WO2020203692A1 - 複合体 - Google Patents

複合体 Download PDF

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Publication number
WO2020203692A1
WO2020203692A1 PCT/JP2020/013826 JP2020013826W WO2020203692A1 WO 2020203692 A1 WO2020203692 A1 WO 2020203692A1 JP 2020013826 W JP2020013826 W JP 2020013826W WO 2020203692 A1 WO2020203692 A1 WO 2020203692A1
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WO
WIPO (PCT)
Prior art keywords
boron nitride
sintered body
nitride sintered
resin
volume
Prior art date
Application number
PCT/JP2020/013826
Other languages
English (en)
French (fr)
Inventor
紗緒梨 井之上
翔二 岩切
仁孝 南方
亮 吉松
竜士 古賀
智也 山口
Original Assignee
デンカ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to EP20783042.3A priority Critical patent/EP3951860A4/en
Priority to JP2021511951A priority patent/JPWO2020203692A1/ja
Priority to CN202080022199.1A priority patent/CN113614909A/zh
Priority to US17/441,763 priority patent/US20220177375A1/en
Publication of WO2020203692A1 publication Critical patent/WO2020203692A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3733—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon having a heterogeneous or anisotropic structure, e.g. powder or fibres in a matrix, wire mesh, porous structures
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    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3731—Ceramic materials or glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
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    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1147—Sealing or impregnating, e.g. of pores

Definitions

  • the present invention relates to a complex.
  • an object of the present invention is to provide a composite having excellent insulating properties.
  • One aspect of the present invention includes a porous boron nitride sintered body and a resin filled in the pores of the boron nitride sintered body, and the average pore diameter of the boron nitride sintered body is 3.5 ⁇ m or less. , A complex.
  • the content of the boron nitride sintered body may be 30% by volume or more and 60% by volume or less, and the resin content may be 40% by volume or more and 70% by volume or less based on the total volume of the composite.
  • the porosity of the boron nitride sintered body may be 10% by volume or more and 70% by volume or less.
  • the average pore size of the boron nitride sintered body is 3.5 ⁇ m or less, and from the viewpoint of further improving the insulating property of the composite, it is preferably 3.0 ⁇ m or less, more preferably 2.5 ⁇ m or less, still more preferably 2.0 ⁇ m. Below, it is particularly preferably 1.5 ⁇ m or less.
  • the average pore size of the boron nitride sintered body is such that the cumulative pore volume is 50% of the total pore volume in the pore size distribution (horizontal axis: pore diameter, vertical axis: cumulative pore volume) measured using a mercury porosimeter. Is defined as the pore size that reaches.
  • a mercury porosimeter for example, a mercury porosimeter manufactured by Shimadzu Corporation can be used, and the measurement can be performed by pressurizing while increasing the pressure from 0.03 atm to 4000 atm.
  • the ratio of pores to the boron nitride sintered body is preferably 10 volumes from the viewpoint of preferably improving the strength of the composite by filling with resin based on the total volume of the boron nitride sintered body. % Or more, 20% by volume or more, or 30% by volume or more, preferably 70% by volume or less, more preferably 50% by volume or less, from the viewpoint of further improving the insulating property and thermal conductivity of the composite.
  • the proportion of the boron nitride sintered body in the composite is preferably 30% by volume or more, more preferably 40% by volume, based on the total volume of the composite, from the viewpoint of further improving the insulating property and thermal conductivity of the composite. % Or more, more preferably 50% by volume or more, for example, 90% by volume or less, 80% by volume or less, 70% by volume or less, or 60% by volume or less.
  • the complex contains one or more resins.
  • the resin include epoxy resin, silicone resin, cyanate resin, silicone rubber, acrylonitrile resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, and polybutylene terephthalate.
  • the resin preferably contains an epoxy resin from the viewpoint of excellent heat resistance and adhesive strength to the circuit.
  • the composite is suitably used for the insulating layer of the printed wiring board.
  • the resin preferably contains a silicone resin from the viewpoint of excellent heat resistance, flexibility, and adhesion to a heat sink or the like.
  • the composite is preferably used as a thermal interface material.
  • the composite may further contain other components (including impurities) in addition to the boron nitride sintered body and the resin.
  • Other components may be a curing agent, an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like.
  • the composite is preferably one or more inorganic fillers (ceramics) selected from the group consisting of aluminum oxide, silicon oxide, zinc oxide, silicon nitride, aluminum nitride and aluminum hydroxide from the viewpoint of excellent thermal conductivity. Powder) is contained.
  • the content of other components may be 10% by volume or less, 5% by volume or less, 3% by volume or less, or 1% by volume or less based on the total volume of the complex.
  • the resin can be sufficiently impregnated by using a boron nitride sintered body having an average pore diameter in a predetermined range.
  • the composite of the present embodiment has an excellent withstand voltage. Therefore, this composite is suitably used as a material for electronic components.
  • the withstand voltage of the composite is, for example, 4.3 kV or more. The withstand voltage is measured by the method described in the examples.
  • the composite as described above can be used, for example, by impregnating the boron nitride sintered body with the resin composition (impregnation step) and curing the resin in the resin composition filled in the pores of the boron nitride sintered body. It is obtained by a manufacturing method including a curing step.
