WO2024057803A1 - Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié revêtu de métal et carte de câblage - Google Patents

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

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WO2024057803A1
WO2024057803A1 PCT/JP2023/029463 JP2023029463W WO2024057803A1 WO 2024057803 A1 WO2024057803 A1 WO 2024057803A1 JP 2023029463 W JP2023029463 W JP 2023029463W WO 2024057803 A1 WO2024057803 A1 WO 2024057803A1
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group
resin composition
compound
resin
composition according
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PCT/JP2023/029463
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Japanese (ja)
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幹男 佐藤
伸一 勝田
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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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

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 board used in various electronic devices it is desirable to use a wiring board compatible with high frequencies, such as a millimeter wave radar board for in-vehicle applications.
  • Wiring boards used in various electronic devices are required to reduce loss during signal transmission in order to increase signal transmission speed, and this is especially required for wiring boards compatible with high frequencies. Therefore, substrate materials for forming the substrates of wiring boards used in various electronic devices are required to have excellent low dielectric properties such as low relative permittivity and low dielectric loss tangent.
  • resin compositions used as substrate materials often contain halogen-based flame retardants such as brominated flame retardants and halogen-containing compounds such as halogen-containing epoxy resins.
  • a resin composition containing such a halogen-containing compound will contain a halogen in its cured product. When this cured product is burned, there is a risk of generating harmful substances such as hydrogen halides, and it has been pointed out that there is a concern that it will have an adverse effect on the human body and the natural environment.
  • substrate materials and the like are required to be halogen-free, that is, to be halogen-free.
  • Such a substrate material for example, includes a thermosetting resin and a curing agent, and is compatible with a mixture of the thermosetting resin and curing agent as a halogen-free flame retardant, as disclosed in Patent Document 1.
  • PPE-containing resin compositions are described that include compatible phosphorus compounds and incompatible phosphorus compounds that are incompatible with the mixture. It has been reported that by curing such a resin composition, a cured product having excellent low dielectric properties, flame retardance, etc. can be obtained (Patent Document 1).
  • the substrate material for constituting the insulating layer of the wiring board is also required to be a material that can yield a cured product that maintains excellent withstand voltage characteristics even after heat treatment and moisture absorption treatment.
  • wiring boards used in various electronic devices are also required to have excellent adhesion between the metal foil (wiring) and the insulating layer.
  • Metal-clad laminates and resin-coated metal foils used in manufacturing wiring boards and the like include not only an insulating layer but also a metal foil on the insulating layer.
  • the wiring board is also provided with not only an insulating layer but also wiring on the insulating layer. Examples of the wiring include wiring derived from metal foil provided in the metal-clad laminate or the like.
  • the wiring board does not peel off from the insulating layer even if the wiring provided on the wiring board is a finer wiring.
  • the wiring and the insulating layer have high adhesion in the wiring board. Therefore, metal-clad laminates are required to have high adhesion between the metal foil and the insulating layer, and the substrate material for forming the insulating layer of the wiring board must be a hardened material that has excellent adhesion to the metal foil. It is required that things be obtained.
  • the present invention has been made in view of the above circumstances, and has low dielectric properties (relative permittivity), excellent flame retardancy and adhesion to metal foil, high thermal conductivity, and It is possible to provide a resin composition from which a cured product is obtained in which deterioration of withstand voltage is suppressed.
  • the resin composition according to one aspect of the present invention comprises a radically polymerizable compound (A) having a carbon-carbon unsaturated double bond in the molecule, and a phosphoric acid ester compound (A) having an alicyclic hydrocarbon structure in the molecule.
  • B) and an inorganic filler (C), and the cured product thereof has a thermal conductivity of 1.0 W/m ⁇ K or more.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present invention.
  • the resin composition according to one embodiment of the present invention comprises a radically polymerizable compound (A) having a carbon-carbon unsaturated double bond in the molecule, and a phosphoric acid ester compound having an alicyclic hydrocarbon structure in the molecule. (B) and an inorganic filler (C), and the cured product has a thermal conductivity of 1.0 W/m ⁇ K or more.
  • a resin composition with such a structure has low dielectric properties (relative permittivity), excellent adhesion to metal foil and flame retardancy, high thermal conductivity, and high resistance to heat and moisture absorption after heat treatment and moisture absorption treatment.
  • a cured product with suppressed deterioration of withstand voltage can be obtained.
  • the thermal conductivity of the cured product of the resin composition is 1.0 W/m ⁇ K or more, the heat dissipation properties of a substrate such as a wiring board using the cured product of the resin composition can be improved.
  • the thermal conductivity is preferably 1.1 W/m ⁇ K or more, more preferably 1.2 W/m ⁇ K or more.
  • the upper limit of the thermal conductivity is not particularly limited, and is preferably a high value, but preferably 2.0 W/m ⁇ K or less. By setting the thermal conductivity to 2.0 W/m ⁇ K or less, a cured product with excellent adhesion to metal foil can be obtained more reliably.
  • the cured product of the resin composition has a relative dielectric constant of 3.2 to 3.8 at a frequency of 10 GHz.
  • the relative dielectric constant is more preferably 3.3 to 3.5.
  • the radically polymerizable compound (A) is not particularly limited as long as it is a radically polymerizable compound having a carbon-carbon unsaturated double bond in its molecule.
  • the radically polymerizable compound (A) preferably includes, for example, a polyphenylene ether compound (A1) having a carbon-carbon unsaturated double bond in the molecule. Thereby, low dielectric properties can be ensured in the cured product of the resin composition. It is more preferable to include the polyphenylene ether compound (A1) and the radically polymerizable compound (other radically polymerizable compound) (A2) other than the polyphenylene ether compound (A1). Examples of the other radically polymerizable compound (A2) include a curing agent for the polyphenylene ether compound (A1).
  • the polyphenylene ether compound (A1) is not particularly limited as long as it is a polyphenylene ether compound having a carbon-carbon unsaturated double bond in the molecule.
  • examples of the polyphenylene ether compound (A1) include polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the end. More specifically, the polyphenylene ether compound (A1) is a substituted polyphenylene ether compound having a carbon-carbon unsaturated double bond, such as a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond. Examples include polyphenylene ether compounds having a group at the end of the molecule.
  • the substituent having a carbon-carbon unsaturated double bond examples include a group represented by the following formula (3) and a group represented by the following formula (4). That is, the polyphenylene ether compound (A1) is, for example, a polyphenylene ether compound having in its molecule at least one selected from a group represented by the following formula (3) and a group represented by the following formula (4). etc.
  • the polyphenylene ether compound (A1) is preferably a polyphenylene ether compound having a group represented by the following formula (3) in the molecule. If so, low dielectric properties can be more reliably obtained in the cured product of the resin composition.
  • p represents 0 to 10.
  • Ar 3 represents an arylene group.
  • R 11 to R 13 are each independent. That is, R 11 to R 13 may be the same group or different groups.
  • R 11 to R 13 represent a hydrogen atom or an alkyl group.
  • the arylene group is not particularly limited.
  • Examples of the arylene group include monocyclic aromatic groups such as a phenylene group, and polycyclic aromatic groups such as a naphthalene ring.
  • the arylene group also includes derivatives in which the hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. .
  • the alkyl group is not particularly limited, 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.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • R 14 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.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • Examples of the group represented by the formula (3) include a vinylbenzyl group (ethenylbenzyl group) represented by the following formula (5). Furthermore, examples of the group represented by the formula (4) include an acryloyl group and a methacryloyl group.
  • the substituent includes vinylbenzyl groups (ethenylbenzyl groups) such as o-ethenylbenzyl group, m-ethenylbenzyl group, and p-ethenylbenzyl group, vinylphenyl group, and acryloyl group. group, and methacryloyl group.
  • the polyphenylene ether compound (A1) may have one type of substituent, or may have two or more types of substituents.
  • the polyphenylene ether compound (A1) may have, for example, any one of an o-ethenylbenzyl group, a m-ethenylbenzyl group, and a p-ethenylbenzyl group, or two types thereof. Or it may have three types.
  • the polyphenylene ether compound (A1) has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (6) in the molecule.
  • t represents 1 to 50.
  • R 15 to R 18 are each independent. That is, R 15 to R 18 may be the same group or different groups. Further, R 15 to R 18 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, hydrogen atoms and alkyl groups are preferred.
  • R 15 to R 18 Specific examples of the functional groups listed in R 15 to R 18 include the following.
  • the alkyl group is not particularly limited, but 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.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
  • the alkenyl group is not particularly limited, but 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.
  • examples of the alkenyl group include a vinyl group, an allyl group, and a 3-butenyl group.
  • the alkynyl group is not particularly limited, but 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.
  • examples of the alkynyl group 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, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable.
  • examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • examples of the alkenylcarbonyl group include an acryloyl group, a methacryloyl group, and a crotonoyl group.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • the alkynylcarbonyl group includes, for example, a propioloyl group.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyphenylene ether compound (A1) are not particularly limited, but specifically, it is preferably 500 to 5000, more preferably 800 to 4000. It is preferably 1,000 to 3,000. Note that the weight average molecular weight and number average molecular weight here may be those measured by a general molecular weight measurement method, and specifically, the values measured using gel permeation chromatography (GPC) are listed. It will be done.
  • t is such that the weight average molecular weight and number average molecular weight of the polyphenylene ether compound are within such ranges. It is preferable that the value is within the range. Specifically, t in the above formula (6) is preferably 1 to 50.
  • the polyphenylene ether compound (A1) When the weight average molecular weight and number average molecular weight of the polyphenylene ether compound (A1) are within the above ranges, the polyphenylene ether has excellent low dielectric properties, and the cured product not only has excellent heat resistance but also has good moldability. will also be excellent. This is thought to be due to the following. When the weight average molecular weight and number average molecular weight of ordinary polyphenylene ether are within the above ranges, the heat resistance tends to decrease because the molecular weight is relatively low. In this regard, since the polyphenylene ether compound (A1) has one or more unsaturated double bonds at the terminal, it is thought that as the curing reaction progresses, a cured product with sufficiently high heat resistance can be obtained. .
