JP3533532B2 - Large particle size aluminum nitride powder and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum nitride powder used as a heat radiation filling material and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, as the degree of integration of semiconductor devices, ICs, and the like has advanced, the amount of heat generated from circuits has also increased, and it is important to efficiently dissipate heat or remove heat. It has become a challenge. Currently, semiconductor devices, ICs, etc. are encapsulated and protected by polymer materials. However, since such a polymer material itself has extremely low thermal conductivity, in order to improve the thermal conductivity, it is necessary to use an inorganic material having high thermal conductivity as a filling material for heat dissipation to form a composite. is there.

Aluminum nitride, which has high thermal conductivity and electrical insulation, is being put to practical use as a substrate material for semiconductors, and is also attracting attention as a heat radiation component material, a heat radiation filling material, and the like.

However, most of the aluminum nitride powders currently on the market are raw material powders for producing a sintered body, and their average particle diameter is as small as 3 μm or less, so that they easily aggregate and are not suitable as a filling material.

The main methods for industrial production of aluminum nitride powder are as follows.

(1) Reductive nitriding method using carbon powder of alumina compound; This method has a slow reaction rate, and therefore, usually only fine powder of raw material for producing a sintered body having an average particle size of less than 2 μm can be obtained.

(2) Direct nitriding method of metallic aluminum powder: In this method, it is generally difficult to control the particle size of the product, and fine powder or whiskers are easily produced depending on the production conditions.

Therefore, when the conventional method as described above is used as it is, it is difficult to obtain a large grain size aluminum nitride powder.

Attempts have been made to improve the method (1) to produce large-grain aluminum nitride. For example, Japanese Patent Laid-Open No. 3-23206 discloses a method of producing a large-sized aluminum nitride powder by combining a carbonization reaction of alumina and a reduction nitriding reaction of aluminum carbide. However, the particle size of the aluminum nitride powder produced by this method is not yet sufficiently large, and it is presumed that the agglomeration of the powder cannot be sufficiently prevented. In addition, this method requires two heat treatments and a complicated gas control under conditions of a considerably high temperature (about 1400 to 1800 ° C.) and a long time (5 hours or more) in the manufacturing process. However, there is also a problem in that mass production is lacking.

[0010]

SUMMARY OF THE INVENTION Therefore, a main object of the present invention is to provide a new method capable of producing aluminum nitride particles having a large particle size under simple operating conditions.

[0011]

The present inventor has conducted extensive studies in view of the problems of the prior art as described above, and as a result,
In the case of directly nitriding metallic aluminum powder to produce aluminum nitride powder, by utilizing nitriding reaction heat generation to simultaneously cause nitriding reaction and sintering to synthesize aluminum nitride coarse powder, and then crushing and classifying Have found that an aluminum nitride powder composed of single particles having a large average particle size can be obtained.

That is, the present invention provides the following large-sized aluminum nitride powder and a method for producing the same.

1. The average particle size (D ₅₀ ) measured by the laser diffraction method is 4 μm or more, and the specific surface area (S ₁ ) calculated from D ₅₀ and the specific surface area (S
The ratio of ₂ ) to S ₁ / S ₂ is 0.3 or more, and a large grain size aluminum nitride powder.

2. The large particle size aluminum nitride powder according to the above 1, wherein the average particle size (D ₅₀ ) measured by a laser diffraction method is in the range of 10 to 50 μm.

3. A total of 30 to 80 parts by weight of metallic aluminum powder and 70 to 20 parts by weight of aluminum nitride powder 1
The mixed granules obtained by press granulating the mixed powder consisting of 00 parts by weight are fired at 800 to 1200 ° C. in a non-oxidizing atmosphere containing nitrogen, and then crushed and classified. Method for producing aluminum nitride powder having a grain size.

In general, in order to synthesize a large particle size aluminum nitride powder, the nitriding reaction product must be grain-grown, that is, the nitriding reaction product must be sintered. For such grain growth or sintering, a high temperature condition of about 2000 ° C. is required. Since the reductive nitriding reaction using alumina is an endothermic reaction, expensive heating equipment from the outside is required to achieve this high temperature condition. As a result, the manufacturing cost of the aluminum nitride powder increases, and mass production becomes difficult. However, in the direct nitriding reaction of metallic aluminum, no external heat supply is necessary,
The reaction temperature reaches about 2000 ° C. only by its own heat of reaction.

