WO2013069327A1

WO2013069327A1 - Heat transfer sheet

Info

Publication number: WO2013069327A1
Application number: PCT/JP2012/064302
Authority: WO
Inventors: 涼介塩野; 川口　康弘
Original assignee: 北川工業株式会社
Priority date: 2011-11-11
Filing date: 2012-06-01
Publication date: 2013-05-16
Also published as: JP2012119674A

Abstract

This heat transfer sheet is obtained by mixing a hollow filler having a bulk specific gravity of 0.1-1.0 and a heat conductive filler into a base material that is composed of an elastomer and by molding the resulting mixture into a sheet form. At least one of the heat conductive fillers contained therein in the largest amount as the heat conductive filler is a heat conductive filler other than boron nitride.

Description

Heat conduction sheet

Cross-reference of related applications

This international application claims priority based on Japanese Patent Application No. 2011-247834 filed with the Japan Patent Office on November 11, 2011, and is based on Japanese Patent Application No. 2011-247834. The entire contents are incorporated herein by reference.

The present invention relates to a heat conductive sheet that is arranged and used so as to be in contact with a heat source in order to promote heat dissipation from a heat source such as an electronic component.

Conventionally, a heat conductive sheet obtained by mixing (filling) a heat conductive filler with an elastomer such as silicone or acrylic resin and molding the sheet into a sheet shape has been considered. This type of heat conductive sheet is interposed between an electronic component that becomes a heat source, for example, and a component that becomes a heat radiating plate such as a heat sink or a housing panel (hereinafter simply referred to as a radiator) in an electric / electronic device. It is arranged to let you.

When the heat conductive sheet is arranged in this way, the heat generated by the electronic components and the like can be released to the radiator side satisfactorily. For this reason, this type of heat conductive sheet is attracting attention as an indispensable material for, for example, extending the life of the CPU.

On the other hand, in the circuit board applications that emphasize high-frequency characteristics, for the following reasons, been requested is possible to reduce the dielectric constant of such thermally conductive sheet. That is, when a heat conductive sheet having a high relative dielectric constant is sandwiched between an electronic component and a radiator, a kind of capacitor is formed. And the higher the relative dielectric constant of the heat conductive sheet, the greater the capacitance of the capacitor, which may cause high-frequency noise in some cases.

Therefore, it has been proposed to provide a low dielectric constant heat conductive sheet by using a large amount of boron nitride as the heat conductive filler (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 9-12982

Since boron nitride is an expensive heat conductive filler, if it is used in a large amount, the manufacturing cost of the heat conductive sheet will increase. Therefore, it is desired to provide a heat conductive sheet having a low dielectric constant without using boron nitride at all or with a small amount of use.

It is an aspect of the present invention that boron nitride is not used or the amount of use is reduced in the low dielectric constant heat conductive sheet.

The present invention relates to a heat conductive sheet obtained by mixing a hollow filler having a bulk specific gravity of 0.1 to 1.0, which is a specific gravity including gas, and a heat conductive filler into a base material made of an elastomer and molding the mixture into a sheet shape. Because
At least one of the heat conductive fillers contained most as the heat conductive filler is a heat conductive filler other than boron nitride.

In addition, the present invention is a heat treatment obtained by mixing a matrix filler made of elastomer with a hollow filler having a bulk specific gravity of 0.1 to 1.0, which is a specific gravity including gas, and a heat conductive filler, and molding the mixture into a sheet shape. A conductive sheet,
A heat conductive filler other than boron nitride is used as the heat conductive filler.

In the heat conductive sheet of the present invention configured as described above, a hollow filler such as an organic balloon or a fly ash balloon is mixed with a base material made of an elastomer. Since the inside of the hollow filler is a gas, the relative dielectric constant is low, and the relative dielectric constant of the heat conductive sheet can be satisfactorily reduced even if boron nitride is not used or the amount of the boron filler is reduced. Therefore, in the present invention, at least one of the heat conductive fillers most contained as the heat conductive filler is a heat conductive filler other than boron nitride.

