WO2021200967A1

WO2021200967A1 - Composite and heat dissipation member

Info

Publication number: WO2021200967A1
Application number: PCT/JP2021/013572
Authority: WO
Inventors: 紗緒梨井之上; 翔二岩切; 賢久上島; 亮吉松; 竜士古賀
Original assignee: デンカ株式会社
Priority date: 2020-03-31
Filing date: 2021-03-30
Publication date: 2021-10-07
Also published as: JPWO2021200967A1

Abstract

Provided is a composite containing: a nitride sintered body having a porous structure; and a semi-cured product of a thermosetting resin composition impregnated in the nitride sintered body, wherein the composite has a thickness change rate of at least 2% when pressed under 5 MPa in the thickness direction. Provided is a heat dissipation member having said composite.

Description

Complex and heat dissipation member

This disclosure relates to a complex and a heat radiating member.

In parts such as power devices, transistors, thyristors, and CPUs, it is required to efficiently dissipate the heat generated during use. In response to such demands, conventional methods have been used to increase the thermal conductivity of the insulating layer of printed wiring boards on which electronic components are mounted, or to use thermal interface materials (Thermal Interface Materials) that have electrical insulation properties for electronic components or printed wiring boards. It has been used to attach it to a heat sink. For such an insulating layer and a thermal interface material, a composite (heat dissipation member) composed of a resin and ceramics such as boron nitride is used.

As such a complex, it is being studied to use a composite in which a porous ceramic molded body is impregnated with a resin. Since boron nitride has lubricity, high thermal conductivity, insulating properties, etc., it is being studied to use ceramics containing boron nitride as a heat radiating member. Patent Document 1 proposes a technique for reducing the anisotropy of thermal conductivity while having excellent thermal conductivity by setting the degree of orientation and the graphitization index within a predetermined range.

Japanese Unexamined Patent Publication No. 2014-162679

In recent years, electronic devices have become highly integrated. Along with this, various parts constituting the electronic device are required to be mounted with high position accuracy. From this point of view, various parts are required to have excellent adhesiveness to other parts.

Therefore, the present disclosure provides a complex having excellent adhesiveness to other members. Further, in the present disclosure, by providing the above-mentioned composite, a heat radiating member having sufficiently high reliability is provided.

The present disclosure is a composite containing a nitride sintered body having a porous structure and a semi-cured product of a thermosetting resin composition impregnated in the nitride sintered body, and is applied in the thickness direction at 5 MPa. Provided is a composite having a thickness change rate of 2% or more when pressed. Such a complex is deformed at a predetermined thickness change rate when, for example, it is sandwiched between a pair of opposing members and pressurized. Here, the composite has a nitride sintered body having a porous structure, and the nitride sintered body is impregnated with a semi-cured product of a thermosetting resin composition. When this complex is sandwiched between a pair of opposing members and pressed to join, the complex is deformed at a predetermined rate of change in thickness. When deformed, the resin component contained in the complex exudes. By the action of the exuded resin component, the complex can be firmly adhered to other members. Therefore, it has excellent adhesiveness.

The thickness change rate of the complex may be 35% or less. By having such a thickness change rate, the shape can be maintained to some extent even if pressure is applied when adhering to other members. Therefore, for example, the dimensional accuracy of the electronic component can be improved.

The porosity of the boron nitride sintered body contained in the above complex may be 40 to 75% by volume. Thereby, the impregnation amount of the semi-cured product of the thermosetting resin composition can be sufficiently increased while maintaining the strength and thermal conductivity of the boron nitride sintered body. Such a complex can achieve both excellent insulation and adhesiveness at a high level. The porosity is the total volume ratio of the pores filled with the resin and the pores not filled with the resin.

The bulk density of the boron nitride sintered body contained in the complex may be 600 to 1400 kg / m ³ . Thereby, the impregnation amount of the semi-cured product of the thermosetting resin composition can be sufficiently increased while maintaining the strength and thermal conductivity of the boron nitride sintered body. Such a complex can achieve both excellent insulation and adhesiveness at a high level.

The orientation index of the boron nitride sintered body contained in the above complex may be 20 or less. Thereby, the anisotropy of thermal conductivity can be sufficiently reduced.

The present disclosure provides a heat radiating member having the above-mentioned complex in one aspect. Since this heat radiating member has the above-mentioned composite, it has excellent adhesiveness.

According to the present disclosure, it is possible to provide a complex having excellent adhesiveness to other members. Further, in the present disclosure, by providing the above-mentioned composite, it is possible to provide a heat radiating member having sufficiently high reliability.

It is a perspective view which shows one Embodiment of a complex.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings in some cases. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents.

