JP6256158B2 - Heat dissipation sheet and heat dissipation sheet manufacturing method, slurry for heat dissipation sheet, and power device device - Google Patents

Description

  The present invention relates to a heat dissipation sheet suitably used for power semiconductor devices. Moreover, it is related with the power device apparatus using the slurry used suitably for manufacture of the thermal radiation sheet of this invention, and this thermal radiation sheet.

In recent years, power semiconductor devices used in various fields such as railways, automobiles, and general household appliances have been changed from conventional Si power semiconductors to SiC, AlN, GaN, etc. for further miniaturization, lower cost, and higher efficiency. It is shifting to the power semiconductor using.
The power semiconductor device is generally used as a power semiconductor module in which a plurality of semiconductor devices are arranged on a common heat sink and packaged.

  Various problems have been pointed out for the practical application of such power semiconductor devices, but one of them is a problem of heat dissipation from the device. This problem generally affects the reliability of power semiconductor devices capable of high output and high density by operating at high temperatures. There is a concern that the heat generated by the switching of the device may reduce the reliability.

  In recent years, particularly in the electric / electronic field, heat generation due to higher density of integrated circuits has become a major problem, and how to dissipate heat has become an urgent issue.

  As one method for solving this problem, a ceramic substrate having high thermal conductivity such as an alumina substrate or an aluminum nitride substrate is used as a heat dissipation substrate for mounting a power semiconductor device. However, these substrates are difficult to be multi-layered, have poor workability, and are very expensive. On the other hand, a heat-dissipating sheet using a resin has a feature that it has excellent workability and can be laminated, but has a problem that its thermal conductivity, which is an index of heat-dissipation property, is very low.

Therefore, as a thermosetting resin constituting the resin component of the composition, a highly heat conductive epoxy resin is used, or such a high heat conductive resin and a high heat conductive inorganic filler are combined to form a composition. High thermal conductivity of objects has been performed. For example, Patent Document 1 describes a composition in which a spherical boron nitride aggregate is blended as a filler. This composition is usually applied to a copper substrate as a coating solution which is dispersed or dissolved in a suitable organic solvent and adjusted to an appropriate viscosity.
However, as described below, conventionally, a heat-dissipating sheet using a resin has not yet been developed that has thermal conductivity comparable to a ceramic substrate.

  In conventional compositions, boron nitride (BN) is used as the filler. Boron nitride (BN) is an insulating ceramic, such as c-BN having a diamond structure, h-BN (hexagonal boron nitride) having a graphite structure, α-BN having a disordered layer structure, β-BN, and the like. Crystal forms are known. Among them, h-BN having a graphite structure has the same layered structure as graphite, has a feature that it is relatively easy to synthesize and is excellent in thermal conductivity, solid lubricity, chemical stability, and heat resistance. It is widely used in the field of electrical and electronic materials.

In addition, h-BN is attracting attention as such a heat conductive filler for heat radiating members, taking advantage of the feature of having high thermal conductivity despite being insulating, and has excellent heat dissipation. It is thought that a heat dissipation sheet can be formed. In addition to the aforementioned Patent Document 1, a technique using a boron nitride powder has been conventionally known. As such boron nitride, for example, a boron nitride powder having a specific particle size and particle size distribution is known. (For example, refer to Patent Document 2). In addition to this, a technique using two types of mixed boron nitrides having different particle characteristics such as surface area, particle size, and tap density (for example, see Patent Document 3) is known.

  Moreover, h-BN powder is known as a material excellent in thermal conductivity. After washing the crude hexagonal boron nitride powder with water, it is heat-treated at 1200 to 1850 ° C. in an inert gas stream. A technique for producing highly crystalline boron nitride is known (see, for example, Patent Document 4). In this technique, the crystallite size (La) of 100 faces of boron nitride crystallites is grown. Patent Document 5 describes that a specific treatment is applied to a crude hexagonal boron nitride powder to obtain a hexagonal boron nitride powder having a large particle size and excellent lubricity. Patent Document 6 also discloses that a 002-plane crystallite is obtained by mixing a crude hexagonal boron nitride powder with a compound containing lanthanum as a main component and heat-treating it in a specific temperature range in a non-oxidizing gas atmosphere. Hexagonal boron nitride powder obtained by growing the size (Lc) is described, and this hexagonal boron nitride powder is described as having excellent dispersibility and high crystallinity.

  However, h-BN has a plate-like particle shape and exhibits high thermal conductivity in the plate surface direction (C-plane direction or (002) plane direction) (usually about 250 W / mK as thermal conductivity). ), Because it exhibits only low thermal conductivity (usually about 2 to 3 W / mK as thermal conductivity) in the plate thickness direction (C-axis direction). When a coating film is formed by heating to a B-stage by heating it and further curing is performed to produce a heat-dissipating sheet, the plate-like BN particles in the film surface direction of the paint film are produced. However, the formed heat-dissipating sheet has a problem of exhibiting only a low thermal conductivity in the thickness direction, although it has excellent thermal conductivity in the film surface direction.

  Conventionally, in order to improve the thermal conductivity anisotropy of such BN particles, attempts have been made to increase heat dissipation in the sheet thickness direction of heat conduction by using secondary particles in which primary particles of boron nitride are aggregated. Has been done.

Japanese translation of PCT publication No. 2008-510878 JP 2008-189818 A Special table 2010-505729 JP-A-61-72605 JP-A-9-263402 Japanese Patent No. 5171798

However, when a composition of boron nitride and a resin is formed into a sheet by coating, the filler and the resin are separated from each other in the sheet (for example, only the resin component collects on the surface and the filler settles). There is a risk that the desired heat dissipation performance cannot be achieved due to problems such as obstructing the heat path.
Furthermore, the secondary particles of boron nitride used for improving the heat dissipation in the thickness direction of the sheet have voids formed between the primary particles. When forming a heat-dissipating sheet by coating, a slurry containing at least boron nitride secondary particles and a solvent is prepared. However, the solvent may be absorbed into the voids of the boron nitride secondary particles, and the coating performance may be extremely inferior. Therefore, when a large amount of a solvent is added to improve the coating performance, the storage stability of the slurry (filler settling) is deteriorated, and the process cost is increased when the solvent is blown for sheeting. There are problems such as.
In addition, there is a problem that high thermal conductivity and high withstand voltage cannot be realized due to voids in the boron nitride secondary particles.
In addition, in a heat dissipation sheet for power devices that becomes high temperature, if the Tg of the resin is exceeded, the physical property values such as linear expansion may change, which may impair the reliability of the power device. However, a resin included in boron nitride, which requires adhesion to boron nitride, and a matrix resin, which requires high Tg, have different physical properties in one heat radiating sheet, but the conventional heat dissipation. In the sheet, the same type of resin was used for the resin contained in boron nitride and the matrix resin.

  This invention makes it a subject to provide the thermal radiation sheet which can implement | achieve the high thermal conductivity and the high withstand voltage which can ensure the reliability at the high temperature of a power device, without producing the said problem.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use different resins for the resin contained in the secondary particles of boron nitride contained in the heat dissipation sheet and the matrix resin, and the matrix. It has been found that the above problem can be solved by setting the Tg of the resin to 150 ° C. or higher.

This will be described in more detail. The boron nitride secondary particles have voids inside. Therefore, by mixing the solvent, the resin, and the boron nitride secondary particles, and removing the solvent from the mixture, the resin is introduced into the voids of the boron nitride secondary particles by utilizing capillary action. Encapsulated boron nitride particles are obtained. High thermal conductivity that increases the reliability of power devices by using boron nitride particles encapsulating the resin, and using a resin different from the resin encapsulated as a matrix resin and using a matrix resin having a high Tg. The present inventors have found that a heat dissipation sheet having high withstand voltage can be provided.
The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] In a heat dissipation sheet including boron nitride secondary particles encapsulating resin A and matrix resin B, resin A and resin B are different resins, and Tg of resin B is 150 ° C. or higher. Heat dissipation sheet.
[2] The heat radiation sheet according to [1], wherein Tg of the resin B is higher than Tg of the resin A.
[3] The heat radiation sheet according to [1] or [2], wherein the resin A has a solubility at 25 ° C. in water of 5 wt% or less.
[4] The heat dissipation sheet according to any one of [1] to [3], wherein the resin A and / or the resin B includes a curable resin.
[5] The heat dissipation sheet according to any one of [1] to [4], wherein the resin A and / or the resin B includes an epoxy resin.
[6] Any of [1] to [5], wherein the resin A and / or the resin B includes a phenoxy resin having at least one of a bisphenol A skeleton, a bisphenol F skeleton, and a biphenyl skeleton. The heat-dissipating sheet according to crab.
[7] The heat radiation sheet according to any one of [1] to [6], wherein, in XRD measurement, the strength ratio I (100) / I (004) between the 100 axis and the 004 axis is 3 or more.
[8] A method for manufacturing a heat radiating sheet according to any one of [1] to [7], comprising a pressurizing step of pressurizing in the thickness direction of the sheet.
[9] The method for manufacturing a heat dissipation sheet according to [8], wherein in the pressurizing step, the resin viscosity at the time of pressurization is lower than that of the resin A.
[10] The method for producing a heat dissipation sheet according to [8] or [9], further comprising a step of curing the resin after the pressing step.
[11] A heat-dissipating sheet slurry comprising boron nitride secondary particles encapsulating resin A and matrix resin B, wherein resin A and resin B are different.
[12] The heat-dissipating sheet slurry according to [11], comprising a solvent.
[13] A method of manufacturing a heat dissipation sheet, comprising: applying the slurry for heat dissipation sheet according to [11] or [12].
[14] The heat dissipation sheet according to any one of [1] to [7] or the heat dissipation sheet manufactured by the manufacturing method according to any one of [8] to [10] and [13] is laminated on the support. A laminated heat dissipation sheet.
[15] A heat dissipation sheet according to any one of [1] to [7] or a heat dissipation sheet manufactured by the manufacturing method according to any one of [8] to [10], [13] and [14]. Including power device equipment.

