WO2023119805A1 - Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, feuille stratifiée plaquée de métal et carte de câblage - Google Patents

Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, feuille stratifiée plaquée de métal et carte de câblage Download PDF

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WO2023119805A1
WO2023119805A1 PCT/JP2022/038224 JP2022038224W WO2023119805A1 WO 2023119805 A1 WO2023119805 A1 WO 2023119805A1 JP 2022038224 W JP2022038224 W JP 2022038224W WO 2023119805 A1 WO2023119805 A1 WO 2023119805A1
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resin composition
particle size
compound
group
resin
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PCT/JP2022/038224
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Japanese (ja)
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幹男 佐藤
智之 阿部
伸一 勝田
泰範 星野
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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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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K5/49—Phosphorus-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

  • the present invention relates to a resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board.
  • wiring boards used in various electronic devices are required to be high-frequency compatible wiring boards, such as millimeter-wave radar boards for in-vehicle applications.
  • Wiring boards used in various electronic devices are required to reduce loss during signal transmission in order to increase the signal transmission speed, and high-frequency compatible wiring boards are particularly required to do so.
  • substrate materials for forming substrates of wiring boards used in various electronic devices are required to have a low dielectric constant and a low dielectric loss tangent.
  • a PPE-containing resin composition containing PPE (polyphenylene ether), a crosslinkable curable compound, and a phosphaphenanthrene derivative is excellent in low dielectric properties, glass transition temperature (Tg), and the like. It has been reported that there are (Patent Document 1).
  • Patent Document 2 a resin composition for derivatives containing anisotropic magnesium oxide has also been reported.
  • Patent Document 3 or Patent Document 4 a technique using boron nitride as an inorganic filler has been reported.
  • the boron nitride fillers described in Patent Documents 3 and 4 certainly improve the thermal conductivity of the resin composition. However, when the resin composition is used as a molding material such as a substrate material, even better flame retardancy is required.
  • a phosphaphenanthrene derivative used as a flame retardant is added to the polyphenylene ether resin. Phosphaphenanthrene derivatives are known as halogen-free phosphorus-based flame retardants.
  • the present invention has been made in view of such circumstances, and a resin having low dielectric properties, high thermal conductivity and glass transition temperature (Tg), and capable of obtaining a cured product having excellent flame retardancy.
  • the object is to provide a composition.
  • Another object of the present invention is to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board obtained using the resin composition.
  • the resin composition according to one aspect of the present invention contains a polyphenylene ether compound (A), a curing agent (B), an inorganic filler containing boron nitride (C), and a phosphorus compound (D),
  • a polyphenylene ether compound (A) a curing agent (B)
  • a phosphorus compound (D) In the particle size distribution of the inorganic filler (C), at least two peaks of the particle size distribution measured by a laser diffraction particle size distribution measurement method exist in the particle size range of 1.0 to 50.0 ⁇ m
  • the phosphorus compound ( D) is a compatible phosphorus compound (D-1) that is compatible with the mixture of the polyphenylene ether compound (A) and the curing agent (B), and an incompatible phosphorus compound that is incompatible with the mixture (D -2).
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the invention.
  • FIG. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the invention.
  • FIG. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the invention.
  • a resin composition according to an embodiment of the present invention comprises a polyphenylene ether compound (A), a curing agent (B), an inorganic filler (C) containing boron nitride, and a phosphorus compound (D), and the inorganic
  • the phosphorus compound (D) is a compatible phosphorus compound (D-1) compatible with a mixture of the polyphenylene ether compound (A) and the curing agent (B)
  • the polyphenylene ether compound (A) and the curing agent (B) It is characterized by containing an incompatible phosphorus compound (D-2) that is incompatible with the mixture of.
  • the resin composition that has low dielectric properties (relative dielectric constant), high thermal conductivity and high Tg, and gives a cured product that is excellent in adhesion and flame retardancy.
  • the resin composition by using the resin composition, it is possible to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring substrate having excellent performance.
  • polyphenylene ether compound (A) Although the polyphenylene ether compound (A) of the present embodiment is not particularly limited, it is preferably a modified polyphenylene ether compound from the viewpoint of lowering the dielectric properties. More preferably, it is a modified polyphenylene ether compound (A-1) having a group represented by formula (1) or formula (2) described below. By containing such a polyphenylene ether compound, it is considered that a resin composition having low dielectric properties and capable of obtaining a cured product having high heat resistance can be obtained.
  • s represents an integer of 0-10.
  • Z represents an arylene group.
  • R 1 to R 3 are each independent. That is, R 1 to R 3 may each be the same group or different groups. Also, R 1 to R 3 represent a hydrogen atom or an alkyl group.
  • the arylene group of Z is not particularly limited.
  • the arylene group includes, for example, a monocyclic aromatic group such as a phenylene group, and a polycyclic aromatic group in which the aromatic is not monocyclic but polycyclic aromatic such as a naphthalene ring.
  • the arylene group also includes derivatives in which a hydrogen atom bonded to an 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, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.
  • R4 represents a hydrogen atom or an alkyl group.
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.
  • Preferred specific examples of the substituent represented by formula (1) include, for example, a substituent containing a vinylbenzyl group.
  • substituent containing the vinylbenzyl group include substituents represented by the following formula (6).
  • substituent represented by formula (2) include an acrylate group and a methacrylate group.
  • the substituents include vinylbenzyl groups (ethenylbenzyl groups) such as p-ethenylbenzyl group and m-ethenylbenzyl group, vinylphenyl groups, acrylate groups, and methacrylate groups. be done.
  • the polyphenylene ether compound preferably has a polyphenylene ether chain in its molecule and, for example, a repeating unit represented by the following formula (7) in its molecule.
  • t represents 1-50.
  • R 5 to R 8 are each independent. That is, R 5 to R 8 may each be the same group or different groups.
  • R 5 to R 8 each 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.
  • alkyl group is not particularly limited, for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.
  • alkenyl group is not particularly limited, for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable.
  • Specific examples include vinyl groups, allyl groups, and 3-butenyl groups.
  • alkynyl group is not particularly limited, for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).
  • the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group.
  • an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable.
  • Specific examples include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, cyclohexylcarbonyl group and the like.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group.
  • an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • Specific examples 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.
  • an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • Specific examples thereof include a propioloyl group and the like.
  • the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited. Specifically, it is preferably from 500 to 5,000, more preferably from 800 to 4,000, even more preferably from 1,000 to 3,000.
  • the weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically includes a value measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • t is a numerical value such that the weight average molecular weight of the polyphenylene ether compound is within such a range.
  • t is preferably 1-50.
  • the weight average molecular weight of the polyphenylene ether compound When the weight average molecular weight of the polyphenylene ether compound is within such a range, it has excellent low dielectric properties possessed by polyphenylene ether, and not only is the cured product more excellent in heat resistance, but also excellent in moldability. Become. This is believed to be due to the following. If the weight-average molecular weight of ordinary polyphenylene ether is within this range, the heat resistance of the cured product tends to be lowered because of its relatively low molecular weight. In this regard, since the polyphenylene ether compound according to the present embodiment has one or more unsaturated double bonds at the terminal, it is considered that a cured product having sufficiently high heat resistance can be obtained.
  • the weight average molecular weight of the polyphenylene ether compound is within such a range, it is considered to be excellent in moldability because it has a relatively low molecular weight. Therefore, such a polyphenylene ether compound is considered to provide a cured product having not only excellent heat resistance but also excellent moldability.
  • the average number of the substituents (the number of terminal functional groups) per molecule of the polyphenylene ether compound at the molecular end is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal functional groups is too large, the reactivity becomes too high, and problems such as deterioration in the storage stability of the resin composition and deterioration in fluidity of the resin composition may occur. . That is, when such a polyphenylene ether compound is used, molding defects such as voids occur during multilayer molding due to insufficient fluidity, etc., and it is difficult to obtain a highly reliable printed wiring board. Problems can arise.
  • the number of terminal functional groups of the polyphenylene ether compound includes a numerical value representing the average value of the substituents per molecule of all modified polyphenylene ether compounds present in 1 mol of the polyphenylene ether compound.
  • the number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the resulting modified polyphenylene ether compound and calculating the decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups.
  • the method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to the solution of the modified polyphenylene ether compound, and measure the UV absorbance of the mixed solution.