FIG. 1 is a perspective view of a complex in one embodiment. The sheet-like composite 10 contains a nitride sintered body 20 having a porous structure and a semi-cured product of a thermosetting resin composition impregnated in the nitride sintered body 20. The nitride sintered body 20 contains boron nitride particles and pores formed by sintering primary boron nitride particles. From the viewpoint of further improving the adhesiveness of the complex 10, the thickness change rate when pressurized at 5 MPa in the thickness direction may be 2% or more, or 5% or more. On the other hand, from the viewpoint of suppressing excessive deformation of the complex 10 and maintaining the shape of the complex 10, the thickness change rate may be 35% or less, or 20% or less. An example of the thickness change rate is 2 to 35%.

The thickness change rate in the present disclosure is determined as the ratio (%) of the thickness t1 when the composite 10 is pressed along the thickness direction at 5 MPa in the thickness direction with respect to the thickness t before the pressure is applied. That is, the thickness change rate is calculated by the following formula (1).
Thickness change rate (%) = (t1 / t) x 100 (1)

The thickness change rate can be measured at a measurement temperature of 200 ° C. using a precision universal testing machine (trade name: Autograph AG-X) manufactured by Shimadzu Corporation. If the

main surfaces

10a and 10b of the complex 10 have irregularities or protrusions that affect the measurement of the thickness change rate, the

main surfaces

10a and 10b are processed to remove the irregularities. These processes may be performed using, for example, a machining center (trade name: Dualvertical 635 eco) operated by MORI SEIKI.

The thickness t of the complex 10 may be less than 2 mm, less than 1 mm, and less than 0.5 mm. From the viewpoint of maintaining a certain level of strength, the thickness t of the complex 10 may be 0.1 mm or more, or 0.2 mm or more. An example of the thickness of the complex 10 is 0.1 mm or more and less than 2 mm. The areas of the

main surfaces

10a and 10b of the complex 10 may be 25 mm ² or more, 100 mm ² or more, 500 mm ² or more, 800 mm ² or more, 1000 mm ² or more, respectively. May be.

The thickness t of the nitride sintered body 20 may be less than 2 mm, less than 1 mm, or less than 0.5 mm. From the viewpoint of ease of molding, the thickness of the nitride sintered body 20 may be 0.1 mm or more, or 0.2 mm or more. The main surface 20a of the nitride sintered body 20, the area of the 20b, may be at 25 mm ² or more, may be at 100 mm ² or more, may be at 500 mm ² or more, may be at 800 mm ² or more, 1000 mm ² It may be the above.

The average pore diameter of the pores contained in the nitride sintered body 20 may be less than 10 μm. By reducing the size of the pores, the contact area between the primary particles of the boron nitride particles can be sufficiently increased. Therefore, the strength can be maintained even if the porosity is increased.

The average pore size of the pores is determined based on the pore size distribution when pressure is applied while increasing the pressure from 0.5 psia to 60,000 psia using a mercury porosimeter. When the horizontal axis is the pore diameter and the vertical axis is the cumulative pore volume, the pore diameter when the cumulative pore volume reaches 50% of the total pore volume is the average pore diameter. As the mercury porosimeter, one manufactured by Shimadzu Corporation can be used.

The porosity of the nitride sintered body 20, that is, the volume ratio of the pores in the nitride sintered body 20 may be 40 to 75% by volume or 45 to 70% by volume. If the porosity becomes too large, the strength and thermal conductivity of the nitride sintered body tend to decrease. On the other hand, if the porosity becomes too small, the content of the semi-cured product of the thermosetting resin composition when the composite is produced tends to decrease.

For the pore ratio, the bulk density [B (kg / m ³ )] was calculated from the volume and mass of the nitride sintered body 20, and the bulk density and the theoretical density of boron nitride [2280 (kg / m ³ )] were used. Therefore, it can be obtained by the following formula (2). When measuring the porosity of the nitride sintered body contained in the composite, it can be measured by burning and removing the semi-cured product of the thermosetting resin composition contained in the composite. ..
Porosity (% by volume) = [1- (B / 2280)] x 100 (2)

The bulk density B may be 600 to 1400 kg / m ³ or 800 to 1200 kg / m ³ . If the bulk density B becomes too small, the strength of the nitride sintered body 20 tends to decrease. On the other hand, if the bulk density B becomes too large, the impregnation amount of the semi-cured product of the thermosetting resin composition tends to decrease, and the insulating property of the composite tends to decrease.