  • the weight average molecular weight and number average molecular weight of the polyphenylene ether compound (A1) are within the above ranges, it is considered to have a relatively low molecular weight and therefore has excellent moldability. Therefore, it is thought that such a polyphenylene ether compound not only provides a cured product with excellent heat resistance but also excellent moldability.
  • the average number of the substituents (number of terminal functional groups) at the molecular ends per molecule of the polyphenylene ether compound is not particularly limited, but specifically, 1 to 5.
  • the number is preferably 1 to 3, more preferably 1 to 3, and 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. Furthermore, if the number of terminal functional groups is too large, the reactivity becomes too high, which may cause problems such as a decrease in the storage stability of the resin composition or a decrease in the fluidity of the resin composition. In other words, when such a polyphenylene ether compound is used, molding defects such as voids occur during multilayer molding due to insufficient fluidity, resulting in poor moldability that makes it difficult to obtain a highly reliable printed wiring board. Problems may occur.
  • 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 polyphenylene ether compounds present in 1 mole of the polyphenylene ether compound.
  • the number of terminal functional groups can be determined, for example, by measuring the number of hydroxyl groups remaining in the obtained polyphenylene ether compound and calculating the decrease from the number of hydroxyl groups in the polyphenylene ether before having the substituent (before modification). , can be measured.
  • the number of terminal functional groups is the decrease from the number of hydroxyl groups in the polyphenylene ether before modification.
  • the method for measuring the number of hydroxyl groups remaining in a polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of the polyphenylene ether compound, and measure the UV absorbance of the mixed solution. It can be found by
  • the intrinsic viscosity of the polyphenylene ether compound (A1) is not particularly limited, but specifically, it may be from 0.03 to 0.12 dl/g, but preferably from 0.04 to 0.11 dl/g. It is preferably 0.06 to 0.095 dl/g, and more preferably 0.06 to 0.095 dl/g. If the intrinsic viscosity is too low, the molecular weight tends to be low, making it difficult to obtain low dielectric properties such as a low dielectric constant and a low dielectric loss tangent. Moreover, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. 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, and more specifically, for example, a 0.18 g/45 ml methylene chloride solution (liquid temperature 25°C) is measured using a viscometer. These are the values measured in . Examples of this viscometer include AVS500 Visco System manufactured by Schott.
  • polyphenylene ether compound (A1) examples include a polyphenylene ether compound represented by the following formula (7), a polyphenylene ether compound represented by the following formula (8), and the like. Further, as the polyphenylene ether compound (A1), these polyphenylene ether compounds may be used alone, or these two types of polyphenylene ether compounds may be used in combination.
  • R 19 to R 26 and R 27 to R 34 are each independent. That is, R 19 to R 26 and R 27 to R 34 may be the same group or different groups. Furthermore, R 19 to R 26 and R 27 to R 34 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • X 1 and X 2 are each independent. That is, X 1 and X 2 may be the same group or different groups. X 1 and X 2 represent substituents having a carbon-carbon unsaturated double bond.
  • a and B represent repeating units represented by the following formula (9) and the following formula (10), respectively.
  • Y represents a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms.
  • R 35 to R 38 and R 39 to R 42 are each independent. That is, R 35 to R 38 and R 39 to R 42 may be the same group or different groups. Further, R 35 to R 38 and R 39 to R 42 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.
  • the polyphenylene ether compound represented by the formula (7) and the polyphenylene ether compound represented by the formula (8) are not particularly limited as long as they satisfy the above configuration.
  • R 19 to R 26 and R 27 to R 34 are each independent, as described above. That is, R 19 to R 26 and R 27 to R 34 may be the same group or different groups.
  • R 19 to R 26 and R 27 to R 34 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, hydrogen atoms and alkyl groups are preferred.
  • m and n each preferably represent 0 to 20, as described above. Further, m and n preferably represent numerical values such that the total value of m and n is 1 to 30. Therefore, it is more preferable that m represents 0 to 20, n represents 0 to 20, and the sum of m and n represents 1 to 30. Further, R 35 to R 38 and R 39 to R 42 are each independent. That is, R 35 to R 38 and R 39 to R 42 may be the same group or different groups.
  • R 35 to R 38 and R 39 to R 42 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.
  • hydrogen atoms and alkyl groups are preferred.
  • R 19 to R 42 are the same as R 15 to R 18 in the above formula (6).
  • Y is a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms, as described above.
  • Examples of Y include a group represented by the following formula (11).
  • R 43 and R 44 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group include a methyl group.
  • the group represented by formula (11) include a methylene group, a methylmethylene group, and a dimethylmethylene group, and among these, a dimethylmethylene group is preferred.
  • X 1 and X 2 are each independently a substituent having a carbon-carbon double bond.
  • X 1 and X 2 may be the same group or different groups. You can.
  • polyphenylene ether compound represented by the formula (7) include, for example, the polyphenylene ether compound represented by the following formula (12).
  • polyphenylene ether compound represented by the formula (8) include, for example, a polyphenylene ether compound represented by the following formula (13), a polyphenylene ether compound represented by the following formula (14), etc. can be mentioned.
  • m and n are the same as m and n in the above formula (9) and the above formula (10). Furthermore, in the above formula (12) and the above formula (13), R 11 to R 13 , p, and Ar 3 are the same as R 11 to R 13 , p, and Ar 3 in the above formula (3). Further, in the above formula (13) and the above formula (14), Y is the same as Y in the above formula (8). Further, in the above formula (14), R 14 is the same as R 14 in the above formula (4).
  • the method for synthesizing the polyphenylene ether compound (A1) used in this embodiment is not particularly limited as long as it can synthesize a polyphenylene ether compound having a carbon-carbon unsaturated double bond in the molecule.
  • this method includes a method in which polyphenylene ether is reacted with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded.
  • Examples of compounds in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include a compound in which a substituent represented by the formulas (3) to (5) above and a halogen atom are bonded.
  • Examples include compounds.
  • Specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and among these, a chlorine atom is preferred.
  • the compounds in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include o-chloromethylstyrene, p-chloromethylstyrene, m-chloromethylstyrene, etc. can be mentioned.
  • the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded may be used alone or in combination of two or more.
  • o-chloromethylstyrene, p-chloromethylstyrene, and m-chloromethylstyrene may be used alone, or two or three types may be used in combination.
  • the raw material polyphenylene ether is not particularly limited as long as it can ultimately synthesize a predetermined polyphenylene ether compound.
  • polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene oxide) and polyphenylene ethers composed of 2,6-dimethylphenol and at least one of bifunctional phenols and trifunctional phenols are used. Examples include those having the main component.
  • a bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like.
  • trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.
  • Examples of the method for synthesizing the polyphenylene ether compound (A1) include the method described above. Specifically, polyphenylene ether as described above and a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded are dissolved in a solvent and stirred. By doing so, the polyphenylene ether and the compound in which the substituent having the carbon-carbon unsaturated double bond and the halogen atom are bonded react, and the polyphenylene ether compound used in this embodiment is obtained.
  • the reaction is preferably carried out in the presence of an alkali metal hydroxide. It is thought that this reaction proceeds suitably by doing so. This is considered to be because the alkali metal hydroxide functions as a dehydrohalogenation agent, specifically, as a dehydrochlorination agent. That is, the alkali metal hydroxide eliminates hydrogen halide from the phenol group of polyphenylene ether, the compound in which the substituent having the carbon-carbon unsaturated double bond and the halogen atom are bonded, and so on. By doing so, it is thought that the substituent having the carbon-carbon unsaturated double bond bonds to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of polyphenylene ether.
  • the alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide. Further, the alkali metal hydroxide is usually used in the form of an aqueous solution, specifically, as an aqueous sodium hydroxide solution.
  • Reaction conditions such as reaction time and reaction temperature vary depending on the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and the reaction conditions such as reaction time and reaction temperature are determined under conditions that allow the above-mentioned reaction to proceed suitably. If so, there are no particular limitations.
  • the reaction temperature is preferably room temperature to 100°C, more preferably 30 to 100°C.
  • the reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.
  • the solvent used during the reaction can dissolve polyphenylene ether and the compound in which a substituent having the carbon-carbon unsaturated double bond and a halogen atom are bonded, and the solvent can dissolve the polyphenylene ether and the compound having the carbon-carbon unsaturated double bond. It is not particularly limited as long as it does not inhibit the reaction between a substituent having a double bond and a compound to which a halogen atom is bonded. Specifically, toluene etc. are mentioned.
  • the above reaction is preferably carried out in the presence of not only the alkali metal hydroxide but also a phase transfer catalyst. That is, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. It is thought that by doing so, the above reaction proceeds more suitably. This is thought to be due to the following. Phase transfer catalysts have the ability to take up alkali metal hydroxides, are soluble in both polar solvent phases such as water, and non-polar solvent phases such as organic solvents, and transfer between these phases. This is thought to be due to the fact that it is a catalyst that can transfer .
  • aqueous sodium hydroxide solution when used as the alkali metal hydroxide and an organic solvent such as toluene that is incompatible with water is used as the solvent, the aqueous sodium hydroxide solution is subjected to the reaction. Even if it is added dropwise to the solvent, the solvent and the aqueous sodium hydroxide solution will separate, and it is thought that the sodium hydroxide will be difficult to transfer to the solvent. In this case, it is thought that the aqueous sodium hydroxide solution added as the alkali metal hydroxide becomes less likely to contribute to the promotion of the reaction.