  • the impregnation step includes the step S1 of preparing the boron nitride sintered body and the resin composition, and the boron nitride sintered body being immersed in the resin composition and placed under reduced pressure conditions, and then baked with boron nitride.
  • Step S2 in which the body is immersed in the resin composition and placed under pressure conditions higher than the above reduced pressure conditions, and the boron nitride sintered body is placed in the resin composition under pressure conditions and then boron nitride.
  • step S1 for example, a boron nitride sintered body and a resin composition are prepared in an impregnation device whose pressure can be controlled.
  • the boron nitride sintered body is obtained by molding the boron nitride powder and then sintering it. That is, in one embodiment, before the impregnation step, a molding step of molding the boron nitride powder to obtain a boron nitride molded body and a sintering step of sintering the boron nitride molded body to obtain a boron nitride sintered body are performed. It may be carried out.
  • a spherical boron nitride powder obtained by spheroidizing a slurry containing a boron nitride powder with a spray dryer or the like is subjected to a press molding method or a cold isotropic pressure method (CIP).
  • CIP cold isotropic pressure method
  • the pressure during molding in the molding step is not particularly limited, but the lower the pressure, the smaller the average pore diameter of the obtained boron nitride sintered body.
  • the sintering aid may be, for example, a carbonate of an alkali metal such as lithium carbonate, sodium carbonate, calcium carbonate or an alkaline earth metal, boric acid, or a combination thereof.
  • the amount of the sintering aid added may be, for example, 0.5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total of the boron nitride powder and the sintering aid.
  • boron nitride sintered body having the average pore size it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the boron nitride molded body obtained in the molding process is sintered.
  • the sintering temperature may be, for example, 1600 ° C. or higher, and may be 2200 ° C. or lower.
  • the sintering time may be, for example, 1 hour or more and 30 hours or less.
  • the atmosphere at the time of sintering may be, for example, an atmosphere of an inert gas such as nitrogen, helium, or argon.
  • ketones such as ketones and hydrocarbons such as toluene and xylene.
  • step S2 the pressure inside the impregnation device is lowered and the pressure is reduced.
  • the pressure P1 under this depressurized condition may be, for example, 1000 Pa or less, 500 Pa or less, 100 Pa or less, or 50 Pa or less.
  • step S2 the boron nitride sintered body is immersed in the resin composition under the above-mentioned reduced pressure conditions, and the immersed state is placed under the reduced pressure conditions for a predetermined time.
  • the predetermined time may be, for example, 10 minutes or more, and may be 720 minutes or less.
  • the temperature of the resin composition at this time may be, for example, 20 ° C. or higher, and may be 150 ° C. or lower.
  • step S2 the pressure in the impregnation device is subsequently increased to a pressure condition higher than the pressure P1 under the above decompression condition.
  • the pressure P2 under this pressure condition may be, for example, 0.01 MPa or more, 0.05 MPa or more, 0.08 MPa or more, or 0.1 MPa or more, 0.5 MPa or less, 0.4 MPa or less, 0.3 MPa or less, Alternatively, it may be 0.2 MPa or less, and may be atmospheric pressure (0.101325 MPa).
  • step S2 the boron nitride sintered body is placed in the resin composition under the above pressure conditions for a predetermined time.
  • the predetermined time may be, for example, 1 minute or more and 60 minutes or less.
  • the temperature of the resin composition at this time may be, for example, 20 ° C. or higher, and may be 150 ° C. or lower.
  • step S3 the pressure inside the impregnation device is increased to set the pressurizing condition.
  • the pressure P3 under this pressurizing condition may be, for example, 0.2 MPa or more, 0.5 MPa or more, 1 MPa or more, or 5 MPa or more, and may be 20 MPa or less, 10 MPa or less, or 5 MPa or less.
  • step S3 the boron nitride sintered body is placed in the resin composition under the above-mentioned pressure conditions for a predetermined time.
  • the predetermined time may be, for example, 5 minutes or more, 15 minutes or more, and 720 minutes or less.
  • the temperature of the resin composition at this time may be, for example, 20 ° C. or higher, and may be 150 ° C. or lower.
  • step S3 the pressure in the impregnation device is subsequently lowered to a pressure condition lower than the pressure P3 under the above pressurization condition.
  • the pressure P4 under this pressure condition may be, for example, 0.01 MPa or more, 0.05 MPa or more, 0.08 MPa or more, or 0.1 MPa or more, 0.5 MPa or less, 0.4 MPa or less, 0.3 MPa or less, Alternatively, it may be 0.2 MPa or less, and may be atmospheric pressure.
  • step S3 the boron nitride sintered body is placed in the resin composition under the above pressure conditions for a predetermined time.
  • the predetermined time may be, for example, 1 minute or more and 60 minutes or less.
  • the temperature of the resin composition at this time may be, for example, 20 ° C. or higher, and may be 150 ° C. or lower.
  • steps S2 and S3 may be repeated a plurality of times.
  • the number of times of execution may be 2 times or more, 5 times or more, or 10 times or more, and may be 20 times or less, 15 times or less, or 13 times or less.