The heat dissipation sheet of the present invention has been achieved in the past by functionally separating the resin (resin A) contained in the boron nitride secondary particles and the matrix resin (resin B) around the boron nitride secondary particles. I was able to lead the high performance that I could not do. First, by setting the Tg of the resin B to a high Tg, it is possible to improve the reliability of the power device that is heated. Furthermore, in order to increase the affinity of the resin A with boron nitride, for example, by making it hydrophobic, voids formed inside the boron nitride secondary particles can be effectively eliminated, and high thermal conductivity and high resistance. Voltage property can be imparted to the heat dissipation sheet.
Further, in the heat dissipation sheet of the present invention, by using the boron nitride secondary particles encapsulating the resin, when preparing the slurry for the heat dissipation sheet, the solvent is not absorbed in the voids of the boron nitride secondary particles, Boron nitride particles and solvent become familiar, and coating performance can be improved. Thereby, the amount of solvent can be suppressed at the time of slurry preparation, the process cost in the solvent removal process at the time of manufacture of a heat-radiating sheet can be suppressed, and the tact time can be increased. Further, since the inside of the boron nitride secondary particles is filled with the resin A, the resin B can be effectively used for the matrix without being trapped by the boron nitride secondary particles.

  In addition, in a preferred embodiment of the heat dissipation sheet of the present invention, since the intensity ratio I (100) / I (004) between the 100 axis and the 004 axis is 3 or more in XRD measurement, the primary particles of conventional boron nitride Are not aligned in parallel with the sheet, but primary boron nitride particles are arranged in a random direction, and thermal conductivity can be increased in the vertical direction of the sheet.

  Therefore, the heat dissipating sheet of the present invention is inexpensive, high quality and excellent in thermal conductivity and voltage resistance, and the power device using the heat dissipating sheet of the present invention realizes the formation of a highly reliable power semiconductor module. be able to.

It is a cross-sectional SEM photograph of the boron nitride particle in a manufacture example (drawing substitute photograph). (A) thru | or (c) are the surface SEM photographs of the boron nitride particle in a manufacture example. (D) is the surface SEM photograph of the boron nitride secondary particle before encapsulating resin (drawing substitute photograph). (A) It is a SEM photograph which shows the card house structure of a boron nitride secondary particle, (b) It is a schematic diagram of the card house structure in the cross section of a boron nitride secondary particle.

  Hereinafter, the present invention will be described in detail, but the present invention is not construed as being limited to the following description, and can be arbitrarily implemented within the scope of the gist thereof.

[1. Heat dissipation sheet]
The heat dissipation sheet of the present invention includes boron nitride secondary particles encapsulating resin A and matrix resin B, and resin A and resin B are different resins, and Tg of resin B is 150 ° C. or higher.
In the heat dissipation sheet of the present invention, since the resin (resin A) contained in the boron nitride secondary particles is different from the matrix resin (resin B) around the boron nitride secondary particles, the functions of both resins are separated. Is possible. Therefore, high performance that could not be achieved before can be derived. Specifically, by setting the Tg of the resin B to 150 ° C. or higher, the reliability of the power device that becomes high in heat can be increased. In addition, the resin A included in the boron nitride secondary particles is made hydrophobic, for example, in order to increase the affinity with the boron nitride, thereby effectively eliminating voids formed inside the boron nitride secondary particles. The heat dissipation sheet of the present invention can be imparted with high thermal conductivity and high withstand voltage.

[1-1. Resin-encapsulated boron nitride secondary particles]
The boron nitride secondary particles used in the present invention contain a resin (hereinafter, the boron nitride secondary particles containing the resin are also referred to as “resin-encapsulated boron nitride particles”). Boron nitride secondary particles obtained by agglomerating primary particles of boron nitride have voids formed when the primary particles are aggregated therein. The resin-encapsulated boron nitride particles are boron nitride particles in which the voids are filled with resin.

In the resin-encapsulated boron nitride particles, that the resin is encapsulated means that a part or all of the voids of the boron nitride secondary particles are filled with the resin. When some of the voids of the boron nitride secondary particles are filled with resin, 10% by volume or more of the voids are preferably filled with resin, more preferably 30% by volume or more, and 50% by volume or more. Is more preferable, 80% by volume or more is particularly preferable, and 90% by volume or more is most preferable.
The content of the resin-encapsulated boron nitride secondary particles in the heat-dissipating sheet is usually 5 wt% or more, preferably 10 wt% or more, more preferably 15 wt% or more, and particularly preferably 20 wt% or more. On the other hand, it is usually 90 wt% or less, preferably 80 wt% or less, more preferably 70 wt% or less, and particularly preferably 60 wt% or less.
Hereinafter, preferable physical properties of the resin-encapsulated boron nitride particles will be described.

<Maximum particle diameter D _max of the volume-based average particle diameter D _50>
The resin-encapsulated boron nitride particles have a volume-based maximum particle diameter D _max (in this specification, sometimes simply referred to as “maximum particle diameter”), which is usually 2 μm or more, preferably 3 μm or more. More preferably, it is 5 micrometers or more, Most preferably, it is 10 micrometers or more. Moreover, it is 300 micrometers or less normally, Preferably it is 200 micrometers or less, More preferably, it is 100 micrometers or less, Most preferably, it is 80 micrometers or less.

When the maximum particle size is not more than the above upper limit, when included in the heat dissipation sheet as a filler, the interface between the matrix resin and the filler is reduced, resulting in a decrease in thermal resistance, high thermal conductivity, surface roughness, etc. It is possible to form a high-quality film without any defects. When the maximum particle size is smaller than the above lower limit, the effect of improving thermal conductivity as a thermal conductive filler required for a power semiconductor device is reduced. When high thermal conductivity filler is used, in order to develop thermal conductivity as a composite material, the interfacial adhesion between the thermal conductive filler and the resin, the adhesion between the composite material and the substrate are important. The interface is considered to be the most cause of thermal conductivity decay. In particular, as a heat radiating sheet for power semiconductor devices, a heat radiating sheet having a thickness of 200 μm to 300 μm is often applied. However, the influence of the above-described interface on the thickness of the sheet becomes significant. It is considered that the size of the conductive filler is 1/10 or less. Therefore, from the viewpoint of thermal conductivity, the volume-based maximum particle size of the filler is preferably larger than the above lower limit. When the volume-based maximum particle size of the filler exceeds the above upper limit,
The filler protrudes from the surface of the heat-dissipating sheet after curing, the surface shape of the heat-dissipating sheet is deteriorated, the adhesiveness when producing a laminated sheet with a copper substrate is lowered, and the withstand voltage characteristic tends to be lowered. On the other hand, if the maximum particle size of the filler is too small, the influence of the above-mentioned interface on the thermal conductivity becomes significant, and the number of heat conduction paths required due to the small filler particles increases, and the heat dissipation sheet The probability of connecting from one surface to the other in the thickness direction of the sheet is reduced, and even when combined with a matrix resin with high thermal conductivity, the effect of improving the thermal conductivity in the thickness direction of the heat dissipation sheet is insufficient, or the matrix resin The interfacial area between the filler and the filler tends to increase, and the withstand voltage characteristic tends to decrease.

  In general, a heat dissipation sheet for power semiconductor devices is assumed to be used at a high temperature of 200 ° C. to 300 ° C. in order to improve performance such as higher speed and higher capacity. In order to extend the life of peripheral members even when used at a high temperature of ℃ or higher and ensure reliability such as high thermal conductivity and withstand voltage characteristics, the maximum particle size of the filler to be blended is relative to the thickness of the heat dissipation sheet. It is usually 1/10 or more, preferably 1/5 or more, more preferably 1/4 or more, and usually 1/2 or less, preferably 1/3 or less.

Further, the volume-based average particle diameter D _{50 of} the resin-encapsulated boron nitride particles (hereinafter sometimes simply referred to as “average particle diameter”) is not particularly limited, but is the value of the volume-based maximum particle diameter. For the same reason, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more. Moreover, it is 250 micrometers or less normally, Preferably it is 150 micrometers or less, More preferably, it is 90 micrometers or less, More preferably, it is 70 micrometers or less. By the average particle diameter D ₅₀ within the above range, when the heat radiation sheet, have sufficient thermal conductivity in the thickness direction, withstand voltage characteristics can be obtained a good heat dissipation sheet.

The maximum particle size and the average particle size are, for example, dispersed in an appropriate solvent. Specifically, the resin-encapsulated boron nitride particles are dispersed in a pure water medium containing sodium hexametaphosphate as a dispersion stabilizer. With respect to the sample, the particle size distribution can be measured with a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd., and the maximum particle size and the average particle size can be obtained from the obtained particle size distribution.
Similarly, the average particle size and the maximum particle size of the boron nitride secondary particles not encapsulating the resin can be dispersed in an appropriate solvent and measured with the same apparatus as described above.

<Pore volume>
Since the resin-encapsulated boron nitride particles have pores inside the boron nitride secondary particles filled with resin, the pore volume is small and the fracture strength is increased. The pore volume is usually 1.5 mL / g or less, preferably 1.0 mL / g or less, more preferably 0.5 mL / g or less.
The pore volume of the boron nitride particles can be measured by a mercury intrusion method.