  • the phase transfer catalyst is not particularly limited, but includes, for example, quaternary ammonium salts such as tetra-n-butylammonium bromide.
  • the resin composition used in this embodiment preferably contains the polyphenylene ether compound obtained as described above as the polyphenylene ether compound.
  • Examples of the radically polymerizable compounds (other radically polymerizable compounds) (A2) other than the polyphenylene ether compound include vinyl compounds, allyl compounds, methacrylate compounds, acrylate compounds, and acenaphthylene compounds.
  • the vinyl compound is a compound having a vinyl group in the molecule.
  • 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 monofunctional vinyl compound include styrene compounds and the like.
  • the polyfunctional vinyl compound include polyfunctional aromatic vinyl compounds, vinyl hydrocarbon compounds, and the like.
  • examples of the polyfunctional aromatic vinyl compound include divinylbenzene and the like.
  • examples of the vinyl hydrocarbon compounds include polybutadiene compounds and the like.
  • the allyl compound is a compound having an allyl group in the molecule, and includes, for example, triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).
  • triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).
  • the methacrylate compound is a compound having a methacryloyl group in the molecule, and includes, for example, a monofunctional methacrylate compound having one methacryloyl group in the molecule, and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule. It will be done.
  • the monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
  • Examples of the polyfunctional methacrylate compound include dimethacrylate compounds such as tricyclodecane dimethanol dimethacrylate (DCP).
  • the acrylate compound is a compound having an acryloyl group in the molecule, and includes, for example, a monofunctional acrylate compound having one acryloyl group in the molecule, and a polyfunctional acrylate compound having two or more acryloyl groups in the molecule. It will be done.
  • the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • Examples of the polyfunctional acrylate compound include diacrylate compounds such as tricyclodecane dimethanol diacrylate.
  • the acenaphthylene compound is a compound having an acenaphthylene structure in its molecule.
  • the acenaphthylene compound include acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes.
  • the alkylacenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, and 3-ethylacenaphthylene.
  • Examples include phthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, and the like.
  • Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, and 3-bromoacenaphthylene.
  • Examples include ethylene, 4-bromoacenaphthylene, 5-bromoacenaphthylene, and the like.
  • phenylacenaphthylenes examples include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, and 5-phenylacenaphthylene.
  • 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. .
  • the radically polymerizable compound (A) may be composed of the polyphenylene ether compound (A1), or may be composed of the radically polymerizable compound (other radically polymerizable compound) other than the polyphenylene ether compound (A1) ( A2) may also be used.
  • the radically polymerizable compound (A) preferably contains the polyphenylene ether compound (A1), and the polyphenylene ether compound (A1) and the other radically polymerizable compound (A2) are combined. It is more preferable to include.
  • the other radically polymerizable compounds (A2) may be used alone or in combination of two or more.
  • the other radically polymerizable compounds (A2) include polyfunctional aromatic vinyl compounds, allyl compounds, polyfunctional methacrylate compounds, polyfunctional acrylate compounds, polybutadiene compounds, acenaphthylene compounds, and styrene. Compounds etc. are preferred.
  • divinylbenzene and acenaphthylene are more preferable among the above-mentioned radically polymerizable compounds. deterioration can be suppressed more reliably.
  • the weight average molecular weight of the radically polymerizable compound (A) varies depending on the radically polymerizable compound (A) and is not particularly limited, but for example, it is preferably less than 10,000, and preferably from 500 to 5000. More preferred.
  • the radically polymerizable compound (A) is, for example, the polyphenylene ether compound (A1)
  • its weight average molecular weight is preferably from 500 to 5,000, and preferably from 800 to 4,000, as described above. is more preferable, and even more preferably 1000 to 3000.
  • the weight average molecular weight here may be one measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC), etc. can be mentioned.
  • the content of the polyphenylene ether compound (A1) is 50 to 90 parts by mass based on 100 parts by mass of the radically polymerizable compound (A). Parts by mass are preferred.
  • the content of the polyphenylene ether compound (A1) is within the above range, the resin composition can be suitably cured, and the cured product has excellent low dielectric properties, adhesion to metal foil, and While maintaining flame retardancy, it is possible to increase thermal conductivity and suppress deterioration of withstand voltage after heat treatment and moisture absorption treatment.
  • a more preferable range is 60 to 80 parts by mass.
  • the phosphoric ester compound (B) is not particularly limited as long as it is a phosphoric ester compound having an alicyclic hydrocarbon structure in its molecule. Since the phosphoric acid ester compound (B) is a phosphoric acid ester compound having an alicyclic hydrocarbon structure in its molecule, even if a compatible phosphorus flame retardant is used as a flame retardant, the cured product of the resin composition is It is possible to suppress the generation of phosphate ions due to heat treatment, suppress deterioration of withstand voltage after heat treatment and moisture absorption treatment, impart flame retardancy, and ensure low dielectric properties.
  • the alicyclic hydrocarbon structure is not particularly limited, and, for example, a 3- to 12-membered saturated alicyclic hydrocarbon structure is preferred, and a 5- to 7-membered saturated alicyclic hydrocarbon structure is more preferred. That is, the phosphoric acid ester compound (B) preferably contains a 3- to 12-membered saturated alicyclic hydrocarbon structure as the alicyclic hydrocarbon structure; More preferably, it contains a hydrocarbon structure.
  • the alicyclic hydrocarbon structure include a divalent group of a saturated alicyclic hydrocarbon, which may have a substituent bonded to carbon forming the ring.
  • the alicyclic hydrocarbon structure may be a monocyclic alicyclic hydrocarbon structure or a polycyclic alicyclic hydrocarbon structure.
  • the alicyclic hydrocarbon structure include divalent groups of cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane.
  • Examples of the polycyclic alicyclic hydrocarbon structure include divalent groups of bicyclic alicyclic hydrocarbons and divalent groups of tricyclic alicyclic hydrocarbons.
  • Examples of the divalent group of the bicyclic alicyclic hydrocarbon include bicyclo[1.1.0]butane, bicyclo[3.2.1]octane, bicyclo[5.2.0]nonane, and bicyclo [4.3.2] Divalent groups of bicyclic alicyclic hydrocarbons such as undecane and the like can be mentioned.
  • Examples of the divalent group of the tricyclic alicyclic hydrocarbon include tricyclic alicyclic groups such as tricyclo[2.2.1.0]heptane and tricyclo[5.3.1.1]dodecane. Examples include divalent groups of formula hydrocarbons.
  • the alicyclic hydrocarbon structure may be used alone or in combination of two or more.
  • the substituent bonded to the carbon forming the ring is not particularly limited, and includes, for example, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group, More specifically, the substituents listed below as R 1 to R 10 may be mentioned. These substituents may be used alone or in combination of two or more. That is, the number of substituents bonded to the carbon constituting the ring of the alicyclic hydrocarbon structure may be one, or two or more, and in the case of two or more, each substituent is , may be the same group or may be different groups.
  • each of the substituents may be bonded to the same carbon among the carbons constituting the ring of the alicyclic hydrocarbon structure, or may be bonded to different carbon atoms. May be bonded to carbon.
  • the alicyclic hydrocarbon structure includes divalent groups represented by the following formulas (15) to (18).
  • Examples of the phosphoric ester compound (B) include phosphoric ester compounds having at least one structure represented by the following formula (1) in the molecule. That is, examples of the phosphoric ester compound (B) include phosphoric ester compounds containing a structure represented by the following formula (1) as a structure containing phosphorus in the phosphoric ester compound (B). More specifically, examples of the phosphoric ester compound (B) include phosphoric ester compounds having the alicyclic hydrocarbon structure and a structure represented by the following formula (1) in the molecule.
  • R 1 to R 10 are each independent. That is, R 1 to R 10 may be the same group or different groups. Further, R 1 to R 10 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 1 , R 5 , R 6 , and R 10 are atoms other than hydrogen atoms, that is, alkyl groups, alkenyl groups, alkynyl groups, formyl groups, and alkyl groups.
  • R 1 to R 10 in the formula (1) include the following groups.
  • the alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. Further, R 1 , R 5 , R 6 and R 10 are particularly preferably alkyl groups having 1 to 4 carbon atoms.
  • the alkyl group may be linear or branched.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1- Methylbutyl group, 1,2-dimethylpropyl group, neopentyl group (2,2-dimethylpropyl group), tert-pentyl group (1,1-dimethylpropyl group), n-hexyl group, isohexyl group, 1-methylpentyl group , 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2 -dimethylbutyl group, 2,3-dimethylbutyl
  • the alkenyl group is not particularly limited, and is preferably an alkenyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 1 to 6 carbon atoms, and even more preferably an alkenyl group having 1 to 4 carbon atoms. Further, R 1 , R 5 , R 6 and R 10 are particularly preferably alkenyl groups having 1 to 4 carbon atoms.
  • the alkenyl group may be linear or branched.
  • alkenyl group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, 2-methyl Butoxy group, 1-methylbutoxy group, 1,2-dimethylpropoxy group, neopentyloxy group (2,2-dimethylpropoxy group), tert-pentyloxy group (1,1-dimethylpropoxy group), n-hexyloxy group, isohexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1,1-dimethylbutoxy group, 1, 2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethyl-1-methylpropoxy
  • the alkynyl group is not particularly limited, but is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms.
  • examples of the alkynyl group 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, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable.
  • examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • examples of the alkenylcarbonyl group include an acryloyl group, a methacryloyl group, and a crotonoyl group.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable.
  • the alkynylcarbonyl group includes, for example, a propioloyl group.
  • the structure represented by the formula (1) includes any one of a hydrogen atom, the alkyl group, the alkenyl group, the alkynyl group, the formyl group, the alkylcarbonyl group, the alkenylcarbonyl group, and the alkynylcarbonyl group. It may have seeds or a combination of two or more types.
