WO2024004526A1 - Matériau de nitrure de bore et son application - Google Patents

Matériau de nitrure de bore et son application Download PDF

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Publication number
WO2024004526A1
WO2024004526A1 PCT/JP2023/020740 JP2023020740W WO2024004526A1 WO 2024004526 A1 WO2024004526 A1 WO 2024004526A1 JP 2023020740 W JP2023020740 W JP 2023020740W WO 2024004526 A1 WO2024004526 A1 WO 2024004526A1
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boron nitride
nitride material
polymer
group
resin composition
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PCT/JP2023/020740
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English (en)
Japanese (ja)
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穂波 伊延
輝彦 齊藤
鉄平 細川
和輝 会田
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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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Publication of WO2024004526A1 publication Critical patent/WO2024004526A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present disclosure relates to boron nitride materials and applied products thereof.
  • 5G 5th generation mobile communication system
  • 5G uses higher frequency bands to provide faster communication speeds than previous generations. Therefore, high frequency compatible wiring boards are required for electronic devices.
  • the transmission loss in the transmission path of the wiring board depends on the frequency. The higher the signal frequency, the greater the transmission loss. Furthermore, transmission loss depends on dielectric constant and dielectric loss tangent. Therefore, in order to reduce the transmission loss of high-frequency signals, the substrate material constituting the insulating layer of the wiring board is required to have a low dielectric constant and a low dielectric loss tangent. Particularly in high frequency bands, the dielectric loss tangent largely depends on the orientational polarization of organic molecules contained in the substrate material. Therefore, it is required to reduce polar groups such as hydroxyl groups and amino groups contained in the substrate material.
  • hexagonal boron nitride having a thickness in the C-axis direction of 5 nm or more; a polymer attached to the hexagonal boron nitride;
  • a boron nitride material comprising: the solubility parameter of the boron nitride material measured by methanol titration is less than 47.9 MPa 0.5 ; Provides boron nitride materials.
  • the dielectric loss tangent of a boron nitride material under high humidity can be reduced.
  • FIG. 1 is a diagram showing a schematic configuration of a boron nitride material in Embodiment 1.
  • FIG. 2 is a graph showing the relationship between the HSP distance between a polymer and water and the dielectric loss tangent of a boron nitride material during humidification.
  • FIG. 3 is a diagram showing a schematic structure of a resin composition in Embodiment 4.
  • FIG. 4 is a cross-sectional view of a resin-coated film in Embodiment 6.
  • FIG. 5 is a cross-sectional view of the resin-coated metal foil in Embodiment 7.
  • FIG. 6 is a cross-sectional view of a metal-clad laminate in Embodiment 8.
  • FIG. 7 is a cross-sectional view of a wiring board in Embodiment 9.
  • Boron nitride is a material with high thermal conductivity and excellent electrical insulation.
  • boron nitride which has a hexagonal crystal structure, has a layered structure similar to graphite, can be synthesized relatively easily, and has excellent properties such as thermal conductivity, electrical insulation, chemical stability, and heat resistance. It has the following characteristics. Therefore, boron nitride is promising as a filler for resin compositions used in heat dissipation sheets, thermally conductive insulating substrates, and the like.
  • boron nitride has a hydrophilic surface and absorbs moisture under high humidity. Therefore, when boron nitride is used as a filler, the amount of water contained in the insulating substrate increases, and there is a concern that the dielectric loss tangent may deteriorate. Since the C-plane occupies most of the surface area of scale-like hexagonal boron nitride, surface modification of the C-plane to make the C-plane hydrophobic suppresses water adsorption and reduces the dielectric loss tangent. It is particularly effective for
  • the amount of functional groups present on the C-plane of boron nitride particles is extremely small compared to other surfaces.
  • the C-plane of boron nitride is chemically inert. Therefore, it is difficult to form a direct covalent bond between a known surface modifier such as a silane coupling agent and the C-plane of boron nitride to suppress water adsorption to the C-plane.
  • Patent Document 1 discloses surface modification of aggregate-like hexagonal boron nitride with a silane coupling agent having a vinyl group.
  • the silane coupling agent is considered to be chemically bonded to boron nitride by dehydration condensation with hydroxyl groups present on the surface of boron nitride.
  • the amount of hydroxyl groups present on the C-plane of scale-like hexagonal boron nitride is small. Therefore, it is unlikely that a sufficient amount of the silane coupling agent can be adsorbed on the C-plane of boron nitride.
  • the dopamine-containing protein secreted from the byssus gland of the mussel a type of bivalve
  • a natural adhesive that exhibits stable adhesive strength even in seawater.
  • dopamine adheres to the surfaces of various materials under basic conditions and undergoes oxidative polymerization to form a polydopamine film.
  • Non-Patent Document 2 discloses coating the C-plane of boron nitride with polydopamine.
  • water is easily adsorbed on surfaces treated with a hydrophilic surface modifier such as polydopamine.
  • Polydopamine itself also has a large amount of hydroxyl groups. Therefore, when polydopamine is used as a surface modifier for boron nitride, the dielectric loss tangent of boron nitride deteriorates.
  • Non-Patent Document 3 discloses surface modification of the C-plane of boron nitride nanosheets with polystyrene moieties of a block copolymer of polystyrene and PMMA.
  • the thickness of the boron nitride nanosheet in the C-axis direction is only a few nm.
  • the surface area of boron nitride nanosheets per unit mass is several tens to hundreds of times larger than that of ordinary scale-like boron nitride. Therefore, when boron nitride nanosheets are formed, the area where water can be adsorbed increases, and it is expected that hygroscopicity and dielectric loss tangent will deteriorate under high humidity conditions.
  • isolation of boron nitride nanosheets requires complicated procedures and has a low yield, which poses challenges for industrial use.
  • the boron nitride nanosheet has a structure in which scale-like boron nitride is thinly exfoliated along the C-plane.
  • the thickness of the boron nitride nanosheet in the C-axis direction is several nm, which corresponds to a monoatomic layer to several atomic layers.
  • boron nitride nanosheets is thermodynamically unstable compared to flaky boron nitride, which has a thickness of several tens of nanometers to several hundreds of nanometers in the C-axis direction. This is considered to be the reason why organic molecules are easily adsorbed on the surface of boron nitride nanosheets.