Also in this case, since the inside of the hollow filler to be mixed is a gas, the relative dielectric constant is low, and the relative dielectric constant of the heat conductive sheet can be satisfactorily reduced without using boron nitride.
In addition, since gas has low thermal conductivity, there is a concern that the thermal conductivity of the thermal conductive sheet itself may be reduced by mixing a hollow filler having a bulk specific gravity of 0.1 to 1.0. Discovered that heat conductivity can be secured by mixing (using) 200 to 300 parts by weight of a heat conductive filler other than boron nitride with 100 parts by weight of the elastomer as the base material.

Therefore, the thermal conductive sheet of the present invention can achieve both a low relative dielectric constant and a high thermal conductivity without using boron nitride.
Here, when the bulk specific gravity of the hollow filler is 1.0 or less, the dielectric constant can be lowered even when a heat conductive filler other than boron nitride is used.

On the other hand, if it is 0.1 or more, the amount of air present in the heat conductive sheet can be reduced, so that the action as a heat insulating layer is suppressed and the heat conductivity of the heat conductive sheet is not lowered. Moreover, mixing with the elastomer, which is a base material, can be easily performed. Further, since the hollow filler is homogeneously mixed in the obtained heat conductive sheet, there is no difference due to the physical properties of the sheet and the sheet becomes stable.

When the bulk specific gravity of the hollow filler is outside the range of 0.1 to 1.0, it becomes difficult to mix the hollow filler into the base material. As a result, the following two problems become apparent. That is,
(1) The said hollow filler is unevenly distributed in a base material, and each physical property of the heat conductive sheet obtained does not express stably.
(2) Since the outer shape of the filler appears outside the heat conductive sheet in the portion where the hollow filler is unevenly distributed, the adhesion to a heat source such as an electronic component or a heat radiating plate is reduced, and the performance of the heat conductive sheet is reduced. Cannot be demonstrated.

Further, when the mixing amount of the heat conductive filler with respect to 100 parts by weight of the elastomer as the base material is 200 parts by weight or more, it is possible to ensure a heat conductivity equal to or higher than that when boron nitride is used.
On the other hand, when the amount is 300 parts by weight or less, mixing with the elastomer, which is a base material, becomes easy, and thus the formation of the heat conductive sheet can be completed in a short time. In addition, since the heat conductive filler is uniformly mixed in the obtained heat conductive sheet, there is no difference depending on the physical properties (particularly, thermal conductivity) of the sheet, and the sheet becomes stable.

In addition, the applicant of the present invention can reduce the relative dielectric constant of the heat conductive sheet satisfactorily by setting the amount of the hollow filler used to 5 to 80 parts by weight relative to 100 parts by weight of the elastomer, and depending on the sheet shape. We have also found that it becomes easy to mold.

When the amount of the hollow filler used is 5 parts by weight or more, the relative dielectric constant can be lowered even when a heat conductive filler other than boron nitride is used.
On the other hand, when the amount is 80 parts by weight or less, mixing with the elastomer, which is a base material, becomes easy, so that the formation of the heat conductive sheet can be completed in a short time. Further, since the hollow filler is homogeneously mixed in the obtained heat conductive sheet, there is no difference depending on the physical properties (particularly relative dielectric constant) of the sheet, and the sheet becomes stable.

Here, when an organic balloon is used as the hollow filler, the organic balloon has elasticity, so that the balloon is not easily broken during the material kneading, and the hardness of the heat conductive sheet is reduced and compression set is not easily generated. You can also Therefore, it has very good characteristics such as low hardness and hardly causing compression set.

Further, when a hollow filler having a bulk specific gravity of 0.1 to 1.0 is used, the specific gravity is close to the specific gravity of the base material, so that it can be easily mixed with the base material. The filler can be dispersed homogeneously. Therefore, the effect of the hollow filler, such as reducing the relative dielectric constant and ensuring the thermal conductivity, is easily expressed uniformly throughout the heat conductive sheet without being biased toward a part of the heat conductive sheet.