  • the step S3 is repeated, the number of times the step S3 is performed may be 2 times or more, 5 times or more, or 10 times or more, and may be 20 times or less, 15 times or less, or 13 times or less.
  • This production method may further include a step (curing step) of curing the resin in the resin composition filled in the pores of the boron nitride sintered body, following the impregnation step.
  • a step (curing step) of curing the resin in the resin composition filled in the pores of the boron nitride sintered body following the impregnation step.
  • the curing step for example, the boron nitride sintered body and the resin composition filled therein are taken out from the impregnation apparatus, and heated and / or irradiated with light depending on the type of resin (or the curing agent added as needed). Cures the resin.
  • a part of the resin may be cured (so-called B stage formation), or the entire resin may be cured.
  • the conditions for heating and light irradiation can be appropriately set according to the type of resin (or a curing agent added as needed), the desired degree of curing, and the like.
  • polyvinyl alcohol (“Gosenol”, manufactured by Nippon Synthetic Chemical Co., Ltd.) is added to the water slurry so as to be 0.5% by mass, heated and stirred at 50 ° C. until dissolved, and then spray-dried.
  • the spheroidizing treatment was performed at a drying temperature of 230 ° C.
  • a rotary atomizer was used as the spheroidizing device of the spray dryer.
  • the obtained processed product was filled in a boron nitride container and pressed at 20 MPa by a cold isotropic pressure method (CIP) for molding.
  • CIP cold isotropic pressure method
  • the boron nitride sintered body was taken out from the boron nitride container after sintering for 10 hours under the conditions of normal pressure, nitrogen flow rate of 5 L / min, and 2050 ° C. in a batch type high frequency furnace.
  • ⁇ Impregnated resin composition The obtained boron nitride sintered body was impregnated with the resin composition by the following procedure. 61 parts by mass of cyanate resin ("TA-CN", manufactured by Mitsubishi Gas Chemical Co., Ltd.), 11 parts by mass of maleimide resin ("BMI-80", manufactured by DIC Corporation), and epoxy resin ("HP-4032D”). 28 parts by mass (manufactured by DIC Corporation) was mixed at 130 ° C. for 1 hour to obtain a resin composition.
  • TA-CN cyanate resin
  • BMI-80 maleimide resin
  • HP-4032D epoxy resin
  • the boron nitride sintered body is immersed in the resin composition and placed under reduced pressure condition P1 (30 Pa) for a predetermined time T1 (120 minutes), and then boron nitride sintered.
  • the step S2 in which the body was immersed in the resin composition and placed under the pressure condition P2 (0.6 MPa) higher than the depressurization condition P1 for a predetermined time T2 (1 minute) was repeated 8 times.
  • the boron nitride sintered body was placed in the resin composition under pressure condition P3 (4 MPa) for a predetermined time for T3 (6 minutes), and then the boron nitride sintered body was immersed in the resin composition.
  • the step S3 of placing T4 (5 minutes) for a predetermined time under the pressure condition P4 (0.1 MPa) lower than the pressurization condition P3 was repeated 11 times. As described above, a resin-filled boron nitride sintered body (composite) was obtained.
  • the content of the resin in the obtained composite was measured by the following procedure. The results are shown in Table 1.
  • the content (% by volume) of the resin in the composite was determined by measuring the bulk density of the boron nitride sintered body and the bulk density of the composite shown below.
  • Resin content in the composite (%) ((composite bulk density-boron nitride sintered bulk density) / (complex theoretical density-boron nitride sintered bulk density)) x 100
  • the theoretical complex density was calculated from the following formula.
  • Composite theoretical density Boron nitride true density + Resin true density x (1-Boron nitride sintered body bulk density / Boron nitride true density)
  • the bulk density of the boron nitride sintered body and the composite conforms to the method of measuring the density and specific gravity by geometric measurement of JIS Z 8807: 2012, and the bulk density of each side of the boron nitride sintered body or the composite having a regular hexahedron shape. It was determined based on the volume calculated from the length (measured by calipers) and the mass of the boron nitride sintered body or composite measured by an electronic balance (see Section 9 of JIS Z 8807: 2012).
  • Example 2 A boron nitride sintered body was produced in the same manner as in Example 1 except that the amounts of the amorphous boron nitride powder, calcium carbonate and boric acid, and the average particle size of the hexagonal boron nitride were changed as shown in Table 1.
  • the average pore diameter and porosity of the obtained boron nitride sintered body were measured in the same manner as in Example 1, and the results were as shown in Table 1.
  • a composite was obtained by impregnating the resin composition in the same manner as in Example 1. As a result of measuring the resin content and evaluating the insulating property of the obtained composite in the same manner as in Example 1, the results are as shown in Table 1.
  • Example 6 to 12 and Comparative Examples 2 to 4 A boron nitride sintered body was produced in the same manner as in Example 1 except that the amounts of the amorphous boron nitride powder, calcium carbonate and boric acid, and the pressure of CIP were changed as shown in Table 2.
  • the average pore size and porosity of the obtained boron nitride sintered body were measured in the same manner as in Example 1, and the results were as shown in Table 2.
  • the resin composition is impregnated in the same manner as in Example 1 except that the pressure conditions in steps S2 and S3, the time placed under each pressure condition, and the number of times each step is performed are changed as shown in Table 2.