  • none of the preceding examples can reduce the hygroscopicity of hexagonal boron nitride under high humidity, nor can it reduce the dielectric loss tangent of boron nitride.
  • the present inventors have conducted intensive studies on polymers that enable surface modification of hexagonal boron nitride. As a result, the present disclosure was completed by discovering that the above problems can be solved by attaching a polymer that can achieve a specific solubility parameter (SP value) to the surface of boron nitride.
  • SP value solubility parameter
  • the boron nitride material according to the first aspect of the present disclosure includes: hexagonal boron nitride having a thickness in the C-axis direction of 5 nm or more; a polymer attached to the hexagonal boron nitride; A boron nitride material comprising: The solubility parameter (SP value) of the boron nitride material measured by methanol titration is less than 47.9 MPa 0.5 .
  • the dielectric loss tangent of a boron nitride material under high humidity can be reduced.
  • the polymer may be attached to the C-plane of the hexagonal boron nitride. Since the polymer is attached to the C-plane of hexagonal boron nitride, a sufficient surface modification effect can be obtained.
  • the polymer may include a polyvinyl aromatic polymer, and the polyvinyl aromatic polymer It may also contain a side chain containing an aromatic ring. Having such a structure allows the polymer to strongly adsorb to the surface of boron nitride.
  • the polymer may include a repeating unit represented by formula (1).
  • n represents a positive integer
  • X is represented by formula (2)
  • any one of R 1 to R 5 in formula (2) is directly connected to the main chain contained in the repeating unit.
  • the other four from R 1 to R 5 independently represent a group consisting of H, B, C, N, O, Si, F, P, S, Cl, I and Br. Contains at least one atom selected from Having such a structure allows the polymer to strongly adsorb to the surface of boron nitride.
  • the other four R 1 to R 5 are independently H atoms or hydrocarbon groups. It may be. It is desirable that the other four of R 1 to R 5 be H atoms or hydrocarbon groups from the viewpoint of increasing the hydrophobicity of the polymer.
  • X in formula (1) may be represented by formula (3).
  • Any one of R 11 to R 19 in formula (3) represents a direct bond to the main chain, and the other eight of R 11 to R 19 independently represent H, B, C , N, O, Si, F, P, S, Cl, I and Br. Having such a structure allows the polymer to strongly adsorb to the surface of boron nitride.
  • the other eight of R 11 to R 19 are independently H atoms or hydrocarbon groups. It may be. It is desirable that the other eight of R 11 to R 19 be H atoms or hydrocarbon groups from the viewpoint of increasing the hydrophobicity of the polymer.
  • the polymer may include a repeating unit containing at least one selected from the group consisting of a carbazole skeleton and a fluorene skeleton. Since the repeating unit of the polymer includes at least one selected from the group consisting of a carbazole skeleton and a fluorene skeleton, the polymer can be strongly adsorbed on the surface of boron nitride.
  • the fluorene skeleton may include at least one substituent.
  • the polymer may include a repeating unit containing a polyphenylene ether skeleton. Since the repeating unit of the polymer contains a polyphenylene ether skeleton, the polymer can be strongly adsorbed on the surface of boron nitride.
  • the polyphenylene ether skeleton may include at least one substituent.
  • the filler according to the twelfth aspect of the present disclosure includes the boron nitride material according to any one of the first to eleventh aspects. According to the filler of the present disclosure, the heat resistance of the filler can be improved. Generation of bubbles when heating the filler can also be suppressed.
  • the resin composition according to the thirteenth aspect of the present disclosure includes the filler according to the twelfth aspect. According to the thirteenth aspect, it is possible to provide a resin composition that exhibits a low dielectric loss tangent and has excellent heat resistance.
  • the prepreg according to the fourteenth aspect of the present disclosure includes the resin composition of the thirteenth aspect or a semi-cured product of the resin composition.
  • the resin-coated film according to the fifteenth aspect of the present disclosure is A resin layer containing the resin composition of the thirteenth aspect or a semi-cured product of the resin composition, a support film; It is equipped with
  • the resin-coated metal foil according to the sixteenth aspect of the present disclosure includes: A resin layer containing the resin composition of the thirteenth aspect or a semi-cured product of the resin composition, metal foil and It is equipped with
  • the metal clad laminate according to the seventeenth aspect of the present disclosure includes: an insulating layer comprising a cured product of the resin composition of the thirteenth aspect or a cured product of the prepreg of the fourteenth aspect; metal foil and It is equipped with
  • an insulating layer comprising a cured product of the resin composition of the thirteenth aspect or a cured product of the prepreg of the fourteenth aspect; wiring and We are prepared.
  • FIG. 1 is a diagram showing a schematic configuration of a boron nitride material 10 in the first embodiment.
  • Boron nitride material 10 comprises boron nitride 1 and polymer 2.
  • Polymer 2 is attached to boron nitride 1.
  • Boron nitride 1 is hexagonal boron nitride (h-BN). Hexagonal boron nitride is suitable for the boron nitride material 10 of the present disclosure because it can be synthesized relatively easily and has excellent properties such as thermal conductivity, electrical insulation, chemical stability, and heat resistance. .
  • Boron nitride 1 has a particle shape.
  • the shape of the particles of boron nitride 1 is not particularly limited as long as the C-plane to be modified is exposed on the surface. Since the area of the C-plane is large, it is desirable that the shape of the particles of boron nitride 1 is scaly.
  • the thickness of the boron nitride 1 in the C-axis direction is, for example, 5 nm or more.
  • the surface area per unit mass of boron nitride 1 can be reduced. This is advantageous in reducing the amount of moisture adsorbed by boron nitride 1 under high humidity and keeping the dielectric loss tangent of boron nitride material 10 low.
  • the upper limit of the thickness of boron nitride 1 in the C-axis direction is not particularly limited.
  • the thickness of boron nitride 1 in the C-axis direction may be 10 ⁇ m or less.
  • the thickness of boron nitride 1 in the C-axis direction may be 10 nm or more and 10 ⁇ m or less.
  • the thickness of boron nitride 1 in the C-axis direction can be measured using a scanning electron microscope image (SEM image) of boron nitride 1.