  • the phosphoric ester compound (B) includes a phosphoric ester compound having a structure represented by the following formula (2), and preferably contains this phosphoric ester compound.
  • Ar 1 and Ar 2 each independently represent an arylene group.
  • T represents a divalent group of a 3- to 12-membered saturated alicyclic hydrocarbon.
  • the arylene group is not particularly limited.
  • Examples of the arylene group include monocyclic aromatic groups such as a phenylene group, and polycyclic aromatic groups such as a naphthalene ring.
  • Examples of the arylene group include a group represented by the following formula (19).
  • R 45 to R 48 are each independent. That is, R 45 to R 48 may be the same group or different groups. Furthermore, R 45 to R 48 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 45 to R 48 in the formula (19) include the same groups as R 1 to R 10 in the formula (1).
  • phosphoric ester compound having the structure represented by the above formula (2) include, for example, the phosphoric ester compound represented by the following formula (20).
  • R 49 to R 68 are each independent. That is, R 49 to R 68 may be the same group or different groups. Further, R 49 to R 68 in the above formula (20) include the same groups as R 1 to R 10 in the above formula (1), such as a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, and an alkyl group. Indicates a carbonyl group, alkenylcarbonyl group, or alkynylcarbonyl group. Moreover, Ar 1 , Ar 2 and T are the same as Ar 1 , Ar 2 and T in the above formula (2).
  • phosphoric acid ester compound (B) include, for example, compounds represented by the following formulas (21) to (24).
  • the phosphoric acid ester compound (B) may be used alone or in combination of two or more.
  • the method for producing the phosphoric ester compound (B) is not particularly limited as long as the phosphoric ester compound (B) can be produced, and any known method can be used.
  • Examples of the method for producing the phosphoric acid ester compound (B) include a method using phosphoryl chloride (phosphorus oxychloride).
  • the content of the phosphoric acid ester compound (B) is preferably 15 to 50 parts by mass, more preferably 15 to 35 parts by mass, based on 100 parts by mass of the radically polymerizable compound (A). , more preferably 15 to 25 parts by mass.
  • the obtained cured product tends to have insufficient flame retardancy.
  • the content of the phosphoric acid ester compound (B) is too large, the content of the radically polymerizable compound (A) becomes relatively too small, and after heat treatment and moisture absorption treatment of the obtained cured product, The withstand voltage tends to deteriorate. From these facts, when the content of the phosphoric acid ester compound (B) is 15 to 50 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A), heat treatment and moisture absorption treatment in the cured product are possible. A resin composition that can exhibit sufficient flame retardancy while suppressing subsequent deterioration of withstand voltage can be obtained.
  • the resin composition may contain a flame retardant other than the phosphoric acid ester compound (B).
  • the resin composition further includes the incompatible phosphorus compound (D). That is, it is preferable that the resin composition contains the phosphoric acid ester compound (B) and the incompatible phosphorus compound (D) as compounds that can act as a flame retardant. By using the phosphoric acid ester compound (B) and the incompatible phosphorus compound (D) together, in the cured product of the resin composition, flame retardance is ensured while reducing adhesion to the metal foil. Can be suppressed.
  • the incompatible phosphorus compound (D) is not particularly limited as long as it acts as a flame retardant and is incompatible with the mixture.
  • the term "incompatible” refers to a state in which the target substance (phosphorus compound) is not compatible with the radically polymerizable compound (A) and is dispersed in the form of islands in the mixture.
  • the incompatible phosphorus compound (D) include compounds containing phosphorus and forming salts, such as phosphinate compounds, polyphosphate compounds, and phosphonium salt compounds, and phosphine oxide compounds.
  • examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, and bisdiphenyl.
  • examples of the polyphosphate compound include melamine polyphosphate, melam polyphosphate, and melem polyphosphate.
  • examples of the phosphonium salt compound include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, and the like.
  • examples of phosphine oxide compounds include phosphine oxide compounds having two or more diphenylphosphine oxide groups in the molecule (diphenylphosphine oxide compounds), and more specifically, paraxylylenebisdiphenylphosphine oxide, etc. can be mentioned. Further, the above-mentioned incompatible phosphorus compounds may be used alone or in combination of two or more.
  • the content of the phosphoric acid ester compound (B) is 25 to 100 parts by mass based on a total of 100 parts by mass of the phosphoric acid ester compound (B) and the incompatible phosphorus compound (D). parts, more preferably 25 to 75 parts by weight, and most preferably 25 to 50 parts by weight.
  • the content of the phosphoric acid ester compound (B) is 25 to 100 parts by mass based on the total of 100 parts by mass of the phosphoric acid ester compound (B) and the incompatible phosphorus compound (D), It is possible to obtain a cured product that has excellent adhesion to metal foil while ensuring flame retardancy.
  • the resin composition according to this embodiment further contains an inorganic filler (C).
  • the inorganic filler (C) is not particularly limited as long as it can be used as an inorganic filler contained in a resin composition, but examples include boron nitride filler, silica filler, aluminum oxide filler, titanium oxide filler, and titanium oxide filler.
  • Metal oxide fillers such as magnesium fillers and mica fillers, aluminum hydroxide fillers, and metal hydroxide fillers such as magnesium hydroxide fillers, talc fillers, aluminum borate fillers, barium sulfate fillers, aluminum nitride fillers, silicon nitride fillers, Examples include magnesium carbonate fillers such as anhydrous magnesium carbonate fillers, calcium carbonate fillers, and the like.
  • the boron nitride filler is not particularly limited, and examples include hexagonal normal pressure phase (h-BN) filler, cubic high pressure phase (c-BN) filler, and the like.
  • the silica filler is not particularly limited, and examples thereof include crushed silica filler and silica particle filler, and silica particle filler is preferable.
  • examples of the silica particle filler include crystalline silica filler, amorphous silica filler, fused silica filler, precipitated silica filler, etc., and fused silica filler is preferable.
  • the magnesium carbonate filler is not particularly limited, but anhydrous magnesium carbonate (synthetic magnesite) filler is preferable.
  • These inorganic fillers may be used alone or in combination of two or more.
  • the inorganic fillers as exemplified above include an inorganic filler (C-1) with a thermal conductivity of 10 W/m ⁇ K or more and an inorganic filler (C-1) with a thermal conductivity of less than 10 W/m ⁇ K.
  • the inorganic filler (C) preferably includes an inorganic filler (C-1) having a thermal conductivity of 10 W/m ⁇ K or more. It is thought that this makes it possible to more reliably achieve high thermal conductivity in the cured product of the resin composition.
  • the inorganic filler (C) includes an inorganic filler (C-1) with a thermal conductivity of 10 W/m ⁇ K or more, and an inorganic filler (C-2) with a thermal conductivity of less than 10 W/m ⁇ K. ).
  • the inorganic filler (C-1) and the inorganic filler (C-2) together as the inorganic filler (C) it is possible to ensure adhesion to the metal foil and to achieve high filling of the inorganic filler. This has the advantage that deterioration of withstand voltage after heat treatment and moisture absorption treatment due to chemical reaction can be suppressed.
  • Examples of the inorganic filler (C-1) include boron nitride filler, aluminum oxide filler, magnesium oxide filler, magnesium carbonate filler, silicon nitride filler, aluminum nitride filler, and the like.
  • the inorganic filler (C-1) boron nitride filler, aluminum oxide filler, magnesium oxide filler, and magnesium carbonate filler are preferable, and boron nitride filler is more preferable.
  • the inorganic filler (C-1) contains a boron nitride filler, that is, the inorganic filler (C) contains a boron nitride filler, thereby ensuring low dielectric properties in the cured product of the resin composition.
  • the heat dissipation properties of a cured product and a substrate such as a wiring board using the cured product can be improved.
  • the inorganic filler (C-1) the inorganic fillers exemplified above may be used alone or in combination of two or more.
  • Examples of the inorganic filler (C-2) include fused silica filler, magnesium hydroxide filler, mica filler, and the like. Among these, fused silica filler is preferable as the inorganic filler (C-2). As the inorganic filler (C-2), the inorganic fillers exemplified above may be used alone or in combination of two or more.
  • the inorganic filler (C) may be a surface-treated inorganic filler or may be a surface-untreated inorganic filler. Furthermore, examples of the surface treatment include treatment with a silane coupling agent.
  • silane coupling agent examples include a silane coupling agent having at least one functional group selected from the group consisting of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group. 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, and also has a methoxy group, an ethoxy group, etc. Examples include compounds having a hydrolyzable group.
  • the silane coupling agent has a vinyl group, and examples thereof include vinyltriethoxysilane and vinyltrimethoxysilane.
  • the silane coupling agent has a styryl group, and examples thereof include p-styryltrimethoxysilane and p-styryltriethoxysilane.
  • the silane coupling agent has a methacryloyl group, and examples thereof include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylethyldiethoxysilane.
  • the silane coupling agent has an acryloyl group, and examples thereof include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.
  • Examples of the silane coupling agent that has a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.
  • the content of the inorganic filler (C) is preferably 100 to 380 parts by mass based on 100 parts by mass of the radically polymerizable compound (A). Thereby, in the cured product of the resin composition, deterioration of withstand voltage after heat treatment and moisture absorption treatment can be more reliably suppressed.
  • the content of the inorganic filler (C) is more preferably 200 to 380 parts by mass, and even more preferably 300 to 380 parts by mass, based on 100 parts by mass of the radically polymerizable compound (A). .
  • the inorganic filler (C) includes an inorganic filler (C-1) having a thermal conductivity of 10 W/m ⁇ K or more
  • the inorganic filler (C-1) is The content of the filler (C-1) is preferably 25 to 100 parts by mass. It is thought that this makes it possible to more reliably achieve high thermal conductivity in the cured product of the resin composition.