The thermal conductivity of the nitride sintered body 20 may be 10 W / (m · K) or more, 15 W / (m · K) or more, and 20 W / (m · K) or more. , 25 W / (m · K) or more. By using the nitride sintered body 20 having a high thermal conductivity, it is possible to obtain a heat radiating member having sufficiently excellent heat radiating performance. The thermal conductivity (H) can be calculated by the following formula (3). The thermal conductivity (H) may be 70 W / (m · K) or less, 60 W / (m · K) or less, and 50 W / (m · K) or less.
H = A × B × C (3)

In formula (3), H is the thermal conductivity (W / (m · K)), A is the thermal diffusivity (m ² / sec), B is the bulk density (kg / m ³ ), and C is the specific heat capacity. (J / (kg · K)) is shown. The thermal diffusivity A can be measured by a laser flash method. The bulk density B can be obtained from the volume and mass of the nitride sintered body 20. The specific heat capacity C can be measured using a differential scanning calorimeter.

The nitride sintered body 20 may be a boron nitride sintered body. The boron nitride sintered body may contain components other than boron nitride. The content of boron nitride in the boron nitride sintered body may be 90% by mass or more, 95% by mass or more, and 98% by mass or more.

The nitride sintered body 20 has a sheet shape (thin plate shape). Since the sheet-shaped nitride sintered body 20 has a _{small thickness t 0} , the resin composition can be smoothly impregnated. As a result, the pores of the nitride sintered body are sufficiently filled with the semi-cured product, and a composite having excellent insulating properties can be obtained.

The orientation index of the boron nitride crystal in the boron nitride sintered body may be 20 or less, 18 or less, and 15 or less. Thereby, the anisotropy of thermal conductivity can be sufficiently reduced. Therefore, in the case of a sheet like a boron nitride sintered body, the thermal conductivity along the thickness direction can be sufficiently increased. The thermal conductivity (H) along the thickness direction of the boron nitride sintered body is preferably the above-mentioned value. The orientation index of the boron nitride sintered body may be 0.5 or more, 3 or more, or 5 or more. The orientation index in the present disclosure is an index for quantifying the degree of orientation of boron nitride crystals. The orientation index can be calculated by the peak intensity ratio [I (002) / I (100)] of the (002) plane and the (100) plane of boron nitride measured by an X-ray diffractometer.

The shape of the nitride sintered body is not limited to the shape shown in FIG. 1, and may be, for example, a disk-shaped sheet or a C-shaped sheet in which the main surfaces 20a and 20b are curved. In this case, the thickness change rate can be measured by processing into a sheet as shown in FIG. Further, the block-shaped nitride sintered body may be cut and / or polished to be processed into a sheet shape as shown in FIG. However, if processing such as cutting is performed, material loss will occur. Therefore, if a sheet-shaped nitride sintered body is produced using the sheet-shaped molded body, material loss can be reduced. Thereby, the yield of the nitride sintered body and the composite can be improved. When the block-shaped nitride sintered body is a polyhedron, for example, all sides have a suitable length, and the block-shaped nitride sintered body has a larger thickness than the sheet-shaped nitride sintered body. That is, the block shape means a shape that can be divided into a plurality of sheet shapes (thin plate shapes) by cutting.

The composite according to one embodiment is a composite of a nitride sintered body and a semi-cured product of a thermosetting resin composition, and is at least a part of the pores of the above-mentioned nitride sintered body and the nitride sintered body. It has a semi-cured product of a thermosetting resin composition filled in. Examples of the thermosetting resin composition include epoxy resin, silicone resin, cyanate resin, silicone rubber, acrylic resin, phenol resin, melamine resin, urea resin, bismaleimide resin unsaturated polyester, fluororesin, polyimide, polyamideimide, and the like. Polyetherimide, Polybutylene terephthalate, Polyethylene terephthalate, Polyphenylene ether, Polyphenylene sulfide, Total aromatic polyester, Polysulfone, Liquid crystal polymer, Polyethersulfone, Polycarbonate, Maleimide resin, Maleimide-modified resin, ABS (Acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber-styrene) resin, polyglycolic acid resin, polyphthalamide, polyacetal and the like can be used. One of these may be contained alone, or two or more thereof may be contained in combination.

When the composite is used for the insulating layer of the printed wiring board, the thermosetting resin composition may contain an epoxy resin from the viewpoint of improving heat resistance and adhesive strength to the circuit. When the composite is used as a thermal interface material, the resin may contain a silicone resin from the viewpoint of improving heat resistance, flexibility, and adhesion to a heat sink or the like. The semi-cured product of the thermosetting resin composition is also referred to as a B stage state.

