above formula (21).
  • R 39 to R 41 are the same as R 39 to R 41 in the above formula (16).
  • R 42 to R 43 are the same as R 42 to R 43 in the above formula (21).
  • R 39 is preferably a hydrogen atom
  • R 40 is an allyl group or a 1-propenyl group
  • R 41 is preferably a hydrogen atom.
  • the phenol compound (C1-21) having a chemical structure represented by the above formula (25) has a bisphenol group having two aromatic rings, and is preferably a bisphenol derivative in which both of the two aromatic rings in the bisphenol group are mono-substituted with an allyl group or a 1-propenyl group.
  • the bisphenol group include a bisphenol A group, a bisphenol AP group, a bisphenol AF group, a bisphenol BP group, a bisphenol E group, and a bisphenol F group, and the like, with the bisphenol A group being preferred.
  • the phenol compound (C1-2) contains a phenol compound (C1-22) represented by the following formula (26) (hereinafter, also simply referred to as phenol compound (C1-22)).
  • the phenol compound (C1-22) has a chemical structure represented by the above formula (16) and a chemical structure represented by the above formula (21). Note that the phenol compound (C1-22) contains the chemical structure represented by the above formula (21) in which R 43 is a hydrogen atom and R 44 is a hydrogen atom, in the repeating unit of the following formula (26).
  • x represents an integer of 2 or more and 4 or less. In addition, x is preferably 3.
  • R 39 to R 40 are the same as R 39 to R 40 in the above formula (16). Since R 41 is a hydrogen atom, it is omitted in the above formula (26).
  • x in the above formula (26) is 2 or more, each of R 39 and R 40 contained in the repeating unit in the above formula (26) is independent for each repeating unit. That is, each of R 39 and R 40 contained in the repeating unit may be the same or different for each repeating unit.
  • R 39 and R 40 are an allyl group or a 1-propenyl group, and the other is a hydrogen atom.
  • the phenol compound (C1-2) preferably contains a phenol compound (C1-23) (hereinafter also simply referred to as phenol compound (C1-23)) represented by the following formula (27), and also preferably contains a phenol compound (C1-24) (hereinafter also simply referred to as phenol compound (C1-24)) represented by the following formula (28). That is, the phenol compound (C1-2) preferably contains at least one of the phenol compound (C1-23) and the phenol compound (C1-24). Both the phenol compound (C1-23) and the phenol compound (C1-24) have a chemical structure represented by the above formula (16) and a chemical structure represented by the above formula (17).
  • each of R 39 to R 41 in the formula (27) to the formula (28) is the same as R 39 to R 41 in the formula (16).
  • each of y in the formula (27) and z in the formula (28) is 2 or more, each of R 39 to R 41 contained in the repeating unit in the formula (27) to the formula (28) is independent for each repeating unit. That is, each of R 39 to R 41 contained in the repeating unit may be the same or different for each repeating unit.
  • it is preferable that one of R 39 and R 40 is an allyl group or a 1-propenyl group, and the other is a hydrogen atom.
  • the phenol compound (C1-2) preferably contains a phenol compound (C1-25) (hereinafter also simply referred to as phenol compound (C1-25)) represented by the following formula (29), and also preferably contains a phenol compound (C1-26) (hereinafter also simply referred to as phenol compound (C1-26)) represented by the following formula (30). That is, the phenol compound (C1-2) preferably contains at least one of the phenol compound (C1-25) and the phenol compound (C1-26). Both the phenol compound (C1-25) and the phenol compound (C1-26) have a chemical structure represented by the above formula (16) and a chemical structure represented by the above formula (17).
  • y represents an integer of 1 or more and 3 or less.
  • z represents an integer of 0 or more and 15 or less.
  • R 39 to R 41 are the same as R 39 to R 41 in the above formula (16), respectively.
  • R 49 is bonded to an aromatic ring contained in the chemical structure represented by the above formula (16) in the above formulas (29) to (30), and represents a hydrogen atom or an organic group.
  • the organic group include an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, an aryl group such as a phenyl group, a hydroxy group, and an aldehyde group.
  • R 39 to R 41 and R 49 contained in the repeating units in formulas (29) to (30) are each independent of each other. That is, R 39 to R 41 and R 49 contained in the repeating units may be the same or different for each repeating unit.
  • R 39 and R 40 is an allyl group or a 1-propenyl group, and the other is a hydrogen atom.
  • composition (X) By including the phenolic compound (C1) as described above in composition (X), the adhesion of the cured product to metal can be improved, and the heat resistance of the cured product can also be improved. In addition, by including the phenolic compound (C1) as described above in composition (X), the cured product of composition (X) can have reduced water absorption, which can suppress deterioration of the dielectric constant and dielectric tangent due to water absorption.
  • phenol compound (C1) can be used as the phenol compound (C1).
  • examples of such commercially available products include diallyl bisphenol A (DABPA manufactured by Daiwa Chemical Industry Co., Ltd.), biphenylene resin (SBA series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl phenol resin (APG series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl phenol resin (LVA series manufactured by Gun-ei Chemical Industry Co., Ltd.), propenylated biphenylene resin (BPN series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl ether phenol resin (FTC-AE series manufactured by Gun-ei Chemical Industry Co., Ltd.), and polyfunctional allyl phenol resin (FATC series manufactured by Gun-ei Chemical Industry Co., Ltd.).
  • DABPA diallyl bisphenol A
  • SBA manufactured by Gun-ei Chemical Industry Co., Ltd.
  • allyl phenol resin APG series manufactured by Gun-ei Chemical Industry Co.
  • the curing agent (C) preferably contains the methacrylate compound (C2).
  • the composition (X) contains the methacrylate compound (C2), the heat resistance of the cured product of the composition (X) can be increased, and the flexibility of the cured product of the composition (X) can be increased.