<Powder X-ray diffraction (XRD) measurement>
The peak intensity ratio of (100) plane and (004) plane by powder X-ray diffraction (XRD) of the resin-encapsulated boron nitride particles is usually 3.0 or more, preferably 3.2 or more, more preferably 3.4 or more, More preferably, it is 3.5 or more, usually 10 or less, preferably 8 or less, more preferably 7 or less. When it is larger than the above upper limit, the particles tend to be crushed when formed into a molded body, and the capillary phenomenon is unlikely to occur and the resin is not sufficiently encapsulated. Moreover, when it is less than the said minimum, there exists a tendency for the heat conductivity of the thickness direction not to improve.
The peak intensity ratio can be calculated from the intensity ratio of the corresponding peak intensity measured by powder X-ray diffraction measurement. The sample used for the measurement may be boron nitride secondary particles before the resin is encapsulated or resin-encapsulated boron nitride particles. Moreover, the molded object containing the resin inclusion boron nitride particle may be sufficient.

[1-2. Boron nitride secondary particles]
Next, the boron nitride secondary particles before the resin is encapsulated will be described.
<Pore diameter>
From the viewpoint of facilitating introduction of the resin into the boron nitride secondary particles by capillary action, the boron nitride secondary particles preferably have a pore diameter of 10 nm or more, more preferably 30 nm or more, and further 50 nm or more. preferable. On the other hand, the pore diameter is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The pore diameter can be measured by a mercury intrusion method.

<Pore volume>
Since the resin-encapsulated boron nitride particles introduce the resin into the voids by capillary action, the boron nitride secondary particles before the resin is encapsulated require an appropriate pore volume.
The pore volume of the boron nitride secondary particles is usually 0.05 mL / g or more, preferably 0.15 mL / g or more, more preferably 0.2 mL / g or more. On the other hand, it is usually 5 mL / g or less, preferably 3 mL / g or less, more preferably 1.5 mL / g or less.
In the case where the pore volume is small, since the inside of the boron nitride secondary particles is dense, it is possible to reduce the interface that hinders heat conduction, but the resin is present in the voids of the boron nitride secondary particles. It becomes difficult to enter, and the voids of the boron nitride secondary particles cannot be sufficiently filled with the resin. On the other hand, if the total pore volume is too large, the gap interval is usually too large, capillary action is unlikely to occur, and the resin is less likely to be taken into the boron nitride secondary particles.
The pore volume of the boron nitride secondary particles can be measured by a mercury intrusion method.

<Specific surface area>
There is no particular restriction, the specific surface area of the boron nitride secondary particles is usually 1 m ² / g or more, preferably 2m ² / g or more, more preferably 3m ² / g or more, more preferably 3.5 m ² / g or more. On the other hand, it is usually 20 m ² / g or less, preferably 18 m ² / g or less, more preferably 16 m ² / g or less, still more preferably 14 m ² / g or less. If it is less than this lower limit, the capillary phenomenon is difficult to work, and if it is more than this upper limit, the primary particles are too small, and in any case, the resin hardly enters the voids of the boron nitride secondary particles.
The specific surface area can be measured by the BET single point method (adsorption gas: nitrogen).

<Powder X-ray diffraction (XRD) measurement>
The average crystallite diameter determined from the (002) plane peak by powder X-ray diffraction (XRD) of the boron nitride secondary particles used in the present invention is 200 mm or more, preferably 250 mm or more, more preferably 280 mm or more, and still more preferably. Is 300 mm or more, usually 5000 mm or less, preferably 2000 mm or less, and more preferably 1000 mm or less. If the above upper limit is exceeded, the primary particles constituting the secondary particles grow too much, so that the gaps in the secondary particles increase and capillary action is less likely to occur, and if it is less than the above lower limit, the primary particles constituting the secondary particles are formed. Since the grain boundaries in the grains increase, phonon scattering occurs at the grain boundaries and tends to have low thermal conductivity.
Here, the “average crystallite diameter” refers to the crystallite diameter determined by the Scherrer equation from the (002) plane peak obtained by powder X-ray diffraction measurement. The sample used for the measurement may be boron nitride secondary particles before the resin is encapsulated, or resin-encapsulated boron nitride secondary particles.

Further, the peak intensity ratio between the (100) plane and the (004) plane by powder X-ray diffraction (XRD) of the boron nitride secondary particles is usually 3.0 or more, preferably 3.2 or more, more preferably 3.4. Above, more preferably 3.5 or more, usually 10 or less, preferably 8 or less, more preferably 7 or less. When it is larger than the above upper limit, the particles tend to collapse when formed into a molded body, and when it is less than the lower limit, thermal conductivity in the thickness direction tends not to be improved.
The peak intensity ratio can be calculated from the intensity ratio of the corresponding peak intensity measured by powder X-ray diffraction measurement.

The boron nitride secondary particles are preferably boron nitride secondary particles having a card house structure. The card house structure is, for example, ceramic 43 No. 2 (issued by the Ceramic Society of Japan in 2008), and has a structure in which plate-like particles are laminated in a complicated manner without orientation. More specifically, the boron nitride secondary particles having a card house structure are aggregates of boron nitride primary particles, and the boron nitride secondary particles having a structure in which the planar portion and the end surface portion of the primary particles are in contact with each other. Particles (see FIGS. 3A and 3B).
More preferably, the boron nitride primary particles are plate-shaped, and are boron nitride secondary particles having a card house structure in which the flat portion and the end face portion are in contact, and more preferably, the boron nitride primary particles are polygonal. Boron nitride secondary particles having a card house structure in which the flat surface portion and the end surface portion are in contact with each other.
The aggregation form of the boron nitride secondary particles can be confirmed by a scanning electron microscope (SEM).

<Boron nitride primary particle size>
Preferred examples of the boron nitride secondary particles are boron nitride secondary particles having a card house structure as described above. However, the major axis of the boron nitride primary particles usually grows to 0.5 to 10 μm, It is also preferable to form a sea urchin-like appearance growing radially from the center side to the surface side of the next particle. The major axis of the boron nitride primary particles constituting the boron nitride secondary particles is preferably 0.6 to 5 μm, more preferably 0.8 to 3 μm, and still more preferably 1.0 to 3. This is a particle in which 0 μm of h-BN is aggregated.
The long axis is the average of the maximum length of primary particles that can be observed on an image of primary particles constituting one particle by enlarging one particle obtained by scanning electron microscope (SEM) measurement. It is the value.

[1-3. Method for producing boron nitride secondary particles]
The method for producing the boron nitride secondary particles used in the present invention is not limited, and in particular, boron nitride as a raw material (hereinafter sometimes referred to as a raw material BN powder together with the pulverized material) may be pulverized. After pulverizing in the step, it is preferable to undergo a heating step of granulating by agglomerating in the granulating step and further heat treatment. More specifically, the raw material BN powder was once dispersed in a medium to obtain a slurry of the raw material BN powder (hereinafter sometimes referred to as “BN slurry”), and then subjected to a pulverization treatment, and then obtained. It is preferable that the slurry is granulated into spherical particles and subjected to a heat treatment in order to crystallize the aggregated BN granulated particles.

<Raw material BN powder>
When producing boron nitride secondary particles (hereinafter also referred to as aggregated BN particles) used in the present invention, boron nitride particles described below can be used as a raw material. However, the raw material for the aggregated BN particles is not particularly limited to the following.
More specifically, commercially available h-BN, commercially available α and β-BN, BN prepared by a reductive nitriding method of a boron compound and ammonia, BN synthesized from a nitrogen-containing compound such as a boron compound and melamine, and boron Any of BN produced from sodium hydride and ammonium chloride can be used without limitation, and h-BN is particularly preferably used.

  From the viewpoint of h-BN crystal growth, it is preferable that oxygen is present to some extent in the raw material BN powder such as h-BN, and the total oxygen content in the raw material BN powder is 1% by mass or more and 10% by mass or less. The total oxygen content in the raw material BN powder is more preferably 3% by mass or more and 10% by mass or less, and further preferably 3% by mass or more and 9% by mass or less.

Since the raw material BN powder having a total oxygen content within the above range has a small primary particle size and many crystals are not yet developed, the crystals are likely to grow by heat treatment. It is preferable to grow the BN crystal by heat-treating the BN granulated particles in which the raw material BN powder is aggregated by granulation, but by using the raw material BN powder in the range of the total oxygen content, the primary particles of the BN crystal Are grown so as to form a card house structure in the normal direction so that the a-axis is directed outward, that is, radial on the surface of the aggregated BN particles from which BN primary particles can be obtained, and the planar portion and the end surface portion of the BN primary particles are Can be placed in contact.
The agglomerated BN particles used for the resin-encapsulated boron nitride particles are arranged such that the primary particles are radially arranged on the surface and the planar portion and the end surface portion of the BN primary particles are in contact with each other. There is also an advantage that it can be easily introduced to the center in the next particle.

When the total oxygen content of the raw material BN powder is less than the above lower limit, since the purity and crystallinity of the raw material BN itself are good, the crystal growth of the C plane is not sufficient, and the BN primary particles are radially distributed on the surface of the aggregated BN particles. In addition, when it cannot be placed in the card house structure and, on the contrary, exceeds the above upper limit, the oxygen content becomes high even after the heat treatment, and it becomes impossible to achieve high thermal conductivity when used as a heat dissipation sheet. Therefore, it is not preferable.
Examples of a method for adjusting the total oxygen content of the raw material BN powder to the above range include a method in which the heating temperature during BN heating is a low temperature of 2500 ° C. or lower.