  • a quaternary ammonium salt tetraethylammonium hydroxide
  • the intrinsic viscosity of the polyphenylene ether compound (A) of the present embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl/g, preferably 0.04 to 0.11 dl/g, more preferably 0.06 to 0.095 dl/g. . If the intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as a low dielectric constant and a low dielectric loss tangent. On the other hand, when the intrinsic viscosity is too high, the viscosity tends to be too high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to deteriorate. Therefore, if the intrinsic viscosity of the polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be achieved.
  • the intrinsic viscosity here is the intrinsic viscosity measured in methylene chloride at 25 ° C. More specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) , etc. Examples of this viscometer include AVS500 Visco System manufactured by Schott.
  • Examples of the polyphenylene ether compound (A) of the present embodiment include a modified polyphenylene ether compound represented by the following formula (8) and a modified polyphenylene ether compound represented by the following formula (9). Moreover, as the polyphenylene ether compound of the present embodiment, these modified polyphenylene ether compounds may be used alone, or these two modified polyphenylene ether compounds may be used in combination.
  • R 9 to R 16 and R 17 to R 24 are each independently 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 represent repeating units represented by the following formulas (10) and (11), respectively.
  • Y represents a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms.
  • m and n each represent 0 to 20.
  • 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 9 to R 16 and R 17 to R 24 are each independent as described above. That is, R 9 to R 16 and R 17 to R 24 may each be the same group or different groups.
  • R 9 to R 16 and R 17 to R 24 each 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.
  • m and n preferably represent 0 to 20, respectively, as described above. Further, m and n preferably represent numerical values in which the total value of m and n is 1-30. Therefore, m represents 0 to 20, n represents 0 to 20, and more preferably the sum of m and n represents 1 to 30.
  • R 25 to R 28 and R 29 to R 32 are each independent. That is, R 25 to R 28 and R 29 to R 32 may each be the same group or different groups.
  • R 25 to R 28 and R 29 to R 32 each 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.
  • a hydrogen atom and an alkyl group are preferred.
  • R 9 to R 32 are the same as R 5 to R 8 in formula (7) above.
  • Y is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms, as described above.
  • Examples of Y include groups represented by the following formula (12).
  • 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 formula (12) include a methylene group, a methylmethylene group, a dimethylmethylene group, and the like, and among these, a dimethylmethylene group is preferred.
  • X 1 and X 2 are each independently a substituent having a carbon-carbon unsaturated double bond.
  • the substituents X 1 and X 2 are not particularly limited as long as they are substituents having a carbon-carbon unsaturated double bond.
  • Examples of the substituents X1 and X2 include the substituent represented by the above formula (1) and the substituent represented by the above formula (2).
  • X 1 and X 2 may be the same substituent or different It may be a substituent.
  • modified polyphenylene ether compound represented by the formula (8) includes, for example, a modified polyphenylene ether compound represented by the following formula (13).
  • modified polyphenylene ether compound represented by the formula (9) include, for example, a modified polyphenylene ether compound represented by the following formula (14) and a modified polyphenylene represented by the following formula (15) ether compounds and the like.
  • m and n are the same as m and n in formulas (10) and (11) above.
  • R 1 to R 3 , p and Z are the same as R 1 to R 3 , s and Z in formula (1) above.
  • Y is the same as Y in the above (9).
  • R 4 is the same as R 4 in formula (2) above.
  • the modified polyphenylene ether compound can be used singly or in combination of two or more.
  • the polyphenylene ether compound (A) used in the resin composition of this embodiment can be synthesized by a known method, or a commercially available product can be used.
  • commercially available products include "OPE-2st 1200” and “OPE-2st 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., and "SA9000” manufactured by SABIC Innovative Plastics.
  • the resin composition of this embodiment further contains a curing agent (B).
  • the curing agent (B) is not particularly limited as long as it can react with the polyphenylene ether compound (A) to cure the resin composition containing the polyphenylene ether compound (A).
  • the curing agent include curing agents having at least one functional group in the molecule that contributes to the reaction with the polyphenylene ether compound (A).
  • a compound having an acryloyl group in the molecule a compound having a methacryloyl group in the molecule, a compound having a vinyl group in the molecule, a compound having an allyl group in the molecule, and a maleimide group in the molecule compounds, compounds having an acenaphthylene structure in the molecule, isocyanurate compounds having an isocyanurate group in the molecule, styrene derivatives, and the like.
  • a compound having an acryloyl group in the molecule is an acrylate compound.
  • the acrylate compound include monofunctional acrylate compounds having one acryloyl group in the molecule and polyfunctional acrylate compounds having two or more acryloyl groups in the molecule.
  • the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • the polyfunctional acrylate compound include tricyclodecanedimethanol diacrylate.
  • a compound having a methacryloyl group in the molecule is a methacrylate compound.
  • the methacrylate compounds include monofunctional methacrylate compounds having one methacryloyl group in the molecule and polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule.
  • the monofunctional methacrylate compounds include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
  • Examples of the polyfunctional methacrylate compound include tricyclodecanedimethanol dimethacrylate.
  • a compound having a vinyl group in the molecule is a vinyl compound.
  • the vinyl compound include monofunctional vinyl compounds (monovinyl compounds) having one vinyl group in the molecule and polyfunctional vinyl compounds having two or more vinyl groups in the molecule.
  • the polyfunctional vinyl compound include divinylbenzene and polybutadiene.
  • a compound having an allyl group in the molecule is an allyl compound.
  • the allyl compound include monofunctional allyl compounds having one allyl group in the molecule and polyfunctional allyl compounds having two or more allyl groups in the molecule.
  • the polyfunctional allyl compound include diallyl phthalate (DAP).
  • a compound having a maleimide group in the molecule is a maleimide compound.
  • the maleimide compound include monofunctional maleimide compounds having one maleimide group in the molecule, polyfunctional maleimide compounds having two or more maleimide groups in the molecule, and modified maleimide compounds.
  • the modified maleimide compound include modified maleimide compounds partially modified with an amine compound, modified maleimide compounds partially modified with a silicone compound, and partially amine compounds. and modified maleimide compounds modified with silicone compounds.
  • a compound having an acenaphthylene structure in the molecule is an acenaphthylene compound.
  • the acenaphthylene compounds include acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes.
  • the alkylacenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, and 3-ethylacenaphthylene.
  • phthalene 4-ethylacenaphthylene, 5-ethylacenaphthylene and the like.
  • halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, and 3-bromoacenaphthylene.
  • rene 4-bromoacenaphthylene, 5-bromoacenaphthylene and the like.
  • phenylacenaphthylenes examples include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene and the like.
  • the acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule. .
  • a compound having an isocyanurate group in the molecule is an isocyanurate compound.
  • isocyanurate compounds include compounds further having an alkenyl group in the molecule (alkenyl isocyanurate compounds), and examples thereof include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC).
  • TAIC triallyl isocyanurate
  • styrene derivative examples include bromostyrene and dibromostyrene.
  • the curing agent (B) used in the present embodiment includes, for example, a polyfunctional acrylate compound having two or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule, Polyfunctional vinyl compounds having two or more vinyl groups in the molecule, styrene derivatives, allyl compounds having an allyl group in the molecule, maleimide compounds having a maleimide group in the molecule, acenaphthylene compounds having an acenaphthylene structure in the molecule, and molecules It preferably contains at least one selected from isocyanurate compounds having an isocyanurate group therein.
  • the curing agents described above may be used alone, or two or more of them may be used in combination.
  • the curing agent (B) preferably has a weight average molecular weight of 100 to 5,000, more preferably 100 to 4,000, even more preferably 100 to 3,000. If the weight average molecular weight of the curing agent is too low, the curing agent may easily volatilize from the component system of the resin composition. Further, if the weight average molecular weight of the curing agent is too high, the viscosity of the varnish of the resin composition and the melt viscosity during heat molding may become too high. Therefore, when the weight-average molecular weight of the curing agent is within such a range, a cured resin composition having excellent heat resistance can be obtained.
  • the resin composition containing the polyphenylene ether compound can be suitably cured by the reaction with the polyphenylene ether compound.
  • the weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically includes a value measured using gel permeation chromatography (GPC).
  • the average number of functional groups that contribute to the reaction with the polyphenylene ether compound (the number of functional groups) per molecule of the curing agent varies depending on the weight average molecular weight of the curing agent. It is preferably 1 to 20, more preferably 2 to 18. If the number of functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of functional groups is too large, the reactivity becomes too high, and problems such as deterioration of the storage stability of the resin composition and deterioration of the fluidity of the resin composition may occur.