  • the methacrylate compound (C2) is preferably a polyfunctional methacrylate having two or more methacryloyl groups in one molecule.
  • the heat resistance of the cured product of the composition (X) can be further improved.
  • a specific example of a polyfunctional methacrylate having two or more methacryloyl groups in one molecule is tricyclodecane dimethanol dimethacrylate (DCP).
  • the composition (X) contains the inorganic filler (D) as described above.
  • the inorganic filler (D) contains the inorganic filler (D1) surface-treated with a hydrophobic silane coupling agent as described above. In this case, the moldability of the composition (X) is improved.
  • the inorganic filler (D) also contains the inorganic filler (D2) surface-treated with a hydrophilic silane coupling agent as described above. In this case, the adhesion of the cured product of the composition (X) to the metal is improved.
  • the composition (X) contains the inorganic filler (D1) and the inorganic filler (D2) at the same time, thereby improving the moldability of the composition (X) and improving the adhesion of the cured product of the composition (X) to the metal.
  • the hydrophobic silane coupling agent means a silane coupling agent having a hydrophobic functional group
  • the hydrophilic silane coupling agent means a silane coupling agent having a hydrophilic functional group.
  • Each of the inorganic fillers (D1) and (D2) is, for example, an untreated inorganic filler that has been surface-treated with a hydrophobic silane coupling agent and a hydrophilic silane coupling agent, respectively.
  • the untreated inorganic filler include silica such as spherical silica, metal oxides such as alumina, titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as talc, aluminum borate, and barium sulfate, and carbonates such as calcium carbonate.
  • the untreated inorganic filler is preferably at least one selected from the group consisting of silica, mica, and talc, and more preferably spherical silica.
  • the untreated inorganic filler may be used alone or in combination of two or more types.
  • "untreated" means that the surface of the inorganic filler has not been chemically treated.
  • the hydrophobic silane coupling agent used to prepare the inorganic filler (D1) includes, for example, a silane coupling agent having at least one hydrophobic functional group selected from the group consisting of a vinyl group, a methacryl group, a styryl group, and the like.
  • silane coupling agents having a vinyl group include vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
  • silane coupling agents having a methacryl group include methacryloxypropylmethyldimethoxysilane, and the like.
  • Examples of silane coupling agents having a styryl group include p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like.
  • one type of hydrophobic silane coupling agent may be used alone, or two or more types may be used.
  • the hydrophilic silane coupling agent used to prepare the inorganic filler (D2) includes, for example, a silane coupling agent having at least one hydrophilic functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, and the like.
  • silane coupling agents having an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
  • silane coupling agents having an epoxy group examples include glycidoxypropyltriethoxysilane, and the like.
  • silane coupling agents having an isocyanate group examples include isocyanatepropyltriethoxysilane, and the like.
  • the hydrophilic silane coupling agent may be used alone or in combination of two or more types.
  • the composition (X) may contain other components (hereinafter also referred to as additives) in addition to the above-mentioned components, as necessary, within the scope of not impairing the effects of the present invention.
  • the additives contained in the composition (X) may contain at least one component selected from the group consisting of, for example, a reaction initiator, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a dye or pigment, a polymerization inhibitor, and a lubricant.
  • the composition (X) may also contain other thermosetting resins. Examples of such thermosetting resins include epoxy resins.
  • composition (X) The contents of the components contained in the composition (X) will be described.
  • the content of the polyphenylene ether compound (A) is preferably 10% by mass or more and 50% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C). In this case, the dielectric constant and dielectric tangent of the cured product of the composition (X) can be further reduced, and the heat resistance of the cured product of the composition (X) can be further improved.
  • the content of the polyphenylene ether compound (A) is preferably 15% by mass or more and 40% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C), and is more preferably 20% by mass or more and 30% by mass or less.
  • the content of the modified polyphenylene ether compound (A1) is preferably 10 mass% or more based on the entire polyphenylene ether compound (A).
  • the dielectric constant and dielectric dissipation factor of the cured product of the composition (X) are likely to be further reduced, and the heat resistance of the cured product of the composition (X) is likely to be further improved.
  • the content of the modified polyphenylene ether compound (A1) is more preferably 40 mass% or more based on the entire polyphenylene ether compound (A), and even more preferably 100 mass%.
  • the content of the maleimide compound (B) is preferably 20% by mass or more and 75% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C). In this case, the heat resistance of the cured product of the composition (X) can be increased while the dielectric constant and the dielectric loss tangent of the cured product of the composition (X) can be reduced.
  • the content of the maleimide compound (B) is more preferably 30% by mass or more and 70% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C), and is even more preferably 40% by mass or more and 60% by mass or less.
  • the maleimide compound (B) preferably contains polyphenylmethane maleimide, and also preferably contains the maleimide compound (B1) represented by the above formula (15).
  • the content of the maleimide compound (B1) is preferably 10 mass% or more based on the total amount of the maleimide compound (B). In this case, the glass transition temperature of the cured product of the composition (X) can be further increased.
  • the content of the maleimide compound (B1) is more preferably 20 mass% or more based on the total amount of the maleimide compound (B), and even more preferably 30 mass% or more.
  • the content of the maleimide compound represented by the formula (15) where s is 1 is preferably 30% by mass or more and 100% by mass or less based on the total amount of the maleimide compound (B1).
  • the water absorption of the cured product of the composition (X) can be reduced, and the glass transition temperature of the cured product of the composition (X) can be particularly increased.
  • the content of the maleimide compound represented by the formula (15) where s is 1 is 50% by mass or more and 100% by mass or less based on the total amount of the maleimide compound (B1).