Moreover, a commercial item can also be used as raw material BN powder whose total oxygen content is the said suitable range, for example, h-BN "ABN" by Nisshin Rifratech, h-BN "AP170S" by MARUKA, etc. Is mentioned.
The oxygen content of the raw material BN powder can be measured by an inert gas melting-infrared absorption method using a HORIBA oxygen / nitrogen analyzer.

Further, as another physical property of the raw material BN powder, for example, the total pore volume of the raw material BN powder is usually 1.0 cm ³ / g or less, preferably 0.3 cm ³ / g or more and 1.0 cm ³ / g. Hereinafter, it is more preferably 0.5 cm ³ / g or more and 1.0 cm ³ / g or less.
The specific surface area of the raw material BN powder is usually 20 m ² / g or more, preferably 20 m ² / g or more and 500 m ² / g or less, more preferably 50 m ² / g or more and 200 m ² / g or less.
When the total pore volume is 1.0 cm ³ / g or less, since the raw material BN powder is dense, granulation with high sphericity is possible when used as the primary particles constituting the aggregated BN particles. It becomes. Moreover, it is preferable for the specific surface area to be 20 m ² / g or more because the dispersed particle diameter in the BN slurry used for spheronization by granulation can be reduced.

  The total pore volume of the raw material BN powder can be measured by a mercury intrusion method, and the specific surface area can be measured by a BET one-point method (adsorption gas: nitrogen).

<Preparation of BN slurry>
There is no restriction | limiting in particular as a medium used for preparation of BN slurry, Although water and / or various organic solvents can be used, from a viewpoint of the ease of spray drying, simplification of an apparatus, etc., water (pure water) is used. It is preferable to use it.
If the amount of water used is too large, the load at the time of spray drying increases, and if it is too small, uniform dispersion is difficult. It is preferable to be 10 mass times.
The viscosity of the BN slurry at 25 ° C. and 1 atm is usually 100 mPa · s or more, and preferably 300 mPa · s or more. Moreover, it is 3000 mPa * s or less normally, Preferably it is 2000 mPa * s or less. By being in this range, it becomes easy to produce boron nitride secondary particles that easily encapsulate the resin.

<Surfactant>
Various surfactants may be added to the BN slurry from the viewpoint of the dispersion stability (inhibition of aggregation) of the BN particles while suppressing an increase in the viscosity of the slurry during the pulverization process described below.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant or the like can be used. These may be used alone or in combination of two or more. May be used.

When a surfactant is added to the BN slurry, the surfactant concentration of the BN slurry is usually 0.1% by mass to 10% by mass, particularly 0.5% by mass to 5% by mass. It is preferable to use it. When the concentration of the BN slurry is equal to or higher than the above lower limit, the above effect due to the addition of the surfactant can be sufficiently obtained, and when the concentration is equal to or lower than the above upper limit, the content of the raw material BN powder is high. After the slurry is prepared, it can be granulated and the influence of residual carbon when subjected to heat treatment can be reduced.
The surfactant may be added before the following pulverization treatment or may be added after the pulverization treatment.

<Binder>
The BN slurry preferably contains a binder in order to effectively granulate the raw material BN powder into aggregated particles. The binder originally acts to firmly bind the raw material BN powder having non-adhesive particles and stabilize the shape of the granulated particles.

  Any binder can be used for the BN slurry as long as it can enhance the adhesion between the BN powders. However, since the granulated particles are heat-treated after agglomeration, the heat resistance against high-temperature conditions in this heat-treatment step is sufficient. What has is preferable.

As such a binder, a metal oxide is preferable, and specifically, aluminum oxide, magnesium oxide, yttrium oxide, calcium oxide, silicon oxide, boron oxide, cerium oxide, zirconium oxide, titanium oxide, and the like are preferably used. Among these, aluminum oxide and yttrium oxide are preferable from the viewpoints of thermal conductivity and heat resistance as an oxide, bonding strength for bonding BN powders, and the like. The binder may be a liquid binder such as alumina sol, or an organic metal compound that is converted into a metal oxide by firing.
These binders may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The amount of the binder used (in the case of a liquid binder, the amount used as a solid content) is usually 1% by mass or more and 30% by mass or less, preferably 1% by mass or more and 20% with respect to the raw material BN powder in the BN slurry. It is 5 mass% or less, More preferably, it is 5 mass% or more and 20 mass% or less. When the amount of the binder used is less than the above lower limit, the effect of binding the BN powders is reduced, so that the granulated particles may not be able to maintain the shape after granulation. The content of BN is reduced, which not only affects the crystal growth, but also when used as a thermally conductive filler, there is a possibility that the effect of improving the thermal conductivity is reduced.

<Crushing process>
The BN slurry may be directly subjected to a granulation step by spray drying, but prior to granulation, it is preferable to pulverize the raw material BN powder in the slurry to make it finer, and by making it finer, agglomeration can be performed. It becomes possible to carry out smoothly.
That is, although depending on the particle diameter of the raw material BN powder, when the raw material BN powder is dispersed in the medium as it is, the BN powder is a plate-like particle, and therefore there is a tendency that many particles are not granulated in the agglomeration step. However, efficient aggregation can be achieved by miniaturization.

  For the pulverization, a normal pulverization method such as a bead mill, a ball mill, or a pin mill can be used. However, a bead mill is preferable from the viewpoint of being able to circulate and pulverize a large amount as a slurry and easily control the pulverized particle diameter. Moreover, since the viscosity of the BN slurry is increased by making the BN particles into fine particles by pulverization, it is preferable that the BN slurry can be pulverized even at a higher concentration and higher viscosity. In addition, as the pulverization proceeds, the temperature of the BN slurry increases. In order to produce, what is equipped with the cooling system is preferable. Examples of such an apparatus include “OB Mill” manufactured by Freund Turbo and “Star Mill LMZ Series” manufactured by Ashizawa Finetech.

<Granulation (aggregation)>
Although there is no restriction | limiting in particular in order to obtain the granulated particle which is aggregated BN particle from BN slurry, A spray-drying method is used suitably. In the spray drying method, granulated particles of a desired size are produced based on the concentration of the slurry used as a raw material, the amount of liquid fed per unit time introduced into the apparatus, and the pressure and pressure when the liquid is sprayed. It is possible to obtain spherical granulated particles. Although there is no restriction | limiting in the spray-drying apparatus used in the case of spheroidization, in order to make larger spherical BN granulated particle, the thing by a rotary disk is optimal. Examples of such an apparatus include a spray dryer F series manufactured by Okawara Chemical Co., Ltd., and a spray dryer “MDL-050M” manufactured by Fujisaki Electric Co., Ltd.

The maximum particle diameter of the granulated particles obtained by granulation is the volume-based average particle diameter D ₅₀ in order to set the range of the volume-based maximum particle diameter to be greater than 25 μm and not more than 200 μm as aggregated BN particles after the heat treatment. Usually, it is 1 μm or more, particularly 10 μm or more and 150 μm or less, and particularly preferably 10 μm or more and 100 μm or less. Here, the volume-based average particle diameter D ₅₀ of the granulated particles can be measured, for example, by “Microtrac HRA” manufactured by Nikkiso Co., Ltd.

<Heat treatment>
The boron nitride granulated particles obtained by the above granulation are preferably further heat-treated in a non-oxidizing gas atmosphere.
Here, the non-oxidizing gas atmosphere is an atmosphere of nitrogen gas, helium gas, argon gas, ammonia gas, hydrogen gas, methane gas, propane gas, carbon monoxide gas, or the like. The crystallization speed of the aggregated BN particles varies depending on the type of the atmospheric gas used here. For example, with argon gas, the crystallization speed is slow and the heat treatment time is long. In order to perform crystallization in a short time, nitrogen gas or a mixed gas using nitrogen gas and another gas in combination is preferably used. Appropriate selection of the conditions for the heat treatment is also important in arranging the boron nitride primary particles radially on the surface while keeping the specific surface area and total pore volume of the aggregated BN particles in a specific range.

  Although heat processing temperature is 1300 degreeC-2500 degreeC normally, Preferably it is 1300 degreeC-2300 degreeC, More preferably, it is 1400 degreeC-2200 degreeC. When the heat treatment temperature is less than the following lower limit, crystallization of h-BN becomes insufficient, and the effect of improving the thermal conductivity when the heat conductive filler is used becomes small. When the heat treatment temperature exceeds the above upper limit, the added binder component is melted and decomposed to aggregate the aggregated BN particles, and the original shape may not be maintained, or BN may be decomposed.

  The heat treatment time is usually 1 hour or more and 50 hours or less, more preferably 3 hours or more and 40 hours or less, and particularly preferably 5 hours or more and 30 hours or less. Furthermore, it is preferable to introduce a holding step of 1300 ° C. to 1500 ° C. for 3 hours or more, particularly within the heat treatment time. By introducing the holding step in the above temperature range, h-BN is crystallized more efficiently, so that the upper heat treatment temperature tends to be lowered. When the heat treatment time is less than the lower limit, crystallization is insufficient, and when the upper limit is exceeded, h-BN may be partially decomposed.