  • SEM image scanning electron microscope image
  • the widest plane of hexagonal boron nitride is the C-plane. Therefore, the thickness of the side surface of boron nitride 1 in the SEM image can be regarded as the thickness in the C-axis direction.
  • the average particle size of boron nitride 1 is not particularly limited.
  • the average particle size of boron nitride 1 may be, for example, 0.05 ⁇ m or more and 100 ⁇ m or less, or 0.1 ⁇ m or more and 50 ⁇ m or less.
  • the average particle size of boron nitride particles means the median diameter.
  • the median diameter means the particle diameter (d50) when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured using, for example, a laser diffraction measuring device.
  • Polymer 2 is an organic compound that serves as a surface modifier for boron nitride 1. Polymer 2 is attached to the C-plane of boron nitride 1. Since most of the surface area of hexagonal boron nitride is the C-plane, a sufficient surface modification effect can be obtained by adhering the polymer 2 to the C-plane.
  • the polymer 2 may form a film on the C-plane of the boron nitride 1.
  • the polymer 2 may be attached to the entire C-plane or only to a part of the C-plane.
  • the polymer 2 may be attached to a surface other than the C-plane. Modification of the C-plane is effective for improving hygroscopicity, but hygroscopicity can also be improved when both the C-plane and surfaces other than the C-plane are modified.
  • the polymer 2 may be a polymer having an aromatic ring within the repeating unit. Since the C-plane of hexagonal boron nitride is inert, it is not easy to chemically modify the C-plane. In this embodiment, polymer 2 is physically adsorbed onto boron nitride 1. "Physical adsorption" means adsorption mainly by van der Waals forces.
  • the polymer 2 may be physically adsorbed to the C-plane of the boron nitride 1 by ⁇ - ⁇ interaction.
  • the ⁇ - ⁇ interaction that acts on aromatic rings is known to be a particularly strong interaction among van der Waals forces.
  • a sufficient amount of polymer 2 can be attached to the C-plane of boron nitride 1 by van der Waals forces including ⁇ - ⁇ interactions.
  • the HSP (Hansen solubility parameter) distance between the polymer 2 and water is greater than 39.5 MPa 0.5 .
  • the HSP distance is calculated by the atomic group contribution method (Hansen method).
  • a sufficiently large HSP distance between polymer 2 and water means that polymer 2 has high hydrophobicity. Since the polymer 2 has high hydrophobicity, the hygroscopicity of the boron nitride material 10 can be reduced. Thereby, the dielectric loss tangent of the boron nitride material 10 under high humidity can be reduced.
  • the upper limit of the HSP distance between polymer 2 and water is not particularly limited. The upper limit of the HSP distance is, for example, 54.8 MPa 0.5 .
  • a compound containing a highly reactive polar group is used as the surface modifier. Since a compound containing a polar group has high hydrophilicity, the HSP distance between the compound and water is likely to be 39.5 MPa 0.5 or less. Therefore, in surface modification using a hydrophobic compound, surface modification by physical adsorption is more preferable than forming a covalent bond by chemical reaction.
  • Whether or not the amount of polymer 2 attached to boron nitride 1 is sufficient, that is, whether the surface modification is sufficient is determined by the solubility parameter (SP value) of boron nitride material 10 measured by methanol titration method. can. In this embodiment, it is determined that the surface modification is sufficient when the SP value is less than 47.9 MPa 0.5 . When the surface of the boron nitride material is hydrophilic, its SP value is 47.9 MPa 0.5 or more. By sufficiently adhering the polymer 2 to the surface of the boron nitride 1, the surface of the boron nitride material changes to be hydrophobic, and its SP value becomes less than 47.9 MPa 0.5 .
  • SP value solubility parameter
  • the boron nitride material 10 When the SP value is suppressed to less than 47.9 MPa 0.5 , the boron nitride material 10 exhibits a low dielectric loss tangent even under high humidity.
  • the lower limit of the SP value of the boron nitride material 10 is not particularly limited.
  • the lower limit of the SP value of the boron nitride material 10 is, for example, 34.1 MPa 0.5 .
  • the polymer 2 may include a polyvinyl aromatic polymer, and the polyvinyl aromatic polymer may include a side chain containing a heteroaromatic ring. Having such a structure allows the polymer 2 to strongly adsorb to the surface of the boron nitride 1.
  • Polymer 2 may have a repeating unit represented by formula (1).
  • n represents a positive integer.
  • X is represented by formula (2).
  • Any one of R 1 to R 5 in formula (2) represents a direct bond to the main chain contained in the repeating unit represented by formula (1).
  • the other four R 1 to R 5 are each independently at least one atom selected from the group consisting of H, B, C, N, O, Si, F, P, S, Cl, I, and Br. including.
  • "The other four from R 1 to R 5 means a site that does not form a bond to the main chain.
  • the main chain is an ethylene skeleton in formula (1). Having such a structure allows the polymer 2 to strongly adsorb to the surface of the boron nitride 1.
  • the other four R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a group containing an oxygen atom, a group containing a nitrogen atom, and a group containing a sulfur atom. , a group containing a silicon atom, a group containing a phosphorus atom, or a group containing a boron atom.
  • halogen atoms include F, Cl, Br and I.
  • hydrocarbon group examples include an aliphatic saturated hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic unsaturated hydrocarbon group.
  • a halogenated hydrocarbon group means a group in which at least one hydrogen atom contained in the hydrocarbon group is substituted with a halogen atom.
  • the halogenated hydrocarbon group may be a group in which all hydrogen atoms contained in the hydrocarbon group are substituted with halogen atoms.
  • Examples of the halogenated hydrocarbon group include a halogenated alkyl group and a halogenated alkenyl group.
  • the group containing an oxygen atom is, for example, a substituent having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group, an ether group, an acyl group, and an ester group.
  • the nitrogen atom-containing group is, for example, a substituent having at least one selected from the group consisting of an amino group, an imino group, a cyano group, an azide group, an amide group, a carbamate group, a nitro group, a cyanamide group, an isocyanate group, and an oxime group. It is the basis.