  • the content of the maleimide compound represented by the above formula (15) where s is 2 or more relative to the total amount of the maleimide compound (B1) is preferably 30% by mass or more. In this case, the water absorption of the cured product of the composition (X) can be particularly reduced. It is more preferable that the content of the maleimide compound represented by the above formula (15) where s is 2 or more relative to the total amount of the maleimide compound (B1) is 30% by mass or more and 100% by mass or less.
  • the content of the phenol compound (C1) is preferably 5% by mass or more and 40% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C). In this case, the adhesion of the cured product of the composition (X) to metal can be improved while the heat resistance of the cured product of the composition (X) can be improved.
  • the content of the phenol compound (C1) is more preferably 10% by mass or more and 30% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C), and is even more preferably 10% by mass or more and 20% by mass or less.
  • the content of the methacrylate compound (C2) is preferably 5% by mass or more and 20% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C). In this case, the heat resistance of the cured product of the composition (X) is particularly likely to be increased, and the flexibility of the composition (X) can be particularly increased.
  • the content of the methacrylate compound (C2) is more preferably 6% by mass or more and 10% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C).
  • the content of the inorganic filler (D) is preferably 150 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C).
  • the adhesion of the cured product of the composition (X) to metal can be further improved, and the moldability of the composition (X) can be further improved.
  • the total content of the inorganic filler (D1) and the inorganic filler (D2) is more preferably 200 parts by mass or more and 370 parts by mass or less, and even more preferably 250 parts by mass or more and 350 parts by mass or less, per 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C).
  • the content of inorganic filler (D1) is 20% by mass or more and 80% by mass or less with respect to the total content of inorganic filler (D1) and inorganic filler (D2).
  • the content of inorganic filler (D) is within the above range, the adhesion of the cured product of composition (X) to metal is improved, and the moldability of composition (X) is improved.
  • the content of inorganic filler (D1) is preferably 30% by mass or more and 70% by mass or less based on the total content of inorganic filler (D1) and inorganic filler (D2). If the content of inorganic filler (D1) is within the above range, the adhesion of the cured product of composition (X) to metal can be further improved, and the moldability of composition (X) can be further improved.
  • the total content of inorganic filler (D1) and inorganic filler (D2) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total amount of inorganic filler (D).
  • composition (X) The physical properties of the composition (X) and the cured product of the composition (X) will be described.
  • the cured product of composition (X) can have high heat resistance.
  • the glass transition temperature of the cured product of composition (X) is preferably 240°C or higher, more preferably 250°C or higher, and even more preferably 255°C or higher.
  • the cured product of composition (X) can have high adhesion to metals.
  • the peel strength of the cured product of composition (X) is preferably 0.50 kN/m or more, and more preferably 0.53 kN/m or more.
  • composition (X) can have good moldability. Specifically, when composition (X) is cured, the generation of voids in the cured product can be suppressed. In the present disclosure, voids generated in composition (X) can be confirmed visually.
  • the method for preparing the composition (X) is not particularly limited, but examples thereof include a method in which the polyphenylene ether compound (A), the maleimide compound (B), the curing agent (C), the inorganic filler (D1), and the inorganic filler (D2) are mixed to a predetermined content. If necessary, other components may be appropriately added and mixed in addition to the polyphenylene ether compound (A), the maleimide compound (B), the curing agent (C), the inorganic filler (D1), and the inorganic filler (D2).
  • composition (X) may contain an organic solvent. That is, composition (X) is preferably used as a varnish-like resin composition containing an organic solvent. Note that a varnish-like resin composition containing an organic solvent is one in which an organic solvent is further added in addition to the components contained in composition (X) described above.
  • Such a varnish-like resin composition can be prepared as follows. First, among the components contained in the composition (X), those that can be dissolved in an organic solvent are added to the organic solvent and dissolved while stirring to prepare a mixture. This mixture may also be prepared by stirring while heating. Next, a component that is not soluble in an organic solvent is added to the mixture and dispersed until a desired dispersion state is reached using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like, to prepare a varnish-like resin composition.
  • the organic solvent used here is preferably one that can dissolve, for example, the polyphenylene ether compound (A), the maleimide compound (B), the curing agent (C), and the like, and does not inhibit the curing reaction of the composition (X).
  • organic solvents include, for example, toluene and methyl ethyl ketone (MEK).
  • composition (X) it is possible to obtain a prepreg 1, a metal-clad laminate 11, a wiring board 21, a resin-coated metal foil 31, and a resin-coated film 41.
  • the resin layer 2 of the prepreg 1 contains at least one of the composition (X) and a semi-cured product of the composition (X).
  • the insulating layer 12 of the metal-clad laminate 11 contains a cured product of the composition (X).
  • the insulating layer 22 of the wiring board 21 contains a cured product of the composition (X).
  • the resin layer 32 of the resin-attached metal foil 31 contains at least one of the composition (X) and a semi-cured product of the composition (X).
  • the resin layer 42 of the resin-attached film 41 contains at least one of the composition (X) and a semi-cured product of the composition (X).
  • the semi-cured product refers to composition (X) in a partially cured state to the extent that it can be further cured.
  • the semi-cured product refers to composition (X) in a semi-cured state, that is, composition (X) in a B-stage.
  • composition (X) according to this embodiment when composition (X) according to this embodiment is heated, the viscosity gradually decreases at the beginning of heating, but then the viscosity gradually increases as the solvent contained in composition (X) evaporates and curing of composition (X) begins.
  • semi-cured refers to the state between when the viscosity starts to increase and when it is completely cured.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present disclosure.
  • the prepreg 1 includes a resin layer 2, as shown in FIG. 1.
  • the resin layer 2 includes at least one of composition (X) and a semi-cured product of composition (X).
  • the resin layer 2 further includes a fibrous base material 3.