  • a complex was obtained.
  • the obtained composite was measured for resin content and evaluated for insulating properties in the same manner as in Example 2, and the results were as shown in Table 2.

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Abstract

本発明の一側面は、多孔性の窒化ホウ素焼結体と、窒化ホウ素焼結体の孔内に充填された樹脂と、を備え、窒化ホウ素焼結体の平均孔径が３．５μｍ以下である、複合体である。

Description

複合体
　本発明は、複合体に関する。
　パワーデバイス、トランジスタ、サイリスタ、ＣＰＵ等の電子部品においては、使用時に発生する熱を効率的に放熱することが課題となっている。この課題に対して、従来、電子部品を実装するプリント配線板の絶縁層の高熱伝導化や、電子部品又はプリント配線板を電気絶縁性の熱インターフェース材（Thermal Interface Materials）を介してヒートシンクに取り付けることが行われてきた。このような絶縁層及び熱インターフェース材には、樹脂と窒化ホウ素等のセラミックスとで構成される複合体（放熱部材）が用いられる。
　このような複合体として、従来、樹脂中にセラミックスの粉末を分散させたものが用いられているが、近年では、多孔性のセラミックス焼結体（例えば窒化ホウ素焼結体）に樹脂を含浸させた複合体も検討されている（例えば特許文献１）。
国際公開第２０１４／１９６４９６号
　本発明者らの検討によれば、上述したような多孔性の窒化ホウ素焼結体に樹脂を含浸させた複合体においては、絶縁性の点で更なる改善の余地がある。
　そこで、本発明は、絶縁性に優れる複合体を提供することを目的とする。
　本発明の一側面は、多孔性の窒化ホウ素焼結体と、窒化ホウ素焼結体の孔内に充填された樹脂と、を備え、窒化ホウ素焼結体の平均孔径が３．５μｍ以下である、複合体である。
　複合体の全体積を基準として、窒化ホウ素焼結体の含有量は３０体積％以上６０体積％以下であってよく、樹脂の含有量は４０体積％以上７０体積％以下であってよい。
　窒化ホウ素焼結体の気孔率は、１０体積％以上７０％体積％以下であってよい。
　本発明によれば、絶縁性に優れる複合体を提供することができる。
　以下、本発明の実施形態について詳細に説明する。
　本発明の一実施形態は、多孔性の窒化ホウ素焼結体（以下、単に「窒化ホウ素焼結体」ともいう）と、窒化ホウ素焼結体の孔内に充填された樹脂とを備える複合体である。樹脂は、窒化ホウ素焼結体の孔内の一部に充填されていてよく、孔内の全部に充填されていてもよい。樹脂は、その一部が硬化（いわゆるＢステージ化）された状態であってよく、その全部が硬化された状態であってもよい。
　窒化ホウ素焼結体は、窒化ホウ素の一次粒子同士が焼結されてなるものである。窒化ホウ素焼結体は、複数の孔（細孔）を有する多孔性の焼結体である。窒化ホウ素焼結体の平均孔径は、例えば０．５μｍ以上であってよく、孔内に樹脂を好適に充填できる観点から、好ましくは０．６μｍ以上、より好ましくは０．８μｍ以上、更に好ましくは１μｍ以上である。窒化ホウ素焼結体の平均孔径は、３．５μｍ以下であり、複合体の絶縁性が更に向上する観点から、好ましくは３．０μｍ以下、より好ましくは２．５μｍ以下、更に好ましくは２．０μｍ以下、特に好ましくは１．５μｍ以下である。
　窒化ホウ素焼結体の平均孔径は、水銀ポロシメーターを用いて測定される細孔径分布（横軸：細孔径、縦軸：累積細孔容積）において、累積細孔容積が全細孔容積の５０％に達する細孔径として定義される。水銀ポロシメーターとしては、例えば、島津製作所社製の水銀ポロシメーターを用いることができ、０．０３気圧から４０００気圧まで圧力を増やしながら加圧して測定することができる。
　窒化ホウ素焼結体に占める孔の割合（気孔率）は、窒化ホウ素焼結体の全体積を基準として、樹脂の充填による複合体の強度向上が好適に図られる観点から、好ましくは、１０体積％以上、２０体積％以上、又は３０体積％以上であり、複合体の絶縁性及び熱伝導率を更に向上させる観点から、好ましくは７０体積％以下、より好ましくは５０体積％以下である。当該割合（気孔率）は、窒化ホウ素焼結体の体積及び質量から求められるかさ密度（Ｄ；ｇ／ｃｍ３）と窒化ホウ素の理論密度（２．２８ｇ／ｃｍ３）とから、下記式：
　気孔率（体積％）＝［１－（Ｄ／２．２８）］×１００
に従って算出される。
　複合体中の窒化ホウ素焼結体の割合は、複合体の全体積を基準として、複合体の絶縁性及び熱伝導率を更に向上させる観点から、好ましくは３０体積％以上、より好ましくは４０体積％以上、更に好ましくは５０体積％以上であり、例えば９０体積％以下、８０体積％以下、７０体積％以下、又は６０体積％以下であってよい。
