Patent Application
20220154059
The present invention relates to aggregated boron nitride particles, a thermally conductive resin composition containing the same, and a heat dissipation member using the thermally conductive resin composition.
A heat generating electronic device, such as a power device, a transistor, a thyristor, and a CPU, has an important issue how to dissipate efficiently the heat generated in use thereof. The heat dissipation measures having been generally performed include (1) high thermal conductivity is imparted to an insulating layer of a printed circuit board having the heat generating electronic device mounted thereon, and (2) the heat generating electronic device or a printed circuit board having the heat generating electronic device mounted thereon is attached to a heatsink via an electrically insulating thermal interface material. As the insulating layer of the printed circuit board and the thermal interface material, a silicone resin or an epoxy resin having ceramic powder filled therein is being used.
The heat generation density inside an electronic equipment is being increased over the years associated with the recent trend including the increase of the speed and the integration density of the circuit inside the heat generating electronic device and the increase of the mounting density of the heat generating electronic device on a printed circuit board. According to the trend, ceramic powder that has a higher thermal conductivity than ever is being demanded.
In view of the background, hexagonal boron nitride powder, which has excellent properties as an electric insulating material, such as high thermal conductivity, high insulating property, and low relative dielectric constant, is receiving attention.
However, hexagonal boron nitride particles have a thermal conductivity of 400 W/(m·K) in the in-plane direction (i.e., the a-axis direction) but a thermal conductivity of 2 W/(m·K) in the thickness direction (i.e., the c-axis direction), and thus has large anisotropy in thermal conductivity derived from the crystallographic structure and the scale-like form thereof. Furthermore, in the case where hexagonal boron nitride powder is filled in a resin, the particles thereof are oriented in the same direction. Therefore, the thickness directions (i.e., the c-axis directions) of the hexagonal boron nitride particles in the resin are arranged homogeneously in the same direction.
Accordingly, for example, in the production of a thermal interface material, the in-plane direction (i.e., the a-axis direction) of the hexagonal boron nitride particles becomes perpendicular to the thickness direction of the thermal interface material, and thereby the high thermal conductivity in the in-plane direction (i.e., the a-axis direction) of the hexagonal boron nitride particles has not been sufficiently used.
PTL 1 proposes a sheet having a high thermal conductivity having hexagonal boron nitride particles, the in-plane direction (i.e., the a-axis direction) of which are oriented in the thickness direction of the sheet, and thereby the high thermal conductivity in the in-plane direction (i.e., the a-axis direction) of the hexagonal boron nitride particles can be used.
However, there are issues including (1) a complicated production process due to the necessity of lamination of the oriented sheets in the subsequent process step, and (2) difficulty in securing the dimensional accuracy of the thickness of the sheet due to the necessity of cutting into a thin sheet form after the lamination and curing. Furthermore, the scale-like form of the hexagonal boron nitride particles increases the viscosity and deteriorates the fluidity in filling in a resin, preventing the particles from being filled in a high density.
For solving the issues, boron nitride powder having various forms with suppressed anisotropy in thermal conductivity of the hexagonal boron nitride particles has been proposed.
PTL 2 proposes the use of boron nitride powder including primary particles of hexagonal boron nitride particles that are aggregated without orientation in the same direction, and thereby the anisotropy in thermal conductivity is suppressed.
In addition, the known methods of producing aggregated boron nitride include spherical boron nitride produced by a spray-drying method (PTL 3), an aggregated material of boron nitride produced from boron carbide as a raw material (PTL 4), and aggregated boron nitride produced through repetition of pressing and pulverizing (PTL 5).
PTL 1: JP 2000-154265 A
PTL 2: JP 9-202663 A
PTL 3: JP 2014-40341 A
PTL 4: JP 2011-98882 A
PTL 5: JP 2007-502770 T
However, the surface of the flat portion of the scale-like hexagonal boron nitride is significantly inactive, and therefore the surface of the boron nitride particles aggregated for suppressing the anisotropy in thermal conductivity is also significantly inactive. Accordingly, in the production of a heat dissipation member by mixing the aggregated boron nitride particles and a resin, there are cases where gaps are formed between the boron nitride particles and the resin, which become a factor of voids in the heat dissipation member. The voids formed in the heat dissipation member deteriorate the thermal conductivity of the heat dissipation member and deteriorate the insulation breakdown characteristics thereof.
Under the circumstances, an object of the present invention is to provide aggregated boron nitride particles that can suppress the formation of voids in a heat dissipation member and can improve the insulation breakdown characteristics and the thermal conductivity of a heat dissipation member, a thermally conductive resin composition including the aggregated boron nitride particles, and a heat dissipation member using the thermally conductive resin composition. Aggregated boron nitride particles having a large crushing strength have issues including performance deterioration due to the voids.
The present inventors have made earnest studies for achieving the object, and can achieve the object by using aggregated boron nitride particles having a prescribed specific surface area and a specific crushing strength.
The present invention is based on the aforementioned knowledge, and the substance thereof includes the following.
[1] Aggregated boron nitride particles including hexagonal boron nitride primary particles aggregated, having a specific surface area measured by the BET method of 2 to 6 m2/g and a crushing strength of 5 MPa or more.
[2] The aggregated boron nitride particles according to the item [1], wherein the hexagonal boron nitride primary particles have a ratio of a long diameter to a thickness (long diameter/thickness) of 8 to 15.