  • the prepreg 1 may include a resin layer 2 in which the fibrous base material 3 is impregnated with at least one of composition (X) and a semi-cured product of composition (X).
  • the prepreg 1 obtained using the composition (X) may contain a semi-cured product of the composition (X) as described above, or may contain the uncured composition (X) itself, i.e., the uncured product of the composition (X). That is, the prepreg 1 may be a prepreg 1 having a resin layer 2 containing a semi-cured product of the composition (X) (B-stage composition (X)) and a fibrous substrate 3, or a prepreg 1 having a resin layer 2 containing an uncured product of the composition (X) (A-stage composition (X)) and a fibrous substrate 3.
  • the prepreg 1 may include a resin layer 2 in which the fibrous substrate 3 is impregnated with at least one of the composition (X) and the semi-cured product of the composition (X).
  • the composition (X) is prepared in a varnish form and used. That is, when the fibrous substrate 3 is impregnated with at least one of the composition (X) and the semi-cured product of the composition (X), it is preferable that a varnish-like resin composition containing the composition (X) and an organic solvent is used.
  • the resin layer 2 may include a varnish-like resin composition containing the composition (X) and an organic solvent. Note that such a varnish-like resin composition is prepared, for example, according to the method described in "3. Method for preparing a resin composition".
  • the fibrous base material 3 include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper.
  • the use of glass cloth can produce a laminate with excellent mechanical strength. It is particularly preferable that the glass cloth has been flattened.
  • a specific example of the flattening process is a method in which the glass cloth is continuously pressed with a press roll at an appropriate pressure to compress the yarns flat.
  • the thickness of the fibrous base material 3 that is generally used is, for example, 0.01 mm or more and 0.3 mm or less.
  • the fibrous substrate 3 is impregnated with the varnish-like resin composition by immersing the fibrous substrate 3 in the varnish-like resin composition or by applying the varnish-like resin composition to the fibrous substrate 3, and it is also possible to repeat the impregnation several times as necessary.
  • the impregnation using several varnish-like resin compositions having different compositions and concentrations it is possible to obtain a resin layer 2 containing the composition (X) or the semi-cured product of the composition (X) with the desired composition and impregnation amount.
  • the organic solvent may be reduced or removed from the resin layer 2 by heating the resin layer 2 produced by impregnating the fibrous base material 3 with a varnish-like resin composition containing the composition (X) and an organic solvent.
  • Conditions for reducing or removing the organic solvent from the resin layer 2 by heating the resin layer 2 include a temperature of, for example, 80°C or higher and 180°C or lower, and a time of, for example, 1 minute or higher and 10 minutes or lower.
  • a prepreg 1 that includes a resin layer 2 that includes at least one of the uncured product of composition (X) (composition (X) in A stage) and the semi-cured product of composition (X) (composition (X) in B stage).
  • an insulating layer 12 of a metal-clad laminate 11 that has improved heat resistance and improved adhesion to metal, or an insulating layer 22 of a wiring board 21, can be produced.
  • the prepreg 1 since the prepreg 1 includes at least one of composition (X) and the semi-cured product of composition (X), its moldability is improved. Therefore, when the prepreg 1 is used to produce the insulating layer 22 of the wiring board 21, the filling property of the prepreg 1 into the circuit pattern can also be improved.
  • the cured product of the prepreg 1 having the resin layer 2 containing at least one of the composition (X) and the semi-cured product of the composition (X) has a low dielectric constant and dielectric tangent, excellent desmear properties, and can suppress surface tack.
  • FIG. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate 11 according to an embodiment of the present disclosure.
  • the metal-clad laminate 11 comprises an insulating layer 12 containing a cured product of composition (X) and a metal foil 13 overlying the insulating layer 12.
  • the insulating layer 12 contains the cured product of the composition (X).
  • the insulating layer 12 may be made of the cured product of the composition (X).
  • the insulating layer 12 may also be made of the cured product of the prepreg 1. That is, the metal-clad laminate 11 includes, for example, the insulating layer 12 including the cured product of the prepreg 1 shown in FIG. 1, and the metal foil 13 overlapping the insulating layer 12.
  • the metal-clad laminate 11 may include another layer in addition to the insulating layer 12 and the metal foil 13.
  • the method for producing the metal-clad laminate 11 includes, for example, producing an insulating layer 12 from a cured product of the composition (X), forming the insulating layer 12 on a metal foil 13, and heating and pressing the insulating layer 12 to produce the metal-clad laminate 11. More specifically, the method for producing the metal-clad laminate 11 includes overlaying a metal foil 13 such as a copper foil on both sides or one side of the insulating layer 12 containing the cured product of the composition (X), and then heating and pressing the metal foil 13 and the insulating layer 12 to form an integrated laminate, thereby producing a metal-clad laminate 11 with the metal foil 13 attached to both sides or one side.
  • a metal foil 13 such as a copper foil
  • the insulating layer 12 may also be produced using the prepreg 1 described above. More specifically, the prepreg 1 is heated and cured to produce the insulating layer 12 containing the cured product of the prepreg 1. Next, a metal foil 13 such as copper foil is laminated on both sides or one side of the insulating layer 12 containing the cured product of the prepreg 1, and the metal foil 13 and the insulating layer 12 are heated and pressurized to form them into an integrated laminate, thereby producing a metal-clad laminate 11 in which the metal foil 13 is attached to both sides or one side of the insulating layer 12 containing the cured product of the prepreg 1.
  • the insulating layer 12 may be produced using a resin-attached metal foil 31 described below. More specifically, the insulating layer 12 of the metal-clad laminate 11 is produced by heating and hardening the resin layer 32 of the resin-attached metal foil 31. In this case, the metal foil 33 of the resin-attached metal foil 31 becomes the metal foil 13 of the metal-clad laminate 11.