  • the inorganic filler (C-1) contains a boron nitride filler
  • the content of the boron nitride filler is the same as that of the inorganic filler (C).
  • the amount is preferably 25 to 100 parts by weight per 100 parts by weight. It is thought that this makes it possible to more reliably achieve high thermal conductivity in the cured product of the resin composition.
  • the content of the boron nitride filler is more preferably 25 to 70 parts by mass, and even more preferably 30 to 50 parts by mass, based on 100 parts by mass of the inorganic filler (C).
  • the inorganic filler (C) includes an inorganic filler (C-1) having a thermal conductivity of 10 W/m ⁇ K or more, and an inorganic filler (C-2) having a thermal conductivity of less than 10 W/m ⁇ K.
  • the content of the inorganic filler (C-1) is 25 parts by mass based on a total of 100 parts by mass of the inorganic filler (C-1) and the inorganic filler (C-2).
  • the amount is preferably 70 parts by mass.
  • the content of the inorganic filler (C-1) is 25 to 50 parts by mass based on a total of 100 parts by mass of the inorganic filler (C-1) and the inorganic filler (C-2).
  • the amount is more preferably 25 to 40 parts by mass.
  • the peak of the particle size distribution measured by laser diffraction particle size distribution measuring method is 1.0 to 50.0 ⁇ m. It is preferable that at least two of them exist in the range of . That is, in the inorganic filler used in this embodiment, it is preferable that inorganic fillers having at least two types of peak particle sizes (peak tops) are mixed.
  • inorganic filler having at least two peaks within the above particle size range high thermal conductivity and low dielectric properties (Dk) can be achieved in the cured product of the resin composition.
  • 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 sizes (peak tops). Fillers are mixed. It is thought that this makes it possible to ensure both adhesion with the metal foil and high thermal conductivity.
  • the particle size distribution is a value measured by particle size distribution measurement using a laser diffraction/scattering method.
  • the particle size distribution measuring device "LA-960V2" used in the examples described below manufactured by Horiba, Ltd.
  • the peak refers to the maximum value in a particle size distribution graph, and specifically, in a particle size distribution graph where the horizontal axis is the particle diameter and the vertical axis is the relative particle amount (frequency). This is the numerical value obtained by the maximum value of .
  • the resin composition according to the present embodiment may contain components other than the above-mentioned components (other components), as necessary, within a range that does not impair the effects of the present invention.
  • 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, It may further contain additives such as antistatic agents, ultraviolet absorbers, dyes and pigments, dispersants, and lubricants.
  • the resin composition of the present embodiment also contains a thermosetting resin such as an epoxy resin, a maleimide resin, an aromatic hydrocarbon resin, and an aliphatic hydrocarbon resin. Good too.
  • the resin composition of the present embodiment may further contain a styrene polymer in addition to the components described above. It is thought that the resin composition containing the styrene polymer has the advantage of further lowering the dielectric constant of the resin.
  • the styrenic polymer used in this embodiment is, for example, a polymer obtained by polymerizing a monomer containing a styrene monomer, and may be a styrene copolymer.
  • the styrenic copolymer is, for example, a copolymer of one or more styrene monomers and one or more other monomers copolymerizable with the styrene monomer. Examples include the resulting copolymers.
  • the styrene monomer include styrene, styrene derivatives, and styrene in which some of the hydrogen atoms are substituted with substituents.
  • polystyrenic polymer As a specific styrenic polymer, a wide variety of conventionally known polymers can be used, and is not particularly limited. Examples include polymers having the following.
  • R 69 to R 71 each independently represent a hydrogen atom or an alkyl group
  • R 72 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an isopropenyl group. Indicates the 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 this embodiment preferably contains at least one type of structural unit represented by the above formula (25), but may contain a combination of two or more different types. Moreover, it is preferable that the styrenic polymer includes a structure in which structural units represented by the above formula (25) are repeated.
  • styrenic polymers include those obtained by polymerizing or copolymerizing one or more styrene monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene, divinylbenzene, and allylstyrene.
  • styrene monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene, divinylbenzene, and allylstyrene.
  • examples include polymers or copolymers, and more specific examples include styrene-butadiene copolymers, styrene-isobutylene copolymers, and the like.
  • the styrenic polymer may be a hydrogenated styrene polymer, such as hydrogenated methylstyrene (ethylene/butylene) methylstyrene copolymer, hydrogenated methylstyrene (ethylene-ethylene /propylene) methylstyrene copolymer, hydrogenated styrene isoprene copolymer, hydrogenated styrene isoprene styrene copolymer, hydrogenated styrene (ethylene/butylene) styrene copolymer, and hydrogenated styrene (ethylene-ethylene/propylene) Examples include styrene copolymers.
  • styrene-based polymer those exemplified above may be used alone, or two or more types may be used in combination.
  • the moisture absorption rate of the cured product of the resin composition can be suppressed, and the deterioration of electrical properties due to an increase in the amount of moisture absorption can be suppressed. It can also be effective.
  • the molar fraction of the structural unit is about 10 to 70% with respect to the entire polymer. It is preferably 15% to 65%, more preferably 15% to 65%.
  • the polymerization form of the styrenic polymer is not particularly limited, and may be a block copolymer, an alternating copolymer, a random copolymer, a 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 this embodiment is preferably about 10,000 to 200,000, more preferably about 20,000 to 150,000.
  • the weight average molecular weight is within the above range, there is an advantage that appropriate resin fluidity can be ensured in the B stage of the cured resin product.
  • the number average molecular weight here may be one measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography, etc. can be mentioned.
  • the styrenic polymer more desirably includes a styrene-isobutylene-styrene block copolymer (SIBS) containing a structural unit represented by the following formula (26).
  • SIBS styrene-isobutylene-styrene block copolymer
  • a1, a2 represents an integer of 1,000 to 60,000
  • b represents an integer of 1,000 to 70,000
  • the sum of a1, a2 and b is 10, 000 to 130,000.
  • the method for producing the styrenic polymer used in this embodiment is not particularly limited, for example, 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. It can be synthesized by polymerization.
  • the styrenic polymer of this embodiment can be a commercially available one, such as "SIBSTAR (registered trademark) 073T", “SIBSTAR (registered trademark) 103T", “SIBSTAR (registered trademark)” manufactured by Kaneka Corporation. ) 102T” and “Septon V9827” manufactured by Kuraray Co., Ltd..
  • the content of the styrene polymer is not particularly limited, but is 1 to 30 parts by mass based on 100 parts by mass of the radically polymerizable compound (A). It is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight.
  • the content of the styrene polymer is 30 parts by mass or less based on 100 parts by mass of the radically polymerizable compound (A)
  • the cured product of the resin composition has excellent moldability and flame retardancy. is more reliably obtained, and by using 1 part by mass or more, low dielectric properties can be more reliably ensured in the cured product of the resin composition.
  • the resin composition of this embodiment may contain a free radical compound. It is thought that the inclusion of the free radical compound in the resin composition has 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 used as a polymerization inhibitor.
  • More specific free radical compounds that can be 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-oxylbenzoate free radical, 4-isothiocyanato-2,2,6, 6-tetramethylpiperidine 1-oxyl free radical, 4-(2-iodoacetamido)-2,2,6,6-tetramethylpiperidine 1-
  • the content of the free radical compound is not particularly limited, but is 0.01 to 0.0 with respect to 100 parts by mass of the radically polymerizable compound (A).
  • the amount is preferably 0.1 part by weight, and more preferably 0.01 to 0.05 part by weight.
  • the resin composition according to the present embodiment may contain a reaction initiator (initiator). Even if the resin composition contains, for example, the polyphenylene ether compound and the curing agent, the curing reaction can proceed. However, depending on the process conditions, it may be difficult to raise the temperature to a high temperature until curing progresses, so a reaction initiator may be added.
  • a reaction initiator initiator
  • the reaction initiator is not particularly limited as long as it can promote the curing reaction of the resin composition.
  • Specific examples include metal oxides, azo compounds, and organic peroxides.
  • metal oxide examples include carboxylic acid metal salts.
  • 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. can be mentioned.
  • the azo compounds include 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'- Examples include azobis(2-methylbutyronitrile).
  • reaction initiators are 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide), and the like. These reaction initiators have little effect on dielectric properties.
  • reaction initiation temperature is relatively high, it is possible to suppress the acceleration of the curing reaction at a time when curing is not necessary, such as when drying the prepreg, and it is possible to suppress a decrease in the storage stability of the resin composition. This is because it has the advantage of being possible.
  • reaction initiators as described above may be used alone or in combination of two or more.
  • the content thereof is not particularly limited, but is 0.5 to 3 parts by mass based on 100 parts by mass of the radically polymerizable compound (A).
  • the amount is preferably 0.5 to 2 parts by mass, and more preferably 0.5 to 2 parts by mass.
  • the resin composition according to this embodiment may contain a silane coupling agent.
  • the silane coupling agent may be contained in the resin composition as it is, or may be contained as a silane coupling agent used when surface-treating the inorganic filler in advance.
  • the silane coupling agent is preferably contained as a silane coupling agent used when surface-treating the inorganic filler in advance.
  • it is more preferable that the silane coupling agent is contained as a silane coupling agent used when surface-treating the inorganic filler in advance, and that the silane coupling agent is further contained in the resin composition as it is.
  • the prepreg may contain a silane coupling agent used when surface-treating the fibrous base material in advance.
  • a silane coupling agent used when surface-treating the fibrous base material in advance.
  • examples of the silane coupling agent include those similar to the silane coupling agents described above used when surface treating the inorganic filler.
  • the resin composition of the present embodiment contains a silane coupling agent
  • its content is not particularly limited, but it should be 1 to 6 parts by mass based on 100 parts by mass of the radically polymerizable compound (A).
  • the amount is preferably 2 to 5 parts by mass, and more preferably 2 to 5 parts by mass.