　複合体は、１種又は２種以上の樹脂を含んでいる。樹脂としては、例えば、エポキシ樹脂、シリコーン樹脂、シアネート樹脂、シリコーンゴム、アクリル樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンエーテル、ポリフェニレンサルファイド、全芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネート、マレイミド樹脂、マレイミド変性樹脂、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＡＡＳ（アクリロニトリル－アクリルゴム・スチレン）樹脂、ＡＥＳ（アクリロニトリル・エチレン・プロピレン・ジエンゴム－スチレン）樹脂、ポリグリコール酸樹脂、ポリフタルアミド、ポリアセタール等を用いることができる。
　樹脂は、一実施形態において、耐熱性及び回路への接着強度に優れる観点から、好ましくはエポキシ樹脂を含む。この場合、複合体は、プリント配線板の絶縁層に好適に用いられる。樹脂は、他の一実施形態において、耐熱性、柔軟性及びヒートシンク等への密着性に優れる観点から、好ましくはシリコーン樹脂を含む。この場合、複合体は、熱インターフェース材に好適に用いられる。
　複合体中の樹脂の含有量は、特に限定されないが、複合体の全体積を基準として、例えば、２０体積％以上、２５体積％以上、３０体積％以上、３５体積％以上、又は４０体積％以上であってよく、７５体積％以下、７０体積％以下、６５体積％以下、６０体積％以下、又は５５体積％以下であってよい。複合体中の樹脂の含有量は、実施例に記載の方法により測定できる。
　複合体は、窒化ホウ素焼結体及び樹脂に加えて、その他の成分（不純物を含む）を更に含有してもよい。その他の成分は、硬化剤、無機フィラー、シランカップリング剤、消泡剤、表面調整剤、湿潤分散剤等であってよい。複合体は、熱伝導率に優れる観点から、好ましくは、酸化アルミニウム、酸化ケイ素、酸化亜鉛、窒化ケイ素、窒化アルミニウム及び水酸化アルミニウムからなる群より選ばれる１種又は２種以上の無機フィラー（セラミックス粉末）を含有する。その他の成分の含有量は、複合体の全体積を基準として、１０体積％以下、５体積％以下、３体積％以下、又は１体積％以下であってよい。
　本実施形態の複合体では、平均孔径が所定の範囲にある窒化ホウ素焼結体を用いることで、樹脂を十分に含浸させることができる。その結果、本実施形態の複合体は、優れた耐電圧を有している。したがって、この複合体は、電子部品用の材料として好適に用いられる。複合体の耐電圧は、例えば４．３ｋＶ以上である。耐電圧は、実施例に記載の方法で測定される。
　以上説明したような複合体は、例えば、窒化ホウ素焼結体に樹脂組成物を含浸させる工程（含浸工程）と、窒化ホウ素焼結体の孔内に充填された樹脂組成物中の樹脂を硬化させる（硬化工程）とを備える製造方法により得られる。
　含浸工程は、一実施形態において、窒化ホウ素焼結体及び樹脂組成物を用意する工程Ｓ１と、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で減圧条件下に置いた後、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記減圧条件より高い圧力条件下に置く工程Ｓ２と、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で加圧条件下に置いた後、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記加圧条件より低い圧力条件下に置く工程Ｓ３と、を含む。
　工程Ｓ１では、例えば圧力を制御可能な含浸装置内に、窒化ホウ素焼結体及び樹脂組成物をそれぞれ用意する。
　窒化ホウ素焼結体は、窒化ホウ素粉末を成型した後、焼結させることにより得られる。すなわち、一実施形態において、含浸工程の前に、窒化ホウ素粉末を成型して窒化ホウ素成型体を得る成型工程と、窒化ホウ素成型体を焼結させて窒化ホウ素焼結体を得る焼結工程が実施されてもよい。より具体的には、成型工程では、例えば、窒化ホウ素粉末を含むスラリーを噴霧乾燥機等で球状化処理して得た球状の窒化ホウ素粉末を、プレス成型法や冷間等方加圧法（ＣＩＰ）により成型することができる。成型工程における成型時の圧力は特に制限されないが、圧力が低いほど得られる窒化ホウ素焼結体の平均孔径は小さくなる。
　成型工程における成型時には、焼結助剤を添加することが好ましい。焼結助剤は、例えば、炭酸リチウム、炭酸ナトリウム、炭酸カルシウム等のアルカリ金属若しくはアルカリ土類金属の炭酸塩、ホウ酸、又はそれらの組み合わせであってよい。焼結助剤の添加量は、窒化ホウ素粉末と焼結助剤との合計１００質量部に対して、例えば、０．５質量部以上であってよく、２５質量部以下であってよく、上述した平均孔径を有する窒化ホウ素焼結体が好適に得られる観点から、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１０質量部以下、特に好ましく５質量部以下である。
　焼結工程では、成型工程で得られた窒化ホウ素成型体を焼結させる。焼結温度は、例えば、１６００℃以上であってよく、２２００℃以下であってよい。焼結時間は、例えば、１時間以上であってよく、３０時間以下であってよい。焼結時の雰囲気は、例えば、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気であってよい。