The content of the boron nitride particles in the complex may be 25 to 65% by volume or 39 to 48% by volume based on the total volume of the complex. The content of the semi-cured product of the thermosetting resin composition in the complex may be 35 to 75% by volume or 52 to 61% by volume based on the total volume of the complex. A composite containing boron nitride particles and a semi-cured product of a thermosetting resin composition at such a ratio can achieve both high adhesiveness and high thermal conductivity at a high level.

The content of the resin containing the semi-cured product in the complex may be 10 to 70% by mass, 10 to 60% by mass, or 20 to 60% by mass based on the total mass of the complex. It may be 20 to 55% by mass, and may be 25 to 55% by mass. A complex containing a resin in such a ratio can achieve both high adhesiveness and thermal conductivity at a high level. The content of the resin in the complex can be determined by heating the complex to decompose and remove the resin, and calculating the mass of the resin from the mass difference before and after heating.

The filling rate of the resin containing the semi-cured product in the complex may be 80% by volume or more, 90% by volume or more, or 92% by volume or more. The resin filling rate is the volume ratio of the pores filled with the resin (semi-cured product + cured product) among all the pores in the boron nitride sintered body.

The porosity in the complex may be 20% by volume or less, 10% by volume or less, 8% by volume or less, 6% by volume or less, and 5% by volume or less. It may be 4% by volume or less. As a result, both high adhesiveness and high insulation can be achieved at a sufficiently high level.

The complex may further contain other components in addition to the nitride sintered body and the semi-cured product of the thermosetting resin composition filled in the pores thereof. Examples of other components include a curing agent, an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like. The inorganic filler may contain one or more selected from the group consisting of aluminum oxide, silicon oxide, zinc oxide, silicon nitride, aluminum nitride and aluminum hydroxide. Thereby, the thermal conductivity of the complex can be further improved. Further, the semi-cured product may contain a completely cured product (C stage). The cured product and the semi-cured product may be collectively referred to as a resin.

The composite may be in the form of a sheet (thin plate shape) as shown in FIG. 1, similarly to the nitride sintered body. Since the sheet-shaped complex 10 has a small thickness, it can be suitably used as a heat radiating member for electronic devices and the like. Moreover, the resin composition is sufficiently impregnated.

The composite 10 contains the above-mentioned nitride sintered body and a semi-cured product of a thermosetting resin composition. When the complex 10 is sandwiched between a pair of opposing members and pressed to join, the complex 10 is deformed at a predetermined thickness change rate. When deformed, the resin component impregnated in the complex exudes. The complex 10 can be firmly adhered to other members by the action of the exuded resin component. Therefore, the complex 10 is excellent in adhesiveness to other members. Therefore, the complex 10 has sufficiently high reliability. Such a complex 10 can be suitably used as a heat radiating member. The shape of the heat radiating member may be the same as that of the complex 10 shown in FIG. 1, or may be different.

An example of a method for manufacturing a complex and a heat radiating member including a boron nitride sintered body as a nitride sintered body will be described below. The above description of the boron nitride sintered body, the complex, and the heat radiating member is applied to the following manufacturing method.

<Manufacturing method of boron nitride sintered body>
The production method of this example includes a sintering step of sintering boron nitride powder to obtain a block-shaped boron nitride sintered body. Examples of the raw material powder include amorphous boron nitride powder having an average particle size of 0.5 to 10 μm and hexagonal boron nitride powder having an average particle size of 3.0 to 40 μm. These powders may be mixed using a Henschel mixer or the like, or may be mixed in a slurry form in water or an ethanol solution using a disparizer. A slurry containing such boron nitride powder may be spheroidized by a spray dryer or the like, molded, and then sintered to obtain a boron nitride sintered body. A mold may be used for molding, or a cold isotropic pressing (CIP) method may be used.

The average particle size of each of the above-mentioned boron nitride powders is a particle size of 50% of the cumulative value of the cumulative particle size distribution in the particle size distribution measurement by the laser diffraction light scattering method. Examples of the particle size distribution measuring machine include "MT3300EX" (manufactured by Nikkiso Co., Ltd.). At the time of measurement, water is used as a solvent, hexametaphosphate is used as a dispersant, and as a pretreatment, a homogenizer is used for 30 seconds to carry out a dispersion treatment with an output of 20 W. 1.33 is used for the refractive index of water, and 1.80 is used for the refractive index of the boron nitride powder. The measurement time per measurement is 30 seconds.

When sintering the boron nitride powder, a sintering aid may be used. The sintering aid may be, for example, an oxide of a rare earth element such as itria oxide, alumina oxide and magnesium oxide, a carbonate of an alkali metal such as lithium carbonate and sodium carbonate, and boric acid. When the sintering aid is blended, the amount of the sintering aid added may be, for example, 1.5 to 25 parts by mass with respect to 100 parts by mass of the total of the boron nitride powder and the sintering aid. , 3.0 to 22 parts by mass. By setting the amount of the sintering aid added within the above range, a boron nitride sintered body having a high porosity and the above-mentioned thickness change rate can be smoothly obtained.