  • the resin composition is used when manufacturing prepreg, as described below. Further, the resin composition is used when forming a resin layer included in a resin-coated metal foil and a resin-coated film, and an insulating layer included in a metal-clad laminate and a wiring board. Further, as described above, the resin composition provides a cured product having excellent low dielectric properties such as a low relative dielectric constant. Therefore, the resin composition is suitably used to form an insulating layer included in a high frequency compatible wiring board such as a wiring board for an antenna or an antenna substrate for millimeter wave radar. That is, the resin composition is suitable for manufacturing wiring boards compatible with high frequencies.
  • the method for producing the resin composition is not particularly limited, and for example, the radically polymerizable compound (A) and the phosphoric acid ester compound (B) are mixed with other organic components as necessary, and then , a method of adding the inorganic filler (C), and the like. Specifically, in the case of obtaining a varnish-like composition containing an organic solvent, the method described in the explanation of the prepreg mentioned later may be used.
  • symbol is 1: prepreg, 2: resin composition or semi-cured product of a resin composition, 3: fibrous base material, 11: metal-clad laminate, 12: insulating layer, 13: metal Foil, 14: Wiring, 21: Wiring board, 31: Metal plate with resin, 32 and 42: Resin layer, 41: Film with resin, 43: Support film.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present invention.
  • the prepreg 1 includes the resin composition or a semi-cured product 2 of the resin composition, and a fibrous base material 3.
  • This prepreg 1 includes the resin composition or a semi-cured product 2 of the resin composition, and a fibrous base material 3 present in the resin composition or the semi-cured product 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 (B-staged) resin composition.
  • the semi-cured product is a semi-cured (B-staged) resin composition.
  • semi-curing includes a state between when the viscosity begins 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 also include the composition itself. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition at the B stage) and a fibrous base material, or a prepreg comprising the semi-cured product of the resin composition (the resin composition at the A stage), or a prepreg comprising the resin composition before curing (the resin composition at the A stage). It may be a prepreg comprising a material) and a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be one obtained by drying or heating drying the resin composition.
  • the resin composition 2 is often prepared in the form of a varnish and used in order to impregnate the fibrous base material 3, which is the base material for forming the prepreg. That is, the resin composition 2 is often 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 resin composition that can be dissolved in an organic solvent is poured into an organic solvent and dissolved therein. At this time, heating may be performed if necessary.
  • components that do not dissolve in organic solvents for example, inorganic fillers, etc.
  • components that do not dissolve in organic solvents are added as necessary, and dispersed using a ball mill, bead mill, planetary mixer, roll mill, etc. until a predetermined dispersion state is achieved.
  • 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, etc. 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. Specifically, when manufacturing a prepreg, the resin composition used in this 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.
  • the flattening process includes, for example, a method in which a glass cloth is continuously pressed with a press roll at an appropriate pressure to compress the yarn into a flat shape.
  • the thickness of the commonly 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. Specifically, when manufacturing a prepreg, 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.
  • Examples of the method for manufacturing the prepreg 1 include a method in which the fibrous base material 3 is impregnated with the resin composition 2, for example, the resin composition 2 prepared in the form of a varnish, and then dried.
  • the resin composition 2 is impregnated into the fibrous base material 3 by dipping, coating, or the like. It is also possible to repeat the impregnation multiple times if necessary. Further, at this time, by repeating impregnation using a plurality of resin compositions having different compositions and concentrations, it is possible to finally adjust the desired composition and impregnation amount.
  • 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 more and 10 minutes or less.
  • desired heating conditions for example, at 80° C. or higher and 180° C. or lower for 1 minute or more and 10 minutes or less.
  • prepreg 1 in a pre-cured (A stage) or semi-cured state (B stage) is obtained.
  • the organic solvent can be volatilized from the resin varnish, and the organic solvent can be reduced or removed.
  • the resin composition according to the present embodiment or the prepreg comprising the semi-cured product of this resin composition has low dielectric properties (relative permittivity), excellent adhesion with metal foil and flame retardancy, and high thermal conductivity. This is a prepreg from which a cured product with suppressed deterioration of withstand voltage after heat treatment and moisture absorption treatment can be obtained.
  • FIG. 2 is a schematic cross-sectional view showing an example of the metal-clad laminate 11 according to the embodiment of the present invention.
  • the metal-clad laminate 11 is composed of an insulating layer 12 containing a cured product of the prepreg 1 shown in FIG. has been done. That is, the metal-clad laminate 11 includes an insulating layer 12 containing a cured resin composition and a metal foil 13 provided on the insulating layer 12. Further, 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. Further, the thickness of the metal foil 13 is not particularly limited and varies depending on the performance required of the ultimately obtained wiring board. The thickness of the metal foil 13 can be appropriately set depending on the desired purpose, and is preferably 0.2 to 70 ⁇ m, for example. Further, examples of the metal foil 13 include copper foil and aluminum foil, and when the metal foil is thin, it may be a carrier-attached copper foil provided with a peeling layer and a carrier to improve handling properties. 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.
  • a method of producing the metal-clad laminate 11 using the prepreg 1 can be mentioned. This method involves stacking one or more prepregs 1, then stacking a metal foil 13 such as copper foil on both or one side of the top and bottom, and forming the metal foil 13 and the prepreg 1 under heat and pressure to form an integrated laminate.
  • a method of producing a laminate 11 with metal foil on both sides or with metal foil on one side 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 pressing conditions can be appropriately set depending on 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 to 220°C
  • the pressure can be 3 to 4 MPa
  • the time can be 60 to 150 minutes.
  • the metal-clad laminate may be manufactured without using prepreg.
  • a method may be used in which a varnish-like resin composition is applied onto a metal foil, a layer containing the resin composition is formed on the metal foil, and then heated and pressed.
  • the metal-clad laminate including the insulating layer containing the cured product of the resin composition according to the present embodiment has low dielectric properties (relative permittivity), excellent adhesion with metal foil and flame retardancy, and high thermal conductivity.
  • This is a metal-clad laminate including an insulating layer that is high in voltage and has suppressed deterioration of withstand voltage after heat treatment and moisture absorption treatment.
  • FIG. 3 is a schematic cross-sectional view showing an example of the wiring board 21 according to the embodiment of the present invention.
  • the wiring board 21 includes an insulating layer 12 used by curing the prepreg 1 shown in FIG.
  • the wiring 14 is formed by partially removing the foil 13. That is, the wiring board 21 has an insulating layer 12 containing a cured resin composition, and wiring 14 provided on both or one side of the upper and lower sides of the insulating layer 12. Further, 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 the wiring board 21 using the prepreg 1 may be mentioned. In 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. For example, a method of manufacturing the printed circuit board 21 may be mentioned. That is, the wiring board 21 is obtained by partially removing the metal foil 13 on the surface of the metal-clad laminate 11 to form a circuit. In addition to the above-mentioned methods, methods for forming the circuit include, for example, semi-additive process (SAP) and modified semi-additive process (MSAP).
  • SAP semi-additive process
  • MSAP modified semi-additive process
  • the wiring board 21 is an insulating layer that has low dielectric properties (relative permittivity), excellent adhesion with metal foil and flame retardancy, high thermal conductivity, and suppresses deterioration of withstand voltage after heat treatment and moisture absorption treatment. It has 12.
  • Such wiring boards have low dielectric properties (relative permittivity), excellent adhesion to metal foil and flame retardancy, high thermal conductivity, and suppressed deterioration of withstand voltage after heat treatment and moisture absorption treatment. It is a wiring board including an insulating layer.
  • FIG. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil 31 according to the present embodiment.
  • the resin-coated metal foil 31 includes a resin layer 32 containing the resin composition or a semi-cured product of the resin composition, and a metal foil 13.
  • This resin-coated metal foil 31 has a metal foil 13 on the surface of the resin layer 32. That is, this 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 include another layer between the resin layer 32 and the metal foil 13.
  • the resin layer 32 may include a semi-cured product of the resin composition as described above, or may include an uncured resin composition.
  • the resin-coated metal foil 31 may be a resin-coated metal foil that includes a resin layer containing a semi-cured product of the resin composition (the B-stage resin composition) and a metal foil, or The resin-coated metal foil may include a resin layer containing the previous resin composition (the A-stage resin composition) and a metal foil.
  • the resin layer only needs to contain the resin composition or a semi-cured product of the resin composition, and may or may not contain a fibrous base material.
  • the resin composition or the semi-cured product of the resin composition may be one obtained by drying or heating drying the resin composition.
  • the fibrous base material the same fibrous base material as the prepreg can be used.
  • metal foils used for metal-clad laminates can be used without limitation.
  • examples of the metal foil include copper foil and aluminum foil.
  • the resin-coated metal foil 31 and the resin-coated film 41 described below may be provided with a cover fill or the like, if necessary.
  • a cover film By providing a cover film, it is possible to prevent foreign matter from entering.
  • the cover film is not particularly limited, but includes, for example, a polyolefin film, a polyester film, a polymethylpentene film, and a film formed by providing a release agent layer on these films.
  • 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 manufacturing 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 using, for example, a bar coater.
  • the applied resin composition is heated under conditions of, for example, 80° C. or higher and 180° C. or lower for 1 minute or more and 10 minutes or less.
  • the heated resin composition is formed on the metal foil 13 as an uncured resin layer 32 .
  • the organic solvent can be volatilized from the resin varnish, and the organic solvent can be reduced or removed.
  • the resin-coated metal foil provided with the resin layer containing the resin composition or semi-cured product of this resin composition according to the present embodiment has low dielectric properties (relative dielectric constant), and has low adhesion with the metal foil and flame retardancy.
  • This is a resin-coated metal foil that can suitably yield a cured product with excellent thermal conductivity and suppressed deterioration of withstand voltage after heat treatment and moisture absorption treatment.