  • the insulating layer 12 may be produced using a resin-attached film 41 described below. More specifically, the insulating layer 12 of the metal-clad laminate 11 is produced by heating and hardening the resin layer 42 of the resin-attached film 41.
  • the heating and pressing conditions when producing the metal-clad laminate 11 are preferably set appropriately depending on the thickness of the metal-clad laminate 11 to be produced and the type of resin composition that forms the insulating layer 12.
  • the heating temperature when producing the metal-clad laminate 11 is, for example, 170°C or higher and 230°C or lower.
  • the pressure when producing the metal-clad laminate 11 is, for example, 1.5 MPa or higher and 5.0 MPa or lower.
  • the heating and pressurizing time when producing the metal-clad laminate 11 is, for example, 60 minutes or higher and 150 minutes or lower.
  • the thickness of the metal foil 13 can be appropriately set according to the desired purpose.
  • the metal foil 13 can be 0.2 ⁇ m or more and 70 ⁇ m or less.
  • the metal foil may be a carrier-attached copper foil having a peeling layer and a carrier to improve handling.
  • the thickness of the metal foil 13 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 adhesion between the insulating layer 12 in the metal-clad laminate 11 and the metal foil 13 is good.
  • the peel strength between the insulating layer 12 and the metal foil 13 is preferably 0.5 kN/m or more, and more preferably 0.53 kN/m or more.
  • the metal-clad laminate 11 of the present disclosure comprises an insulating layer 12 containing at least one of the cured product of composition (X) and the cured product of prepreg 1, and a metal foil 13.
  • the cured product of composition (X) can have high adhesion to metals and high heat resistance. Therefore, the insulating layer 12 provided in the metal-clad laminate 11 can have high adhesion to metals and high heat resistance.
  • a wiring board 21 can be produced from the metal-clad laminate 11, which comprises an insulating layer 22 that has high adhesion to the wiring 23 derived from the metal foil 13 and also has high heat resistance.
  • the metal-clad laminate 11 has an insulating layer 12 containing a cured product of composition (X), which reduces the dielectric constant and dielectric tangent, and also reduces water absorption, so that deterioration of the dielectric constant and dielectric tangent due to water absorption can be suppressed.
  • composition (X) a cured product of composition (X)
  • FIG. 3 is a schematic cross-sectional view illustrating an example of a wiring board 21 according to an embodiment of the present disclosure.
  • the wiring board 21 includes an insulating layer 22 made of composition (X) and wiring 23 overlapping the insulating layer 22.
  • the insulating layer 22 includes the cured product of the composition (X).
  • the insulating layer 22 may be made of the cured product of the composition (X).
  • the insulating layer 22 may also be made of the cured product of the prepreg 1.
  • the wiring board 21 includes the insulating layer 22 used by curing the prepreg 1 shown in FIG. 1, and wiring 23 overlapping the insulating layer 22.
  • the wiring board 21 may be made from the metal-clad laminate 11.
  • the wiring board 21 includes an insulating layer 22 made from the insulating layer 12, and wiring 23 that overlaps the insulating layer 22 and is formed by partially removing the metal foil 13.
  • methods for producing wiring board 21 include a method of producing wiring board 21 using metal-clad laminate 11. More specifically, wiring can be formed by etching metal foil 13 on the surface of metal-clad laminate 11. That is, wiring board 21 can be obtained by forming a circuit by partially removing metal foil 13 on the surface of metal-clad laminate 11. In this manner, wiring board 21 can be produced in which wiring 23 is provided as a circuit on the surface of insulating layer 22.
  • SAP semi-additive process
  • MSAP modified semi-additive process
  • the wiring board 21 of the present disclosure comprises an insulating layer 22 containing at least one of the cured product of the composition (X) and the cured product of the prepreg 1, and wiring 23.
  • the cured product of the composition (X) can have high adhesion to metals and high heat resistance. Therefore, the insulating layer 22 provided in the wiring board 21 can have high adhesion to metals and high heat resistance. The reliability of the wiring board 21 provided with such an insulating layer 22 can be increased.
  • the dielectric constant and dielectric tangent are reduced, and the water absorption is also reduced, so that the deterioration of the dielectric constant and dielectric tangent due to water absorption can be suppressed.
  • FIG. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil 31 according to this embodiment.
  • the resin-coated metal foil 31 comprises a resin layer 32 containing at least one of the composition (X) and the semi-cured product of the composition (X), and a metal foil 33 that overlaps the resin layer 32.
  • the resin-coated metal foil 31 may also comprise other layers between the resin layer 32 and the metal foil 33.
  • the resin layer 32 may contain a semi-cured product of the composition (X), or may contain an uncured product of the composition (X). That is, the resin-coated metal foil 31 may be a resin-coated metal foil 31 that includes a resin layer 32 that includes a semi-cured product of the composition (X) (B-stage composition (X)) and a metal foil 33, or a resin-coated metal foil 31 that includes a resin layer 32 that includes an uncured product of the composition (X) before curing (A-stage composition (X)) and a metal foil 33.
  • the resin layer 32 is made, for example, from a varnish-like resin composition containing the composition (X) and an organic solvent.
  • the organic solvent may be reduced or removed by heating the resin layer 32.
  • the resin layer 32 may or may not include a fibrous base material 3. Furthermore, if the resin layer 32 includes a fibrous base material 3, the same fibrous base material 3 as the fibrous base material 3 of the prepreg 1 can be used as the fibrous base material 3. In other words, the resin layer 32 may be made from the prepreg 1.
  • the metal foil 33 can be the same as the metal foil 13 used in the metal-clad laminate 11.
  • the resin-coated metal foil 31 may be provided with a cover film or the like as necessary.