The sintering temperature in the sintering step may be, for example, 1600 ° C. or higher, or 1700 ° C. or higher. The sintering temperature may be, for example, 2200 ° C. or lower, 2100 ° C. or lower, or 2000 ° C. or lower. The sintering time may be, for example, 1 hour or more, or 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, and argon.

For sintering, for example, a batch type furnace, a continuous type furnace, or the like can be used. Examples of the batch type furnace include a high frequency furnace, a muffle furnace, a tube furnace, an atmosphere furnace, and the like. Examples of the continuous furnace include a rotary kiln, a screw conveyor furnace, a tunnel furnace, a belt furnace, a pusher furnace, a koto-shaped continuous furnace, and the like. In this way, a block-shaped boron nitride sintered body can be obtained.

<Manufacturing method of complex>
The method for producing the complex of this example includes an impregnation step and a cutting step of impregnating a block-shaped (for example, a bulk body having a thickness of more than 2 mm) boron nitride sintered body with a resin composition. The thermosetting resin composition may contain a main agent, a curing agent and a solvent from the viewpoint of improving fluidity and handleability. In addition to these, an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like may be contained.

As the thermosetting resin composition, one that becomes the semi-cured product mentioned in the above description of the complex by the semi-curing reaction can be used. Examples of the solvent include aliphatic alcohols such as ethanol and isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol and 2- (2-methoxyethoxy). ) Ether alcohols such as ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl Examples thereof include ketones such as ketones and hydrocarbons such as toluene and xylene. One of these may be contained alone, or two or more thereof may be contained in combination.

Impregnation is performed by adhering a thermosetting resin composition to a boron nitride sintered body. For example, the boron nitride sintered body may be immersed in a thermosetting resin composition. It may be carried out under atmospheric pressure, pressurization, or depressurization conditions in the immersed state. Further, for example, in the case of a sheet-like boron nitride sintered body having a thickness of 2 mm or less, a thermosetting resin composition can be applied to the boron nitride sintered body to impregnate it. In this way, the pores of the boron nitride sintered body can be filled with the resin.

The impregnation step may be performed in an impregnation device provided with a closed container. As an example, after impregnating in the impregnating device under reduced pressure conditions, the pressure in the impregnating device may be increased to be higher than the atmospheric pressure and impregnated under pressurized conditions. By performing both the reduced pressure condition and the pressurized condition in this way, the pores of the boron nitride sintered body can be sufficiently filled with the thermosetting resin. The depressurization condition and the pressurization condition may be repeated a plurality of times. The impregnation step may be performed while heating. The thermosetting resin composition impregnated in the pores of the boron nitride sintered body becomes a semi-cured product after semi-curing proceeds or the solvent volatilizes. In this way, a composite having a boron nitride sintered body and a semi-cured product filled in its pores is obtained. It is not necessary that all the pores are filled with the semi-cured product, and some of the pores may not be filled with the semi-cured product. Boron nitride sintered bodies and complexes may contain both closed and open pores.

After the impregnation step, there may be a curing step of curing the thermosetting resin composition filled in the pores. In the curing step, for example, the composite filled with the thermosetting resin is taken out from the impregnation device, heated and / or irradiated with light depending on the type of the resin composition (or the curing agent added as needed). Semi-cures the resin.

The impregnation step may be performed by combining impregnation under reduced pressure conditions and impregnation under pressurized conditions. The pressure in the impregnation device when the impregnation step is carried out under reduced pressure conditions may be, for example, 1000 Pa or less, 500 Pa or less, 100 Pa or less, 50 Pa or less, or 30 Pa or less. When the impregnation step is performed under pressurized conditions, the pressure in the impregnation device may be, for example, 1 MPa or more, 3 MPa or more, 10 MPa or more, or 30 MPa or more.

In the impregnation step, the solution containing the thermosetting resin composition may be heated. By heating the solution in the following temperature range, the viscosity of the solution can be adjusted and the impregnation of the thermosetting resin composition can be promoted. The viscosity of the solution containing the thermosetting resin composition at the time of impregnation may be, for example, 500 mPa · s or less. By using a solution having such a viscosity, the thermosetting resin composition can be sufficiently impregnated into the boron nitride sintered body.

In the impregnation step, the nitride sintered body is kept immersed in a solution containing a thermosetting resin composition for a predetermined time. The predetermined time may be, for example, 5 hours or more, or 10 hours or more.