  • FIG. 5 is a schematic cross-sectional view showing an example of the resin-coated film 41 according to the present embodiment.
  • the resin-coated film 41 includes a resin layer 42 containing the resin composition or a semi-cured product of the resin composition, and a support film 43.
  • This 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 include another layer between the resin layer 42 and the support film 43.
  • the resin layer 42 may include a semi-cured product of the resin composition as described above, or may include 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, or may include a support film containing the resin composition before curing.
  • the resin-coated film may include a resin layer containing a substance (the resin composition at A stage) and a support film.
  • the resin layer only needs to contain the resin composition or a semi-cured product of the resin composition, and may or may not contain a fibrous base material.
  • the resin composition or the semi-cured product of the resin composition may be one obtained by drying or heating drying the resin composition.
  • the fibrous base material the same fibrous base material as the prepreg can be used.
  • any support film used for a resin-coated film 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, polyether ether ketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, and polyarylate film. Examples include films.
  • the resin-coated film 41 may include a cover film or the like, if necessary. By providing a cover film, it is possible to prevent foreign matter from entering.
  • the cover film is not particularly limited, and examples thereof include polyolefin film, polyester film, and polymethylpentene film.
  • the support film and cover film may be subjected to surface treatments such as matte treatment, corona treatment, mold release treatment, and roughening treatment, as necessary.
  • the method for producing the resin-coated film 41 is not particularly limited as long as the resin-coated film 41 can be produced.
  • Examples of the method for manufacturing the resin-coated film 41 include a method in which the varnish-like resin composition (resin varnish) is applied onto the support film 43 and heated.
  • the varnish-like resin composition is applied onto the support film 43 using, for example, a bar coater.
  • the applied resin composition is heated under conditions of, for example, 80° C. or higher and 180° C. or lower for 1 minute or more and 10 minutes or less.
  • the heated resin composition is formed on the support film 43 as an uncured resin layer 42 .
  • the organic solvent can be volatilized from the resin varnish, and the organic solvent can be reduced or removed.
  • a resin-coated film including a resin layer containing the resin composition or a semi-cured product of this resin composition according to the present embodiment has low dielectric properties (relative dielectric constant), and has excellent adhesion to metal foil and flame retardancy.
  • This is a resin-coated film that can suitably yield a cured product that has high thermal conductivity and suppresses deterioration of withstand voltage after heat treatment and moisture absorption treatment.
  • the resin composition in the first aspect includes a radically polymerizable compound (A) having a carbon-carbon unsaturated double bond in the molecule, and a phosphoric acid ester compound (B) having an alicyclic hydrocarbon structure in the molecule. and an inorganic filler (C), and the cured product has a thermal conductivity of 1.0 W/m ⁇ K or more.
  • the phosphoric acid ester compound (B) has at least one structure represented by the following formula (1) in the molecule.
  • R 1 to R 10 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.
  • the alicyclic hydrocarbon structure includes a 3- to 12-membered saturated alicyclic hydrocarbon structure.
  • the resin composition according to the fourth aspect is the resin composition according to any one of the first to third aspects, in which the phosphoric acid ester compound (B) has a structure represented by the following formula (2) in the molecule. Contains a phosphoric acid ester compound having at least one of the following.
  • Ar 1 and Ar 2 each independently represent an arylene group, and T represents a divalent group of a 3- to 12-membered saturated alicyclic hydrocarbon.
  • the content of the inorganic filler (C) is 100 parts by mass of the radically polymerizable compound (A). 100 to 380 parts by mass.
  • the inorganic filler (C) is an inorganic filler having a thermal conductivity of 10 W/m ⁇ K or more. (C-1) and an inorganic filler (C-2) having a thermal conductivity of less than 10 W/m ⁇ K.
  • the resin composition according to the seventh aspect is the resin composition according to the sixth aspect, wherein the inorganic filler (C-1) is a boron nitride filler, an aluminum oxide filler, a magnesium oxide filler, a magnesium carbonate filler, a silicon nitride filler. , aluminum nitride filler.
  • the inorganic filler (C-1) is a boron nitride filler, an aluminum oxide filler, a magnesium oxide filler, a magnesium carbonate filler, a silicon nitride filler. , aluminum nitride filler.
  • the resin composition according to the eighth aspect is the resin composition according to the sixth or seventh aspect, wherein the inorganic filler (C-2) is selected from the group consisting of fused silica filler, magnesium hydroxide filler, and mica filler. Contains at least one species.
  • the content of the inorganic filler (C-1) is higher than that of the inorganic filler (C-1).
  • the amount is 25 to 70 parts by mass based on 100 parts by mass in total with the inorganic filler (C-2).
  • the content of the phosphoric acid ester compound (B) is 100% by mass of the radically polymerizable compound (A). 15 to 50 parts by mass.
  • the resin composition in the eleventh aspect further includes an incompatible phosphorus compound (D) that is not compatible with the radically polymerizable compound (A) in the resin composition in any one of the first to tenth aspects. .
  • the resin composition according to the twelfth aspect is the resin composition according to any one of the first to eleventh aspects, wherein the incompatible phosphorus compound (D) is a phosphine oxide compound, a phosphinate compound, a polyphosphate compound, and at least one selected from the group consisting of phosphonium salt compounds.
  • the incompatible phosphorus compound (D) is a phosphine oxide compound, a phosphinate compound, a polyphosphate compound, and at least one selected from the group consisting of phosphonium salt compounds.
  • the content of the phosphoric ester compound (B) is such that the content of the phosphoric ester compound (B) and the content of the phosphoric ester compound (B) are as follows.
  • the amount is 25 to 100 parts by mass based on 100 parts by mass in total with the incompatible phosphorus compound (D).
  • the resin composition according to the fourteenth aspect is the resin composition according to any one of the first to thirteenth aspects, wherein the radically polymerizable compound (A) has a carbon-carbon unsaturated double bond in the molecule.
  • the radically polymerizable compound (A) has a carbon-carbon unsaturated double bond in the molecule.
  • the resin composition according to the fifteenth aspect is the resin composition according to the fourteenth aspect, wherein the polyphenylene ether compound is at least one of a group represented by the following formula (3) and a group represented by the following formula (4). Contains polyphenylene ether compounds having in the molecule.
  • R 14 represents a hydrogen atom or an alkyl group.
  • the resin composition according to a sixteenth aspect is the resin composition according to any one of the first to fifteenth aspects, wherein a cured product of the resin composition has a dielectric constant of 3.2 to 3.8 at 10 GHz. be.
  • the prepreg in the seventeenth embodiment includes the resin composition in any one of the first to sixteenth embodiments or a semi-cured product of the resin composition, and a fibrous base material.
  • the resin-coated film in the eighteenth embodiment includes a resin layer containing the resin composition in any one of the first to sixteenth embodiments or a semi-cured product of the resin composition, and a support film.
  • the resin-coated metal foil in the nineteenth embodiment includes a resin layer containing the resin composition in any one of the first to sixteenth embodiments or a semi-cured product of the resin composition, and a metal foil.
  • the metal-clad laminate in the 20th embodiment includes an insulating layer containing the cured product of the resin composition in any one of the 1st to 16th embodiments or the cured prepreg in the 17th embodiment, and a metal foil. .
  • the wiring board in the 21st embodiment includes an insulating layer containing a cured product of the resin composition in any one of the 1st to 16th embodiments or a cured product of the prepreg in the 17th embodiment, and wiring.
  • ⁇ PPE-1 Modified polyphenylene ether in which the terminal hydroxyl group of polyphenylene ether is modified with a methacryloyl group (SA9000 manufactured by SABIC Innovative Plastics, number average molecular weight Mn 2300, number of terminal functional groups: 2)
  • PPE-2 A polyphenylene ether compound (modified polyphenylene ether compound obtained by reacting polyphenylene ether and chloromethylstyrene) having a vinylbenzyl group (ethenylbenzyl group) at the end. Specifically, it is a modified polyphenylene ether compound obtained by reacting as follows.
  • polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, number of terminal hydroxyl groups: 2, weight average molecular weight Mw 1700) was placed in a 1 liter three-necked flask equipped with a temperature controller, stirring device, cooling equipment, and dropping funnel. 200 g, 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene: CMS manufactured by Tokyo Chemical Industry Co., Ltd.), and tetra-n-butylammonium as a phase transfer catalyst. 1.227 g of bromide and 400 g of toluene were charged and stirred.
  • the obtained solid was analyzed by 1 H-NMR (400 MHz, CDCl 3 , TMS). As a result of NMR measurement, a peak derived from vinylbenzyl group (ethenylbenzyl group) was confirmed at 5 to 7 ppm. This confirmed that the obtained solid was a modified polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) as the substituent in the molecule at the end of the molecule. Specifically, it was confirmed that it was ethenylbenzylated polyphenylene ether.
  • the obtained modified polyphenylene ether compound is represented by the above formula (13), Y in formula (13) is a dimethylmethylene group (represented by formula (11), and R 43 and R 44 in formula (11) was a methyl group), Ar 3 was a phenylene group, R 11 to R 13 were hydrogen atoms, and p was 1.
  • the number of terminal functional groups of the modified polyphenylene ether was measured as follows.
  • TEAH tetraethylammonium hydroxide
  • Residual OH amount ( ⁇ mol/g) [(25 ⁇ Abs)/( ⁇ OPL ⁇ X)] ⁇ 106
  • ⁇ indicates the extinction coefficient and is 4700 L/mol ⁇ cm.
  • OPL is the cell optical path length and is 1 cm.