  The heat treatment is preferably performed in a non-oxidizing gas atmosphere, and for this purpose, usually, the furnace is heated while being pulled with a vacuum pump, and after exhausting until the decomposition gas accompanying the heating is reduced, While introducing the non-oxidizing gas, it is preferable to continue heating to a desired temperature to raise the temperature. As a guideline of the temperature at which the vacuum pump is evacuated, after heating up to about 200 to 500 ° C., for example, around 400 ° C. for about 30 to 60 minutes, the evacuation is continued for about 30 to 60 minutes while maintaining the temperature, It is preferable to perform evacuation until the degree of vacuum is 10 Pa or less, and then introduce a non-oxidizing gas. Although the flow rate of the non-oxidizing gas depends on the size of the furnace, there is no problem as long as it is usually 2 L (liter) / min or more. Thereafter, the temperature is increased to about 1500 ° C. at 50 to 100 ° C./hour while introducing a non-oxidizing gas, and then the temperature is increased from 1500 ° C. to a predetermined heat treatment temperature at 30 to 50 ° C./hour. After heating at this temperature for the above heat treatment time, it is preferable to cool to room temperature at about 5 to 50 ° C./min.

For example, when heat treatment is performed in a nitrogen gas atmosphere, the growth is performed radially at about 2000 ° C. for about 5 hours, and in the case of an argon gas atmosphere at about 2000 ° C. for about 5 to 15 hours. Can do.
Examples of firing furnaces for heat treatment include batch furnaces such as muffle furnaces, tubular furnaces, and atmospheric furnaces, and rotary kilns, screw conveyor furnaces, tunnel furnaces, belt furnaces, pusher furnaces, vertical furnaces, and other continuous furnaces. It is used properly according to the.

In addition, immediately after manufacture, the obtained BN particles may be further aggregated and may not satisfy the particle diameter range suitable for the present invention. Therefore, the aggregated BN particles may be pulverized so as to satisfy the range of the particle diameter suitable for the present invention, if necessary.
The method for pulverizing the aggregated BN particles is not particularly limited, and a conventionally known pulverization method such as a method of stirring and mixing together with a pulverizing medium such as zirconia beads or jet injection can be applied.

<Classification>
The aggregated BN particles after the heat treatment are preferably subjected to a classification treatment in order to increase the average particle size and suppress an increase in viscosity when blended in the composition. This classification is usually performed after the heat treatment of the granulated particles, but may be performed on the granulated particles before the heat treatment and then subjected to the heat treatment.

Although classification may be either wet or dry, dry classification is preferable from the viewpoint of suppressing the decomposition of h-BN. In particular, when the binder has water solubility, dry classification is particularly preferably used.
Dry classification includes air classification that classifies by the difference between centrifugal force and fluid drag, in addition to classification by sieve, but from the viewpoint of classification accuracy, wind classification is preferred, swirling air classifier, forced vortex centrifuge It can be carried out using a classifier such as a classifier or a semi-free vortex centrifugal classifier. Among these, particles to be classified such as a swirling air classifier to classify small particles in the submicron to single micron range, and a semi-free vortex centrifugal classifier to classify relatively larger particles. What is necessary is just to use properly according to the particle diameter of this.

  In order to obtain aggregated BN particles having a volume-based maximum particle size of 25 μm or more and 200 μm or less, it is preferable to perform a classification operation for removing fine particles and / or a semi-free vortex centrifugal classification using a swirling airflow classifier. .

<Boron nitride secondary particle shape>
As described above, the raw material BN powder is granulated and subjected to heat treatment to grow h-BN crystals while maintaining its shape. Boron nitride primary particles of 0.05 μm or more and 5 μm or less (hereinafter sometimes referred to as “BN primary particles”) can be disposed, and aggregated particles having a card house structure can be obtained. Preferably, it can be a boron nitride secondary particle having a card house structure in which the planar portion and the end surface portion of the plate-like BN primary particles are in contact with each other, more preferably, the planar portion and the end surface of the polygonal boron nitride primary particle. It can be set as the boron nitride secondary particle which has the card house structure where the part is contacting. More preferably, it can be expressed as another form of the above physical property that the aggregated BN particles are spherical. The term “spherical” means that the aspect ratio (ratio of major axis to minor axis) is 1 or more and 2 or less, preferably 1 or more and 1.5 or less. Aggregated BN particles are particles obtained by agglomerating raw material BN powder, which will be described later, and are preferably “spherical”, and “preferably spherical” It is not preferable that the shape is spherical. The aspect ratio of the aggregated BN particles is obtained by arbitrarily selecting 200 or more particles from an image taken with a scanning electron microscope (SEM) and calculating the average value by calculating the ratio of the major axis and minor axis of each particle. decide.

  In addition, BN primary particles having an average particle diameter of 0.05 μm or more exist on the surface of the aggregated BN particles, but “0.05 μm or more” of “BN primary particles having an average particle diameter of 0.05 μm or more” It refers to the length corresponding to the particle diameter of BN primary particles. The crystal size of the BN primary particles is observed at a magnification of about 20,000 times using a scanning electron microscope (SEM), and the maximum particle size of any 100 particles observed on the surface is measured. And it can measure by calculating | requiring an average value.

In the aggregated BN particles, how crystals grow is one of the important requirements for use as a high thermal conductive filler.
The boron nitride secondary particles used in the present invention are obtained by such specific crystal growth, and thus have an effect of being excellent in thermal conductivity isotropic, kneadability with a matrix resin, and collapse resistance. .

  As a means for preparing such preferable aggregated BN particles, h-BN powder having a total oxygen content of usually 1% by mass or more and 10% by mass or less is used as a raw material, and the heat treatment conditions are as described above. Manufacturing becomes possible by controlling.

  Specifically, in the preferred aggregated BN particles used in the present invention, the crystal growth direction of h-BN is radial from the center with respect to the sphere, that is, the normal direction so that the primary particles of the BN crystal face the a-axis outward. When the raw material h-BN having a total oxygen content of less than 1% by mass is used, the crystal growth (the C-plane of h-BN is formed in the circumferential direction). As a result, it is considered that the specific surface area is small and the total pore volume is large.

[1-4. Encapsulation resin A]
The type of the encapsulating resin A used in the heat dissipation sheet of the present invention is not particularly limited. Either a curable resin or a thermoplastic resin can be used without limitation.
The heat dissipation sheet of the present invention is suitably applied to a power semiconductor module in which a plurality of power semiconductor devices are integrated. Usually, the carrier of thermal conductivity is boron nitride secondary particles, which are fillers. However, since a heat dissipation sheet for power semiconductor devices requires high thermal conductivity of 10 W / mK or more, boron nitride secondary particles are required. It is desirable that the thermal conductivity of the resin A included in the particles is also high. The thermal conductivity of the resin A is preferably 0.2 W / mK or more, and particularly preferably 0.22 W / mK or more.
The resin A usually has a glass transition temperature Tg of 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and particularly preferably 180 ° C. or higher. Although there is no restriction | limiting in an upper limit, Usually, it is 400 degrees C or less. Tg is measured with a differential scanning calorimeter.

  The weight content ratio of the encapsulating resin A in the boron nitride secondary particles contained in the sheet of the present invention is usually 5 wt% or more and 50 wt% or less, preferably 8 wt% or more and 45 wt% or less, more preferably 10 wt% or more and 40 wt%. Hereinafter, it is particularly preferably 15 wt% or more and 35 wt% or less. If it exceeds this upper limit, the resin will protrude out of the boron nitride secondary particles, and the particles will easily aggregate and become difficult to handle. On the other hand, if it is less than this lower limit, the boron nitride secondary particles cannot be sufficiently covered with the resin, and the amount of absorption of the solvent in the composition cannot be sufficiently suppressed, making it difficult to form a slurry.

  The inclusion resin A encapsulated in the boron nitride particles has a solubility in water of usually 5 wt% or less, preferably 4 wt% or less, more preferably 3 wt% or less, and particularly preferably 2 wt% or less. This is because the basal surface of boron nitride is hydrophobic. This is because in order to introduce the resin into the boron nitride secondary particles by capillary action, the solvent used is water-insoluble, and the encapsulated resin A is also required to be dissolved in the water-insoluble solvent. That is, the resin required for the encapsulating resin A is preferably a hydrophobic resin. In addition, even when the encapsulating resin fills the inside of the boron nitride secondary particles after removing the water-insoluble solvent, a hydrophobic resin is desirable in order to increase the adhesion between the boron nitride and the encapsulating resin.

Further, the encapsulating resin A encapsulated in the boron nitride secondary particles preferably contains a curable resin, and preferably contains an epoxy resin. Furthermore, it is preferable to include a phenoxy resin having at least one skeleton among the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, and a biphenyl skeleton. By including these resins, good heat dissipation can be obtained when the heat dissipation sheet is formed.
A surfactant can be added to the encapsulating resin A. As addition amount of surfactant, it is 0.001-5 mass% normally with respect to the inclusion resin A whole quantity, and 0.005-3 mass% is preferable. If the addition amount of the surfactant is less than the above lower limit, the encapsulated resin A may not sufficiently penetrate into the boron nitride secondary particles, and if it exceeds the above upper limit, the adhesion between the boron nitride and the encapsulated resin A is inferior, It is not preferable.

  Further, the encapsulating resin A may contain a curing agent and other additives that can be contained in the matrix resin B described later. For the content and the like, the description described later can be referred to.

<Manufacturing method>
Below, the manufacturing method of the boron nitride secondary particle in which resin A was included is shown. The method for producing the boron nitride secondary particles is not particularly limited, and a conventionally known method can be used.
Any method may be used for introducing the encapsulating resin A into the boron nitride secondary particles, but in order to reduce the process cost, it can be performed by a solvent casting method. In the solvent casting method, the boron nitride secondary particles and the encapsulating resin A are dispersed and mixed with a solvent to form a slurry, and then the boron nitride secondary particles are filled with the encapsulating resin A by removing the solvent. Is the method.