Further, a fly ash balloon may be used as a hollow filler. In this case, since the specific gravity of the fly ash balloon is close to the specific gravity of the base material, it becomes easier to mix and the handleability as a filler is improved. In addition, since fly ash balloons have high strength, there is an effect that the balloons are not easily broken during material kneading.

Here, fly ash balloons are hollow and spherical particles contained in a small amount in fly ash (fly ash) generated from a coal-fired power plant, and are also called “floating ash” and “cenosphere”. The main components are silica and alumina. Fly ash balloons are collected by mixing fly ash with water and collecting only those floating in the water.

In the heat conductive sheet of the present invention, the heat conductivity may be 0.8 W / (m · K) or more, and the relative dielectric constant at 100 MHz may be 4.0 or less. If the mixing amount of the heat conductive filler is adjusted so as to satisfy such characteristics, the heat conductive sheet of the present invention can transfer heat of a heat source such as an electronic component to a radiator very well, It exhibits remarkable characteristics such as being extremely difficult to cause noise.

Furthermore, in the heat conductive sheet of the present invention, the Asker C hardness may be 30 or less. If the mixing amount of the heat conductive filler or the like is adjusted so as to satisfy such characteristics, the heat conductive sheet of the present invention increases the adhesion to a heat source such as an electronic component. It exhibits significant properties that can be transmitted.

Next, an embodiment of the present invention will be described. In the present embodiment, a heat conductive sheet was manufactured by the following manufacturing method. That is, the hollow filler and the heat conductive filler were uniformly dispersed in the liquid silicone by mixing and kneading the hollow filler and the heat conductive filler with the liquid silicone used as the base material elastomer.

Examples of the elastomer that is the base material include acrylic resins and the like in addition to the liquid silicone described above.
In addition to the kneading method using a machine such as a vacuum defoaming mixer, various methods such as extrusion, two-roll, kneader, Banbury mixer and the like can be applied as the mixing method. Of these, kneading using a mixer is desirable in terms of improving workability.

Subsequently, the liquid silicone in which the hollow filler and the heat conductive filler were mixed in this way was formed into a 0.5 mm sheet, and then vulcanized. As the forming method, various methods such as a method of forming using a machine such as a coater, a calender roll, an extrusion, and a press can be applied. Among these, when molding using a coater, it is easy to produce a thin sheet (film), suitable for mass production because of good productivity, and easy to obtain sheet (film) thickness accuracy. desirable.

It describes a material or the like used in respective Experimental Examples 1-4 below.
Liquid silicone (base material): Two-part silicone elastomer (Toray Dow, viscosity 1000 mPa · s at 25 ° C.)
-Thermal conductive filler A: Boron nitride (National Nitride Technologies, average particle size of about 6 μm)
B: aluminum hydroxide (Nippon Light Metal Co., Ltd., average particle size of about 10 [mu] m)
C: Magnesium hydroxide (manufactured by Kamishima Chemical Industry, average particle size of about 1 μm)
D: Alumina (Nippon Light Metal, average particle size of about 12μm)
E: silicon carbide (produced by Showa Denko, the average particle size of about 8 [mu] m)
Hollow filler a: Fly ash balloon (trade name “Phylite”: manufactured by Nihon Philite, particle size distribution 5 to 300 μm, bulk specific gravity 0.65 to 0.85)
b: Organic balloon (trade name “Expansel EMC40 (B)”: manufactured by Nippon Philite, average particle size of about 40 μm, bulk specific gravity of 0.13 to 0.18)
c: Fly ash balloon (Senosphere (a type of fly ash balloon): Sakai Kogyo, average particle size of about 50 μm, bulk specific gravity 0.8))
d: Hollow filler [glass balloon] (manufactured by Potters Barotini, average particle size of about 40 μm, bulk specific gravity of 0.2)
e: Hollow filler [Shirasu Balloon] (Marunaka clay, average particle size of about 40 μm, bulk specific gravity of 0.15 to 0.20)
f: Organic balloon (trade name “Expansel”: manufactured by Nippon Philite, average particle size of about 40 μm, bulk specific gravity of 0.03 to 0.08)
g: Hollow filler [Shirasu Balloon] (manufactured by Shirazuku, average particle size of about 40 μm, bulk specific gravity 1.1)
(Experimental example 1: amount of heat conductive filler mixed)
Next, the heat conductive sheet of the Example was manufactured by specifying the formulation as shown in the left column of Table 1. (Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-4)
Furthermore, the physical properties and evaluation of the heat conductive sheet obtained by forming the liquid silicone kneaded with such a composition into a sheet shape and vulcanizing under a vulcanization condition of 130 ° C., 10 minutes, t = 0.5 mm. These are shown in the right column of Table 1.