  • a cover film By providing a cover film, it is possible to prevent the intrusion of foreign matter.
  • the cover film is not particularly limited, but examples include polyolefin films, polyester films, polymethylpentene films, and films formed by providing these films with a release agent layer.
  • the cover film may be subjected to a surface treatment such as a matte treatment, corona treatment, release treatment, or roughening treatment as necessary.
  • the resin-coated metal foil 31 can be produced, for example, by applying the above-mentioned varnish-like resin composition onto the metal foil 33 and heating it.
  • the varnish-like resin composition is applied onto the metal foil 33, for example, by using a bar coater.
  • the organic solvent can be volatilized from the varnish-like resin composition, and the organic solvent can be reduced or removed.
  • the applied varnish-like resin composition is heated, for example, at a temperature of 80° C. or higher and 180° C. or lower for a time period of 1 minute or higher and 10 minutes or lower.
  • the conditions for reducing or removing the organic solvent from the resin layer 32 by heating the resin layer 32 may be the same as the conditions for reducing or removing the organic solvent from the resin layer 2 by heating the resin layer 2 when producing the prepreg 1.
  • a resin-coated metal foil 31 that has a resin layer 32 that includes at least one of composition (X) and a semi-cured product of composition (X). From this resin-coated metal foil 31, a cured product of composition (X) having improved heat resistance and improved adhesion to metal can be obtained. Then, from the resin layer 32 of this resin-coated metal foil 31, an insulating layer 12 of a metal-clad laminate 11 or an insulating layer 22 of a wiring board 21 that has improved heat resistance and improved adhesion to metal can be produced.
  • composition (X) from the resin-coated metal foil 31 that has a reduced dielectric constant and dielectric tangent, improved desmearing properties, and reduced surface tack.
  • composition (X) has enhanced moldability. Therefore, when resin-coated metal foil 31 is used to produce insulating layer 22 of wiring board 21, the filling ability of resin layer 32 of resin-coated metal foil 31 into the circuit pattern can also be improved.
  • FIG. 5 is a schematic cross-sectional view showing an example of a resin-attached film 41 according to the present embodiment.
  • the resin-attached film 41 comprises a resin layer 42 containing at least one of composition (X) and a semi-cured product of composition (X), and a support film 43. That is, the resin-attached film 41 comprises a resin layer 42 containing at least one of composition (X) and a semi-cured product of composition (X), and a support film 43 overlapping the resin layer 42.
  • the resin-attached film 41 may comprise other layers between the resin layer 42 and the support film 43.
  • the resin layer 42 may contain a semi-cured product of the composition (X), or may contain an uncured product of the composition (X). That is, the resin-attached film 41 may be a resin-attached film 41 that includes a resin layer 42 that includes a semi-cured product of the composition (X) (B-stage composition (X)) and a support film 43, or a resin-attached film 41 that includes a resin layer 42 that includes an uncured product of the composition (X) before curing (A-stage composition (X)) and a support film 43.
  • the resin layer 42 is made, for example, from a varnish-like resin composition containing the composition (X) and an organic solvent.
  • the organic solvent may be reduced or removed by heating the resin layer 42.
  • the resin layer 42 may or may not include a fibrous base material 3. Furthermore, if the resin layer 42 includes a fibrous base material 3, the fibrous base material 3 may be the same as the fibrous base material 3 of the prepreg 1. In other words, the resin layer 42 may be made from the prepreg 1.
  • the support film 43 also includes at least one electrically insulating film selected from the group consisting of polyester film, polyethylene terephthalate (PET) film, polyimide film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, and polyarylate film, etc.
  • PET polyethylene terephthalate
  • PET polyimide film
  • polyparabanic acid film polyether ether ketone film
  • polyphenylene sulfide film polyamide film
  • polycarbonate film and polyarylate film, etc.
  • the resin-coated film 41 may be provided with a cover film or the like as necessary.
  • the cover film may be the same as that used for the resin-coated metal foil 31.
  • the support film 43 and the cover film may be subjected to surface treatment such as matte treatment, corona treatment, release treatment, or roughening treatment, if necessary.
  • Examples of methods for producing the resin-coated film 41 include a method in which a varnish-like resin composition is applied onto a support film 43 and heated to form a resin layer 42 that overlaps the support film 43, thereby producing the resin-coated film 41.
  • One example of a method for applying the varnish-like resin composition to the support film 43 is to use a bar coater.
  • the organic solvent can be volatilized from the varnish-like resin composition, and the organic solvent can be reduced or removed.
  • the applied varnish-like resin composition is heated, for example, at a temperature of 80°C or higher and 180°C or lower for a time period of 1 minute or higher and 10 minutes or lower.
  • the conditions for reducing or removing the organic solvent from the resin layer 42 by heating the resin layer 42 may be the same as the conditions for reducing or removing the organic solvent from the resin layer 2 by heating the resin layer 2 when producing the prepreg 1.
  • the resin layer 42 containing at least one of the composition (X) and the semi-cured product of the composition (X) is formed on the support film 43, and the resin-attached film 41 is produced.
  • a resin-attached film 41 that includes a resin layer 42 that includes at least one of the composition (X) and the semi-cured product of the composition (X). From this resin-attached film 41, a cured product of the composition (X) having improved heat resistance and improved adhesion to metals can be obtained. Then, from the resin layer 42 of this resin-attached film 41, an insulating layer 12 of a metal-clad laminate 11 or an insulating layer 22 of a wiring board 21 that has improved heat resistance and improved adhesion to metals can be produced.
  • composition (X) a cured product of composition (X) from the resin-coated film 41 that has a reduced dielectric constant and dielectric tangent, improved desmearing properties, and reduced surface tackiness.