[3] The aggregated boron nitride particles according to the item [1] or [2], wherein the aggregated boron nitride particles have an average particle diameter of 15 to 90 μm.
[4] A thermally conductive resin composition including the aggregated boron nitride particles according to any one of the items [1] to [3].
[5] A heat dissipation member including the thermally conductive resin composition according to the item [4].
According to the present invention, aggregated boron nitride particles that can suppress the formation of voids in a heat dissipation member and can improve the insulation breakdown characteristics and the thermal conductivity of a heat dissipation member, a thermally conductive resin composition including the aggregated boron nitride particles, and a heat dissipation member using the thermally conductive resin composition can be provided.
The present invention relates to aggregated boron nitride particles including hexagonal boron nitride primary particles aggregated, having a specific surface area measured by the BET method of 2 to 6 m2/g and a crushing strength of 5 MPa or more. The use of the aggregated boron nitride particles can suppress the formation of voids in the heat dissipation member and can improve the insulation breakdown characteristics and the thermal conductivity of the heat dissipation member.
The specific surface area measured by the BET method of the aggregated boron nitride particles of the present invention is 2 to 6 m2/g. In the case where the specific surface area measured by the BET method of the aggregated boron nitride particles is less than 2 m2/g, the contact area between the aggregated boron nitride particles and the resin becomes small, and voids are likely formed in the heat dissipation member. Furthermore, the aggregation form that exhibits the high thermal conductivity is difficult to retain, and the insulation breakdown characteristics and the thermal conductivity of the heat dissipation member are deteriorated. In the case where the specific surface area measured by the BET method of the aggregated boron nitride particles exceeds 6 m2/g, on the other hand, the aggregated boron nitride particles cannot be added to the resin in a high density, resulting in voids likely formed in the heat dissipation member, and the insulation breakdown characteristics are also deteriorated. From the standpoint described above, the specific surface area measured by the BET method of the aggregated boron nitride particles is preferably 2.0 to 5.5 m2/g, and more preferably 2.5 to 5.0 m2/g. The specific surface area measured by the BET method of the aggregated boron nitride particles may be measured by the method described in the section of Measurement Methods shown later.
The crushing strength of the aggregated boron nitride particles of the present invention is 5 MPa or more. In the case where the crushing strength of the aggregated boron nitride particles is less than 5 MPa, there is a concern that the aggregated boron nitride particles are collapsed with the stress in mixing with a resin, pressing, or the like, and the thermal conductivity is lowered. From the standpoint described above, the crushing strength of the aggregated boron nitride particles is preferably 6 MPa or more, more preferably 7 MPa or more, and further preferably 8 MPa or more. The upper limit of the crushing strength of the aggregated boron nitride particles is not particularly limited, and is, for example, 30 MPa. The crushing strength of the aggregated boron nitride particles may be measured by the method described in the section of Measurement Methods shown later.
The average particle diameter of the aggregated boron nitride particles of the present invention is preferably 15 to 90 μm. In the case where the average particle diameter of the aggregated boron nitride particles is 15 μm or more, the long diameter of the hexagonal boron nitride primary particles constituting the aggregated boron nitride particles can be increased, and the thermal conductivity of the aggregated boron nitride particles can be increased. Furthermore, the insulation breakdown characteristics of the heat dissipation member can also be enhanced. In the case where the average particle diameter of the aggregated boron nitride particles is 90 μm or less, on the other hand, the heat dissipation member can be thinned. A thin heat dissipation member is demanded since the heat flow rate is proportional to the thermal conductivity and the thickness of the heat dissipation member. In the case where the average particle diameter of the aggregated boron nitride particles is 90 μm or less, furthermore, the heat dissipation member can be brought into sufficiently close contact with an object, from which heat is to be dissipated. In this case, the insulation breakdown characteristics of the heat dissipation member can also be enhanced. From the standpoint described above, the average particle diameter of the aggregated boron nitride particles is more preferably 20 to 70 μm, further preferably 25 to 50 μm, and particularly preferably 25 to 45 μm. The average particle diameter of the aggregated boron nitride particles may be measured by the method described in the section of Measurement Methods shown later.
The aggregated boron nitride particles of the present invention can be favorably applied, for example, to a raw material of a heat dissipation member for a heat generating electronic device, such as a power device, and in particular, can be favorably used by filling in a resin composition for an insulating layer and a thermal interface material for a printed circuit board.
In the aggregated boron nitride particles of the present invention, the ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles is preferably 8 to 15. In the case where the ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles is 8 to 15, the insulation breakdown characteristics of the heat dissipation member are further enhanced. From the standpoint described above, the ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles is more preferably 8 to 14, and further preferably 8 to 13. The ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles is a value obtained by dividing the average value of the long diameter of the hexagonal boron nitride primary particles by the average value of the thickness thereof. The average value of the long diameter and the average value of the thickness of the hexagonal boron nitride primary particles may be measured by the method described in the section of Measurement Methods shown later.
In the aggregated boron nitride particles of the present invention, the average value of the long diameter of the hexagonal boron nitride primary particles is preferably 2 to 12 μm. In the case where the average value of the long diameter of the hexagonal boron nitride primary particles is 2 μm or more, the thermal conductivity of the aggregated boron nitride particles can be improved. In the case where the average value of the long diameter of the hexagonal boron nitride primary particles is 2 μm or more, furthermore, the resin can readily penetrate to the aggregated boron nitride particles, and voids in the heat dissipation member can be suppressed from being formed. In the case where the average value of the long diameter of the hexagonal boron nitride primary particles is 12 μm or less, the aggregated boron nitride particles have a dense structure inside, by which the crushing strength of the aggregated boron nitride particles can be enhanced, and the thermal conductivity of the aggregated boron nitride particles can be improved. From the standpoint described above, the average value of the long diameter of the hexagonal boron nitride primary particles is more preferably 3 to 11 μm, and further preferably 3 to 10 μm.