In addition, all the blending ratios described in Tables 1 to 3 and 5 below are parts by weight.

Reference examples 1 to 3 were prepared using boron nitride as the heat conductive filler and fly ash balloon (trade name “Phylite”) as the hollow filler. From this, boron nitride, when mixed with 65 parts by weight of elastomer with respect to 100 parts by weight of the elastomer, deteriorated moldability due to the scale-like particle shape, and cannot be molded with 80 parts by weight. The thermal conductivity was 0.90, and the relative dielectric constant was 4.2.

For the evaluation, the results of “formability”, “thermal conductivity”, “relative dielectric constant”, and “Asker C hardness” are comprehensively judged, and the following results are all “○” and “○”. If there is at least one “Δ”, it is “Δ”, and if there is at least one “×”, it is “x”.

In the evaluation method of each result, “good” for the heat conductive sheet of the present invention is “◯”, “appropriate” is “Δ”, and “unsuitable” is “x”. Specifically:
1. Formability ○: Can be suitably formed into a sheet of 0.5 mm. Δ: Can be formed, but heat conductive filler and hollow filler are heterogeneous depending on the site. X: Difficult or impossible to form. Thermal conductivity ○: 0.8 W / (m · K) or more (numerical values required for general thermal conductive sheets)
Δ: Less than 0.8 W / (m · K) Dielectric constant ○: less than 4.0 (typically numerically desirable high frequency noise in suppressing)
Δ: 4.0 or more Asker C hardness ○: 30 or less △: More than 30

As shown in Table 1, it was confirmed that when aluminum hydroxide or magnesium hydroxide was used as the heat conductive filler, molding could not be performed when the mixed amount was 350 parts by weight.

Further, when aluminum hydroxide or magnesium hydroxide is used as the heat conductive filler, the evaluation is “◯” when the mixing amount is 200 to 300 parts by weight, and “△” when the mixing amount is less than 200 parts by weight. confirmed.

For the hollow filler, the evaluation was “◯” or “Δ” regardless of the type of the filler in the range of 5 to 80 parts by weight.
At the same time, the preferred mixing amount of the hollow filler is largely related to its bulk density, and it has been confirmed that 30 parts by weight of a: fly ash balloon exhibits substantially the same effect as 8 parts by weight of b: organic balloon. It was.

From this, it is surmised that the suitable mixing amount of the hollow filler has a positive correlation with the bulk density ratio.
Further, in Example 1-15, the Asker C hardness exceeded 65 and 30, and it was found that the followability to the unevenness of the electronic component and the heat sink during mounting was poor. In contrast, in Examples 1-1 to 1-14, the Asker C hardness is a good value of 30 or less, and the followability to the unevenness of the electronic component or the heat sink is excellent. It has been found that the heat of the source can be transferred very well to the heat sink. In addition, since this compound was mixed and kneaded by hand, in Examples 1-14 and 1-15, the hollow filler was not broken. However, when kneaded using a mixer during mass production, it was broken and the properties deteriorated. Is concerned.
(Experimental example 2: amount of hollow filler mixed)
Next, the heat conductive sheets of the examples were manufactured by specifying the composition as shown in the left column of Table 2 (Examples 1-3, 2-1 to 2-2, Comparative Examples 2-1 to 2- 3) In the same manner as in Experimental Example 1, it was molded into a sheet shape, and a heat conductive sheet was produced under the same conditions. The physical properties and evaluation thereof are shown in the right column of Table 2.