  • Groups containing a sulfur atom include, for example, a thiol group, a sulfide group, a sulfinyl group, a sulfonyl group, a sulfino group, a sulfonic acid group, an acylthio group, a sulfenamide group, a sulfonamide group, a thioamide group, a thiocarbamide group, and a thiocyano group. It is a substituent having at least one member selected from the group consisting of:
  • the group containing a silicon atom is, for example, a substituent having at least one selected from the group consisting of a silyl group and a siloxy group.
  • the group containing a phosphorus atom is, for example, a substituent having at least one selected from the group consisting of a phosphino group and a phosphoryl group.
  • the group containing a boron atom is, for example, a substituent having a boronic acid group.
  • substituent having a boronic acid group include the boronic acid group itself and a hydrocarbon group having a boronic acid group.
  • the other four R 1 to R 5 may be independently H atoms or hydrocarbon groups. H atoms or hydrocarbon groups do not increase the polarity of polymer 2. Therefore, from the viewpoint of increasing the hydrophobicity of the polymer 2, it is desirable that the other four of R 1 to R 5 are H atoms or hydrocarbon groups.
  • hydrocarbon group examples include an aliphatic saturated hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic unsaturated hydrocarbon group.
  • the aliphatic saturated hydrocarbon group may be an alkyl group.
  • Examples of aliphatic saturated hydrocarbon groups include -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 , -C(CH 3 ) 3 , -CH2CH ( CH3 ) 2 , -( CH2 ) 3CH3 , -( CH2 ) 4CH3 , -C( CH2CH3 ) ( CH3 ) 2 , -CH2C (CH 3 ) 3 , -(CH 2 ) 5 CH 3 , -(CH 2 ) 6 CH 3 , -(CH 2 ) 7 CH 3 , -(CH 2 ) 8 CH 3 , -(CH 2 ) 9 CH
  • Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
  • the number of carbon atoms in the hydrocarbon group is not particularly limited, and is, for example, 1 or more and 20 or less, may be 1 or more and 10 or less, or may be 1 or more and 5 or less.
  • the hydrocarbon group may be linear, branched, or cyclic.
  • X may be represented by formula (3). Any one of R 11 to R 19 in formula (3) represents a direct bond to the main chain contained in the repeating unit represented by formula (1).
  • the other eight R 11 to R 19 are each independently at least one atom selected from the group consisting of H, B, C, N, O, Si, F, P, S, Cl, I, and Br. including. "The other eight from R 11 to R 19 " means sites that do not form a bond to the main chain. Having such a structure allows the polymer 2 to strongly adsorb to the surface of the boron nitride 1.
  • the other eight R 11 to R 19 are, independently of each other, a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a group containing an oxygen atom, a group containing a nitrogen atom, a group containing a sulfur atom. , a group containing a silicon atom, a group containing a phosphorus atom, or a group containing a boron atom.
  • R 1 to R 5 can be applied to specific examples of R 11 to R 19 .
  • the other eight of R 11 to R 19 may be independently H atoms or hydrocarbon groups. H atoms or hydrocarbon groups do not increase the polarity of polymer 2. Therefore, from the viewpoint of increasing the hydrophobicity of the polymer 2, it is desirable that the other eight atoms from R 11 to R 19 are H atoms or hydrocarbon groups.
  • Polymer 2 may be a polymer represented by formula (4). That is, the polymer 2 may have a structure other than the repeating unit represented by formula (1).
  • n represents a positive integer
  • m represents an integer of 0 or more.
  • X is represented by formula (2) or formula (3).
  • R 6 contains at least one atom selected from the group consisting of H, B, C, N, O, Si, F, P, S, Cl, I and Br. Having such a structure allows the polymer 2 to strongly adsorb to the surface of the boron nitride 1.
  • R 1 to R 5 can be applied to specific examples of R 6 .
  • R 6 may be an H atom or a hydrocarbon group. H atoms or hydrocarbon groups do not increase the polarity of polymer 2. It is desirable that R 6 be an H atom or a hydrocarbon group from the viewpoint of increasing the hydrophobicity of the polymer 2.
  • m may be zero.
  • the polymer 2 may have a repeating unit containing at least one selected from the group consisting of a carbazole skeleton and a fluorene skeleton.
  • a carbazole skeleton and a fluorene skeleton When polymer 2 has a carbazole skeleton and a fluorene skeleton, it can exhibit strong adhesion to the C-plane of boron nitride 1.
  • the carbazole skeleton and fluorene skeleton may be included in the main chain of the polymer 2, or may be included in the side chain.
  • the carbazole skeleton and the fluorene skeleton may each have at least one substituent. At least one substituent can be a group containing at least one atom selected from the group consisting of H, B, C, N, O, Si, F, P, S, Cl, I and Br. Examples of such groups include the groups described above for formula (1).
  • Polymer 2 may have a repeating unit containing a polyphenylene ether skeleton. When having a polyphenylene ether skeleton, the polymer 2 can exhibit strong adhesion to the C-plane of the boron nitride 1.
  • the polyphenylene ether skeleton may be included in the main chain of the polymer 2, or may be included in the side chain.
  • Each polyphenylene ether skeleton may have at least one substituent. At least one substituent can be a group containing at least one atom selected from the group consisting of H, B, C, N, O, Si, F, P, S, Cl, I and Br. Examples of such groups include the groups described above for formula (1).
  • the polymer 2 can strongly adsorb to the surface of the boron nitride 1.
  • the HSP distance between the polymer 2 and water be large.
  • the content of polar groups such as hydroxyl groups, carboxyl groups, unsubstituted amino groups, thiol groups, sulfonic acid groups, and silanol groups
  • the HSP distance between the polymer 2 and water can become large.
  • the content of polar groups is small, the dielectric loss tangent of the polymer 2 itself can also be suppressed. Therefore, polymer 2 does not need to have these polar groups. Further, it is desirable that the polymer 2 does not generate these polar groups through reactions such as hydrolysis when absorbing moisture.
  • the molecular weight of polymer 2 is not particularly limited.
  • Polymer 2 has, for example, a number average molecular weight Mn of 100 or more.
  • the upper limit of the number average molecular weight Mn of the polymer 2 is not particularly limited, and is, for example, 500,000.
  • the thermal decomposition temperature and boiling point of the polymer 2 are, for example, 200°C or higher, and may be 250°C or higher.