The aggregated boron nitride particles of the present invention contribute to the improvement of the insulation breakdown characteristics and the thermal conductivity. The extent of the contribution is 41 (kV/mm) or more in terms of insulation breakdown strength measured by the method described in Example 1. According to the present invention, it is likely possible to achieve an insulation breakdown strength of 45 (kV/mm) or more, or 50 (kV/mm) or more.
The aggregated boron nitride particles of the present invention can be produced by a production method of aggregated boron nitride particles, including a pressure nitridation firing step and a decarbonization crystallization step. The steps each will be described in detail below.
In the pressure nitridation firing step, boron carbide having an average particle diameter of 6 μm or more and 55 μm or less and a carbon amount of 18% or more and 21% or less is subjected to pressure nitridation firing. According to the procedure, boron carbonitride that is favorable as a raw material of the aggregated boron nitride particles of the present invention can be obtained.
Since the particle diameter of the boron carbide as the raw material used in the pressure nitridation step strongly influences the aggregated boron nitride particles finally obtained, it is necessary to select boron carbide having a suitable particle diameter, and boron carbide having an average particle diameter of 6 to 55 μm is preferably used as the raw material. At this time, the amounts of boric acid and free carbon as impurities are preferably small.
The average particle diameter of the boron carbide as the raw material is preferably 6 μm or more, more preferably 7 μm or more, and further preferably 10 μm or more, and is preferably 55 μm or less, more preferably 50 μm or less, and further preferably 45 μm or less. The average particle diameter of the boron carbide as the raw material is preferably 7 to 50 μm, and more preferably 7 to 45 μm. The average particle diameter of the boron carbide can be measured in the similar manner as for the aggregated boron nitride particles.
The carbon amount of the boron carbide as the raw material used in the pressure nitridation step is preferably lower than the composition of B4C (21.7%), and boron carbide having a carbon amount of 18 to 21% is preferably used. The carbon amount of the boron carbide is preferably 18% or more, and more preferably 19% or more, and is preferably 21% or less, and more preferably 20.5% or less. The carbon amount of the boron carbide is preferably 18% to 20.5%. The carbon amount of the boron carbide is to be regulated to the range since the dense aggregated boron nitride particles can be formed with a less amount of carbon discharged in the decarbonization crystallization step described later, and also since the carbon amount of the aggregated boron nitride particles finally produced is reduced. It is difficult to produce stable boron carbide having a carbon amount of less than 18% due to the too large deviation from the theoretical composition.
As a method for producing the boron carbide as the raw material, boric acid and acetylene black may be mixed and then heated at 1,800 to 2,400° C. for 1 to 10 hours in an atmosphere, and thus bulk boron carbide can be obtained. The bulk raw material obtained may be pulverized and then sieved, and appropriately subjected to washing, removal of impurities, drying, and the like, and thus boron carbide powder can be obtained. In mixing boric acid and acetylene black as raw materials of the boron carbide, the amount of acetylene black is preferably 25 to 40 parts by mass per 100 parts by mass of boric acid.
The atmosphere for the production of boron carbide is preferably an inert gas, and examples of the inert gas include argon gas and nitrogen gas, which may be appropriately used alone or as a combination thereof. In these, argon gas is preferred.
The bulk boron nitride may be pulverized by using a common pulverizing or cracking machine, and may be pulverized, for example, for 0.5 to 3 hours. The boron carbide after the pulverization is preferably sieved to a particle diameter of 75 μm or less with a sieve net.
The pressure nitridation firing is performed in an atmosphere having a particular firing temperature and a particular pressure condition.
The firing temperature in the pressure nitridation firing is preferably 1,700° C. or more, and more preferably 1,800° C. or more, and is preferably 2,400° C. or less, and more preferably 2,200° C. or less. The firing temperature in the pressure nitridation firing is preferably 1,800 to 2,200° C.
The pressure in the pressure nitridation firing is preferably 0.6 MPa or more, and more preferably 0.7 MPa or more, and is preferably 1.0 MPa or less, and more preferably 0.9 MPa or less. The pressure in the pressure nitridation firing is preferably 0.7 to 1.0 MPa.
The combination of the firing temperature and the pressure condition in the pressure nitridation firing is preferably a firing temperature of 1,800° C. or more and a pressure of 0.7 to 1.0 MPa. With a firing temperature of 1,800° C. or more and a pressure of 0.7 MPa or more, the nitridation of boron carbide can be sufficiently performed. The production is industrially preferably performed under a pressure of 1.0 MPa or less.
A gas that can proceed nitridation reaction is demanded for the atmosphere for the pressure nitridation firing, and examples thereof include nitrogen gas and ammonia gas, which may be used alone or as a combination of two or more kinds thereof. In these, nitrogen gas is preferred from the standpoint of the nitridation and the cost. The atmosphere preferably contains nitrogen gas in an amount of 95% (v/v) or more, and more preferably 99.9% or more.
The firing time in the pressure nitridation firing is preferably 6 to 30 hours, and more preferably 8 to 20 hours.