  For the purpose of dispersing and mixing boron nitride secondary particles, encapsulated resin A, solvent and other additives, paint shaker, bead mill, planetary mixer, stirring type disperser, self-revolving stirring mixer, three roll, kneader It is preferable to mix using a general kneading apparatus such as a single-screw or twin-screw kneader.

The reason why the resin is introduced into the boron nitride secondary particles by the solvent casting method is a capillary phenomenon that works in the gaps between the boron nitride primary particles. Therefore, in the method of removing the solvent by freeze drying or the like, it is difficult to introduce the resin solution into the boron nitride secondary particles, and the resin-encapsulated boron nitride secondary particles may not be obtained. Further, when the solvent is removed at a boiling point or higher that will be described later, the solvent boils and bubbles are formed, which may be formed in the boron nitride secondary particles. From the viewpoint of eliminating bubbles, drying under reduced pressure is also an effective method.

  Depending on the type of secondary boron nitride particles, if the encapsulation resin A is insufficiently introduced even by capillary action, an appropriate surfactant or the like may be added to the mixture as necessary, or the mixture may be deaerated. Is preferable. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant or the like can be used. These may be used alone or in combination of two or more. May be used.

The solvent used for introducing the encapsulating resin A into the boron nitride secondary particles using capillary action is not particularly limited. However, since the basal surface of boron nitride has a hydrophobic surface, it is organic. It is preferable to use a solvent.
Examples of the organic solvent include alcohol solvents, aromatic solvents, amide solvents, alkane solvents, ethylene glycol ethers and ether / ester solvents, propylene glycol ethers and ether / ester solvents, and ketone solvents exemplified below. From the solvent and the ester solvent, it can be suitably selected and used in consideration of the solubility of the resin A and the like.
As specific examples of the organic solvent, those exemplified in WO2013 / 081061 can be used.
An organic solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

<Other inorganic substances>
Resin-encapsulated boron nitride particles contained in the heat dissipation sheet of the present invention include aggregated boron nitride other than boron nitride secondary particles used in the present invention, such as inorganic substances other than boron nitride, tabular boron nitride, and silica as necessary. One or more inorganic fillers selected from alumina, aluminum nitride, silicon nitride, and magnesium oxide may be contained.
The content of these inorganic fillers is usually 50 wt% or less, preferably 40 wt% or less, more preferably 30 wt% or less with respect to the resin-encapsulated boron nitride particles. Moreover, it is 0.5 wt% or more normally.

[1-5. Matrix resin B]
The matrix resin B contained in the heat dissipation sheet of the present invention preferably has a thermal conductivity of 0.2 W / mK or more, particularly 0.22 W / m in order to obtain high thermal conductivity when combined with a filler. It is preferably mK or more.

  In the present invention, the thermal conductivity of the matrix resin B is only the curing agent when the matrix resin B, the organic solvent, and further the curing agent is included in the composition among the components constituting the composition for heat dissipation sheet. Is a value determined by the following method for a cured film formed according to a normal curing method.

<Measuring method of thermal conductivity of matrix resin B>
About the cured film of the matrix resin B, the thermal diffusivity, specific gravity, and specific heat are measured using the following apparatuses, and the thermal conductivity is obtained by multiplying these three measured values.
(1) Thermal diffusivity: "Eye Phase Mobile 1u" manufactured by Eye Phase
(2) Specific gravity: “Balance XS-204” manufactured by METTLER TOLEDO
(Using solid specific gravity measurement kit)
(3) Specific heat: “DSC320 / 6200” manufactured by Seiko Instruments Inc.

As the matrix resin B, any of a curable resin and a thermoplastic resin can be used without limitation. Any curable resin may be used as long as it is crosslinkable, such as thermosetting, photocurable, and electron beam curable. However, a thermosetting resin is preferable in terms of heat resistance, water absorption, dimensional stability, and the like. Used.

As a thermosetting resin and a thermosetting resin, what was illustrated by WO2013 / 081061, for example can be used. Among these, it is preferable to use a thermosetting resin, and it is particularly preferable to use an epoxy resin.
The epoxy resin is preferably a phenoxy resin having at least one skeleton selected from the group consisting of naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton and dicyclopentadiene skeleton. Among them, a phenoxy resin having a fluorene skeleton and / or a biphenyl skeleton is particularly preferable because heat resistance is further improved, and in particular, it has at least one skeleton of a building phenol A skeleton, a bisphenol F skeleton, and a biphenyl skeleton. A phenoxy resin is preferred.

The matrix resin B is preferably used as long as it is used for the above-described encapsulating resin A. However, the matrix resin B usually has a glass transition temperature Tg of 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and particularly preferably 180 ° C. or higher. Although there is no restriction | limiting in an upper limit, Usually, it is 400 degrees C or less. Tg is measured with a differential scanning calorimeter.
Usually, various physical properties such as a linear expansion coefficient in the cured resin greatly change with Tg as a boundary. Therefore, the reliability of a power device can be improved by using the heat dissipation sheet containing the matrix resin B with high Tg for a power device.

The matrix resin B desirably has a higher Tg than the encapsulated resin A of boron nitride secondary particles. The inclusion resin A tends to have a low Tg in order to improve adhesion and affinity with boron nitride. However, the matrix resin B has a high Tg, so that it can be prevented from flowing out of the boron nitride secondary particles. There is expected.
In addition, the below-mentioned additive can be added to the matrix resin B.
On the other hand, as the matrix resin B, a hydrophilic resin can be used in addition to the example of the encapsulating resin A described above. As the hydrophilic resin, polyacrylic acid, PVA, PVB or the like is used as the hydrophilic resin.

  The ratio of the encapsulating resin A and the matrix resin B in the heat radiation sheet is not particularly limited, but the ratio of the encapsulating resin A / (encapsulating resin A + matrix resin B) is usually 20 wt% or more, preferably 40 wt% or more. Preferably it is 60 wt% or more, particularly preferably 70 wt% or more, and even more preferably 80 wt% or more. The ratio of matrix resin B / (encapsulated resin A + matrix resin B) is usually 20 wt% or more, preferably 40 wt% or more, more preferably 60 wt% or more, particularly preferably 70 wt% or more, and even more preferably 80 wt% or more. is there.

[1-6. Curing agent]
You may make a thermal radiation sheet contain a hardening | curing agent as needed.
The curing agent refers to a substance that contributes to a crosslinking reaction between the crosslinking groups of the matrix resin B such as an epoxy group of the epoxy resin.
In the epoxy resin, a curing agent for epoxy resin and a curing accelerator are used together as necessary.

What is necessary is just to select a hardening accelerator suitably according to the kind of resin and hardening agent to be used. For example, examples of the curing accelerator for the acid anhydride curing agent include boron trifluoride monoethylamine, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, and 2-phenyl-4-methylimidazole. Can be mentioned. These may be used alone or in combination of two or more. These curing accelerators are usually used in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.

There is no restriction | limiting in particular as a hardening | curing agent, According to the kind of thermosetting resin to be used, it selects and uses. When the thermosetting resin is an epoxy resin, any one generally known as an epoxy resin curing agent can be used. For example, phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and the like Derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like.
As specific examples of the curing agent, those exemplified in WO2013 / 081061 can be used.
These curing agents may be used alone or in a combination of two or more in any combination and ratio.
Among the above curing agents, imidazole or its derivatives and dicyandiamine compounds are preferably used.
Content of a hardening | curing agent is 0.1-60 mass parts normally with respect to 100 mass parts of matrix resin B, and 0.5-40 mass parts is preferable.

[1-7. Other additives]
The heat-dissipating sheet may contain various additives (other additives) within the range not impairing the effects of the present invention for the purpose of further improving the functionality. Other additives include, for example, functional resins obtained by adding functionality to the matrix resin, such as liquid crystal epoxy resin, nitride particles such as aluminum nitride, silicon nitride, and fibrous boron nitride, alumina, and fibrous Insulating metal oxides such as alumina, zinc oxide, magnesium oxide, beryllium oxide, and titanium oxide, insulating carbon components such as diamond and fullerene, resin curing agents, resin curing accelerators, viscosity modifiers, and dispersion stabilizers .

In addition, as other additives, as additive components for improving the adhesion to the base material and the adhesion between the matrix resin and the filler, coupling agents such as silane coupling agents and titanate coupling agents, storage stability Examples thereof include an ultraviolet ray inhibitor, an antioxidant, a plasticizer, a flame retardant, a colorant, a dispersant, a fluidity improver, and an adhesion improver with a base material for improving the property.
In addition, thermoplastic oligomers can be added to the heat-dissipating sheet from the viewpoint of improving the fluidity during molding and improving the adhesion to the substrate.

In addition, surfactants, emulsifiers, low elasticity agents, diluents, antifoaming agents, ion trapping agents, etc. that improve the dispersibility of each component in the heat dissipation sheet composition or coating solution may be added. it can.
Any of these may be used alone or in a combination of two or more in any combination and ratio.
About the specific example of an additive, what was illustrated by WO2013 / 081061 can be used, and it can also be set as the range as described in WO2013 / 081061 about addition amount.

[2. Slurry for heat dissipation sheet]
Another embodiment of the present invention is a heat-dissipating sheet slurry comprising boron nitride secondary particles encapsulating resin A and matrix resin B, wherein resin A and resin B are different. The resin-encapsulated boron nitride secondary particles and the matrix resin B described above are dispersed in a solvent and made into a slurry, whereby a slurry (coating liquid) for producing a heat dissipation sheet can be obtained.
As the solvent, the above-mentioned solvent used when producing the resin-encapsulated boron nitride secondary particles can be used, and water can be used when added. Since the boron nitride secondary particles encapsulate the resin, the hydrophobic basal surface is covered with the resin, so that the above-described surfactant can be used to make a slurry using water as a solvent. The use of water is also preferable from the viewpoint of green chemistry and the manufacturing cost cut of the heat dissipation sheet.