  • the boron nitride material 10 is used, for example, as a filler in an insulating layer of a wiring board.
  • the generation of bubbles due to evaporation of adsorbed water in the solder reflow process can also be suppressed.
  • the amount of polymer 2 attached to boron nitride 1 is not particularly limited.
  • the ratio of the mass of polymer 2 to the mass of boron nitride 1 is 10% or less.
  • the amount of gas generated during thermal decomposition of the boron nitride material 10 can be suppressed. This is particularly significant when using boron nitride material 10 as a filler.
  • the lower limit of the ratio of the mass of polymer 2 to the mass of boron nitride 1 is not particularly limited. The lower limit of the ratio is, for example, 0.01%.
  • boron nitride material 10 is obtained by mixing a solution containing polymer 2 and boron nitride 1, and filtering, washing, and drying the solid matter.
  • the temperature at which the surface of boron nitride 1 is modified with polymer 2 is not particularly limited as long as it is below the boiling point of the solvent. Surface modification may be performed at room temperature (20°C ⁇ 15°C).
  • the type of solvent is not particularly limited as long as it can dissolve the polymer 2.
  • the amount of polymer 2 used is also not particularly limited.
  • the ratio of the mass of polymer 2 to the mass of boron nitride 1 may be 0.01% or more and 10% or less, or 0.75% or more and 5% or less.
  • the boron nitride material 10 has a configuration that is advantageous in reducing the dielectric loss tangent under high humidity.
  • the ratio of the dielectric loss tangent of the boron nitride material 10 at 1 GHz in an atmosphere with 90% humidity to the dielectric loss tangent of boron nitride 1 at 1 GHz is less than 1. Therefore, the boron nitride material 10 is suitable for applications requiring a low dielectric loss tangent, for example, as a filler for wiring boards.
  • the lower limit of the ratio of the dielectric loss tangent of the boron nitride material 10 to the dielectric loss tangent of the boron nitride 1 is not particularly limited.
  • the lower limit of the ratio is, for example, 0.001.
  • humidity means relative humidity.
  • the boron nitride material 10 has a configuration that is advantageous in reducing the amount of water adsorption.
  • the ratio of the amount of moisture adsorbed by the boron nitride material 10 in an atmosphere with a humidity of 90% to the amount of moisture adsorbed by the boron nitride 1 in an atmosphere with a humidity of 90% is less than 1.
  • the lower limit of the ratio of the amount of moisture adsorbed by the boron nitride material 10 to the amount of moisture adsorbed by the boron nitride 1 is not particularly limited. The lower limit of the ratio is, for example, 0.01.
  • the heat dissipation gap filler according to the present embodiment includes the boron nitride material 10 according to the first embodiment.
  • a heat dissipation gap filler is a filler used to dissipate heat from an electronic component by applying it to an electronic component such as a substrate material to fill air pockets or gaps.
  • the heat dissipation gap filler is a hardening type heat dissipation paste that hardens from a paste form to a sheet form. According to the heat dissipation gap filler according to the present embodiment, the heat resistance of the filler can be improved. Generation of bubbles during heating can also be suppressed.
  • the heat dissipation gap filler according to the present embodiment is produced by, for example, kneading the boron nitride material 10 according to the first embodiment with an epoxy resin, a silicone resin, or a non-silicone acrylic resin or a ceramic resin. It can be manufactured by
  • the filler for thermal grease according to the present embodiment includes the boron nitride material 10 according to the first embodiment.
  • a filler for heat-radiating grease is a filler used for heat-radiating grease.
  • Thermal grease is a non-hardening thermal paste used to dissipate heat from electronic components by applying them to electronic components, such as substrate materials, to fill air pockets or gaps.
  • the heat resistance of the filler can be improved. Generation of bubbles during heating can also be suppressed.
  • the heat dissipation grease filler according to the present embodiment is produced by, for example, kneading the boron nitride material 10 according to Embodiment 1 with an epoxy resin, a silicone resin, or a non-silicone acrylic resin or ceramic resin. It can be manufactured by
  • FIG. 3 is a diagram showing a schematic configuration of a resin composition 20 in Embodiment 4.
  • the resin composition 20 includes, for example, a filler 22 and a curable resin 24.
  • the filler 22 includes the boron nitride material 10 described in the first embodiment. According to this embodiment, it is possible to provide a resin composition 20 that exhibits a low dielectric loss tangent and has excellent heat resistance. As the filler 22, the boron nitride material 10 alone may be used, or other filler materials such as silica particles may be used in combination with the boron nitride material 10.
  • curable resin 24 examples include epoxy resins, cyanate ester compounds, maleimide compounds, phenol resins, acrylic resins, polyamide resins, polyamideimide resins, thermosetting polyimide resins, and polyphenylene ether resins.
  • epoxy resins cyanate ester compounds
  • maleimide compounds phenol resins
  • acrylic resins acrylic resins
  • polyamide resins polyamideimide resins
  • thermosetting polyimide resins thermosetting polyimide resins
  • polyphenylene ether resins examples include epoxy resins, cyanate ester compounds, maleimide compounds, phenol resins, acrylic resins, polyamide resins, polyamideimide resins, thermosetting polyimide resins, and polyphenylene ether resins.
  • the curable resin 24 one kind or a combination of two or more kinds selected from these can be used.
  • the resin composition 20 may contain other components.
  • Other ingredients include curing agents, flame retardants, ultraviolet absorbers, antioxidants, reaction initiators, silane coupling agents, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, and erasers. Examples include foaming agents, dispersants, leveling agents, brighteners, antistatic agents, polymerization inhibitors, and organic solvents. If necessary, the resin composition 20 can use one type or a combination of two or more types selected from these.
  • the prepreg according to Embodiment 5 includes the resin composition 20 of Embodiment 4 shown in FIG. 3 or a semi-cured product thereof, and a fibrous base material.
  • the fibrous base material is present in the matrix of the resin composition 20 or semi-cured material.
  • Prepreg is a composite material of the resin composition 20 and a fibrous base material. According to this embodiment, it is possible to provide a prepreg suitable for high-frequency wiring boards.