　樹脂組成物は、上述した樹脂を含有し、必要に応じて上述したその他の成分を更に含有してよい。樹脂組成物は、溶剤の１種又は２種以上を更に含有してもよい。溶剤としては、例えば、エタノール、イソプロパノール等の脂肪族アルコール、２－メトキシエタノール、１－メトキシエタノール、２－エトキシエタノール、１－エトキシ－２－プロパノール、２－ブトキシエタノール、２－（２－メトキシエトキシ）エタノール、２－（２－エトキシエトキシ）エタノール、２－（２－ブトキシエトキシ）エタノール等のエーテルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のグリコールエーテル、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトンケトン等のケトン、トルエン、キシレン等の炭化水素が挙げられる。
　工程Ｓ２では、含浸装置内の圧力を低くし減圧条件とする。この減圧条件における圧力Ｐ１は、例えば、１０００Ｐａ以下、５００Ｐａ以下、１００Ｐａ以下、又は５０Ｐａ以下であってよい。
　工程Ｓ２では、上記のような減圧条件下において、窒化ホウ素焼結体を樹脂組成物に浸漬し、浸漬した状態で減圧条件下に所定の時間置く。当該所定の時間は、例えば、１０分間以上であってよく、７２０分間以下であってよい。このときの樹脂組成物の温度は、例えば、２０℃以上であってよく、１５０℃以下であってよい。
　工程Ｓ２では、続いて、含浸装置内の圧力を高くし、上記の減圧条件における圧力Ｐ１より高い圧力条件とする。この圧力条件における圧力Ｐ２は、例えば、０．０１ＭＰａ以上、０．０５ＭＰａ以上、０．０８ＭＰａ以上、又は０．１ＭＰａ以上であってよく、０．５ＭＰａ以下、０．４ＭＰａ以下、０．３ＭＰａ以下、又は０．２ＭＰａ以下であってよく、大気圧（０．１０１３２５ＭＰａ）であってもよい。
　工程Ｓ２では、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記のような圧力条件下に所定の時間置く。当該所定の時間は、例えば、１分間以上であってよく、６０分間以下であってよい。このときの樹脂組成物の温度は、例えば、２０℃以上であってよく、１５０℃以下であってよい。
　工程Ｓ３では、含浸装置内の圧力を高くし、加圧条件とする。この加圧条件における圧力Ｐ３は、例えば、０．２ＭＰａ以上、０．５ＭＰａ以上、１ＭＰａ以上、又は５ＭＰａ以上であってよく、２０ＭＰａ以下、１０ＭＰａ以下、又は５ＭＰａ以下であってよい。
　工程Ｓ３では、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記のような加圧条件下に所定の時間置く。当該所定の時間は、例えば、５分間以上又は１５分間以上であってよく、７２０分間以下であってよい。このときの樹脂組成物の温度は、例えば、２０℃以上であってよく、１５０℃以下であってよい。
　工程Ｓ３では、続いて、含浸装置内の圧力を低くし、上記の加圧条件における圧力Ｐ３より低い圧力条件とする。この圧力条件における圧力Ｐ４は、例えば、０．０１ＭＰａ以上、０．０５ＭＰａ以上、０．０８ＭＰａ以上、又は０．１ＭＰａ以上であってよく、０．５ＭＰａ以下、０．４ＭＰａ以下、０．３ＭＰａ以下、又は０．２ＭＰａ以下であってよく、大気圧であってもよい。
　工程Ｓ３では、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記のような圧力条件下に所定の時間置く。当該所定の時間は、例えば、１分間以上であってよく、６０分間以下であってよい。このときの樹脂組成物の温度は、例えば、２０℃以上であってよく、１５０℃以下であってよい。
　以上説明した含浸工程においては、工程Ｓ２及び工程Ｓ３の一方又は両方を複数回繰り返し実施してもよい。工程Ｓ２を繰り返す場合の実施回数は、２回以上、５回以上、又は１０回以上であってよく、２０回以下、１５回以下、又は１３回以下であってよい。工程Ｓ３を繰り返す場合の工程Ｓ３の実施回数は、２回以上、５回以上、又は１０回以上であってよく、２０回以下、１５回以下、又は１３回以下であってよい。
　この製造方法は、含浸工程に続いて、窒化ホウ素焼結体の孔内に充填された樹脂組成物中の樹脂を硬化させる工程（硬化工程）を更に備えてもよい。硬化工程では、例えば、窒化ホウ素焼結体及びそこに充填された樹脂組成物を含浸装置から取り出し、樹脂（又は必要に応じて添加される硬化剤）の種類に応じて、加熱及び／光照射により、樹脂を硬化させる。硬化工程では、樹脂の一部を硬化（いわゆるＢステージ化）させてよく、樹脂の全部を硬化させてもよい。加熱及び光照射の条件は、樹脂（又は必要に応じて添加される硬化剤）の種類、所望の硬化の程度等に応じて適宜設定できる。
　以下、実施例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。
（実施例１）
＜窒化ホウ素焼結体の作製＞