  • the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, it was found that the hydroxyl groups of the polyphenylene ether before modification were almost modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of polyphenylene ether before modification was the number of terminal hydroxyl groups of polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of polyphenylene ether before modification is the number of terminal functional groups of modified polyphenylene ether. In other words, 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 determined by measuring a 0.18 g/45 ml methylene chloride solution (liquid temperature 25°C) of the modified polyphenylene ether using 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-1 Triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd., "TAIC")
  • TAIC Triggerlyl isocyanurate
  • TAIC Divinylbenzene
  • ((B) Phosphoric ester compound) ⁇ (B) Phosphoric ester compound-1 Phosphoric ester compound having an alicyclic hydrocarbon structure in the molecule (3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane and 2, It is a phosphoric acid ester compound obtained by reacting 6-xylenol and phosphoryl chloride. Specifically, it is a phosphoric acid ester compound obtained by reacting as follows.
  • DXPC dixylyl phosphorochloridate
  • the liquid in the four-necked flask was heated while stirring until the liquid temperature reached 65°C. Thereafter, while maintaining the same temperature (65° C.), triethylamine in the dropping funnel was added dropwise over 1 hour and 30 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature (65°C) for 2 hours.
  • the reaction product thus obtained was washed with dilute hydrochloric acid and water, neutralized and washed with an aqueous sodium hydroxide solution, and washed again with water. Thereafter, the solution was heated until the temperature reached 110° C., the pressure was reduced to 1 kPa, and water, toluene, and tetrahydrofuran were recovered. Furthermore, steam distillation was performed at 110° C.
  • Inorganic filler ((C) Inorganic filler) ⁇ (C-1)
  • Inorganic filler-1 Boron nitride filler (manufactured by Denka Co., Ltd., "SGP”, thermal conductivity 40 to 80 W/m K, volume average particle diameter 18 ⁇ m)
  • Inorganic filler-2 Boron nitride filler (manufactured by MARUKA Co., Ltd., "AP-20S”, thermal conductivity 60 W/m K, volume average particle diameter 0.7 ⁇ m)
  • Inorganic filler-3 Aluminum oxide filler (manufactured by Denka Co., Ltd., "DAW-03DC”, thermal conductivity 20 to 40 W/m K, volume average particle diameter 4.9 ⁇ m)
  • Inorganic filler-4 Magnesium carbonate filler (manufactured by Kamishima Chemical Co., Ltd., "Magthermo MS-L”, thermal conductivity 15 W/m K, volume average particle diameter
  • reaction initiator ⁇ Reaction initiator-1: peroxide (1,3-bis(butylperoxyisopropyl)benzene, manufactured by NOF Corporation, "Perbutyl P")
  • Coupled agent Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-503")
  • Free radical compound-1 4-benzoyloxy TEMPO, a free radical compound represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd., "H0878")
  • each organic resin component other than the inorganic filler is added to toluene as a solvent and mixed in the composition (parts by mass) shown in Tables 1 and 2 so that the solid content concentration is 60 to 70% by mass. Ta. The mixture was stirred for 60 minutes. Thereafter, each component was added to the resulting liquid in the proportions (parts by mass) listed in Tables 1 and 2, and the inorganic filler was dispersed using a bead mill. By doing so, a varnish-like resin composition (varnish) was obtained.
  • an evaluation board (cured prepreg) was obtained as follows.
  • a prepreg was produced by impregnating a fibrous base material (glass cloth: #1078 type, L glass manufactured by Asahi Kasei Corporation) with the obtained varnish, and then heating and drying it at 120° C. for 2 minutes. Then, 1, 2, 4, and 6 sheets of each of the obtained prepregs were stacked, and each side was laminated with copper foil (Fukuda Metal Foil & Powder Industries Co., Ltd. "CF-T4X-SV" copper foil thickness: 35 ⁇ m) and heated. Copper-clad laminates of four different thicknesses were prepared by heating to a temperature of 200°C at a rate of 4°C/min and heating and pressing at 200°C for 120 minutes at a pressure of 3 MPa.
  • the copper-clad laminate prepared as described above was used as an evaluation board and evaluated by the method shown below.
  • a copper-clad laminate made of four prepregs from which the copper foil was removed (cured prepreg) was used.
  • a copper-clad laminate made of four prepreg layers was used.
  • thermal conductivity a cured product of one prepreg and a copper-clad laminate made of two prepregs from which the copper foil was removed (cured prepreg) were used.
  • a copper-clad laminate made of six prepregs from which the copper foil was removed (cured prepreg) was used.
  • an evaluation substrate (cured prepreg) was obtained as follows.
  • a prepreg was produced by impregnating a fibrous base material (glass cloth: #3313 type, E glass, manufactured by Nitto Boseki Co., Ltd.) with the obtained varnish, and then heating and drying it at 110° C. for 2 minutes.
  • Four sheets of each of the obtained prepregs were stacked, and copper foil (Fukuda Metal Foil & Powder Industries Co., Ltd. "CF-T4X-SV" copper foil thickness: 35 ⁇ m) was laminated on both sides, and the temperature was increased at a heating rate of 4°C/min.
  • Copper-clad laminates of three different thicknesses were produced by heating to 200° C. and heating and pressing at 200° C. for 120 minutes at a pressure of 3 MPa.
  • the obtained copper-clad laminate from which the copper foil was removed (cured prepreg) was used.
  • the relative dielectric constant (Dk) of the evaluation substrate (cured prepreg) at a frequency of 10 GHz was measured using the cavity resonator perturbation method. Specifically, the dielectric constant of the evaluation board at 10 GHz was measured using a network analyzer (N5230A manufactured by Keysight Technologies, Inc.). Note that a dielectric constant of 3.2 to 3.8 is favorable.
  • Thermal conductivity of the obtained evaluation board (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 thermal conductivity in this example was 1.0 W/m ⁇ K or more.
  • test pieces Each having a diameter of 100 ⁇ 5 mm and a thickness of 0.5 mm were further cut out from the evaluation board.
  • the cut test pieces were subjected to aging treatment at a treatment temperature of 150° C. and treatment times of 500 hours, 750 hours, and 1000 hours, respectively.
  • the test pieces subjected to each aging treatment were subjected to a moisture absorption treatment at 35° C. and 90% for 96 hours.
  • Example 2 when comparing Example 1 and Example 2, the sample of Example 2 using divinylbenzene as a curing agent was more heat-treated and moisture-absorbing than the sample of Example 1 using triallylisocyanurate as a curing agent. It was confirmed that the subsequent deterioration of withstand voltage was suppressed.
  • Example 3 when comparing Example 1 and Example 3, the sample of Example 3 using a modified polyphenylene ether compound having a vinylbenzyl group at the end is different from the sample using a polyphenylene ether compound in which the terminal hydroxyl group of polyphenylene ether is modified with a methacroyl group. It was confirmed that the sample had a lower dielectric property superior to that of the sample of Example 1 used.
  • the samples of Examples 7, 16, and 17 had a lower content of inorganic filler (C-2) than Example 1, and together with boron nitride filler as inorganic filler (C-1), aluminum oxide filler, Magnesium carbonate filler and magnesium oxide filler are used respectively. It was confirmed that the samples of Examples 7, 16, and 17 had better thermal conductivity than the sample of Example 1. This is because the thermal conductivity of the inorganic filler itself is higher for the inorganic filler (C-1) than for the inorganic filler (C-2), so the thermal conductivity of the cured product also tends to be higher. It is thought that.
  • the present invention has wide industrial applicability in technical fields related to electronic materials and various devices using the same.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Un aspect de la présente invention concerne une composition de résine comprenant un composé polymérisable par voie radicalaire (A) qui a une double liaison insaturée carbone-carbone dans chaque molécule, un composé ester de phosphate (B) qui a une structure hydrocarbonée alicyclique dans chaque molécule, et une charge inorganique (C), un produit durci de ladite composition de résine ayant une conductivité thermique non inférieure à 1,0 W/m.K.
PCT/JP2023/029463 2022-09-16 2023-08-14 Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié revêtu de métal et carte de câblage WO2024057803A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173855A (ja) * 2007-12-27 2009-08-06 Daiso Co Ltd 熱硬化性樹脂組成物
JP2011084657A (ja) * 2009-10-15 2011-04-28 Daiso Co Ltd 熱硬化性樹脂組成物
WO2019012954A1 (fr) * 2017-07-12 2019-01-17 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film contenant ladite résine, feuille métallique la contenant et carte de circuit imprimé
JP2019021829A (ja) * 2017-07-20 2019-02-07 日立化成株式会社 放熱性ダイボンディングフィルム及びダイシングダイボンディングフィルム
WO2021079900A1 (fr) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Composition de résine, film de résine, film métallique attaché à la résine, préimprégné, feuille stratifiée à plaquage métallique, et carte de câblage imprimée
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
WO2022259851A1 (fr) * 2021-06-08 2022-12-15 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique et carte de câblage
WO2023119805A1 (fr) * 2021-12-24 2023-06-29 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, feuille stratifiée plaquée de métal et carte de câblage

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173855A (ja) * 2007-12-27 2009-08-06 Daiso Co Ltd 熱硬化性樹脂組成物
JP2011084657A (ja) * 2009-10-15 2011-04-28 Daiso Co Ltd 熱硬化性樹脂組成物
WO2019012954A1 (fr) * 2017-07-12 2019-01-17 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film contenant ladite résine, feuille métallique la contenant et carte de circuit imprimé
JP2019021829A (ja) * 2017-07-20 2019-02-07 日立化成株式会社 放熱性ダイボンディングフィルム及びダイシングダイボンディングフィルム
WO2021079900A1 (fr) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Composition de résine, film de résine, film métallique attaché à la résine, préimprégné, feuille stratifiée à plaquage métallique, et carte de câblage imprimée
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
WO2022259851A1 (fr) * 2021-06-08 2022-12-15 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique et carte de câblage
WO2023119805A1 (fr) * 2021-12-24 2023-06-29 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, feuille stratifiée plaquée de métal et carte de câblage

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