  • the semi-cured material refers to a material that is partially cured to the extent that the resin composition 20 can be further cured. That is, the semi-cured material is a material obtained by semi-curing the resin composition 20. For example, when the resin composition 20 is heated, its viscosity gradually decreases. If heating is continued, curing will then begin and its viscosity will gradually increase. In such a case, the semi-cured state includes the state of the resin composition 20 during the period from the time when the viscosity starts to increase until the time when it is completely cured.
  • the fibrous base material known materials used in various electrically insulating material laminates can be used.
  • 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 resin composition 20 is impregnated into the fibrous base material through treatments such as dipping and coating.
  • a pre-cured or semi-cured prepreg according to the present embodiment can be obtained.
  • FIG. 4 is a cross-sectional view of a resin-coated film 30 in Embodiment 6.
  • the resin-coated film 30 includes a resin layer 32 containing the resin composition 20 or a semi-cured product thereof, and a support film 34.
  • a resin-coated film 30 suitable for an insulating layer can be provided.
  • the resin layer 32 is supported by a support film 34.
  • a support film 34 is placed on the surface of the resin layer 32.
  • another layer such as an adhesive layer may be provided between the resin layer 32 and the support film 34.
  • the resin layer 32 contains the resin composition 20 of Embodiment 4 shown in FIG. 3 or a semi-cured product thereof, and may or may not contain a fibrous base material.
  • the fibrous base material the same material as the fibrous base material of the prepreg can be used.
  • the resin layer 32 hardens and changes into an insulating layer.
  • An example of such an insulating layer is an insulating layer of a wiring board.
  • any support film used for resin-coated films can be used without limitation.
  • the support film 34 include resin films such as polyester films and polyethylene terephthalate films.
  • FIG. 5 is a cross-sectional view of resin-coated metal foil 40 in Embodiment 7.
  • the resin-coated metal foil 40 includes a resin layer 42 containing the resin composition 20 or a semi-cured product thereof, and a metal foil 44.
  • a resin layer 42 is supported by a metal foil 44.
  • a resin-coated metal foil 40 suitable for electronic circuit components such as wiring boards can be provided.
  • a metal foil 44 is placed on the surface of the resin layer 42.
  • another layer such as an adhesive layer may be provided between the resin layer 42 and the metal foil 44.
  • the resin layer 42 contains the resin composition of Embodiment 4 shown in FIG. 3 or a semi-cured product thereof, and may or may not contain a fibrous base material.
  • the fibrous base material the same material as the fibrous base material of the prepreg can be used.
  • the resin layer 42 hardens and changes into an insulating layer.
  • An example of such an insulating layer is an insulating layer of a wiring board.
  • metal foil 44 resin-coated metal foil and metal foil used for metal-clad laminates can be used without limitation.
  • the metal foil include copper foil and aluminum foil.
  • FIG. 6 is a cross-sectional view of a metal-clad laminate 50 in Embodiment 8.
  • Metal-clad laminate 50 includes an insulating layer 52 and at least one metal foil 54 .
  • a metal-clad laminate 50 suitable for a wiring board can be provided.
  • the insulating layer 52 includes a cured product of the resin composition 20 of the fourth embodiment shown in FIG. 3 or a cured product of the prepreg of the fifth embodiment.
  • Metal foil 54 is placed on the surface of insulating layer 52. In this embodiment, metal foils 54 are placed on each of the front and back surfaces of the insulating layer 52.
  • the metal-clad laminate 50 is typically manufactured using the prepreg of Embodiment 5.
  • a laminate is formed by stacking 1 to 20 sheets of prepreg.
  • a metal-clad laminate 50 is obtained by placing metal foil on one or both sides of the prepreg laminate and heating and pressurizing the prepreg laminate.
  • the metal foil 54 include copper foil, aluminum foil, and the like.
  • the molding conditions for manufacturing a laminate for electrically insulating materials and a multilayer board can be applied to the molding conditions for manufacturing the metal-clad laminate 50.
  • FIG. 7 is a cross-sectional view of wiring board 60 in the ninth embodiment.
  • Wiring board 60 includes an insulating layer 62 and wiring 64.
  • a wiring board 60 suitable for high frequencies can be provided.
  • the insulating layer 62 includes a cured product of the resin composition 20 of the fourth embodiment shown in FIG. 3 or a cured product of the prepreg of the fifth embodiment.
  • the wiring 64 is supported by the insulating layer 62. Specifically, the wiring 64 is arranged on the insulating layer 62. Wiring 64 may be formed by partially removing the metal foil.
  • a wiring board 60 in which wiring 64 forming a circuit is provided on the surface of the insulating layer 62 is obtained. That is, the wiring board 60 is obtained by partially removing the metal foil 54 on the surface of the metal-clad laminate 50 so that a circuit is formed.
  • a new laminate may be formed by laminating the prepreg of Embodiment 5 on at least one surface of the wiring board 60 and applying heat and pressure.
  • a multilayer wiring board can be obtained by patterning the metal foil on the surface of the obtained laminate to form wiring.
  • boron nitride manufactured by Denka, GP grade
  • Example 1 A solution was obtained by dissolving 15 mg of poly(9-vinylcarbazole) represented by formula (5) (manufactured by Aldrich, number average molecular weight Mn 25,000 to 50,000) in 1 mL of toluene. 200 mg of boron nitride was suspended in the solution and stirred at 100°C overnight. After isolation of boron nitride by suction filtration, it was washed with toluene and vacuum dried at room temperature. As a result, about 200 mg of powder of the boron nitride material of Example 1 was obtained.
  • Example 2 A solution was obtained by dissolving 15 mg of poly(N-ethyl-2-vinylcarbazole) (manufactured by Aldrich) represented by formula (6) in 1 mL of toluene. 200 mg of boron nitride was suspended in the solution and stirred at 100°C overnight. After isolation of boron nitride by suction filtration, it was washed with toluene and vacuum dried at room temperature. As a result, about 200 mg of powder of the boron nitride material of Example 2 was obtained.
  • Example 3 A solution was obtained by dissolving 15 mg of Poly(9,9-di-n-dodecylfluorenyl-2,7-diyl) (LT-A1016, manufactured by Luminescence Technology) represented by formula (7) in 1 mL of toluene. 200 mg of boron nitride was suspended in the solution and stirred at 100°C overnight. After isolation of boron nitride by suction filtration, it was washed with toluene and vacuum dried at room temperature. As a result, about 200 mg of powder of the boron nitride material of Example 3 was obtained.