In the decarbonization crystallization step, the boron carbonitride obtained in the pressure nitridation step is subjected to a heat treatment in (a) an atmosphere of ordinary pressure or more, at (b) a particular temperature rise rate, (c) heating to a firing temperature in a particular temperature range, and (d) retaining the firing temperature for a certain period of time. According to the procedure, the aggregated boron nitride particles including primary particles (i.e., scale-like hexagonal boron nitride as primary particles) aggregated into clumps can be obtained. In particular, in the case where the condition of the heat treatment is in the range described later, the aggregated boron nitride particles can have a specific surface area measured by the BET method of 2 to 6 m2/g, a crushing strength of 5 MPa or more, and a ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles in the aggregated boron nitride particles of 8 to 15.
In the decarbonization crystallization step, the boron carbonitride obtained from the boron carbide thus prepared above is decarbonized, and is simultaneously made into a scale form having the prescribed size and aggregated to the aggregated boron nitride particles.
More specifically, in the decarbonization crystallization step, 100 parts by mass of the boron carbonitride obtained in the pressure nitridation firing step and 70 to 120 parts by mass of at least one compound of boron oxide and boric acid are mixed to produce a mixture, and the resulting mixture is subjected to a heat treatment of heating to a temperature where the decarbonization can be started, then heating to a firing temperature of 2,000 to 2,100° C. at a temperature rise rate of 5° C./min or less, and retaining at the firing temperature for more than 0.5 hour to less than 20 hours. According to the heat treatment performed, the aggregated boron nitride particles including primary particles (i.e., scale-like hexagonal boron nitride as primary particles) aggregated into clumps can be obtained. The heat treatment performed can provide a specific surface area measured by the BET method of the aggregated boron nitride particles of 2 to 6 m2/g and a crushing strength thereof of 5 MPa or more. Furthermore, the heat treatment can provide a ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles in the aggregated boron nitride particles of 8 to 15. Moreover, the treatment performed can provide the aggregated boron nitride particles having improved insulation breakdown characteristics and improved thermal conductivity.
The decarbonization crystallization step is preferably a heat treatment performed in an atmosphere of ordinary pressure or more by heating to a temperature where the decarbonization can be started, then heating to a firing temperature of 1,950 to 2,100° C. at a temperature rise rate of 5° C./min or less, and retaining at the firing temperature for more than 0.5 hour to less than 20 hours. The decarbonization crystallization step is more preferably a heat treatment performed in an atmosphere of ordinary pressure or more by heating to a temperature where the decarbonization can be started, then heating to a firing temperature of 2,000 to 2,080° C. at a temperature rise rate of 5° C./min or less, and retaining at the firing temperature for 2 to 8 hours.
In the decarbonization crystallization step, it is preferred that the boron carbonitride obtained in the pressure nitridation firing step and at least one compound of boron oxide and boric acid (and other raw materials depending on necessity) are mixed to produce a mixture, and the resulting mixture is subjected to decarbonization crystallization. From the standpoint of the achievement of a specific surface area measured by the BET method of the aggregated boron nitride particles of 2 to 6 m2/g and a crushing strength thereof of 5 MPa or more and the standpoint of the achievement of a ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles in the aggregated boron nitride particles of 8 to 15, the mixing ratio of the boron carbonitride and the at least one compound of boron oxide and boric acid is preferably 65 to 130 parts by mass of the at least one compound of boron oxide and boric acid, and more preferably 70 to 120 parts by mass of the at least one compound of boron oxide and boric acid, per 100 parts by mass of the boron carbonitride. For boron oxide, the mixing ratio converted to boric acid is used.
In the decarbonization crystallization step, the pressure condition of “(a) the atmosphere of ordinary pressure or more” is preferably ordinary pressure or more, and more preferably 0.1 MPa or more. The upper limit of the pressure condition of the atmosphere is not particularly limited, and is preferably 1 MPa or less, and more preferably 0.5 MPa or less. The pressure condition of the atmosphere is preferably 0.1 to 0.3 MPa.
In the decarbonization crystallization step, the “atmosphere” is preferably nitrogen gas, and is preferably 90% (v/v) or more of nitrogen gas in the atmosphere, and more preferably high purity nitrogen gas (99.9% or more).
In the decarbonization crystallization step, the heating at “(b) the particular temperature rise rate” may be performed in single stage or in multiple stages. Multiple stages are preferably selected for shortening the period of time for heating to the temperature where the decarbonization can be started. The “first stage heating” in the multiple stages is preferably heating to the “temperature where the decarbonization can be started”. The “temperature where the decarbonization can be started” is not particularly limited and may be a temperature having been ordinarily used, and for example, the temperature may be approximately 800 to 1,200° C. (preferably approximately 1,000° C.). The “first stage heating” may be performed, for example, in a range of 5 to 20° C./min, and preferably 8 to 12° C./min.
After the first stage heating, the second stage heating is preferably performed. The “second stage heating” is more preferably performed as the “(c) heating to a firing temperature in a particular temperature range” in the decarbonization crystallization step.
The upper limit of the “second stage heating” is preferably 5° C./min or less, more preferably 4° C./min or less, further preferably 3° C./min or less, and still further preferably 2° C./min or less. A lower temperature rise rate is preferred since the particle growth can be readily homogeneous.