After the impregnation step, there is a curing step of semi-curing the thermosetting resin composition filled in the pores. In the curing step, for example, the composite filled with the thermosetting resin composition is taken out from the impregnation device and heated according to the type of the thermosetting resin composition (or the curing agent added as needed). And / or light irradiation causes the thermosetting resin composition to be semi-cured. "Semi-hardening" (also referred to as B stage) means that it can be further hardened by a subsequent hardening treatment. Utilizing the fact that it is in a semi-cured state, it may be temporarily pressure-bonded to an adherend such as a metal substrate and then heated to adhere to the adherend. By further curing the semi-cured product, it can be in a "completely cured" (also referred to as C stage) state. Whether or not the thermosetting resin composition is in a semi-cured state can be confirmed by, for example, a differential scanning calorimeter.

In the cutting step, the obtained resin impregnated body is cut using, for example, a wire saw. The wire saw may be, for example, a multi-cut wire saw or the like. ) Can be cut and prepared. In this way, a sheet-like complex can be obtained.

Although examples of methods for producing boron nitride sintered bodies and composites have been described, these production methods are not limited to the above examples. Nitride sintered bodies other than the boron nitride sintered body can be produced by a known method.

As described above, some embodiments have been described, but the present disclosure is not limited to the above embodiments. For example, in the sintering step, a boron nitride sintered body may be obtained by hot pressing in which molding and sintering are performed at the same time.

The contents of the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited to the following Examples.

(Example 1)
<Preparation of Boron Nitride Sintered Body>
Hexagonal boron nitride powder (oxygen content 0.8% by mass, boron nitride purity 99.0% by mass) having an average particle size of 8.0 μm is 40.0% by mass, and the average particle size is 13.0 μm. A certain hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass) is measured so as to be 60.0% by mass, and these are mixed to prepare a raw material powder. bottom.

A sintering aid was prepared by blending powdered boric acid and calcium carbonate. In the preparation, 60 parts by mass of calcium carbonate was added to 100 parts by mass of boric acid. 14 parts by mass of a sintering aid and 10 parts by mass of a binder (polyvinyl alcohol (“Gosenol”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)) were blended with respect to 100 parts by mass of the raw material powder. The obtained compound was heated and stirred at 50 ° C. until it was dissolved, and then spheroidized at a drying temperature of 230 ° C. using a spray dryer. In this way, a spheroidized mixed powder was prepared. A rotary atomizer was used as the spheroidizing device of the spray dryer.

The above mixed powder was filled in a cold isotropic pressure (CIP) device (manufactured by Kobe Steel, Ltd., trade name: ADW800) and compressed at a pressure of 30 MPa to prepare a molded product. The produced molded product was sintered by holding it at 2000 ° C. for 10 hours using a batch type high frequency furnace (manufactured by Fuji Dempa Kogyo Co., Ltd., trade name: FTH-300-1H). As a result, a block-shaped nitride sintered body was obtained. The firing was carried out by adjusting the inside of the furnace under a nitrogen atmosphere while flowing nitrogen into the furnace in a standard state so that the flow rate was 10 L / min.

<Measurement of thermal conductivity>
The thermal conductivity (H) of the boron nitride sintered body in the thickness direction was calculated by the following formula (4).
H = A × B × C (4)

In formula (4), H is the thermal conductivity (W / (m · K)), A is the thermal diffusivity (m ² / sec), B is the bulk density (kg / m ³ ), and C is the specific heat capacity. (J / (kg · K)) is shown. The thermal diffusivity A was measured by a laser flash method using a sample obtained by processing a boron nitride sintered body into a size of length × width × thickness = 10 mm × 10 mm × 5 mm. A xenon flash analyzer (manufactured by NETZSCH, trade name: LFA447NanoFlash) was used as the measuring device.

The bulk density B was calculated from the volume and mass of the boron nitride sintered body. The specific heat capacity C was measured using a differential scanning calorimeter (manufactured by Rigaku Co., Ltd., device name: ThermoPlusEvo DSC8230). The results of thermal conductivity H and bulk density B are shown in Table 1.

<Measurement of porosity>
The volume and mass of the obtained boron nitride sintered body were measured, and the bulk density B (kg / m ³ ) was calculated from the volume and mass. From this bulk density and the theoretical density of boron nitride (2280 kg / m ³ ), the porosity was calculated by the following formula (5). The results are as shown in Table 1.
Porosity (% by volume) = [1- (D / 2280)] x 100 (5)

<Measurement of orientation index>
The orientation index [I (002) / I (100)] of the boron nitride sintered body was determined using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., trade name: ULTIMA-IV). The measurement sample (boron nitride sintered body) set in the sample holder of the X-ray diffractometer was irradiated with X-rays to perform baseline correction. Then, the peak intensity ratio of the (002) plane and the (100) plane of boron nitride was calculated. This was defined as the orientation index [I (002) / I (100)]. The results are as shown in Table 1.