  • composition (X) has enhanced moldability. Therefore, when resin-attached film 41 is used to produce insulating layer 22 of wiring board 21, the filling ability of resin layer 42 of resin-attached film 41 into the circuit pattern can also be improved.
  • a multi-layer wiring board 21 may be produced by laminating a resin-coated film 41 on the wiring board 21, peeling off the support film 43, and then superimposing a resin layer 42 on the wiring board 21, or by peeling off the support film 43 from the resin-coated film 41 and then superimposing the resin layer 42 on the wiring board 21.
  • the composition (X) according to the first aspect of the present disclosure contains a polyphenylene ether compound (A), a maleimide compound (B), a curing agent (C), and an inorganic filler (D).
  • the inorganic filler (D) includes an inorganic filler (D1) surface-treated with a hydrophobic silane coupling agent, and an inorganic filler (D2) surface-treated with a hydrophilic silane coupling agent.
  • the curing agent (C) includes a phenol compound (C1) having at least one of a group represented by formula (1) and a group represented by formula (2).
  • the content of the inorganic filler (D1) is 20% by mass or more and 80% by mass or less with respect to the total amount of the inorganic filler (D1) and the inorganic filler (D2).
  • composition (X) that has improved moldability and improved adhesion of the cured product to metal, as well as a prepreg (1), a metal-clad laminate (11), a wiring board (21), a resin-coated metal foil (31), and a resin-coated film (41) made from the composition (X).
  • the phenol compound (C1) includes a phenol compound (C1-0) having a total of two or more groups represented by the above formula (1) and two or more groups represented by the above formula (2) in one molecule.
  • the phenol compound (C1) includes a polyfunctional phenol compound (C1-2) having at least two chemical structures represented by formula (16) in one molecule.
  • R 39 represents an allyl group, a 1-propenyl group, or a hydrogen atom.
  • R 40 represents an allyl group, a 1-propenyl group, or a hydrogen atom. At least one of R 39 and R 40 represents an allyl group or a 1-propenyl group.
  • R 41 represents a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, an aldehyde group, or a phenyl group.
  • composition (X) according to the fourth aspect of the present disclosure in any one of the first to third aspects, contains a modified polyphenylene ether compound (A1) in which a polyphenylene ether compound (A) is terminally modified with a substituent having a carbon-carbon unsaturated double bond, and the modified polyphenylene ether compound (A1) has at least one of a group represented by formula (3) and a group represented by formula (4).
  • p represents an integer of 0 or more and 10 or less.
  • 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 curing agent (C) further contains a methacrylate compound (C2).
  • the hydrophobic silane coupling agent includes at least one selected from the group consisting of a vinyl group, a methacryl group, and a styryl group.
  • the hydrophilic silane coupling agent contains at least one selected from the group consisting of an amino group, an epoxy group, and an isocyanate group.
  • composition (X) according to the eighth aspect of the present disclosure is any one of the first to seventh aspects, in which the content of the phenol compound (C1) is 5% by mass or more and 40% by mass or less based on the total amount of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C).
  • composition (X) according to the ninth aspect of the present disclosure is any one of the first to eighth aspects, in which the content of the inorganic filler (D) is 150 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the curing agent (C).
  • the prepreg (1) according to the tenth aspect of the present disclosure comprises a resin layer (2) containing at least one of the composition (X) according to any one of the first to ninth aspects and a semi-cured product of the composition (X), and the resin layer (2) further contains a fibrous base material (3).
  • the metal-clad laminate (11) according to an eleventh aspect of the present disclosure comprises an insulating layer (12) containing at least one of a cured product of the composition (X) according to any one of the first to ninth aspects and a cured product of the prepreg (1), and a metal foil (13).
  • the wiring board (21) according to the twelfth aspect of the present disclosure comprises an insulating layer (22) containing at least one of a cured product of the composition (X) according to any one of the first to ninth aspects and a cured product of the prepreg (1), and wiring (23).
  • the resin-coated metal foil (31) according to the thirteenth aspect of the present disclosure comprises a resin layer (32) containing at least one of the composition (X) of any one of the first to ninth aspects and a semi-cured product of the composition (X), and a metal foil (33).
  • the resin-coated film (41) according to the fourteenth aspect of the present disclosure comprises a resin layer (42) containing at least one of the composition (X) of any one of the first to ninth aspects and a semi-cured product of the composition (X), and a support film (43).
  • Polyphenylene ether compound 1 a polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) at the end ("OPE-2st 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., Mn 1,200, a polyphenylene ether compound represented by the above formula (12), in which Z is a phenylene group, R 2 to R 4 are hydrogen atoms, and p is 1).
  • Maleimide compound 1 A maleimide compound represented by the above formula (15), in which R 35 to R 38 are hydrogen atoms ("MIR-3000” manufactured by Nippon Kayaku Co., Ltd., number average molecular weight 690, weight average molecular weight 870).
  • Phenolic compound 1 2,2'-diallyl bisphenol A ("DABPA” manufactured by Daiwa Chemical Industry Co., Ltd.).
  • Phenolic compound 2 a phenolic compound having an allyl group in the molecule ("LVA” manufactured by Gun-ei Chemical Industry Co., Ltd.).
  • Methacrylate compound tricyclodecane dimethanol dimethacrylate ("NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • Inorganic filler 1 Silica particles surface-treated with a silane coupling agent having a vinyl group in the molecule ("SC2500-SV” manufactured by Admatechs Co., Ltd.).
  • Inorganic filler 2 Silica particles surface-treated with a silane coupling agent having a phenylamino group in the molecule ("SC2500-SXJ" manufactured by Admatechs Co., Ltd.).