The “second stage heating” is preferably 0.1° C./min or more, more preferably 0.5° C./min or more, and further preferably 1° C./min or more. The case where the “second stage heating” that is 1° C. or more is preferred from the standpoint of cost since the production time can be reduced. The “second stage heating” is preferably 0.1 to 5° C./min. In the case where the temperature rise rate in the “second stage heating” exceeds 5° C./min, the particle growth may occur heterogeneously to fail to provide a homogeneous structure, resulting in a possibility that the crushing strength of the aggregated boron nitride particles is lowered.
In the “(c) heating to a firing temperature in a particular temperature range”, the particular temperature range (i.e., the firing temperature after heating) is preferably 1,950° C. or more, more preferably 1,960° C. or more, and further preferably 2,000° C. or more, and is preferably 2,100° C. or less, and more preferably 2,080° C. or less.
In the “(d) retaining the firing temperature for a certain period of time”, the certain period of time (i.e., the firing time after heating) is preferably more than 0.5 hour and less than 20 hours. The “firing time” is more preferably 1 hour or more, further preferably 3 hours or more, still further preferably 5 hours or more, and still more further preferably 10 hours or more, and is more preferably 18 hours or less, and further preferably 16 hours or less. In the case where the firing time after heating exceeds 0.5 hour, the particle growth occurs favorably, and in the case where the firing time after heating is less than 20 hours, excessive particle growth deteriorating the particle strength can be suppressed, and the industrial disadvantage due to the long firing time can be reduced.
The aggregated boron nitride particles of the present invention can be obtained through the pressure nitridation firing step and the decarbonization crystallization step described above. Furthermore, in the case where the weak agglomeration among the aggregated boron nitride particles is to be relieved, the aggregated boron nitride particles obtained through the decarbonization crystallization step are preferably pulverized or cracked, and then classified. The pulverization and cracking are not particularly limited, and may be performed by using a common pulverizing or cracking machine, and the classification may be performed by a common sieving method providing an average particle diameter of 15 to 90 μm. Examples thereof include a method of pulverizing with a Henschel mixer or a mortar, and then classifying with a vibration sieving machine.
The features of the aggregated boron nitride particles obtained by the production method of aggregated boron nitride particles described above have been described in the section of the aggregated boron nitride particles.
(Surface Treatment with Metal Coupling Agent)
The aggregated boron nitride particles of the present invention may be surface-treated with a metal coupling agent. According to the procedure, the aggregated boron nitride particles having a metal element and an organic functional group existing on the surface thereof can be obtained. The bond between the aggregated boron nitride particles and the resin can be further enhanced thereby, and voids in the heat dissipation member can be further suppressed from being formed. The surface treatment with the metal coupling agent may be performed by dry-mixing the aggregated boron nitride particles and the metal coupling agent, or may be performed by adding a solvent to the aggregated boron nitride particles and the metal coupling agent, and wet-mixing them.
The metal coupling agent used for the surface treatment of the aggregated boron nitride particles is not particularly limited since various metal coupling agents can provide a metal element and an organic functional group existing on the surface of the aggregated boron nitride particles. However, the coupling agent is preferably selected corresponding to the resin used.
Examples of the metal coupling agent used for the surface treatment of the aggregated boron nitride particles include metal coupling agents containing Si, Ti, Zr, or Al in the form of a metal alkoxide, a metal chelate, or a metal halide, with no particular limitation, and the coupling agent is preferably selected corresponding to the resin used. Examples of the preferred metal coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent. One kind of the metal coupling agent may be used alone, or two or more kinds thereof may be used in combination. Among the metal coupling agents, a silane coupling agent is more preferred. In the case where an alkyl group is to be applied directly to the surface of the aggregated boron nitride particles, a coupling agent having a linear alkyl group having 5 or more carbon atoms is preferred.
Examples of the silane coupling agent include a vinyl silane, such as vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and 7-octenyltrimethoxysilane; γ-methacryloxypropyltrimethoxysilane; an epoxy silane, such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 8-glycidoxyoctyltrimethoxysilane; an amino silane, such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-8-aminooctyltrimethoxysilane; and other silane coupling agents, such as γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and 8-methacryloxyoctyltrimethoxysilane. One kind of the silane coupling agent may be used alone, or two or more kinds thereof may be used in combination.
Among these, preferred are 3-glycidoxypropyltrimethoxysilane, p-stylyltrimethoxysilane (metal alkoxide), 3-isocyanatopropyltriethoxysilane (metal alkoxide), vinyltrimethoxysilane (metal alkoxide), cyclohexylmethyldimethoxysilane (metal alkoxide), 7-octenyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, and more preferred are 7-octenyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and N-2-(aminoethyl)-8-aminooctyltrimethoxysilane.
Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl) bis(ditridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, dicumyl phenyloxyacetate titanate, and diisostearoyl ethylene titanate. One kind of the titanium coupling agent may be used alone, or two or more kinds thereof may be used in combination.
Among these, preferred are isopropyl triisostearoyl titanate (metal alkoxide), tetraisopropyl bis(dioctyl phosphite) titanate (metal chelate), and tetraoctyl bis(ditridecyl phosphite) titanate (metal chelate).
Examples of the zirconium coupling agent include tetra-n-propoxy zirconium, tetrabutoxy zirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconium tributoxyethylacetolacetate, zirconium butoxyacetylacetonate bis(ethylacetoacetate), and tetrakis(2,4-pentanedionate) zirconium. One kind of the zirconium coupling agent may be used alone, or two or more kinds thereof may be used in combination.
Among these, preferred is tetrakis(2,4-pentanedionate) zirconium (metal alkoxide).