　酸素含有量２．０％、平均粒径３．４μｍであるアモルファス窒化ホウ素粉末９質量部と、酸素含有量０．３％、平均粒径１２．５μｍである六方晶窒化ホウ素粉末１３質量部と、炭酸カルシウム（「ＰＣ－７００」、白石工業社製）０．１質量部と、ホウ酸０．２質量部とを、ヘンシェルミキサーを用いて混合した後、水７６．０質量部を添加してボールミルで５時間粉砕し、水スラリーを得た。さらに、水スラリーに対して、ポリビニルアルコール（「ゴーセノール」、日本合成化学社製）を０．５質量％となるように添加し、溶解するまで５０℃で加熱撹拌した後、噴霧乾燥機にて乾燥温度２３０℃で球状化処理を行った。なお、噴霧乾燥機の球状化装置としては、回転式アトマイザーを使用した。得られた処理物を窒化ホウ素製容器に充填し、冷間等方加圧法（ＣＩＰ）により２０ＭＰａで加圧して成型を行った。続いて、バッチ式高周波炉にて、常圧、窒素流量５Ｌ／分、２０５０℃の条件で１０時間焼結させた後、窒化ホウ素容器から窒化ホウ素焼結体を取り出した。
＜平均孔径の測定＞
　得られた窒化ホウ素焼結体について、島津製作所社製の水銀ポロシメーターを用い、０．０３気圧から４０００気圧まで圧力を増やしながら加圧したときの細孔径分布（横軸：細孔径、縦軸：累積細孔容積）を測定した。その細孔径分布から、累積細孔容積が全細孔容積の５０％に達する細孔径として平均孔径を算出した。結果を表１に示す。
＜気孔率の測定＞
　得られた窒化ホウ素焼結体の体積及び質量を測定し、当該体積及び質量からかさ密度（Ｄ；ｇ／ｃｍ３）を算出した。このかさ密度と窒化ホウ素の理論密度（２．２８ｇ／ｃｍ３）とから、下記式：
　気孔率（体積％）＝［１－（Ｄ／２．２８）］×１００
に従って、気孔率を算出した。結果を表１に示す。
＜樹脂組成物の含浸＞
　得られた窒化ホウ素焼結体に対して、以下の手順で樹脂組成物の含浸を行った。
　シアネート樹脂（「ＴＡ－ＣＮ」、三菱ガス化学株式会社製）６１質量部と、マレイミド樹脂（「ＢＭＩ－８０）ケイ・アイ化成株式会社製）１１質量部と、エポキシ樹脂（「ＨＰ－４０３２Ｄ）ＤＩＣ株式会社製）２８質量部とを、１３０℃で１時間混合して樹脂組成物を得た。
　続いて、圧力を制御可能な含浸装置内で、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で減圧条件Ｐ１（３０Ｐａ）下に所定時間Ｔ１（１２０分間）置いた後、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記減圧条件Ｐ１より高い圧力条件Ｐ２（０．６ＭＰａ）下に所定時間Ｔ２（１分間）置く工程Ｓ２を８回繰り返し実施した。その後、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で加圧条件Ｐ３（４ＭＰａ）下に所定時間Ｔ３（６分間）置いた後、窒化ホウ素焼結体を樹脂組成物に浸漬した状態で上記加圧条件Ｐ３より低い圧力条件Ｐ４（０．１ＭＰａ）下に所定時間Ｔ４（５分間）置く工程Ｓ３を１１回繰り返し実施した。
　以上のようにして、樹脂が充填された窒化ホウ素焼結体（複合体）を得た。
＜樹脂の含有量の測定＞
　得られた複合体中の樹脂の含有量を以下の手順で測定した。結果を表１に示す。
　複合体中の樹脂の含有量（体積％）は、以下に示す窒化ホウ素焼結体のかさ密度と複合体のかさ密度とを測定することにより求めた。
　複合体中の樹脂の含有量（％）＝（（複合体かさ密度－窒化ホウ素焼結体かさ密度）／（複合体理論密度－窒化ホウ素焼結体かさ密度））×１００
なお、複合体理論密度は、下記式より求めた。
　複合体理論密度＝窒化ホウ素真密度＋樹脂真密度×（１－窒化ホウ素焼結体かさ密度／窒化ホウ素真密度）
窒化ホウ素焼結体及び複合体のかさ密度は、ＪＩＳ　Ｚ　８８０７：２０１２の幾何学的測定による密度及び比重の測定方法に準拠し、正六面体形状の窒化ホウ素焼結体又は複合体の各辺の長さ（ノギスにより測定）から計算した体積と、電子天秤により測定した窒化ホウ素焼結体又は複合体の質量に基づいて求めた（ＪＩＳ　Ｚ　８８０７：２０１２の９項参照）。窒化ホウ素焼結体及び樹脂の真密度は、ＪＩＳ　Ｚ　８８０７：２０１２の気体置換法による密度及び比重の測定方法に準拠し、乾式自動密度計を用いて測定した窒化ホウ素焼結体及び樹脂の体積及び質量より求めた（ＪＩＳ　Ｚ　８８０７：２０１２の１１項の式（１４）～（１７）参照）。
＜絶縁性の評価＞
　得られた各複合体を２０ｍｍ×２０ｍｍの大きさに切り出し、これに対して１６ｍｍ×１６ｍｍの大きさの導電テープを接着したものを評価用試料とした。菊水電子工業社製のＴＯＳ５１０１を用いて、評価用試料に対して、０．５ｋＶ／３０ｓの昇圧条件で絶縁破壊電圧（ｋＶ）を測定した。結果を表１に示す。絶縁破壊電圧が高いほど、絶縁性に優れている。
（実施例２～５）
　アモルファス窒化ホウ素粉末、炭酸カルシウム及びホウ酸の配合量、並びに六方晶窒化ホウ素の平均粒径を表１に示すとおりに変更した以外は、実施例１と同様に窒化ホウ素焼結体を作製した。得られた窒化ホウ素焼結体について、実施例１と同様に平均孔径及び気孔率を測定したところ、表１に示すとおりとなった。続いて、実施例１と同様に樹脂組成物を含浸させることにより、複合体を得た。得られた複合体について、実施例１と同様に樹脂の含有量の測定及び絶縁性の評価を行ったところ、表１に示すとおりとなった。