  • PFOTBT Poly[2,7-(9,9-di-octyl-fluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3- thiadiazole] (manufactured by Luminescence Technology, LT-S9419) was dissolved in 1 mL of toluene to obtain a solution. 200 mg of boron nitride was suspended in the solution and stirred at 100°C overnight. After isolation of boron nitride by suction filtration, it was washed with toluene and vacuum dried at room temperature. As a result, about 200 mg of powder of the boron nitride material of Example 4 was obtained.
  • Example 5 A solution was obtained by dissolving 15 mg of polyphenylene ether represented by formula (9) (manufactured by SABIC Japan) in 1 mL of toluene. 200 mg of boron nitride was suspended in the solution and stirred at 100°C overnight. After isolation of boron nitride by suction filtration, it was washed with toluene and vacuum dried at room temperature. As a result, about 200 mg of powder of the boron nitride material of Example 5 was obtained.
  • polyphenylene ether represented by formula (9) manufactured by SABIC Japan
  • the dispersion term ⁇ d , polarity term ⁇ p and hydrogen bond term ⁇ h of the HSP value were calculated from the molecular structure of the polymer.
  • the HSP distance (MPa 0.5 ) between the polymer and water was calculated. 15.5 MPa 0.5 , 16.0 MPa 0.5 and 42.3 MPa 0.5 were used as the dispersion term ⁇ d , polar term ⁇ p and hydrogen bond term ⁇ h of the HSP value of water, respectively.
  • Table 1 The results are shown in Table 1.
  • HSP distance [4( ⁇ d -15.5) 2 +( ⁇ p -16.0) 2 +( ⁇ h -42.3) 2 ] 1/2 ...(A1)
  • Polydopamine used in Comparative Example 3 is known to be a mixture having multiple molecular structures.
  • the HSP distance was calculated assuming that polydopamine has a single structure described in formula (11).
  • Actual polydopamine is known as a highly hydrophilic polymer. Even if polydopamine has a structure other than formula (11), its HSP distance will not be less than 39.5 MPa 0.5 .
  • the HSP distance is used as an index representing the ease of solubility and dispersibility between solvents or organic molecules. Therefore, the HSP distance between water and a polymer can be used as a standard for quantitatively determining the degree of hydrophobicity or hydrophilicity of a polymer. As can be understood from the measurement results described later in Example and Comparative Example 2, a polymer having an HSP distance of more than 39.5 MPa 0.5 has sufficient hydrophobicity to reduce the dielectric loss tangent during humidification of boron nitride. I can judge.
  • the boron nitride materials of Examples and Comparative Examples were humidified by the following method.
  • the boron nitride material was placed in a container with an open lid.
  • the container was placed in a transparent plastic bag along with the hygrometer.
  • the boron nitride material was humidified by flowing air at 25° C. whose humidity was adjusted to 90% into the plastic bag and leaving it in that state for 15 hours.
  • a hygrometer was used to confirm that the humidity inside the plastic bag was maintained at 90% during humidification.
  • the boron nitride material after humidification was taken out from the plastic bag.
  • the dielectric loss tangent of the boron nitride material at a frequency of 1 GHz was measured.
  • a cavity resonator manufactured by AET, MS46122B was used to measure the dielectric loss tangent.
  • the boron nitride material was exposed to outside air at room temperature (25° C.). The measurement was performed 20 minutes after the end of humidification. The results are shown in Table 1.
  • Table 1 the dielectric loss tangent during humidification indicates a value normalized by setting the dielectric loss tangent during humidification of Comparative Example 1 to 1.
  • the dielectric loss tangent of the boron nitride material was normalized by setting the dielectric loss tangent of unmodified boron nitride (Comparative Example 1) to 1. That is, the ratio of the dielectric loss tangent of the boron nitride material to the dielectric loss tangent of unmodified boron nitride was calculated. If the calculated value is less than 1, it can be determined that the dielectric loss tangent is good.
  • the boron nitride materials of the Examples and Comparative Examples were humidified in the manner described above.
  • the amount of moisture adsorbed by the humidified boron nitride material was measured using the Karl Fischer method.
  • a Karl Fischer moisture meter manufactured by Kyoto Electronics Industry Co., Ltd., MKC-610
  • a vaporizer manufactured by Kyoto Electronics Industry Co., Ltd., ADP-611
  • the vaporization temperature was 150°C.
  • the end point was when the drift value reached +0.1 ⁇ g/sec.
  • Nitrogen 200 mL/min
  • the measurement was performed twice, and the average value of the two measurements was used as the result.
  • the boron nitride material was stored in a gas displacement desiccator filled with air with a humidity of 90%, and the boron nitride material was not exposed to outside air until the start of measurement.
  • Table 1 the amount of water adsorption during humidification is a value normalized with the amount of water adsorption during humidification of Comparative Example 1 taken as 1.
  • This measurement was conducted to determine the amount of moisture adsorbed by the boron nitride material during humidification.
  • the moisture adsorption amount of the boron nitride material was standardized by setting the moisture adsorption amount of unmodified boron nitride (Comparative Example 1) during humidification to 1. That is, the ratio of the amount of moisture adsorbed by the boron nitride material to the amount of moisture adsorbed by unmodified boron nitride was calculated. If the calculated value is less than 1, it can be determined that the amount of water adsorption is good.
  • SP values of the boron nitride materials of Examples and Comparative Examples were measured by the method shown below. 50 mL of ion exchange water was placed in a 200 mL beaker, and 50 mg of the boron nitride material was floated on the water surface. Thereafter, the mixture was stirred for 3 minutes using a magnetic stirrer at a rotation speed of 300 rpm to obtain a dispersion.
  • the tip of a buret containing methanol was placed in the dispersion liquid, methanol was added dropwise under stirring, and the amount of methanol added Y (mL) required for all the particles of the boron nitride material to settle into the liquid was measured. .
  • the SP value was calculated by substituting the measured addition amount Y into formula (A2). In this example, 47.9 MPa 0.5 was used as the SP value (literature value) of water. 29.6 MPa 0.5 was used as the SP value (literature value) of methanol. The results are shown in Table 1.