Examples of the aluminum coupling agent include aluminum isopropylate, mono-sec-butoxy aluminum diisopropylate, aluminum sec-butylate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris(ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis(ethyl acetoacetate), aluminum tris(acetyl acetoacetate), and aluminum bisethyl acetoacetate monoacetyl acetonate. One kind of the aluminum coupling agent may be used alone, or two or more kinds thereof may be used in combination.
Among these, preferred is aluminum bisethyl acetoacetate monoacetyl acetonate (metal chelate compound).
In the surface treatment, the temperature in the coupling reaction condition is preferably 10 to 70° C., and more preferably 20 to 70° C. In the surface treatment, the period of time in the coupling reaction condition is preferably 0.2 to 5 hours, and more preferably 0.5 to 3 hours.
The thermally conductive resin composition of the present invention includes the aggregated boron nitride particles of the present invention. The thermally conductive resin composition can be produced by a known production method. The resulting thermally conductive resin composition can be widely applied to thermal grease, heat dissipation members, and the like.
Examples of the resin used in the thermally conductive resin composition of the present invention include an epoxy resin, a silicone resin, silicone rubber, an acrylic resin, a phenol resin, a melamine resin, a urea resin, an unsaturated polyester, a fluorine resin, a polyamide (such as polyimide, polyamideimide, and polyetherimide), a polyester (such as polybutylene terephthalate and polyethylene terephthalate), a polyphenylene ether, a polyphenylene sulfide, a wholly aromatic polyester, a polysulfone, a liquid crystal polymer, a polyether sulfone, a polycarbonate, a maleimide-modified resin, an ABS resin, an AAS (acrylonitrile-acrylic rubber-styrene) resin, an AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin. An epoxy resin (preferably a naphthalene type epoxy resin) is preferred particularly as an insulating layer of a printed circuit board due to the excellent properties thereof including the heat resistance and the adhesion strength to a copper foil circuit. A silicone resin is preferred particularly as a thermal interface material due to the excellent property thereof including the heat resistance, the flexibility, and the adhesiveness to a heatsink or the like.
The content of the aggregated boron nitride particles in 100% by volume of the thermally conductive resin composition is preferably 30 to 85% by volume, and more preferably 40 to 80% by volume. In the case where the content of the aggregated boron nitride particles is 30% by volume or more, the thermal conductivity can be enhanced, and a sufficient heat dissipation capability can be readily obtained. In the case where the content of the aggregated boron nitride particles is 85% by volume or less, the tendency of the formation of voids in molding can be reduced, and the deterioration of the insulating property and the mechanical strength can be reduced.
The thermally conductive resin composition may include additional components other than the aggregated boron nitride particles and the resin. The additional components include an additive, an impurity, and the like, and the content thereof may be 5% by volume or less, 3% by volume or less, or 1% by volume or less.
The heat dissipation member of the present invention includes the thermally conductive resin composition of the present invention. The heat dissipation member of the present invention is not particularly limited, as far as the member is used for a heat dissipation measure. Examples of the heat dissipation member of the present invention include a printed circuit board having a heat generating electronic device, such as a power device, a transistor, a thyristor, and a CPU, mounted thereon, the heat generating electronic device and an electrically insulating thermal interface material used for attaching the heat generating electronic device or the printed circuit board having the heat generating electronic device mounted thereon to a heatsink. The heat dissipation member can be produced, for example, in such a manner that the thermally conductive resin composition is molded to produce a molded article, the molded article thus produced is spontaneously dried, the molded article thus spontaneously dried is pressed, the molded article thus pressed is heat dried, and the molded article thus heat dried is worked.
The measurement methods are as follows.
The specific surface area of the aggregated boron nitride particles is measured by the BET one point method with a specific surface area measuring equipment (Quantasorb, produced by Yuasa-Ionics Co., Ltd.). In the measurement, 1 g of a specimen is dried and deaerated at 300° C. for 15 minutes, and then measured.
The crushing strength is measured according to JIS R1639-5. The measurement equipment used is a micro compression testing machine (“MCT-W500”, produced by Shimadzu Corporation). The particle strength (σ: MPa) is obtained in such a manner that 20 or more particles are measured according to the expression σ=α×P/(π×d2) from the dimensionless number (α=2.48) varying depending on the position within the particle, the crushing test force (P: N), and the particle diameter (d: μm), and the value at an accumulated crushing rate of 63.2% is calculated.
For the aggregated boron nitride particles thus produced, particles having a long diameter and a short diameter that can be confirmed in the surface state are observed with a scanning electron microscope (for example, “JSM-6010LA” (produced by JEOL, Ltd.) at an observation magnification of 1,000 to 5,000. The resulting particle images are incorporated to an image analysis software, such as “Mac-view”, and measured for the long diameters and the thicknesses of the incorporated particles, and the average values of the long diameters and the thicknesses of arbitrary 100 particles are calculated and designated as the average value of the long diameter and the average value of the thickness respectively.
The average particle diameter is measured with a laser diffraction scattering particle size distribution analyzer (LS-13 320), produced by Beckman Coulter Inc. The average particle diameter of the specimen that is not subjected to a homogenizer before the measurement treatment is designated as the average particle diameter. The resulting average particle diameter is an average particle diameter by the volume statistics value.
The carbon amount is measured with a carbon/sulfur simultaneous analyzer “CS-444LS” (produced by LECO Corporation).
The present invention will be described in detail with reference to examples and comparative examples below. The present invention is not limited to the examples.