<Preparation of complex>
Epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Epicoat 807) and curing agent (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Acmex H-84B) in an impregnation device whose pressure is controlled to 0.03 kPa. The boron nitride sintered body was immersed in the thermosetting resin composition containing the above, and the boron nitride sintered body was impregnated with the thermosetting resin composition. After impregnation, the thermosetting resin composition was semi-cured by heating at a temperature of 150 ° C. for 60 minutes under atmospheric pressure, and cooled to room temperature (25 ° C.) to prepare a complex. The semi-cured product layer constituting the surface portion of the complex was cut and removed, and then the complex was cut with a multi-cut wire saw to obtain a complex sheet having a thickness of 0.4 mm. The filling rate of the resin (semi-cured product) in the complex sheet was 94.0% by volume as shown in Table 2. This content was determined by the following procedure.

<Plastic (semi-cured) filling rate>
The filling rate of the resin in the complex was determined by the following formula (6) from the bulk density and the theoretical density before and after the complex was produced.

Resin filling rate in the composite (volume%) = ((composite bulk density-boron nitride sintered bulk density) / (complex theoretical density-boron nitride sintered bulk density)) x 100.・・ (6)

The theoretical density of the complex was calculated from the following equation (7).
Theoretical density of composite = true density of boron nitride sintered body + true density of resin x (1-bulk density of boron nitride sintered body / true density of boron nitride sintered body) ... (7)

The bulk density of the boron nitride sintered body (composite) conforms to the measurement method of density and specific gravity by geometric measurement of JIS Z 8807: 2012, and is a sheet-shaped (rectangular) boron nitride sintered body (composite). It was obtained from the volume calculated from the length of each side (measured by a caliper) and the mass measured by an electronic balance (see item 9 of JIS Z 8807: 2012). The true density of the boron nitride sintered body and the resin conforms to the method of measuring the density and specific gravity by the gas substitution method of JIS Z 8807: 2012, and the volume of the boron nitride sintered body and the resin measured using a dry automatic densitometer. (Refer to equations (14) to (17) in paragraph 11 of JIS Z 8807: 2012).

<Content of resin (semi-cured product)>
The resin content in the complex sheet is as shown in Table 2. The content (% by mass) of this resin is the mass ratio of the semi-cured product to the entire complex. The content of the semi-cured product was calculated by calculating the mass of the semi-cured product from the mass difference between the boron nitride sintered body and the composite, and dividing the mass of the semi-cured product by the mass of the composite.

<Porosity of complex>
From the porosity of the boron nitride sintered body obtained as described above and the filling rate of the resin in the composite, the porosity of the composite was calculated by the following formula (8). The results are shown in Table 2.
Porosity of composite (volume%) = Porosity of boron nitride sintered body (volume%)-(Porosity of boron nitride sintered body (volume%) x resin filling rate (volume%) x 100) ...・ (8)

<Thickness change rate>
The thickness change rate at 200 ° C. was measured using a precision universal testing machine (trade name: Autograph AG-X) manufactured by Shimadzu Corporation. The complex sheet was processed to prepare a measurement sample having a square pillar shape (length x width x thickness = 10 mm x 10 mm x 4 mm). The measurement was performed using the above-mentioned measuring device under the conditions of a compression rate of 1 mm / min, a load cell of 100 kN (pressurizing pressure: 5 MPa), and 200 ° C. The thickness change rate was calculated by the above formula (1). The results are shown in Table 2.

<Evaluation of adhesiveness>
The above-mentioned sheet-like composite between a sheet-shaped copper foil (length x width x thickness = 100 mm x 20 mm x 0.035 mm) and a flat plate-shaped copper plate (length x width x thickness = 100 mm x 20 mm x 1 mm). A body sheet (length x width x thickness = 40 mm x 20 mm x 0.4 mm) was arranged. In this way, a laminate having a copper foil, a composite, and a copper plate in this order was obtained. The laminate was heated and pressurized under the conditions of 200 ° C. and 5 MPa for 5 minutes, and then heat-treated under the conditions of 200 ° C. and atmospheric pressure for 2 hours.