  The content ratio of the resin-encapsulated boron nitride secondary particles in the heat dissipation sheet slurry is usually 5 wt% or more, preferably 10 wt% or more, more preferably 15 wt% or more, and particularly preferably 20 wt% or more. On the other hand, it is usually 90 wt% or less, preferably 80 wt% or less, more preferably 70 wt% or less, and particularly preferably 60 wt% or less.

  When the content of the resin-encapsulated boron nitride secondary particles is equal to or more than the upper limit, the slurry is excessively thickened, the leveling property is deteriorated, and a uniform coating film cannot be formed. On the other hand, in the case of the lower limit or less, it is necessary to increase the wet film thickness in order to obtain a desired dry film thickness in the heat dissipation sheet. Increasing the wet film thickness not only increases the manufacturing cost for drying the film, but also increases the tact time. In addition, unevenness in drying may occur.

  In addition, when water is used as the solvent for the slurry for the heat dissipation sheet, the matrix resin B may be a hydrophilic resin. As the hydrophilic resin, polyacrylic acid, PVA, PVB or the like is used.

  The content of the matrix resin B in the heat dissipation sheet slurry is usually 1 wt% or more, preferably 2 wt% or more, more preferably 3 wt% or more, and particularly preferably 4 wt% or more. On the other hand, it is usually 50 wt% or less, preferably 45 wt% or less, more preferably 40 wt% or less, and particularly preferably 35 wt% or less. Above the upper limit of this range, the bonding between boron nitrides is hindered and the desired thermal conductivity may not be achieved. On the other hand, below the lower limit of this range, the heat-dissipating sheet may become brittle. In order to compensate for the brittleness, the inclusion resin A in the boron nitride secondary particles is extruded to give the role of the matrix resin B. The press process cost may increase.

  The above-described heat-dissipating sheet slurry can be appropriately added with the above-mentioned heat-dissipating sheet additives (inorganic materials other than the above-described boron nitride, curing agents, dispersing agents, etc.).

<Method for preparing slurry for heat dissipation sheet>
The manufacturing method of the slurry for heat radiating sheets is not specifically limited, A conventionally well-known method can be used and it can manufacture by mixing the component of the said composition for heat radiating sheets. As the dispersion / mixing method, the above-described disperser / mixer described when the resin-encapsulated boron nitride secondary particles are produced can be used.

  The mixing order of each blending component is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two components or three or more components among the constituent components of the heat dissipation sheet slurry are mixed in advance, and then The remaining components may be mixed together or all at once.

[3. Method for producing molded body]
Various molded objects can be manufactured using the slurry for heat dissipation sheets.
As a method for molding the molded body, a method generally used for molding a resin composition can be used.

For example, when the slurry for heat-dissipating sheets has plasticity and fluidity, it can be molded by curing the slurry in a desired shape, for example, in a state filled in a mold. As a manufacturing method of such a molded body, an injection molding method, an injection compression molding method, an extrusion molding method, and a compression molding method can be used.
Moreover, when the slurry for heat dissipation sheets contains thermosetting resin compositions, such as an epoxy resin and a silicone resin, shaping | molding of a molded object, ie, hardening, can be performed on the curing temperature conditions according to each composition.

  Moreover, when the slurry for thermal radiation sheet contains a thermoplastic resin composition, shaping | molding of a molded object can be performed on the conditions of the temperature more than the melting temperature of a thermoplastic resin, and predetermined | prescribed shaping | molding speed | rates or pressure. Moreover, a molded object can also be obtained by cutting out the heat-radiating sheet slurry from a solid material obtained by molding and hardening into a desired shape.

[4. Manufacturing method of heat dissipation sheet]
Hereinafter, a method for producing a heat dissipation sheet using the slurry for heat dissipation sheet will be specifically described.

<Application process>
First, a coating film is formed on the surface of the substrate with the slurry for a heat dissipation sheet.
That is, a coating film is formed by the dip method, the spin coat method, the spray coat method, the blade method, and other arbitrary methods using the slurry for the heat radiation sheet. For coating the composition coating liquid, it is possible to uniformly form a coating film with a predetermined film thickness on the substrate by using a coating device such as a spin coater, slit coater, die coater, blade coater, preferable.
In addition, as a board | substrate, the copper foil of the below-mentioned thickness is generally used, However, It is not limited to a copper board | substrate at all.

<Drying process>
The coating film formed by applying the slurry for the heat dissipation sheet is usually 10 to 150 ° C., preferably 25 to 100 ° C., more preferably 30 to 90 ° C., particularly for removing the solvent and low molecular components. Preferably, it can be dried at an arbitrary temperature of 40 to 80 ° C. However, it is desirable not to exceed the boiling point of the solvent. When the temperature is above the upper limit of the temperature range, the surface of the coating film may be roughened due to convection of the solvent when the solvent is removed. In addition, when the heat radiation sheet slurry contains a thermosetting resin, the slurry is cured, and the resin may not flow in the subsequent press process, and the void may not be removed. If the temperature is below the lower limit of the temperature range, the solvent cannot be removed effectively, and it may take time to remove the solvent. The drying time is usually 5 minutes to 10 days, preferably 10 minutes to 3 days, more preferably 20 minutes to 1 day, and particularly preferably 30 minutes to 4 hours, to form a dry film.
If the drying time is too short, the solvent cannot be removed sufficiently and the residual solvent may become a void in the heat dissipation sheet. If the drying time is too long, the productivity cannot be increased and the manufacturing process cost may increase.

<Pressurization process>
After the drying step, a pressurizing step may be performed. Sheeting process is the purpose of bonding boron nitrides together to form a heat path, the purpose of eliminating voids and voids in the sheet, the purpose of adhering to the base material, the inclusion resin contained in the boron nitride secondary particles inside the sheet It is desirable to apply pressure for the purpose of bonding. Pressurization step is usually 10kgf / cm ² ~2000Kgf / cm ² to a dry film on a copper substrate, preferably ^{50Kgf / cm 2 ~1000kgf / cm 2} , more preferably ^{80Kgf / cm 2 ~800kgf / cm 2} , particularly preferably Is preferably carried out with a load of 100 kgf / cm ^{2 to} 500 kgf / cm ² . By setting the weight during pressurization to the upper limit or less, the boron nitride secondary particles are not crushed, and a sheet having high thermal conductivity without voids in the sheet can be obtained. Further, by setting the weight to the above lower limit or more, the contact between the aggregated BN particles becomes good and it becomes easy to form a heat conduction path, so that a sheet having high heat conductivity can be obtained.
In the pressurizing step, it is desirable to heat the composition film coated and dried on the copper substrate usually at 25 to 300 ° C, preferably 40 to 250 ° C, more preferably 50 to 200 ° C, particularly preferably 60 to 160 ° C. . By performing the sheet forming step in this temperature range, heating can reduce the melt viscosity of the resin in the dry film, and voids and voids in the sheet can be eliminated. If the temperature is higher than this temperature range, the organic components may be decomposed, and the residual solvent may become vapor and form voids.
The pressurizing step is usually 30 seconds to 4 hours, preferably 1 minute to 2 hours, more preferably 3 minutes to 1 hour, and particularly preferably 5 minutes to 45 minutes. Above this upper limit time, the manufacturing process time of the heat dissipation sheet is too long, and the production cost may increase. Below this lower limit time, voids and voids in the sheet cannot be removed sufficiently, which may affect heat transfer performance and withstand voltage characteristics.
In the pressurization step, it is preferable that the resin viscosity at the time of pressurization is lower in the matrix resin B than in the encapsulating resin A. With the resin viscosity having such a relationship, voids and voids in the sheet can be eliminated.

The curing step for completely carrying out the curing reaction may be performed under pressure, or may be performed without pressure, but in the case of applying pressure, for the same reason as described above, the same conditions as the above-described pressure step It is desirable to do in. In addition, you may perform a pressurization process and a hardening process simultaneously.
In particular, in the sheet forming step that undergoes a pressurizing step and a curing step, it is preferable to apply pressure in the above range and perform pressurization and curing so as to be in the compression rate range described below.

In manufacturing the heat dissipation sheet, there is a tendency that the effect of the present invention is easily exhibited by forming a sheet by applying a large weight to the dry film.
When a heat dissipation sheet is manufactured using conventional boron nitride, the boron nitride secondary particles are crushed in the pressurizing step, and the low heat conduction surface is oriented in the in-plane direction of the sheet. Only conductivity can be obtained. On the other hand, the boron nitride secondary particles used in the present invention contain resin, and there are few voids inside the boron nitride secondary particles, so that the structure of the boron nitride secondary particles is crushed in the pressurizing step. It is difficult to form a heat conduction path by contact of particles in the sheet efficiently by compressing under pressure. For this reason, when resin-encapsulated boron nitride secondary particles are used, a sheet having high thermal conductivity in the thickness direction can be obtained by pressurization in the sheet forming step.