Incidentally, those not using the hollow filler are shown as Reference Examples 4 to 6.

As shown in Table 2, in Reference Examples 4 to 6 in which no hollow filler is mixed, the relative dielectric constant at 100 MHz is 4.7, 5.1, and 5.8, respectively, which is desirable for suppressing high frequency noise. It was far above the 4.0 that was said. In contrast, each of Examples 2-1 and 2-2 in which a hollow filler was mixed had a relative dielectric constant of 3.1 and 4.1, respectively. This is due to the low dielectric constant of the gas contained in the hollow filler. Moreover, since gas has low thermal conductivity, there was a concern about a decrease in thermal conductivity of the thermal conductive sheet itself. However, as apparent from Experimental Examples 1 and 2, the thermal conductivity could be secured.

Further, when the mixing amount of the hollow filler is 5 parts by weight or less (Example 2-2), the relative dielectric constant is 4.1, which is not lower than that close to 4, but exceeds 80 parts by weight (85 parts by weight: Comparative Example 2-1) A heat conductive sheet could not be formed.

Furthermore, when a hollow filler having a bulk specific gravity outside the range of 0.1 to 1.0 was used (Comparative Examples 2-2 and 2-3), no heat conductive sheet could be formed. In any of the comparative examples, it was confirmed from the outside that the hollow filler was unevenly distributed on the upper side (Comparative Example 2-2) or the lower side (Comparative Example 2-3) of the heat conductive sheet.
(Experimental example 3: When oxide (alumina) is used as a heat conductive filler)
Next, the heat conductive sheets of the examples were manufactured by specifying the composition as shown in the left column of Table 3 (Examples 3-1 to 3-10, Comparative Examples 3-1 to 3-6), and The sheet was molded in the same manner as in Example 1 to produce a heat conductive sheet under the same conditions, and the physical properties and evaluation thereof are shown in the right column of Table 3.

Reference Example 7 shows a heat conductive filler using only silicon carbide having a high relative dielectric constant of 9 or more and a fly ash balloon (trade name “Philite”) as a hollow filler.

As shown in Table 3, in Reference Example 7 and Examples 3-1 to 3-6 in which only alumina or silicon carbide was used as the heat conductive filler, the results of using hydroxide as the heat conductive filler (in Experimental Example 1) There was a tendency for the relative dielectric constant at 100 MHz to be higher than in each example. However, by using a mixture of these fillers and boron nitride or aluminum hydroxide having a relatively low relative dielectric constant, the relative dielectric constant can be satisfactorily lowered as shown in Examples 3-7 to 3-10. I was able to.

In Examples 3-9 and 3-10 in which part of the boron nitride is used, the amount used is small (50 parts by weight (about 12% by volume)) (based on 100 parts by weight of the base material). Since it is not necessary to use boron nitride in an Example, the manufacturing cost of a heat conductive sheet can be reduced favorably. In addition, when only the hollow filler is mixed with the liquid elastomer base material, the hollow filler is lifted and it is difficult to mix. Can be manufactured easily.

Furthermore, as shown in Table 4 below, alumina and magnesia have similar dielectric constants. For this reason, it is presumed that the same result can be obtained even if alumina and magnesia are interchanged in the composition of Table 3.

Furthermore, in each of the examples in which aluminum hydroxide and magnesium hydroxide are interchanged in the formulation shown in Table 1, similar results are obtained for the relative dielectric constant. This is obvious from the point that aluminum hydroxide and magnesium hydroxide have the same relative dielectric constant (see Table 4).