  • the two resin-coated metal foils prepared by the above method were laminated together so that the resin layers were bonded to each other, and then heated and pressed for 120 minutes under vacuum conditions at a temperature of 200°C and a pressure of 5 to 10 kg/ cm2 to obtain a metal-clad laminate (evaluation substrate) having a 100 ⁇ m-thick insulating layer and thin copper foils with carrier copper foils on both sides of the insulating layer.
  • Glass transition temperature (Tg) The glass transition temperatures of the cured resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 prepared according to the method described in "1. Preparation of Resin Composition” were measured. A viscoelasticity spectrometer "DMS6100” manufactured by Seiko Instruments Inc. was used to measure the glass transition temperatures. Dynamic viscoelasticity measurements were performed with a bending module at a frequency of 10 Hz, and the glass transition temperature was determined as the temperature at which the loss tangent (tan ⁇ ) was maximized when the temperature was raised from room temperature to 300°C at a heating rate of 5°C/min. For the evaluation, the cured resin compositions of each Example and Comparative Example were used as insulating layers peeled off from evaluation boards prepared according to the method described in "2.1 Preparation of Evaluation Boards".
  • the peel strength was evaluated by the following method. First, the carrier copper foil (thickness 18 ⁇ m) of one of the two thin copper foils with carrier copper foils provided in the metal-clad laminate (evaluation substrate) was peeled off. Next, the thin copper foil (thickness 3 ⁇ m) that overlapped the peeled carrier copper foil was plated up by electroless/electrolytic copper plating or the like to form a metal layer (thickness 35 ⁇ m) containing the thin copper foil. Then, the metal layer was peeled off, and the peel strength at that time was measured in accordance with JIS C6481 (1996).
  • the evaluation substrate was cut to a size of 10 mm wide and 100 mm long, and the metal layer was peeled off from the evaluation substrate obtained by cutting at a speed of 50 mm/min using a tensile tester, and the peel strength (kN/m) at that time was measured.
  • the moldability was evaluated by the following method. First, the carrier copper foil (thickness 18 ⁇ m) of one of the two thin copper foils with carrier copper foils provided in the metal-clad laminate (evaluation substrate) was peeled off. Next, the thin copper foil (thickness 3 ⁇ m) that overlapped the peeled carrier copper foil was plated up by electroless/electrolytic copper plating or the like to form a metal layer (thickness 35 ⁇ m) containing the thin copper foil. Next, the metal layer was peeled off, and the appearance of the insulating layer after the copper foil was peeled off was visually observed and evaluated. The case where no voids were confirmed in the insulating layer was evaluated as "A”, and the case where voids were confirmed was evaluated as "B".

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Abstract

La présente divulgation aborde le problème consistant à fournir : une composition de résine qui a une aptitude au moulage améliorée et permet l'obtention d'un produit durci qui a une adhérence plus élevée à un métal ; un préimprégné qui est produit à partir de cette composition de résine ; un stratifié revêtu de métal ; une carte de câblage ; une feuille métallique avec une résine ; et un film avec une résine.　Cette composition de résine contient (A) un composé d'éther de polyphénylène, (B) un composé maléimide, (C) un agent de durcissement et (D) une charge inorganique. La charge inorganique (D) contient (D1) une charge inorganique qui est traitée en surface avec un agent de couplage silane hydrophobe, et (D2) une charge inorganique qui est traitée en surface avec un agent de couplage silane hydrophile. L'agent de durcissement (C) contient (C1) un composé phénolique qui a au moins l'un d'un groupe représenté par la formule (1) et d'un groupe représenté par la formule (2). La teneur de la charge inorganique (D1) est de 20 % en masse à 80 % en masse par rapport à la quantité totale de la charge inorganique (D1) et de la charge inorganique (D2).
PCT/JP2023/040084 2022-11-08 2023-11-07 Composition de résine, préimprégné, stratifié revêtu de métal, carte de câblage, feuille métallique avec résine, et film avec résine WO2024101362A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131306A1 (fr) * 2017-12-28 2019-07-04 パナソニックＩｐマネジメント株式会社 Composition de résine, pré-imprégné, film comprenant de la résine, feuille métallique comprenant de la résine, stratifié à revêtement métallique, et tableau de connexions
WO2020262089A1 (fr) * 2019-06-27 2020-12-30 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film fixé à une résine, feuille métallique fixée à une résine, feuille stratifiée plaquée de métal et carte de câblage
JP2021123682A (ja) * 2020-02-07 2021-08-30 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板
JP2021138802A (ja) * 2020-03-03 2021-09-16 住友ベークライト株式会社 樹脂組成物、それを用いたキャリア付樹脂膜、プリプレグ、積層板、プリント配線基板および半導体装置
WO2023074429A1 (fr) * 2021-10-25 2023-05-04 パナソニックＩｐマネジメント株式会社 Composition de résine thermodurcissable, feuille de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique et carte à circuit imprimé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131306A1 (fr) * 2017-12-28 2019-07-04 パナソニックＩｐマネジメント株式会社 Composition de résine, pré-imprégné, film comprenant de la résine, feuille métallique comprenant de la résine, stratifié à revêtement métallique, et tableau de connexions
WO2020262089A1 (fr) * 2019-06-27 2020-12-30 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film fixé à une résine, feuille métallique fixée à une résine, feuille stratifiée plaquée de métal et carte de câblage
JP2021123682A (ja) * 2020-02-07 2021-08-30 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板
JP2021138802A (ja) * 2020-03-03 2021-09-16 住友ベークライト株式会社 樹脂組成物、それを用いたキャリア付樹脂膜、プリプレグ、積層板、プリント配線基板および半導体装置
WO2023074429A1 (fr) * 2021-10-25 2023-05-04 パナソニックＩｐマネジメント株式会社 Composition de résine thermodurcissable, feuille de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique et carte à circuit imprimé

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