After the above treatment, a 90 ° peeling test was performed to peel the copper foil from the composite in accordance with JIS K 6854-1: 1999 “Adhesive-Peeling Adhesive Strength Test Method”. In this test, the peel strength of the complex at 20 ° C. was determined using a universal testing machine (manufactured by A & D Co., Ltd., trade name: RTG-1310). The measurement was carried out under the conditions of a test speed: 50 mm / min, a load cell: 5 kN, and a measurement temperature: room temperature (20 ° C.), and the area of the agglomerated fracture portion was measured. From the measurement results, the adhesiveness was evaluated according to the following criteria. The results are shown in Table 2. The cohesive fracture portion is the area of the portion of the adhesive surface of the composite that has been adhered to the copper foil and that the composite has broken.
A: Area ratio of agglomerated fractured portion to the entire adhesive surface is 80% or more B: Area ratio of agglomerated fractured portion to the entire adhesive surface is 70% or more and less than 80% C: Area ratio of agglomerated fractured portion to the entire adhesive surface is 20% More than 70%

(Example 2)
Boron nitride firing was performed in the same procedure as in Example 1 except that when the molded product was produced, the mixed powder was compressed at a pressure of 35 MPa with a cold isotropic pressure (CIP) device to obtain the molded product. Bounds and complexes were made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 3)
Boron nitride sintered body and composite were obtained by the same procedure as in Example 1 except that the molded product was obtained by compressing it with a cold isotropic pressure (CIP) device at a pressure of 90 MPa when producing the molded product. The body was made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 4)
Boron nitride sintered body and composite were obtained by the same procedure as in Example 1 except that the molded product was obtained by compressing it with a cold isotropic pressure (CIP) device at a pressure of 10 MPa when producing the molded product. The body was made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 5)
Amorphous boron nitride powder (oxygen content: 1.8% by mass, boron nitride purity: 97.2% by mass) having an average particle size of 0.8 μm is 40.0% by mass, and an average particle size is 13.0 μm. Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass) was measured so as to be 60.0% by mass, and blended to prepare a raw material powder. .. A boron nitride sintered body and a complex were prepared in the same procedure as in Example 1 except that this raw material powder was used. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 6)
The boron nitride sintered body and the composite were prepared in the same procedure as in Example 1 except that the method for producing the molded product was changed from cold isotropic pressure (CIP) to mold molding (molding pressure: 50 MPa). Made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 7)
The boron nitride sintered body and the composite were prepared in the same procedure as in Example 1 except that the method for producing the molded product was changed from cold isotropic pressure (CIP) to mold molding (molding pressure: 15 MPa). Made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 8)
No spheroidizing treatment was performed with a spray dryer, and a mixed powder was prepared by stirring the raw material powder and the sintering aid using a Henschel mixer, which was used in a cold isotropic pressurizer. A boron nitride sintered body and a composite were prepared in the same procedure as in Example 1 except that the molded product was produced. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Example 9)
A boron nitride sintered body and a composite were prepared in the same procedure as in Example 8 except that the molded product was produced by mold molding (molding pressure: 30 MPa) instead of the cold isotropic pressurizing device. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Comparative Example 1)
Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.1% by mass) having an average particle size of 18.0 μm is 40.0% by mass, and the average particle size is 13. Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass), which is 0 μm, is measured so as to be 60.0% by mass, and these are mixed and used as a raw material. A powder was prepared. A boron nitride sintered body and a complex were prepared in the same procedure as in Example 1 except that this raw material powder was used. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Comparative Example 2)
Boron nitride sintered body and composite were obtained by the same procedure as in Example 1 except that the molded product was obtained by compressing it with a cold isotropic pressure (CIP) device at a pressure of 150 MPa when producing the molded product. The body was made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

(Comparative Example 3)
When preparing the sintering aid, 57 parts by mass of calcium carbonate was mixed with 100 parts by mass of boric acid to prepare the sintering aid, and 1 part of the sintering aid was added to 100 parts by mass of the raw material powder. A boron nitride sintered body and a composite were prepared in the same procedure as in Example 1 except that 0.0 parts by mass was blended. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

10 ... complex (heat dissipation member), 20 ... nitride sintered body.

Claims

A composite containing a nitride sintered body having a porous structure and a semi-cured product of a thermosetting resin composition impregnated in the nitride sintered body, when pressurized at 5 MPa in the thickness direction. A complex having a thickness change rate of 2% or more.
The complex according to claim 1, wherein the thickness change rate is 35% or less.
The complex according to claim 1 or 2, wherein the nitride sintered body has a porosity of 40 to 75% by volume.
The complex according to any one of claims 1 to 3, wherein the nitride sintered body has a bulk density of 600 to 1400 kg / m 3.
The complex according to any one of claims 1 to 4, wherein the orientation index of the nitride sintered body is 20 or less.
A heat radiating member having the complex according to any one of claims 1 to 5.