  • the resin composition according to this embodiment further contains an inorganic filler (C) containing boron nitride.
  • the boron nitride can be used as an inorganic filler contained in the resin composition, and is not particularly limited as long as it satisfies the regulation of particle size distribution described later. Examples of boron nitride include a hexagonal normal-pressure phase (h-BN) and a cubic high-pressure phase (c-BN).
  • the peak of the particle size distribution measured by a laser diffraction particle size distribution measurement method is in the range of 1.0 to 50.0 ⁇ m in particle size.
  • the inorganic filler used in the present embodiment is a mixture of inorganic fillers having at least two or more peak particle sizes (peak tops).
  • the inorganic fillers used in a more preferred embodiment include an inorganic filler with a relatively small particle size, an inorganic filler with a relatively large particle size, and an inorganic filler with at least two types of peak particle size (peak top). Fillers are mixed. As a result, it is considered that both the guarantee of adhesion to the metal foil and the high thermal conductivity can be achieved.
  • the adhesiveness of the resulting cured product of the resin composition to the metal foil cannot be sufficiently enhanced. Tend. Moreover, when there is a peak only in the large particle size range, the thermal conductivity of the obtained resin composition tends to decrease.
  • the particle size distribution is a value measured by particle size distribution measurement by a laser diffraction/scattering method. manufactured by Horiba, Ltd.).
  • the peak refers to the maximum value in the graph of the particle size distribution, and specifically, the graph of the particle size distribution when the horizontal axis is the particle diameter and the vertical axis is the relative particle amount (frequency). is the numerical value obtained by the local maximum in
  • the cumulative proportion of particles having a particle size of 0.1 to 5.0 ⁇ m is 25 to 75% by volume with respect to 100% by volume of the entire particle size distribution of the inorganic filler (C), and the particle size is 5.0 to 100%. It is preferable that the cumulative proportion of particles of 0.0 ⁇ m is 25 to 75% by volume.
  • Each of these integrated ratios (%) is a value obtained by calculating from the integrated value of the relative amount of particles in each particle size range.
  • the boron nitride contained in the inorganic filler (C) of the present embodiment is obtained by energy dispersive X-ray analysis (EDX analysis observation) of a vertical cross-sectional view of the cured product of the resin composition of the present embodiment.
  • EDX analysis observation energy dispersive X-ray analysis
  • Boron nitride is discriminated, and among the boron nitrides present in the range of 50 ⁇ m on one side in SEM observation, the longest length from end to end of boron nitride is 10 ⁇ m or more and 50 ⁇ m or less. It is more preferable that the range is one.
  • the copper foil adhesion can be ensured while maintaining a high thermal conductivity.
  • the resin composition of the present embodiment may contain only the boron nitride, or may contain an inorganic filler other than the boron nitride.
  • the content of the boron nitride in the inorganic filler (C) is preferably 20 to 100 parts by mass and 30 to 80 parts by mass with respect to 100 parts by mass of the inorganic filler (C). is more preferred. It is considered that there is an advantage that high thermal conductivity can be ensured when the boron nitride content is within the above range.
  • the particle size distribution of the inorganic filler (C) satisfies the above-mentioned regulations.
  • the particle size distribution of the inorganic filler (C) satisfies the above-mentioned regulation by comparing the particle size of the boron nitride and the particle size of the inorganic filler other than boron nitride. can be adjusted as follows.
  • the inorganic filler other than boron nitride is not particularly limited as long as it can be used as an inorganic filler contained in the resin composition.
  • examples of inorganic fillers other than boron nitride include metal oxides such as silica, alumina, titanium oxide, magnesium oxide and mica, aluminum hydroxide, metal hydroxides such as magnesium hydroxide, talc, and aluminum borate. , barium sulfate, aluminum nitride, silicon nitride, magnesium carbonate such as anhydrous magnesium carbonate, and calcium carbonate.
  • silica is not particularly limited, and examples thereof include pulverized silica and silica particles, with silica particles being preferred.
  • magnesium carbonate is not particularly limited, anhydrous magnesium carbonate (synthetic magnesite) is preferable.
  • the inorganic filler other than boron nitride may be a surface-treated inorganic filler or may be an inorganic filler that is not surface-treated.
  • Examples of the surface treatment include treatment with a silane coupling agent.
  • silane coupling agent examples include silane coupling agents having at least one functional group selected from the group consisting of vinyl groups, styryl groups, methacryloyl groups, acryloyl groups, and phenylamino groups. That is, this silane coupling agent has at least one of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group as a reactive functional group; Examples thereof include compounds having a hydrolyzable group.
  • silane coupling agent having a vinyl group examples include vinyltriethoxysilane and vinyltrimethoxysilane.
  • silane coupling agent having a styryl group examples include p-styryltrimethoxysilane and p-styryltriethoxysilane.
  • silane coupling agent having a methacryloyl group examples include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxypropylethyldiethoxysilane, and the like.
  • silane coupling agent having an acryloyl group examples include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.
  • silane coupling agent having a phenylamino group examples include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.
  • the inorganic filler of the present embodiment contains an inorganic filler other than the boron nitride
  • the content of the boron nitride in the inorganic filler is 20 to 20 to 100 parts by volume of the inorganic filler. Preferably 100 parts by volume. It is believed that high thermal conductivity can thereby be achieved more reliably. A more preferred range is 30 to 70 parts by volume.
  • the average particle size of the boron nitride and/or the average particle size of the inorganic filler other than the boron nitride is such that the particle size distribution of the inorganic filler (C) satisfies the above-described regulations. As long as it is within the range, there is no particular limitation.
  • the inorganic filler (C) of the present embodiment not only two peaks of the particle size distribution as described above exist in the range of the particle size of 1.0 to 50.0 ⁇ m, but also a third peak in the range may be present. In that case, the third peak preferably exists in the particle size range of 20.0 to 50.0 ⁇ m.
  • the filler can be evenly dispersed in the resin component, which is expected to have the advantage of improving the thermal conductivity.
  • the resin composition of the present embodiment preferably contains the boron nitride and silica as the inorganic filler (C).
  • the particle size distribution of the inorganic filler containing boron nitride and silica at least three peaks of the particle size distribution measured by a laser diffraction particle size distribution measurement method exist within a particle size range of 1.0 to 50.0 ⁇ m. and at least one peak in the particle size range of 1.0 to 5.0 ⁇ m, at least one in the particle size range of 5.0 to 20.0 ⁇ m, and at least one in the particle size range of 20.0 to 50.0 ⁇ m. It is more preferable to have one.
  • At least three peaks are present in the particle size distribution of the inorganic filler of the present embodiment. is preferably adjusted. It is considered that such a configuration further has the advantage of improving the thermal conductivity by uniformly dispersing the filler with high thermal conductivity in the resin component.
  • the phosphorus compound (D) of the present embodiment includes a compatible phosphorus compound (D-1) that is compatible with the mixture of the polyphenylene ether compound (A) and the curing agent (B), and a non-compatible phosphorus compound that is not compatible with the mixture. and a compatible phosphorus compound (D-2).
  • the compatible phosphorus compound (D-1) is not particularly limited as long as it acts as a flame retardant and is compatible with the mixture.
  • the term “compatibility” means that the polyphenylene ether compound (A) and the curing agent (B) are finely dispersed, for example, at the molecular level in the mixture.
  • compatible phosphorus compounds (D-1) include compounds containing phosphorus and not forming salts, such as phosphate ester compounds, phosphazene compounds, phosphite ester compounds, and phosphine compounds. .
  • Phosphazene compounds include, for example, cyclic or chain phosphazene compounds.
  • the cyclic phosphazene compound also called cyclophosphazene, is a compound having a double bond in its molecule composed of phosphorus and nitrogen, and has a cyclic structure.
  • Examples of phosphoric ester compounds include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylene bis(di-2,6-xylenyl phosphate), 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), condensed phosphate compounds such as aromatic condensed phosphate compounds, and cyclic phosphate compounds.
  • Examples of phosphite compounds include trimethyl phosphite and triethyl phosphite.
  • phosphine compounds include tris-(4-methoxyphenyl)phosphine and triphenylphosphine.
  • the said compatible phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the incompatible phosphorus compound (D-2) is not particularly limited as long as it acts as a flame retardant and is incompatible with the mixture.
  • incompatibility means that the polyphenylene ether compound (A) and the curing agent (B) are not compatible in the mixture, and the target substance (phosphorus compound) is dispersed in islands in the mixture.