  • Example 1 to 5 the HSP distance between the polymer and water was greater than 39.5 MPa 0.5 .
  • the SP values of the boron nitride materials of Examples 1 to 5 were less than 47.9 MPa 0.5 , and the surfaces of the particles of the boron nitride materials had sufficient hydrophobicity. From this, it can be concluded that in Examples 1 to 5, the surface of boron nitride was sufficiently modified with the polymer.
  • the dielectric loss tangent (ratio to Comparative Example 1) of the boron nitride materials of Examples 1 to 5 was less than 1. In other words, Examples 1 to 5 exhibited lower dielectric loss tangents than hexagonal boron nitride under high humidity.
  • the moisture adsorption amount (ratio to Comparative Example 1) of the boron nitride materials of Examples 1 to 5 was less than 1, which was lower than that of Comparative Examples 1 and 3.
  • FIG. 2 is a graph showing the relationship between the HSP distance between a polymer and water and the dielectric loss tangent of a boron nitride material during humidification.
  • the horizontal axis shows the HSP distance between the polymers used in Examples 1 to 5 and Comparative Example 2 and water.
  • the vertical axis indicates the dielectric loss tangent of the boron nitride materials of Examples 1 to 5 and Comparative Example 2 during humidification.
  • a total of six points in Examples 1 to 5 and Comparative Example 2 were subjected to linear approximation using the least squares method to obtain an approximate straight line shown in FIG.
  • the HSP distance when the dielectric loss tangent during humidification was 1 was calculated from the approximate straight line.
  • the HSP distance when the dielectric loss tangent during humidification was 1 was 39.5 MPa 0.5 . Therefore, it is considered that if the surface of boron nitride is sufficiently modified with a polymer whose HSP distance to water is greater than 39.5 MPa 0.5 , the dielectric loss tangent during humidification can be lowered than before the surface modification.
  • Comparative Example 2 showed a small amount of water adsorption, but a high dielectric loss tangent. It is presumed that the main reason for this result is that there is a discrepancy between the amount of water measured by the Karl Fischer method and the amount of water measured by the dielectric loss tangent. The dielectric loss tangent was measured 20 minutes after the boron nitride material was transferred from an environment with a humidity of 90% to the atmosphere. In other words, "dielectric loss tangent during humidification" represents the dielectric loss tangent in a state where moisture desorption has progressed to some extent. In Examples 1 to 5, moisture desorption progressed sufficiently, but in Comparative Example 2, it is presumed that moisture desorption did not proceed sufficiently.
  • Comparative Example 3 The measured values of Comparative Example 3 were not used to calculate the approximate straight line. This is because the polymer contained in the boron nitride material of Comparative Example 3 is polydopamine. Polydopamine does not have a single molecular structure, making it impossible to accurately calculate the HSP distance, and the large amount of hydroxyl groups contained within its structure directly causes deterioration of the dielectric loss tangent. The data of Comparative Example 3 was judged to be inappropriate for discussing the influence of moisture absorption on the dielectric loss tangent and was therefore excluded.
  • Comparative Example 4 the HSP distance between the polymer (polystyrene) and water was sufficiently large. However, the SP value of the boron nitride material of Comparative Example 4 exceeded 47.9 MP 0.5 . In other words, in Comparative Example 4, sufficient surface modification was not performed.
  • the boron nitride material of the present disclosure exhibits a low dielectric loss tangent even under high humidity, so it is suitable for wiring boards of electronic devices used for large-capacity communications.

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Abstract

Un matériau de nitrure de bore (10) selon la présente invention comprend : un nitrure de bore hexagonal qui a une épaisseur supérieure ou égale à 5 nm dans la direction de l'axe c ; et un polymère (2) qui adhère au nitrure de bore hexagonal. Le paramètre de solubilité du matériau de nitrure de bore (10) tel que déterminé par une méthode de titrage de méthanol est inférieur à 47,9 MPa0.5. Un matériau de nitrure de bore (10) selon la présente invention est utilisé dans des applications telles qu'une charge, une composition de résine, un préimprégné, un film avec une résine, une feuille métallique avec une résine, un stratifié revêtu de métal et une carte de câblage.
PCT/JP2023/020740 2022-06-30 2023-06-05 Matériau de nitrure de bore et son application WO2024004526A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257392A (ja) * 2005-03-14 2006-09-28 General Electric Co <Ge> 改良窒化ホウ素組成物及び該組成物を配合したポリマー系組成物
WO2017163674A1 (fr) * 2016-03-23 2017-09-28 パナソニックＩｐマネジメント株式会社 Préimprégné, stratifié revêtu de métal, carte de circuit imprimé et procédé de production de préimprégné
WO2017195902A1 (fr) * 2016-05-13 2017-11-16 日立化成株式会社 Composition de résine, préimprégné, feuille métallique dotée d'une résine, stratifié, panneau de circuit imprimé, et procédé de production d'une composition de résine
US20180337359A1 (en) * 2017-05-18 2018-11-22 University Of Pittsburgh-Of The Commonwealth System Of Higher Education Nanoscale light emitting diode, and methods of making same
JP2019527280A (ja) * 2016-07-25 2019-09-26 エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ 潤滑添加剤として有用なポリマー無機粒子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257392A (ja) * 2005-03-14 2006-09-28 General Electric Co <Ge> 改良窒化ホウ素組成物及び該組成物を配合したポリマー系組成物
WO2017163674A1 (fr) * 2016-03-23 2017-09-28 パナソニックＩｐマネジメント株式会社 Préimprégné, stratifié revêtu de métal, carte de circuit imprimé et procédé de production de préimprégné
WO2017195902A1 (fr) * 2016-05-13 2017-11-16 日立化成株式会社 Composition de résine, préimprégné, feuille métallique dotée d'une résine, stratifié, panneau de circuit imprimé, et procédé de production d'une composition de résine
JP2019527280A (ja) * 2016-07-25 2019-09-26 エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ 潤滑添加剤として有用なポリマー無機粒子
US20180337359A1 (en) * 2017-05-18 2018-11-22 University Of Pittsburgh-Of The Commonwealth System Of Higher Education Nanoscale light emitting diode, and methods of making same

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