Heat dissipation members of the examples and the comparative examples were evaluated as follows.
The insulation breakdown strength of the heat dissipation member were measured according to JIS C2110.
Specifically, the heat dissipation member in a sheet form was worked into a size of 10 cm×10 cm, a circular copper layer having a diameter of 25 mm was formed on one surface of the worked heat dissipation member, and a copper layer was formed on the entire of the other surface thereof so as to produce a test specimen.
Electrodes were disposed to hold the test specimen, and an alternating voltage was applied to the test specimen in an electric insulating oil (trade name: FC-3283, produced by 3M Japan, Ltd.). The voltage applied to the test specimen was increased from 0 V at a rate (500 V/s) that caused insulation breakdown after 10 to 20 seconds in average from the start of application of voltage. The voltage V15 (kV) at the insulation breakdown occurring 15 times per one test specimen was measured. The voltage V15 (kV) was divided by the thickness (mm) of the test specimen, so as to calculate the insulation breakdown strength (kV/mm). An insulation breakdown strength of 41 (kV/mm) or more is favorable, that of 45 (kV/mm) or more is more favorable, and that of 50 (kV/mm) or more is further favorable.
The thermal conductivity of the heat dissipation member was measured according to ASTM D5470.
The heat dissipation member was held with two copper fixtures under a load of 100 N. Grease (trade name: G-747, produced by Shin-Etsu Chemical Co., Ltd.) was applied between the heat dissipation member and the copper fixture. The upper copper fixture was heated with a heater, and the temperature (TU) of the upper copper fixture and the temperature (TB) of the bottom copper fixture were measured. The thermal conductivity (H) was calculated according to the following expression (1).
H=t/((TU−TB)/Q×S) (1)
In the expression, t represents the thickness (m) of the heat dissipation member, Q represents the heat flow rate (W) calculated from the electric power of the heater, and S represents the area (m2) of the heat dissipation member.
The thermal conductivity was measured for three specimens, and the average value of the thermal conductivity of the three specimens was designated as the thermal conductivity of the heat dissipation member. The thermal conductivity of the heat dissipation member was divided by the thermal conductivity of the heat dissipation member of Comparative Example 1, so as to calculate the relative thermal conductivity.
The heat dissipation member was worked with a diamond cutter to provide a cross section, which was then processed by the CP (cross section polisher) method, and after fixing to a specimen stage, subjected to osmium coating. The cross section of the heat dissipation member was observed with a scanning electron microscope (for example, “JSM-6010LA” (produced by JEOL, Ltd.) at a magnification of 500 for 10 view fields, and voids of the heat dissipation member were investigated. In the observation of 10 view fields in the vicinity of the surface of the sheet at a magnification of 500, the case where 5 or more voids having a length of 5 μm or more in terms of average per one view field were not observed was evaluated as “none”, and the case where the voids were observed was evaluated as “found”. As examples of the cross sectional observation photograph,
In Example 1, aggregated boron nitride particles were synthesized through the boron carbide synthesis, the pressure nitridation step, and the decarbonization crystallization step in the following manner, and filled in a resin.
100 parts by mass of orthoboric acid (hereinafter referred to as boric acid), produced by Nippon Denko Co., Ltd., and 35 parts by mass of acetylene black (HS100), produced by Denka Co., Ltd., were mixed with a Henschel mixer, then charged in a graphite crucible, and heated in an arc furnace in an argon atmosphere at 2,200° C. for 5 hours, so as to synthesize boron carbide (B4C). The bulk boron carbide thus synthesized was pulverized with a ball mill for 1 hour, sieved to a particle diameter of 75 μm or less with a sieve net, and further washed with a nitric acid aqueous solution to remove impurities, such as an iron content, followed by filtering and drying, so as to produce boron carbide powder having an average particle diameter of 20 μm. The carbon amount of the resulting boron carbide powder was 20.0%.
The boron carbide thus synthesized was charged in a boron nitride crucible, and heated in a resistance heating furnace in a nitrogen atmosphere under condition of 2,000° C. and 9 atm (0.8 MPa) for 10 hours, so as to provide boron carbonitride (B4CN4).
100 parts by mass of the boron carbonitride thus synthesized and 90 parts by mass of boric acid were mixed with a Henschel mixer, then charged in a boron nitride crucible, and heated in a resistance heating furnace under a pressure condition of 0.2 MPa in a nitrogen atmosphere at a temperature rise rate from room temperature to 1,000° C. of 10° C./min and a temperature rise rate at 1,000° C. or more of 2° C./min to a firing temperature of 2,020° C. for a retention time of 10 hours, so as to synthesize aggregated boron nitride particles including primary particles aggregated into clumps. The aggregated boron nitride particles thus synthesized were cracked with a Henschel mixer for 10 minutes, and then classified with a nylon sieve having a mesh of 75 μm as a sieve net. The fired material was cracked and classified to provide aggregated boron nitride particles including primary particles aggregated into clumps.
The specific surface area measured by the BET method of the resulting aggregated boron nitride particles was 4 m2/g, and the crashing strength thereof was 9 MPa. The ratio of the long diameter to the thickness (long diameter/thickness) of the hexagonal boron nitride primary particles of the resulting aggregated boron nitride particles was 11. The average particle diameter of the resulting aggregated boron nitride particles was 35 μm, and the carbon amount thereof was 0.06%.