  • the particle diameter of the island-shaped phosphorus compound is not particularly limited, but the average particle diameter is 0.1 ⁇ m to 100 ⁇ m.
  • the average particle size is preferably 0.1 ⁇ m to 70 ⁇ m, and more preferably 0.1 ⁇ m to 40 ⁇ m.
  • Specific incompatible phosphorus compounds (D-2) include compounds containing phosphorus to form a salt, such as phosphinate compounds, polyphosphate compounds, and phosphonium salt compounds, and phosphine oxide compounds. etc.
  • Examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, and bisdiphenylphosphinate. zinc, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, titanyl bisdiphenylphosphinate and the like.
  • Examples of polyphosphate compounds include melamine polyphosphate, melam polyphosphate, and melem polyphosphate.
  • Phosphonium salt compounds include, for example, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium bromide.
  • the phosphine oxide compound includes, for example, a phosphine oxide compound having two or more diphenylphosphine oxide groups in the molecule (diphenylphosphine oxide compound), and more specifically, paraxylylenebisdiphenylphosphine oxide and the like. is mentioned.
  • the immiscible phosphorus compounds may be used singly or in combination of two or more.
  • the content ratio of the compatible phosphorus compound (D-1) and the incompatible phosphorus compound (D-2) is preferably 1:2 to 2:1, more preferably 1:1 to 3:2 in terms of mass ratio. It is more preferable to have Such a content ratio is considered to provide a resin composition having a high Tg in a cured product and having excellent flame retardancy.
  • the resin composition according to the present embodiment may contain, as a flame retardant, only the phosphorus compound (D) consisting of the compatible phosphorus compound (D-1) and the incompatible phosphorus compound (D-1).
  • flame retardants other than these two types may also be contained.
  • a flame retardant other than the compatible phosphorus compound (D-1) and the incompatible phosphorus compound (D-2) may be contained. It is preferable not to contain a flame retardant.
  • the content of the polyphenylene ether compound (A) is 100 parts by mass in total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). On the other hand, it is preferably 15 to 40 parts by mass, more preferably 15 to 30 parts by mass, even more preferably 15 to 25 parts by mass. If the content of the polyphenylene ether compound (A) is within the above range, it is believed that a resin composition with low dielectric properties and a cured product with high heat resistance can be obtained more reliably.
  • the content of the curing agent (B) is 5 to 20 parts by mass with respect to a total of 100 parts by mass of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). preferably 6 to 18 parts by mass, even more preferably 7 to 16 parts by mass. If the content of the curing agent (B) is within the above range, the cured resin composition will be more excellent in heat resistance. It is considered that this is because the curing reaction between the resin component of the present embodiment and the curing agent proceeds favorably.
  • the content of the inorganic filler (C) in the resin composition of the present embodiment is, with respect to a total of 100 parts by mass of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C), It is preferably 40 to 80 parts by mass, more preferably 50 to 80 parts by mass, even more preferably 60 to 80 parts by mass. If the content of the inorganic filler (C) is within the above range, it is believed that a cured product with high thermal conductivity can be obtained more reliably.
  • the content of the boron nitride in the resin composition of the present embodiment is 15 parts with respect to a total of 100 parts by mass of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). It is preferably up to 50 parts by mass, more preferably 20 to 50 parts by mass. It is considered that high thermal conductivity can thereby be obtained more reliably.
  • the content of the phosphorus compound (D) is 100 parts by mass in total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). On the other hand, it is preferably from 2 to 15 parts by mass, more preferably from 2 to 12 parts by mass, and even more preferably from 2 to 10 parts by mass.
  • the content of the compatible phosphorus compound (D-1) in the resin composition of the present embodiment is a total of 100 mass of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). It is preferably from 2 to 15 parts by mass, more preferably from 2 to 12 parts by mass.
  • the content of the incompatible phosphorus compound (D-2) is 5 parts per 100 parts by mass in total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). It is preferably from 5 to 25 parts by mass, more preferably from 5 to 22 parts by mass.
  • the content of the compatible phosphorus compound (D-1) is 100 parts by mass in total of the compatible phosphorus compound (D-1) and the compatible phosphorus compound (D-2). On the other hand, it is preferably 25 to 65 parts by mass, more preferably 40 to 60 parts by mass.
  • the content of the compatible phosphorus compound (D-1) and the incompatible phosphorus compound (D-2) is within the above range, there is an advantage that both flame retardancy and high Tg can be ensured. Conceivable.
  • the resin composition according to the present embodiment may contain components (other components) other than the components described above, if necessary, as long as the effects of the present invention are not impaired.
  • Other components contained in the resin composition according to the present embodiment include, for example, a styrene polymer, a free radical compound, a reaction initiator, a silane coupling agent, an antifoaming agent, an antioxidant, a heat stabilizer, Additives such as antistatic agents, UV absorbers, dyes and pigments, dispersants and lubricants may be further included.
  • the resin composition of the present embodiment includes epoxy resins, maleimide resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and the like. of thermosetting resin.
  • the resin composition of the present embodiment may further contain a styrenic polymer in addition to the components described above.
  • a styrenic polymer By containing a styrene-based polymer, it is considered that there is an advantage of further lowering the dielectric constant of the resin.
  • the styrenic polymer used in the present embodiment is, for example, a polymer obtained by polymerizing a monomer containing a styrenic monomer, and may be a styrenic copolymer.
  • a styrene-based copolymer for example, one or more styrene-based monomers and one or more other monomers copolymerizable with the styrene-based monomers are copolymerized.
  • the obtained copolymer etc. are mentioned.
  • the styrene-based monomers include styrene, styrene derivatives, and those in which some of the hydrogen atoms of styrene are substituted with substituents.
  • R 35 to R 37 each independently represent a hydrogen atom or an alkyl group
  • R 38 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an isopropenyl group. indicates a group.
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
  • the alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.
  • the styrenic polymer of the present embodiment preferably contains at least one type of structural unit represented by the above formula (3), but may contain two or more different types in combination. Moreover, it preferably contains a structure in which the structural unit represented by the above formula (3) is repeated.
  • styrenic polymers include styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene, divinylbenzene, allylstyrene, and other styrenic monomers. Polymers or copolymers may be mentioned. More specific examples include styrene-butadiene copolymers and styrene-isobutylene copolymers.
  • it may be a hydrogenated (hydrogenated) styrene polymer, for example, hydrogenated methylstyrene (ethylene / butylene) methylstyrene copolymer, hydrogenated methylstyrene (ethylene-ethylene / propylene) methylstyrene copolymer polymers, hydrogenated styrene isoprene copolymers, hydrogenated styrene isoprene styrene copolymers, hydrogenated styrene (ethylene/butylene) styrene copolymers, hydrogenated styrene (ethylene-ethylene/propylene) styrene copolymers, etc. mentioned.
  • hydrogenated (hydrogenated) styrene polymer for example, hydrogenated methylstyrene (ethylene / butylene) methylstyrene copolymer, hydrogenated methylstyrene (ethylene-ethylene / propylene)
  • the ones exemplified above may be used alone, or two or more of them may be used in combination.
  • the moisture absorption rate of the cured product of the resin composition can be suppressed, and deterioration of electrical properties due to an increase in moisture absorption can be suppressed. can also be effective.
  • the molar fraction of the structural unit is about 10 to 70% relative to the entire polymer. is preferably 15 to 65%.
  • the polymerization form of the styrene-based polymer is not particularly limited, and may be a block copolymer, alternating copolymer, random copolymer, graft copolymer, or the like. It may also be in the form of an elastomer.
  • the weight average molecular weight of the styrenic polymer of the present embodiment is preferably about 10,000 to 200,000, more preferably about 20,000 to 150,000. If the weight-average molecular weight is within the above range, there is an advantage that it is possible to secure appropriate resin fluidity in the B stage of the cured resin.
  • the number average molecular weight may be one measured by a general molecular weight measurement method, and specifically includes a value measured using gel permeation chromatography.
  • the styrene-based polymer more desirably includes a styrene/isobutylene/styrene-based block copolymer (SIBS) containing a structural unit represented by the following formula (16).
  • SIBS styrene/isobutylene/styrene-based block copolymer
  • the sum of a1 and a2 represents an integer of 1,000 to 60,000, b represents an integer of 1,000 to 70,000, and the sum of a1, a2 and b is 10, 000 to 130,000.