The heat-dissipating sheet containing the resin-encapsulated boron nitride secondary particles having high particle strength as described above is manufactured by forming into a sheet under a large load as described above. Compression ratio (1- (cured sheet thickness) / (before curing) calculated from the ratio of cured sheet thickness ((cured sheet thickness) / (sheet thickness before curing)) after being completely cured by applying thickness and weight When the sheet thickness)) is a compression ratio of 0.2 or more and 0.8 or less, high thermal conductivity of 10 W / mK or more and 50 W / mK or less is developed in the thickness direction. This compression rate is more preferably 0.3 or more and 0.7 or less, further preferably 0.4 or more and 0.7 or less, and particularly preferably 0.5 or more and 0.7 or less. By setting the compressibility to the above upper limit or less, a sheet having high thermal conductivity without voids in the sheet can be obtained without crushing the boron nitride secondary particles. Moreover, since the contact between the boron nitride secondary particles becomes good and the heat conduction path is easily formed by setting the compressibility to the above lower limit or more, a sheet having high heat conductivity can be obtained.
Moreover, the heat conductivity of the thickness direction of the heat-radiation sheet obtained by making it harden | cure with such a compression rate becomes like this. More preferably, it is 15-40 W / mK, Most preferably, it is 20-40 W / mK.
Further, the heat dissipation sheet has an intensity ratio I (100) / I between the 100 axis and the 004 axis in XRD measurement.
(004) is preferably 3.0 or more. By being in the above range, the boron nitride secondary particles are not crushed even in the pressurizing step, and the plate-like boron nitride particles are randomly oriented, so that high thermal conductivity can be achieved in the thickness direction of the heat dissipation sheet.

[5. Laminated heat dissipation sheet]
The heat dissipation sheet may be a laminated heat dissipation sheet bonded to a substrate in order to increase thermal conductivity. In particular, it is preferable to use a copper foil. For example, it is preferable to use a copper foil laminated and integrated by the above-described method for manufacturing a heat dissipation sheet.

Although there is no restriction | limiting in particular about the thickness of the thermal radiation sheet laminated | stacked with the copper foil on the thermal radiation sheet or the copper bonding thermal radiation sheet, Usually, it is preferable that it is 100-300 micrometers, especially 150-250 micrometers. If the thickness of the heat dissipation sheet is less than the above lower limit, the thickness of the cured film is too thin, the withstand voltage characteristics deteriorate, and the dielectric breakdown voltage is lowered. This is not preferable because thinning cannot be achieved.
Also, the thickness of the copper foil is usually 30 to 200 μm, particularly preferably 30 to 150 μm, from the viewpoint of ensuring sufficient heat dissipation.

[6. Power device device]
The heat dissipation sheet or the copper-bonded heat dissipation sheet can be mounted on a power device device as a heat dissipation substrate. The heat-dissipating sheet of the present invention can achieve high output and high density with high reliability due to the heat dissipation effect due to its high thermal conductivity. In the power semiconductor device device, conventionally known members can be appropriately adopted as members such as aluminum wiring, sealing material, package material, heat sink, thermal paste, and solder other than the heat radiating sheet or the copper-bonded heat radiating sheet.

Hereinafter, the present invention will be described in more detail with reference to production examples.
<Preparation of boron nitride secondary particles>
BN-A aggregated particles were prepared by the method described below.
In order to produce BN-A aggregated particles, as a raw material, the (002) plane peak half-value width obtained by powder X-ray diffraction measurement is 2θ = 0.67 °, and the oxygen concentration is 7.5 mass%. -BN (hereinafter referred to as raw material h-BN powder) was used.
・ Production of aggregated particles from BN slurry
[Slurry A]
A slurry A having a viscosity of 810 mPa · s was prepared with the following composition.
Slurry A formulation Raw material h-BN powder: 10000 g
Pure water: 0g
Binder (Takiseram M160L, manufactured by Taki Chemical Co., Ltd., solid content concentration: 21% by mass): 11496 g
Surfactant (surfactant “Ammonium Lauryl Sulfate” manufactured by Kao Corporation: solid concentration 14% by mass): 250 g
[Preparation of slurry]
A predetermined amount of the raw material h-BN powder was weighed into a resin bottle, and then a predetermined amount was added in the order of pure water and binder. Further, after adding a predetermined amount of a surfactant, zirconia ceramic balls were added and stirred on a pot mill rotary table. Stirring was performed for 1-5 hours until the desired viscosity was reached.
[Granulation]
Granulation from the BN slurry was performed using FOC-20 manufactured by Okawara Chemical Industries Co., Ltd.
It was carried out at a disk rotational speed of 20000 to 23000 rpm and a drying temperature of 80 ° C.

[Preparation of BN-A aggregated particles]
The BN granulated particles were heat-treated at 1600 ° C. for 2 hours and at 1500 ° C. for 24 hours under a nitrogen gas flow. Then, it cooled to room temperature and obtained the BN-A aggregated particle.
[Classification]
Further, the BN aggregated particles after the heat treatment were lightly pulverized using a mortar and pestle, and then classified using a sieve having an opening of 90 μm. After classification, the average crystallite diameter of the BN-A aggregated particles, the D ₅₀ , and the peak intensity ratio between the (100) plane and the (004) plane measured by XRD were measured. The measurement results are shown in Table 1.

<Introduction of resin into boron nitride secondary particles>
7.3 g of the prepared BN-A aggregated particles and 1.0 g of epoxy resin were added to 6.1 g of a methyl ethyl ketone / cyclohexanone mixed solution, and the mixture was stirred for 3 minutes by a disperser. After stirring, the solvent was removed by holding at 60 ° C. for 1 hour, and the solvent-removed product was pulverized with a mortar for 15 minutes to obtain resin-encapsulated boron nitride aggregated particles having an average particle diameter of 50 μm.
SEM images of the obtained particles are shown in FIGS. FIG. 2D is an SEM image of the secondary boron nitride particles before encapsulating the resin.

<Manufacture of heat dissipation sheet>
The resin-encapsulated boron nitride agglomerated particles and epoxy resin produced above are added to water and mixed to prepare a heat dissipation sheet slurry. The prepared slurry is applied in a sheet form on a copper plate and dried to remove water, thereby obtaining a heat dissipation sheet.

The resin-encapsulated boron nitride secondary particles produced by the above production example have a very advantageous effect when producing a heat-dissipating sheet. First, when preparing a slurry for a heat dissipation sheet, the boron nitride particles and the solvent become familiar and the coating performance can be improved without the solvent being absorbed into the voids of the boron nitride secondary particles. Thereby, the amount of solvent can be suppressed at the time of slurry preparation, the process cost in the solvent removal process at the time of manufacture of a heat-radiating sheet can be suppressed, and the tact time can be increased. Furthermore, since the inside of the boron nitride secondary particles is filled with the resin, the resin B can be effectively used for the matrix without being trapped by the boron nitride secondary particles.
The heat dissipation sheet manufactured from the slurry for the heat dissipation sheet employs different resins for the resin contained in the boron nitride secondary particles and the matrix resin around the boron nitride secondary particles. By separating the functions, high performance that could not be achieved before can be derived.
For example, by setting the Tg of the matrix resin to a high Tg, it is possible to improve the reliability of the power device that becomes high in heat. Furthermore, in order to increase the affinity of the encapsulating resin with boron nitride, for example, by using a hydrophobic resin, voids formed inside the boron nitride secondary particles can be effectively eliminated, and high thermal conductivity / High voltage resistance can be imparted to the heat dissipation sheet.
Thus, it can be understood that the heat radiating sheet of the present invention containing the resin-encapsulated boron nitride and having the encapsulated resin and the matrix resin different from each other is a very excellent heat radiating sheet.

Claims (15)

  A heat dissipation sheet comprising boron nitride secondary particles encapsulating resin A and matrix resin B, wherein the resin A and the resin B are different resins, and the Tg of the resin B is 150 ° C. or higher.   2. The heat dissipation sheet according to claim 1, wherein Tg of the resin B is higher than Tg of the resin A. 3.   The heat dissipation sheet according to claim 1 or 2, wherein the resin A has a solubility at 25 ° C in water of 5 wt% or less.   Resin A and / or resin B contains curable resin, The heat-radiation sheet of any one of Claims 1-3 characterized by the above-mentioned.   Resin A and / or resin B contains an epoxy resin, The heat-radiation sheet of any one of Claims 1-4 characterized by the above-mentioned.   6. The resin A and / or the resin B includes a phenoxy resin having at least one skeleton among a bisphenol A skeleton, a bisphenol F skeleton, and a biphenyl skeleton. Heat dissipation sheet.   The XRD measurement WHEREIN: The intensity ratio I (100) / I (004) of a 100 axis | shaft and a 004 axis | shaft is 3 or more, The heat radiating sheet of any one of Claims 1-6 characterized by the above-mentioned.   It is a manufacturing method of the thermal radiation sheet of any one of Claims 1-7, Comprising: The manufacturing method of the thermal radiation sheet characterized by including the pressurization step pressurized in the thickness direction of a sheet | seat.   The method for manufacturing a heat-radiating sheet according to claim 8, wherein in the pressurizing step, the resin viscosity at the time of pressurization is lower than that of the resin A.   The method for manufacturing a heat dissipation sheet according to claim 8, further comprising a step of curing the resin after the pressurizing step.   A heat-dissipating sheet slurry comprising boron nitride secondary particles encapsulating resin A and matrix resin B, wherein resin A and resin B are different.   The slurry for heat-radiating sheets according to claim 11, comprising a solvent.   The manufacturing method of the heat-radiation sheet characterized by including the step of apply | coating the slurry for heat-radiation sheets of Claim 11 or Claim 12.   A heat radiation sheet according to any one of claims 1 to 7, or a heat radiation sheet produced by the production method according to any one of claims 8 to 10 and 13, wherein the heat radiation sheet is laminated on a support. Sheet.   The power device apparatus containing the heat radiating sheet of any one of Claims 1-7, or the heat radiating sheet manufactured by the manufacturing method of any one of Claims 8-10, 13 and 14.