（比較例１）
　アモルファス窒化ホウ素粉末、炭酸カルシウム及びホウ酸の配合量、並びにＣＩＰの圧力を表１に示すとおりに変更した以外は、実施例１と同様に窒化ホウ素焼結体を作製した。得られた窒化ホウ素焼結体について、実施例１と同様に平均孔径及び気孔率を測定したところ、表１に示すとおりとなった。続いて、実施例１と同様に樹脂組成物を含浸させることにより、複合体を得た。得られた複合体について、実施例１と同様に樹脂の含有量の測定及び絶縁性の評価を行ったところ、表１に示すとおりとなった。
Figure JPOXMLDOC01-appb-T000001
（実施例６～１２及び比較例２～４）
　アモルファス窒化ホウ素粉末、炭酸カルシウム及びホウ酸の配合量、並びにＣＩＰの圧力を表２に示すとおりに変更した以外は、実施例１と同様に窒化ホウ素焼結体を作製した。得られた窒化ホウ素焼結体について、実施例１と同様に平均孔径及び気孔率を測定したところ、表２に示すとおりとなった。
　続いて、工程Ｓ２及び工程Ｓ３における圧力条件、各圧力条件に置かれる時間、及び各工程の実施回数を表２に示すとおりに変更した以外は、実施例１と同様に樹脂組成物を含浸させることにより、複合体を得た。得られた複合体について、実施例２と同様に樹脂の含有量の測定及び絶縁性の評価を行ったところ、表２に示すとおりとなった。
Figure JPOXMLDOC01-appb-T000002

Claims (3)

  1. 　多孔性の窒化ホウ素焼結体と、
    　前記窒化ホウ素焼結体の孔内に充填された樹脂と、を備え、
    　前記窒化ホウ素焼結体の平均孔径が３．５μｍ以下である、複合体。
  2. 　前記複合体の全体積を基準として、前記窒化ホウ素焼結体の含有量が３０体積％以上６０体積％以下であり、前記樹脂の含有量が４０体積％以上７０体積％以下である、請求項１に記載の複合体。
  3. 　前記窒化ホウ素焼結体の気孔率が１０体積％以上７０％体積％以下である、請求項１又は２に記載の複合体。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08244163A (ja) * 1994-11-30 1996-09-24 Mitsubishi Gas Chem Co Inc 金属箔張複合セラミックス板及びその製造法
WO2014196496A1 (ja) 2013-06-03 2014-12-11 電気化学工業株式会社 樹脂含浸窒化ホウ素焼結体およびその用途
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI505985B (zh) * 2013-03-07 2015-11-01 Denki Kagaku Kogyo Kk Boron nitride powder and a resin composition containing the same
WO2015022956A1 (ja) * 2013-08-14 2015-02-19 電気化学工業株式会社 窒化ホウ素－樹脂複合体回路基板、窒化ホウ素－樹脂複合体放熱板一体型回路基板
JP6262522B2 (ja) * 2013-12-26 2018-01-17 デンカ株式会社 樹脂含浸窒化ホウ素焼結体およびその用途
JP6348610B2 (ja) * 2014-12-08 2018-06-27 昭和電工株式会社 六方晶窒化ホウ素粉末、その製造方法、樹脂組成物及び樹脂シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08244163A (ja) * 1994-11-30 1996-09-24 Mitsubishi Gas Chem Co Inc 金属箔張複合セラミックス板及びその製造法
WO2014196496A1 (ja) 2013-06-03 2014-12-11 電気化学工業株式会社 樹脂含浸窒化ホウ素焼結体およびその用途
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3951860A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022209402A1 (ja) * 2021-03-30 2022-10-06
WO2022209402A1 (ja) * 2021-03-30 2022-10-06 デンカ株式会社 回路基板の製造方法及び回路基板
JP7328464B2 (ja) 2021-03-30 2023-08-16 デンカ株式会社 回路基板の製造方法及び回路基板
JPWO2023027122A1 (ja) * 2021-08-26 2023-03-02
WO2023027122A1 (ja) * 2021-08-26 2023-03-02 デンカ株式会社 セラミックス板の製造方法、セラミックス板、複合シート、及び積層基板
JP7319482B2 (ja) 2021-08-26 2023-08-01 デンカ株式会社 セラミックス板の製造方法、セラミックス板、複合シート、及び積層基板

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