  • the method for producing the styrenic polymer used in the present embodiment is not particularly limited, but to show an example of the method for producing the SIBS, first, isobutylene is polymerized by a living cationic polymerization method, and then styrene is added. can be synthesized by polymerizing
  • the styrene-based polymer of the present embodiment can also use a commercially available one, for example, Kaneka Corporation "SIBSTAR (registered trademark) 073T", “SIBSTAR (registered trademark) 103T", “SIBSTAR (registered trademark) ) 102T”, “Septon V9827” manufactured by Kuraray Co., Ltd., and the like.
  • the content of the styrene-based polymer is the amount of the polyphenylene ether compound (A), the curing agent (B), and the inorganic filler (C). It is preferably 1 to 6 parts by mass, more preferably 1 to 4 parts by mass, based on 100 parts by mass in total.
  • the resin composition of the present embodiment can also contain a free radical compound. Containing a free radical compound is considered to have the advantage of improving the flowability of the resin and improving the moldability.
  • the free radical compound is not particularly limited as long as it is a free radical compound that can be used as a polymerization inhibitor.
  • More specific free radical compounds preferably used in this embodiment include 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free Radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-glycidyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2 , 2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl benzoate free radical, 4-isothiocyanato-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 4-(2-iodoacetamide)-2,2,6,6-tetramethylpiperidine
  • the content of the free radical compound is 100 in total of the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C). It is preferably 0.005 to 0.05 parts by mass, more preferably 0.005 to 0.03 parts by mass.
  • the resin composition according to the present embodiment may contain a reaction initiator (initiator). Even if the resin composition contains the polyphenylene ether compound (A) and the curing agent (B), the curing reaction can proceed. However, depending on the process conditions, it may be difficult to increase the temperature until curing proceeds, so a reaction initiator may be added.
  • a reaction initiator may be added.
  • the reaction initiator is not particularly limited as long as it can accelerate the curing reaction of the resin composition.
  • Specific examples include metal oxides, azo compounds, organic peroxides, and the like.
  • metal oxides include carboxylic acid metal salts and the like.
  • organic peroxides examples include ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile, etc. is mentioned.
  • azo compounds include 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′- and azobis(2-methylbutyronitrile).
  • reaction initiators are 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide) and the like. These initiators have little effect on the dielectric properties.
  • reaction initiation temperature is relatively high, it is possible to suppress the acceleration of the curing reaction at the time when the prepreg is not required to be cured, such as when drying the prepreg, and it is possible to suppress the deterioration of the storage stability of the resin composition. This is because it has the advantage of being able to
  • reaction initiators may be used alone or in combination of two or more.
  • the content thereof is not particularly limited, but for example, the polyphenylene ether compound (A), the curing agent (B) and the inorganic filler (C ) is preferably 0.1 to 0.5 parts by mass, and more preferably 0.2 to 0.4 parts by mass, with respect to 100 parts by mass in total.
  • the method for producing the resin composition is not particularly limited.
  • the polyphenylene ether compound (A), the curing agent (B), the phosphorus compound (D), and, if necessary, other organic components A method of mixing and then adding the inorganic filler (C) may be mentioned.
  • the method described in the explanation of the prepreg to be described later can be used.
  • a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film can be obtained as follows.
  • the cured product of the resin composition preferably has a thermal conductivity of 1.0 W/m ⁇ K or more and a dielectric constant of 4.0 or less at a frequency of 10 GHz.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the invention.
  • each reference symbol in the drawings represents 1 prepreg, 2 resin composition or semi-cured resin composition, 3 fibrous base material, 11 metal-clad laminate, 12 insulating layer, 13 metal 14 wiring, 21 wiring board, 31 metal foil with resin, 32, 42 resin layer, 41 film with resin, 43 support film.
  • a prepreg 1 according to the present embodiment includes the resin composition or a semi-cured material 2 of the resin composition, and a fibrous base material 3, as shown in FIG.
  • the prepreg 1 comprises the resin composition or a semi-cured material 2 of the resin composition, and a fibrous base material 3 present in the resin composition or the semi-cured material 2 of the resin composition.
  • the semi-cured product is a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a semi-cured resin composition (B-staged). For example, when the resin composition is heated, the viscosity first gradually decreases, then curing starts, and then curing starts and the viscosity gradually increases. In such a case, semi-curing includes the state between when the viscosity starts to rise and before it is completely cured.
  • the prepreg obtained using the resin composition according to the present embodiment may include a semi-cured product of the resin composition as described above, or may include the uncured resin composition. It may comprise the composition itself. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition in the B stage) and a fibrous base material, or the resin composition before curing (the resin composition in the A stage). and a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be obtained by drying or heat-drying the resin composition.
  • the resin composition 2 is often prepared in the form of a varnish and used to impregnate the fibrous base material 3, which is the base material for forming the prepreg. That is, the resin composition 2 is usually a resin varnish prepared in the form of a varnish.
  • a varnish-like resin composition (resin varnish) is prepared, for example, as follows.
  • each component of the composition of the resin composition that can be dissolved in an organic solvent is put into the organic solvent and dissolved. At this time, it may be heated, if necessary.
  • a component that is not soluble in an organic solvent for example, an inorganic filler, etc.
  • a varnish-like resin composition is prepared.
  • the organic solvent used here is not particularly limited as long as it dissolves the modified polyphenylene ether compound, the curing agent and the like and does not inhibit the curing reaction. Specific examples include toluene and methyl ethyl ketone (MEK).
  • the method for manufacturing the prepreg is not particularly limited as long as the prepreg can be manufactured.
  • the resin composition used in the present embodiment described above is often prepared in the form of a varnish and used as a resin varnish, as described above.
  • the fibrous base material include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper.
  • glass cloth When glass cloth is used, a laminate having excellent mechanical strength can be obtained, and flattened glass cloth is particularly preferable.
  • the flattening process there is a method in which glass cloth is continuously pressed with press rolls at an appropriate pressure to flatten the yarn.
  • the thickness of the generally used fibrous base material is, for example, 0.01 mm or more and 0.3 mm or less.
  • the method for manufacturing the prepreg is not particularly limited as long as the prepreg can be manufactured.
  • the resin composition according to the present embodiment described above is often prepared in the form of a varnish and used as a resin varnish, as described above.
  • the prepreg 1 As a method of manufacturing the prepreg 1, for example, a method of impregnating the fibrous base material 3 with the resin composition 2, for example, the resin composition 2 prepared in the form of a varnish, and then drying.
  • the resin composition 2 is impregnated into the fibrous base material 3 by dipping, coating, or the like. It is also possible to repeat impregnation several times as needed. In this case, it is also possible to adjust the desired composition and impregnation amount by repeating the impregnation using a plurality of resin compositions having different compositions and concentrations.
  • the fibrous base material 3 impregnated with the resin composition (resin varnish) 2 is heated under desired heating conditions, for example, at 80° C. or higher and 180° C. or lower for 1 minute or longer and 10 minutes or shorter.
  • desired heating conditions for example, at 80° C. or higher and 180° C. or lower for 1 minute or longer and 10 minutes or shorter.
  • the prepreg 1 is obtained before curing (A stage) or in a semi-cured state (B stage).
  • the heating can volatilize the organic solvent from the resin varnish and reduce or remove the organic solvent.
  • a prepreg comprising the resin composition according to the present embodiment or a semi-cured product of the resin composition preferably provides a cured product having low dielectric properties, high thermal conductivity and Tg, and excellent adhesion and flame retardancy. It is a prepreg that can be
  • FIG. 2 is a schematic cross-sectional view showing an example of the metal-clad laminate 11 according to the embodiment of the invention.
  • the metal-clad laminate 11 is composed of an insulating layer 12 containing the cured prepreg 1 shown in FIG. 1 and a metal foil 13 laminated together with the insulating layer 12. That is, the metal-clad laminate 11 has an insulating layer 12 containing a cured resin composition and a metal foil 13 provided on the insulating layer 12 . Moreover, the insulating layer 12 may be made of a cured product of the resin composition, or may be made of a cured product of the prepreg. Moreover, the thickness of the metal foil 13 is not particularly limited, and varies depending on the performance required for the finally obtained wiring board.
  • the thickness of the metal foil 13 can be appropriately set according to the desired purpose, and is preferably 0.2 to 70 ⁇ m, for example.
  • Examples of the metal foil 13 include copper foil and aluminum foil.
  • a carrier-attached copper foil having a peeling layer and a carrier for improving handling properties can be used. good too.