1 part by mass of a silane coupling agent (trade name: KBM-1083, produced by Shin-Etsu Chemical Co., Ltd., 7-octenyltrimethoxysilane) was added to 100 parts by mass of the aggregated boron nitride particles, and the mixture was dry-mixed for 0.5 hour and sieved with a sieve of 75 μm, so as to provide surface-treated aggregated boron nitride particles.
50% by volume of the resulting surface-treated aggregated boron nitride particles and 50% by volume of a silicone resin (trade name: CF-3110, produced by Toray Dow Corning Silicone Co., Ltd.), based on 100% by volume in total of the aggregated boron nitride particles and the silicone resin, 1 part by mass of a crosslinking agent (trade name: Kayahexa AD, produced by Kayak Akzo Corporation) per 100 parts by mass of the silicone resin, and toluene as a viscosity modifier weighed to make a solid concentration of 60% by weight were placed in an agitator (trade name: Three-One Motor, produced by HEIDON) and mixed with a turbine agitation blade for 15 hours, so as to produce a thermally conductive resin composition.
The thermally conductive resin composition thus produced was coated on one surface of a glass cloth (trade name: H25, produced by Unitika, Ltd.) to a thickness of 0.2 mm with a comma coater, and dried at 75° C. for 5 minutes. Thereafter, the thermally conductive resin composition was coated on the other surface of the glass cloth to a thickness of 0.2 mm with the comma coater and dried at 75° C. for 5 minutes, so as to produce a laminate.
The laminate was subjected to thermal press under condition of a temperature of 150° C. and a pressure of 150 kgf/cm2 for 45 minutes with a plate press machine (produced by Yanase Seisakusho Co., Ltd.), so as to produce a heat dissipation member in a sheet form having a thickness of 0.3 mm. The heat dissipation member was further subjected to secondary heating at 150° C. at a normal pressure for 4 hours, so as to produce a heat dissipation member of Example 1.
In Example 2, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the amount of boric acid mixed with 100 parts by mass of boron carbonitride was changed from 90 parts by mass to 110 parts by mass.
In Example 3, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the amount of boric acid mixed with 100 parts by mass of boron carbonitride was changed from 90 parts by mass to 75 parts by mass.
In Example 4, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the temperature rise rate at 1,000° C. or more was changed from 2° C./min to 0.4° C./min.
In Example 5, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the temperature rise rate at 1,000° C. or more was changed from 2° C./min to 4° C./min.
In Example 6, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the boron carbide synthesis step, the pulverization time of the bulk boron carbide with a ball mill was changed from 1 hour to 2.5 hours, and the sieving was changed from 75 μm or less to 33 μm or less to change the average particle diameter of the boron carbide powder from 20 μm to 7 μm.
In Example 7, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the boron carbide synthesis step, the pulverization time of the bulk boron carbide with a ball mill was changed from 1 hour to 20 minutes, and the sieving was changed from 75 μm or less to 150 μm or less to change the average particle diameter of the boron carbide powder from 20 μm to 48 μm.
In Comparative Example 1, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the amount of boric acid mixed with 100 parts by mass of boron carbonitride was changed from 90 parts by mass to 50 parts by mass, and, in the decarbonization crystallization step, the firing temperature was changed from 2,020° C. to 1,950° C.
In Comparative Example 2, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the amount of boric acid mixed with 100 parts by mass of boron carbonitride was changed from 90 parts by mass to 150 parts by mass, and 1 part by mass of sodium carbonate was mixed with 100 parts by mass of boron carbonitride, and, in the decarbonization crystallization step, the firing temperature was changed from 2,020° C. to 1,950° C.
In Comparative Example 3, aggregated boron nitride particles were synthesized and a heat dissipation member was produced in the same manner as in Example 1 except that, in the decarbonization crystallization step, the amount of boric acid mixed with 100 parts by mass of boron carbonitride was changed from 90 parts by mass to 50 parts by mass, and 3 parts by mass of calcium carbonate was mixed with 100 parts by mass of boron carbonitride, and, in the decarbonization crystallization step, the firing temperature was changed from 2,020° C. to 1,950° C.
The evaluation results of the aggregated boron nitride particles, the primary particles thereof, and the heat dissipation members produced in Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Tables 1 to 3.
It was found from these evaluation results that the use of the aggregated boron nitride particles having a specific surface area measured by the BET method of 2 to 6 m2/g and a crushing strength of 5 MPa or more in the heat dissipation member suppressed the formation of voids in the heat dissipation member and improved the insulation breakdown characteristics and the thermal conductivity of the heat dissipation member.
It was also found that the use of the aggregated boron nitride particles having the hexagonal boron nitride primary particles having a ratio of the long diameter to the thickness (long diameter/thickness) of 8 to 15 in the heat dissipation member further improved the insulation breakdown characteristics of the heat dissipation member.
It was also found that the use of the aggregated boron nitride particles having an average particle diameter of 15 to 90 μm in the heat dissipation member further improved the insulation breakdown characteristics of the heat dissipation member.
The present invention particularly preferably relates to aggregated boron nitride particles excellent in thermal conductivity to be filled in a resin composition for an insulating layer of a printed circuit board and a thermal interface material, a method for producing the same, and a thermally conductive resin composition using the same.
The present invention specifically can be favorably applied to a raw material of a heat dissipation member for a heat generating electronic device, such as a power device.
The thermally conductive resin composition of the present invention can be widely applied to a heat dissipation member and the like.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-060286 | Mar 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/013385 | 3/25/2020 | WO | 00 |