(Experimental Example 4: compression set due to the type of hollow filler)
Next, an experiment for investigating the difference in compression set characteristics between the case where the same organic (resin) balloon as in Experiment 1 was used as the hollow filler and the case where the glass balloon similar to that in Example 1-14 was used. Went. In addition, in this experiment, in order to make the mixing amount of a hollow filler uniform, the heat conductive sheet was created by the said method by the mixing | blending shown in following Table 5, respectively.

Then, three 10 mm square samples are prepared from the prepared heat conductive sheet, the thickness is measured with a thickness gauge, the gap is sandwiched with a compression plate at a gap of 0.5 mm, and the sample is then left at room temperature. The change in thickness was measured. Table 6 shows the measurement results.

As shown in Table 6, it was found that when a resin balloon is used as the hollow filler, compression set hardly remains. This is considered to be due to the elasticity of the resin balloon, and the reason why the hardness of the heat conductive sheet is low as described above is also considered to be the same.

Therefore, the thermal conductive sheet of Example 4-1 does not use boron nitride or reduces the amount of usage to achieve both a low relative dielectric constant and a high thermal conductivity. It has extremely good characteristics that it is difficult to cause distortion.

Therefore, in the heat conductive sheet of the present embodiment, the heat of the heat source such as an electronic component can be transmitted to the heat sink very well and stably for a long period of time, and the generation of high frequency noise is suppressed. Can do.

Furthermore, the present invention is not limited to the above embodiment, and can be implemented in various forms without departing from the gist of the present invention. For example, as the elastomer, in addition to liquid silicone, acrylic elastomer such as silicone gel and acrylic gel, and EPDM can also be applied.

As organic balloons, in addition to the above-mentioned EXPANSELL made by Nihon Filament, UCAR and PHENOLIC MICROBALOLONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, and ECCOSPHERES VF-O made by EMERSON & CUMING as urea balloons. , SARAN MICROSPHERES made by DOW CHEMICAL as a Saran balloon, Matsumoto Microsphere made by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTRENENE made by ARCO POLYMERS as a polystyrene balloon, EXPANDABLEPOLE made by BASF WYANDOTE EADS, crosslinked styrene - such as SX863 (P) of Japan Synthetic Rubber Ltd. as acrylic acid balloons, it is possible to use various commercial products.

Further, as in Examples 1-1 to 1-6, 1-13, 2-1, 2-2, 3-1, 3-2, 3-4, 3-5, 3-7, 3-9 When filler, cenosphere, etc., which is an example of a fly ash balloon, is used as the hollow filler, the specific gravity is 0.8, which is close to the specific gravity of the liquid silicone as the base material. In addition to the same effects as those in the above embodiments in which both the dielectric constant and the high thermal conductivity can be achieved, there is also an effect that the base material is easily mixed.

Claims

A heat conductive sheet obtained by mixing a hollow filler having a bulk specific gravity of 0.1 to 1.0 and a heat conductive filler into a base material made of an elastomer, and molding the sheet into a sheet shape,
A heat conductive sheet, wherein at least one of the heat conductive fillers most contained as the heat conductive filler is a heat conductive filler other than boron nitride.
A heat conductive sheet obtained by mixing a hollow filler having a bulk specific gravity of 0.1 to 1.0 and a heat conductive filler into a base material made of an elastomer, and molding the sheet into a sheet shape,
A heat conductive sheet other than boron nitride is used as the heat conductive filler.
The heat conductive sheet according to claim 2, wherein the mixing amount of the heat conductive filler is 200 to 300 parts by weight with respect to 100 parts by weight of the elastomer.
The heat conductive sheet according to any one of claims 1 to 3, wherein a mixing amount of the hollow filler is 5 to 80 parts by weight with respect to 100 parts by weight of the elastomer.
The heat conductive sheet according to any one of claims 1 to 4, wherein the hollow filler is an organic balloon or a fly ash balloon.