  • the method for manufacturing the metal-clad laminate 11 is not particularly limited as long as the metal-clad laminate 11 can be manufactured. Specifically, a method of producing a metal-clad laminate 11 using the prepreg 1 can be mentioned. As this method, one or more prepregs 1 are stacked, and metal foils 13 such as copper foils are stacked on both sides or one side of the prepregs 1, and the metal foils 13 and the prepregs 1 are heat-pressed and laminated to integrate. A method of manufacturing a laminate 11 with metal foil on both sides or with metal foil on one side, etc., can be mentioned. That is, the metal-clad laminate 11 is obtained by laminating the metal foil 13 on the prepreg 1 and molding it under heat and pressure.
  • the heating and pressurizing conditions can be appropriately set according to the thickness of the metal-clad laminate 11 to be manufactured, the type of composition of the prepreg 1, and the like.
  • the temperature can be 170-210° C.
  • the pressure can be 3-4 MPa
  • the time can be 60-150 minutes.
  • the metal-clad laminate may be produced without using a prepreg. For example, there is a method of applying a varnish-like resin composition onto a metal foil, forming a layer containing the resin composition on the metal foil, and heating and pressurizing the layer.
  • the metal-clad laminate provided with the insulating layer containing the cured product of the resin composition according to the present embodiment has low dielectric properties, high thermal conductivity and Tg, and excellent adhesion to the metal foil and flame retardancy.
  • a metal-clad laminate having an insulating layer having an insulating layer.
  • FIG. 3 is a schematic cross-sectional view showing an example of the wiring board 21 according to the embodiment of the invention.
  • a wiring board 21 according to the present embodiment is laminated with an insulating layer 12 that is used by curing the prepreg 1 shown in FIG. and a wiring 14 formed as follows. That is, the wiring board 21 has an insulating layer 12 containing a cured product of a resin composition and wirings 14 provided on the insulating layer 12 . Moreover, the insulating layer 12 may be made of a cured product of the resin composition, or may be made of a cured product of the prepreg.
  • the method for manufacturing the wiring board 21 is not particularly limited as long as the wiring board 21 can be manufactured. Specifically, a method of manufacturing a wiring board 21 using the prepreg 1, and the like can be mentioned. As this method, for example, wiring is provided as a circuit on the surface of the insulating layer 12 by etching the metal foil 13 on the surface of the metal-clad laminate 11 produced as described above to form wiring. and a method for fabricating the wiring board 21 . That is, wiring board 21 is obtained by partially removing metal foil 13 from the surface of metal-clad laminate 11 to form a circuit.
  • the method of forming a circuit includes, for example, circuit formation by a semi-additive process (SAP: Semi-Additive Process) or a modified semi-additive process (MSAP: Modified Semi-Additive Process).
  • the wiring board 21 has an insulating layer 12 that has low dielectric properties, high heat resistance, and can preferably maintain low dielectric properties even after water absorption treatment.
  • Such a wiring board is a wiring board provided with an insulating layer that has low dielectric properties, high thermal conductivity and Tg, excellent adhesion to metal foil, and excellent flame retardancy.
  • FIG. 4 is a schematic cross-sectional view showing an example of the resin-coated metal foil 31 according to this embodiment.
  • the resin-coated metal foil 31 includes a resin layer 32 containing the resin composition or a semi-cured material of the resin composition, and a metal foil 13, as shown in FIG.
  • This resin-coated metal foil 31 has a metal foil 13 on the surface of the resin layer 32 . That is, the resin-coated metal foil 31 includes the resin layer 32 and the metal foil 13 laminated together with the resin layer 32 . Further, the resin-coated metal foil 31 may have another layer between the resin layer 32 and the metal foil 13 .
  • the resin layer 32 may contain a semi-cured material of the resin composition as described above, or may contain the uncured resin composition.
  • the resin-coated metal foil 31 may include a resin layer containing a semi-cured product of the resin composition (the B-stage resin composition) and a metal foil, or the resin before curing It may be a resin-coated metal foil comprising a resin layer containing the composition (the resin composition in the A stage) and a metal foil.
  • the resin layer may contain the resin composition or a semi-cured material of the resin composition, and may or may not contain a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be obtained by drying or heat-drying the resin composition.
  • the fibrous base material the same fibrous base material as that of the prepreg can be used.
  • metal foil any metal foil used for metal-clad laminates can be used without limitation.
  • metal foil include copper foil and aluminum foil.
  • the resin-coated metal foil 31 and the resin-coated film 41 may be provided with a cover fill or the like, if necessary.
  • a cover fill or the like By providing the cover film, it is possible to prevent foreign matter from entering.
  • the cover film include, but are not limited to, polyolefin films, polyester films, polymethylpentene films, and films formed by providing these films with a release agent layer.
  • the method for manufacturing the resin-coated metal foil 31 is not particularly limited as long as the resin-coated metal foil 31 can be manufactured.
  • Examples of the method for producing the resin-coated metal foil 31 include a method in which the varnish-like resin composition (resin varnish) is applied onto the metal foil 13 and heated.
  • the varnish-like resin composition is applied onto the metal foil 13 by using, for example, a bar coater.
  • the applied resin composition is heated, for example, under conditions of 80° C. to 180° C. and 1 minute to 10 minutes.
  • the heated resin composition is formed on the metal foil 13 as an uncured resin layer 32 .
  • the heating can volatilize the organic solvent from the resin varnish and reduce or remove the organic solvent.
  • the resin-coated metal foil comprising the resin layer containing the resin composition or the semi-cured product of the resin composition according to the present embodiment has low dielectric properties, high thermal conductivity and Tg, and adhesion to the metal foil. It is a resin-coated metal foil from which a cured product having excellent flame resistance can be suitably obtained.
  • FIG. 5 is a schematic cross-sectional view showing an example of the resin-coated film 41 according to this embodiment.
  • the resin-coated film 41 includes a resin layer 42 containing the resin composition or a semi-cured material of the resin composition, and a support film 43, as shown in FIG.
  • the resin-coated film 41 includes the resin layer 42 and a support film 43 laminated together with the resin layer 42 . Further, the resin-coated film 41 may have another layer between the resin layer 42 and the support film 43 .
  • the resin layer 42 may contain a semi-cured material of the resin composition as described above, or may contain an uncured resin composition.
  • the resin-coated film 41 may include a resin layer containing a semi-cured product of the resin composition (the B-stage resin composition) and a support film. It may be a resin-coated film comprising a resin layer containing a substance (the resin composition in the A stage) and a support film.
  • the resin layer may contain the resin composition or a semi-cured material of the resin composition, and may or may not contain a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be obtained by drying or heat-drying the resin composition.
  • the fibrous base material the same fibrous base material as that of the prepreg can be used.
  • a support film used for resin-coated films can be used without limitation.
  • the support film include electrically insulating films such as polyester film, polyethylene terephthalate (PET) film, polyimide film, polyparabanic acid film, polyetheretherketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, and polyarylate film. A film etc. are mentioned.
  • the resin-coated film 41 may be provided with a cover film or the like, if necessary. By providing the cover film, it is possible to prevent foreign matter from entering. Examples of the cover film include, but are not limited to, polyolefin film, polyester film, and polymethylpentene film.
  • the support film and cover film may be subjected to surface treatment such as matte treatment, corona treatment, mold release treatment, and roughening treatment, if necessary.
  • the method for manufacturing the resin-coated film 41 is not particularly limited as long as the resin-coated film 41 can be manufactured.
  • Examples of the method for manufacturing the resin-coated film 41 include a method for manufacturing by applying the varnish-like resin composition (resin varnish) on the support film 43 and heating.
  • the varnish-like resin composition is applied onto the support film 43 by using, for example, a bar coater.
  • the applied resin composition is heated, for example, under conditions of 80° C. to 180° C. and 1 minute to 10 minutes.
  • the heated resin composition is formed on the support film 43 as an uncured resin layer 42 .
  • the heating can volatilize the organic solvent from the resin varnish and reduce or remove the organic solvent.
  • a resin-coated film comprising a resin layer containing the resin composition or a semi-cured product of the resin composition according to the present embodiment has low dielectric properties, high thermal conductivity and Tg, and excellent adhesion and flame retardancy. It is a resin-coated film from which a cured product can be suitably obtained.
  • the resin composition according to the first aspect of the present invention comprises a polyphenylene ether compound (A), a curing agent (B), an inorganic filler containing boron nitride (C), and a phosphorus compound (D),
  • a polyphenylene ether compound (A) a curing agent (B)
  • a phosphorus compound (D) In the particle size distribution of the inorganic filler (C), at least two peaks of the particle size distribution measured by a laser diffraction particle size distribution measurement method exist in the particle size range of 1.0 to 50.0 ⁇ m
  • the phosphorus compound ( D) is a compatible phosphorus compound (D-1) that is compatible with the mixture of the polyphenylene ether compound (A) and the curing agent (B), and an incompatible phosphorus compound that is incompatible with the mixture (D -2).
  • a resin composition according to a second aspect is the resin composition according to the first aspect, wherein at least one peak of the particle size distribution is in the range of 1.0 to 10.0 ⁇ m in particle size and 50 At least one exists in the range of 0 ⁇ m or less.
  • a resin composition according to a third aspect is the resin composition of the first or second aspect, wherein the inorganic filler (C) has a particle size of 0.1 to 5 with respect to 100% by volume of the entire particle size distribution.
  • the cumulative proportion of particles in the range of 0.0 ⁇ m is 25-75% by volume, and the cumulative proportion of particles with a diameter of 5.0-100.0 ⁇ m is 25-75% by volume.
  • a resin composition according to a fourth aspect is the resin composition according to any one of the first to third aspects, wherein the inorganic filler (C) is silica, anhydrous magnesium carbonate, magnesium oxide, alumina, silicon nitride, and and at least one filler selected from the group consisting of aluminum nitride.
  • the inorganic filler (C) is silica, anhydrous magnesium carbonate, magnesium oxide, alumina, silicon nitride, and at least one filler selected from the group consisting of aluminum nitride.
  • a resin composition according to a fifth aspect is the resin composition of the fourth aspect, wherein the inorganic filler (C) contains a silica filler, and in the particle size distribution of the inorganic filler (C), the laser diffraction particle size There are at least three peaks in the particle size distribution measured by the distribution measurement method in the particle size range of 1.0 to 50.0 ⁇ m, and at least one of these peaks is in the particle size range of 1.0 to 5.0 ⁇ m. At least one grain size range is from 10.0 to 20.0 ⁇ m and at least one grain size range is from 20.0 to 50.0 ⁇ m.
  • a resin composition according to a sixth aspect is the resin composition according to any one of the first to fifth aspects, wherein the content of the inorganic filler (C) is the polyphenylene ether compound (A) and the curing agent It is 40 to 80 parts by mass with respect to a total of 100 parts by mass of (B) and the inorganic filler (C).
  • a resin composition according to a seventh aspect is the resin composition of the sixth aspect, wherein the content of the boron nitride is the polyphenylene ether compound (A), the curing agent (B), and the inorganic filler. It is 15 to 50 parts by mass with respect to 100 parts by mass in total with (C). Furthermore, the content of the boron nitride in the inorganic filler (C) is preferably 20 to 100 parts by mass with respect to 100 parts by mass of the inorganic filler (C).
  • a resin composition according to an eighth aspect is the resin composition of the sixth aspect, wherein the content of the inorganic filler other than the boron nitride in the inorganic filler (C) is the same as the polyphenylene ether compound (A). , 20 to 60 parts by mass with respect to a total of 100 parts by mass of the curing agent (B) and the inorganic filler (C).
  • a resin composition according to a ninth aspect is the resin composition according to any one of the first to eighth aspects, wherein the compatible phosphorus compound (D-1) comprises a phosphate ester compound, a phosphazene compound, a phosphite ester compound, and , at least one selected from the group consisting of phosphine compounds.
  • the compatible phosphorus compound (D-1) comprises a phosphate ester compound, a phosphazene compound, a phosphite ester compound, and , at least one selected from the group consisting of phosphine compounds.
  • a resin composition according to a tenth aspect is the resin composition according to any one of the first to ninth aspects, wherein the incompatible phosphorus compound (D-2) is a phosphinate compound, a polyphosphate compound, a phosphonium salt compound, and at least one selected from the group consisting of phosphine oxide compounds.
  • the incompatible phosphorus compound (D-2) is a phosphinate compound, a polyphosphate compound, a phosphonium salt compound, and at least one selected from the group consisting of phosphine oxide compounds.
  • a resin composition according to an eleventh aspect is the resin composition of the first to tenth aspects, wherein the content of the compatible phosphorus compound (D-1) is It is 25 to 65 parts by mass with respect to a total of 100 parts by mass of the compatible phosphorus compound (D-2).
  • a resin composition according to a twelfth aspect is the resin composition of any one of the first to eleventh aspects, wherein the polyphenylene ether compound (A) is at least one of the groups represented by the above formulas (1) and (2) It contains a modified polyphenylene ether compound (A-1) having one.
  • a resin composition according to a thirteenth aspect is the resin composition according to the first to twelfth aspects, wherein the curing agent (B) is a polyfunctional acrylate compound having two or more acryloyl groups in the molecule, methacryloyl in the molecule polyfunctional methacrylate compounds having two or more groups, polyfunctional vinyl compounds having two or more vinyl groups in the molecule, styrene derivatives, allyl compounds having an allyl group in the molecule, maleimide compounds having a maleimide group in the molecule, It contains at least one selected from the group consisting of acenaphthylene compounds having an acenaphthylene structure in the molecule and isocyanurate compounds having an isocyanurate group in the molecule.
  • the curing agent (B) is a polyfunctional acrylate compound having two or more acryloyl groups in the molecule, methacryloyl in the molecule polyfunctional methacrylate compounds having two or more groups, polyfunctional vinyl
  • the resin composition according to the fourteenth aspect in addition to the resin compositions of the first to thirteenth aspects, further contains a styrenic polymer.
  • the resin composition according to the fifteenth aspect is the cured product of the resin composition of the first to fourteenth aspects, having a thermal conductivity of 1.0 W / m K or more and a relative dielectric constant at a frequency of 10 GHz 4.0 or less.
  • a prepreg according to a sixteenth aspect of the present invention is characterized by comprising the resin composition of the first to fifteenth aspects or a semi-cured product of the resin composition, and a fibrous base material.
  • a film with resin according to the seventeenth aspect of the present invention is characterized by comprising a resin layer containing the resin composition of the first to fifteenth aspects or a semi-cured product of the resin composition, and a support film.
  • a resin-coated metal foil according to an eighteenth aspect of the present invention comprises a resin layer containing the resin composition of any one of the first to fifteenth aspects or a semi-cured product of the resin composition, and a metal foil. .
  • a metal-clad laminate according to a nineteenth aspect of the present invention comprises an insulating layer containing a cured product of the resin composition of the first to fifteenth aspects or a cured product of the prepreg of the sixteenth aspect, and a metal foil. characterized by
  • a wiring board according to a twentieth aspect of the present invention comprises an insulating layer containing a cured product of the resin composition of the first to fifteenth aspects or a cured product of the prepreg of the sixteenth aspect, and wiring. do.
  • PPE1 polyphenylene ether compound having a methacryloyl group at the end (modified polyphenylene ether obtained by modifying the terminal hydroxyl group of polyphenylene ether with a methacryloyl group, represented by the above formula (15), where Y in formula (15) is a dimethylmethylene group (formula (12), wherein R 33 and R 34 in formula (12) are methyl groups) modified polyphenylene ether compound, SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw 2000, terminal functional group number 2 Individual) •
  • PPE2 Modified polyphenylene ether obtained by reacting polyphenylene ether with chloromethylstyrene. Specifically, it is a modified polyphenylene ether obtained by reacting as follows.
  • polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, 2 terminal hydroxyl groups, weight average molecular weight Mw 1700) was added to a 1-liter three-necked flask equipped with a temperature controller, a stirrer, a cooling device, and a dropping funnel.
  • 200 g a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene: CMS manufactured by Tokyo Chemical Industry Co., Ltd.) 30 g, tetra-n-butylammonium as a phase transfer catalyst 1.227 g of bromide and 400 g of toluene were charged and stirred.
  • the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were stirred until they were dissolved in toluene. At that time, it was gradually heated until the liquid temperature finally reached 75°C. Then, an aqueous sodium hydroxide solution (20 g of sodium hydroxide/20 g of water) was added dropwise to the solution as an alkali metal hydroxide over 20 minutes. After that, the mixture was further stirred at 75° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass hydrochloric acid, a large amount of methanol was added. By doing so, the liquid in the flask was caused to precipitate.
  • the solid obtained was analyzed by 1 H-NMR (400 MHz, CDCl 3 , TMS). As a result of NMR measurement, a peak derived from a vinylbenzyl group (ethenylbenzyl group) was confirmed at 5 to 7 ppm. As a result, it was confirmed that the obtained solid was a modified polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) as the substituent at the molecular terminal in the molecule. Specifically, it was confirmed to be an ethenylbenzylated polyphenylene ether.
  • the resulting modified polyphenylene ether compound is represented by the above formula (14), Y is represented by a dimethylmethylene group (formula (12), and R 33 and R 34 in formula (12) are methyl groups. ), Z is a phenylene group, R 1 to R 3 are hydrogen atoms, and n is 1.
  • terminal functional group number of the modified polyphenylene ether was measured as follows.
  • TEAH tetraethylammonium hydroxide
  • Residual OH amount ( ⁇ mol/g) [(25 ⁇ Abs)/( ⁇ OPL ⁇ X)] ⁇ 10 6
  • ⁇ indicates the extinction coefficient, which is 4700 L/mol ⁇ cm.
  • OPL is the cell optical path length and is 1 cm.
  • the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, it was found that the hydroxyl groups of the polyphenylene ether before modification were almost modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups was two.
  • the intrinsic viscosity (IV) of the modified polyphenylene ether was measured in methylene chloride at 25°C. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured using a 0.18 g/45 ml methylene chloride solution (liquid temperature: 25°C) of the modified polyphenylene ether with a viscometer (AVS500 Visco System manufactured by Schott). It was measured. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl/g.
  • Mw weight average molecular weight
  • Curing agent (curing agent) ⁇ Curing agent 1: triallyl isocyanurate (TAIC manufactured by Nippon Kasei Co., Ltd.) Curing agent 2: divinylbenzene (DVB manufactured by Nippon Steel & Sumitomo Metal Corporation)
  • Styrene-based polymer Styrene-based polymer
  • Styrene-based polymer 1 Hydrogenated methylstyrene (ethylene/butylene) methylstyrene copolymer (Septon V9827 manufactured by Kuraray Co., Ltd., weight average molecular weight: 92000)
  • Styrene-based polymer 2 styrene/isobutylene/styrene-based triblock copolymer (manufactured by Kaneka Corporation, number average molecular weight 85,000, styrene mole fraction: 30%)
  • Free radical compound 1 4-benzoyloxy tempo, a free radical compound represented by the following formula ("H0878” manufactured by Tokyo Chemical Industry Co., Ltd.)
  • each organic resin component other than the inorganic filler is added to toluene as a solvent in the composition (parts by mass) shown in Tables 1 and 2 so that the solid content concentration is 60 to 70% by mass, and mixed. rice field. The mixture was stirred for 60 minutes. After that, each filler was added to the obtained liquid according to the formulation (parts by mass) shown in Tables 1 and 2, and the inorganic filler was dispersed with a bead mill. By doing so, a varnish-like resin composition (varnish) was obtained.
  • an evaluation substrate (cured material of prepreg) was obtained as follows.
  • a fibrous base material (glass cloth: #1078 type, L glass manufactured by Asahi Kasei Corporation) was impregnated with the obtained varnish, and then dried by heating at 110°C for 3 minutes to prepare a prepreg. Then, 1, 2, 4, and 6 sheets of each of the obtained prepregs were laminated, and each side was laminated with copper foil ("FV-WS" copper foil thickness: 35 ⁇ m manufactured by Furukawa Electric Co., Ltd.) at a heating rate of 4 ° C. /min to 200° C., followed by heating and pressurizing at 200° C. for 120 minutes at a pressure of 3 MPa to prepare copper-clad laminates with three different thicknesses.
  • the dielectric constant (Dk) of the evaluation substrate (hardened prepreg) at 10 GHz was measured by the cavity resonator perturbation method. Specifically, a network analyzer (N5230A manufactured by Keysight Technologies, Inc.) was used to measure the dielectric constant of the evaluation substrate at 10 GHz. The acceptance criterion in this example was set to Dk ⁇ 4.0.
  • a copper clad laminate (CCL) was produced using the prepregs of each example and comparative example. Specifically, four sheets of prepreg are stacked, and copper foil (“FV-WS” manufactured by Furukawa Electric Co., Ltd.) with a thickness of 35 ⁇ m is laminated on both surfaces, under vacuum conditions, at a temperature of 200 ° C. and a pressure of 3 MPa. to obtain a copper clad laminate (CCL) (evaluation substrate) having a thickness of 510 ⁇ m and having copper foils adhered to both sides thereof.
  • FV-WS Furukawa Electric Co., Ltd.
  • the peel strength of the copper foil from the insulating layer was measured according to JIS C 6481.
  • a pattern with a width of 10 mm and a length of 100 mm was formed and peeled off at a speed of 50 mm/min using a tensile tester, and the peel strength at that time (peel strength) was measured.
  • the unit of measurement is N/mm.
  • the acceptance criterion in this example was 0.40 N/mm or more.
  • Thermal conductivity of the obtained evaluation substrate (cured prepreg) was measured by a method based on ASTM D5470. Specifically, using a thermal property evaluation device (T3Ster DynTIM Tester manufactured by Mentor Graphics), the thermal resistance and The thickness was measured, the measured values were plotted on a graph, approximated by a straight line, and the thermal conductivity was calculated from the increase in thermal resistance and thickness.
  • the acceptance criterion for the thermal conductivity in this example was 1.0 W/m ⁇ K or more.
  • Tg Glass transition temperature
  • the specifications of the measurement unit are as follows. Dispersion: Ultrasonic probe Circulation: Centrifugal pump Stirring: Rotating blade flow type Cell material: Synthetic quartz
  • the particle size distribution measurement conditions are as follows.
  • Each measurement sample was put into a flow cell via a sample bath using toluene as a dispersion solvent, and laser diffraction/scattering particle size distribution measurement was performed in a stirred state.
  • the particle size distribution was analyzed and calculated using the analysis software LA-960 for Windows attached to LA-960V2. Then, the peak in the particle size distribution was obtained by calculating using the volume ratio of the measured particle size distribution.
  • the particle size distribution of the inorganic filler (C) has only one peak in the particle size range of 1.0 to 50.0 ⁇ m. Otherwise, sufficient adhesion with the copper foil could not be obtained. Furthermore, from the results of Comparative Example 6, even if boron nitride is used as the inorganic filler (C), if at least two peaks are not in the particle size range of 1.0 to 50.00 ⁇ m, sufficient thermal conductivity I also found that I can't get
  • the present invention has wide industrial applicability in technical fields such as electronic materials, electronic devices, and optical devices.

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Abstract

Un aspect de la présente invention concerne une composition de résine qui contient un composé de poly(éther de phénylène) (A), un agent de durcissement (B), une charge inorganique (C) contenant du nitrure de bore, et un composé de phosphore (D). Dans une distribution de taille de particule de la charge inorganique (C), au moins deux pics sont présents dans une plage de taille de particule de 1,0 à 50,0 µm dans une distribution de taille de particule mesurée à l'aide d'un procédé de mesure de distribution de taille de particule de type à diffraction laser. Le composé de phosphore (D) contient : un composé de phosphore compatible (D-1) qui est compatible avec un mélange du composé de poly(éther de phénylène) (A) et de l'agent de durcissement (B) ; et un composé de phosphore incompatible (D-2) qui n'est pas compatible avec le mélange.
PCT/JP2022/038224 2021-12-24 2022-10-13 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, feuille stratifiée plaquée de métal et carte de câblage WO2023119805A1 (fr)

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JP2021004316A (ja) * 2019-06-26 2021-01-14 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、プリプレグの製造方法、積層板及びプリント配線板
WO2021059911A1 (fr) * 2019-09-27 2021-04-01 パナソニックＩｐマネジメント株式会社 Composition de résine, pré-imprégné, film pourvu de résine, feuille de métal pourvue de résine, plaque stratifiée plaquée de métal, et carte de circuit imprimé
WO2022014584A1 (fr) * 2020-07-17 2022-01-20 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film pourvu de résine, feuille métallique pourvue de résine, stratifié revêtu de métal et carte de câblage
WO2022014582A1 (fr) * 2020-07-17 2022-01-20 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film pourvu de résine, feuille métallique pourvue de résine, stratifié revêtu de métal et carte de câblage
CN112111074A (zh) * 2020-09-28 2020-12-22 常州中英科技股份有限公司 一种可交联碳氢树脂组合物的均匀分散液及其制备的半固化片和高导热热固型覆铜板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024057803A1 (fr) * 2022-09-16 2024-03-21 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié revêtu de métal et carte de câblage

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