In the method of the present invention utilizing the exothermic reaction of metal aluminum powder, the amount of heat generation, that is, the reaction temperature, controls the mixing ratio of the metal aluminum powder in the raw material mixed powder consisting of the metal aluminum powder and the aluminum nitride powder. Therefore, it can be easily controlled.

The metal aluminum powder is a fine powder of high purity (99.5% or more) (for example, an average particle size of 60 μm).
The following level of atomized aluminum powder) is preferable.

The aluminum nitride powder is also fine powder of high purity (99.5% or more) (for example, an average particle size of 10).
A powder of about μm or less) is preferable. In addition, as the aluminum nitride powder, it is possible to add a small amount of an alkaline earth metal (calcium, strontium, barium, etc.), a rare earth metal element (yttrium, lanthanum, cerium, etc.) or a compound thereof (yttria, etc.) if necessary. Can be used. By adding such a third component, the particles are further coarsened by promoting the sintering, and the thermal conductivity of the powder is improved by the oxygen trapping effect. In the present invention, a material containing such a third component is also referred to as aluminum nitride.

In the present invention, the raw material mixture used is
30-80 parts by weight of metal aluminum powder (more preferably 40-70 parts by weight) and aluminum nitride powder 70-2
A total of 100 parts by weight of 0 parts by weight (more preferably 60 to 30 parts by weight) is used as a raw material. If the blending ratio of metallic aluminum is too low, the reaction exothermic amount becomes insufficient, and the formation rate of large particles becomes low, while if the blending ratio of metallic aluminum is too high, the fusion of the metallic aluminum particles with each other occurs. The garment becomes more vigorous, rather the nitriding reaction is hindered and the nitriding rate decreases.

In the direct nitriding reaction, the reaction rate is fast and the residence time of the reactant at high temperature is extremely short (about several minutes to several tens of minutes), so that the solid solution of impurity oxygen in aluminum nitride is small and the thermal conductivity is high. The formation of aluminum oxynitride (AlON), which adversely affects the formation of AlN, is suppressed, but sufficient time cannot be obtained for grain growth of the product. Therefore, in the present invention, in order to allow the reaction to proceed steadily and promote the sintering, it is necessary to shape and granulate the raw material mixture powder consisting of the metal aluminum powder and the aluminum nitride powder. At this time, the reaction sintering rate can be further accelerated by adding a small amount (up to about 7%) of the above-mentioned alkaline earth metal, rare earth metal element and compound thereof. The shape, size, bulk density and the like of the granulated body are not particularly limited, but it is preferable to make pellets having a thickness of about 0.5 to 5 mm and a bulk density of about 30 to 70% of the theoretical density. Granulation is not particularly limited and can be performed by any known method. At the time of granulation, it is preferable not to use a binder in order to avoid mixing of impurities. Since the raw material aluminum powder used in the present invention is a soft material and also exhibits a function as a binder, it is not necessary to add a binder separately.

Next, the granules obtained above are filled in a container such as a crucible and fired at a temperature of about 800 to 1200 ° C. in an inert atmosphere containing nitrogen. The firing time varies depending on the filling amount and the like, but is usually about 10 minutes to 3 hours.

The aluminum nitride sintered body obtained as described above is crushed into powder. The crushing method is not particularly limited, and a vibration mill, a ball mill, a jet mill or the like can be used.

The aluminum nitride powder crushed as described above is then classified, if necessary. For classification, the uncrushed agglomerated powder may be removed by screen classification or the like, and then fine powder of 4 μm or less may be removed by dry classification such as turbo classification or wet classification such as sedimentation. The particle size of the aluminum nitride powder in the present invention is more preferably in the range of about 10 to 50 μm. Further, the aluminum nitride powder in the present invention has an average particle size (D ₅₀ ) of 4 μm or more measured by a laser diffraction method, and a specific surface area (S ₁ ) calculated from D ₅₀ and a specific surface area (S It is essential that the ratio with ₂ ) = S ₁ / S ₂ is 0.3 or more.

As the heat radiation filling material, a single particle powder having a large particle size and a low cohesiveness is generally required. When the average particle diameter (D ₅₀ ) of the aluminum nitride powder is less than 4 μm, the powder easily aggregates. If aggregated particles are formed,
Since it is difficult for the resin to enter the voids in the agglomerated particles, the properties such as the density, strength and thermal conductivity of the molded product are poor. In addition, since the aggregated particles have a large specific surface area and high chemical activity, they are also inferior in chemical stability as a heat radiation filling material. On the other hand, it is difficult to distinguish between the aluminum nitride single particles and the agglomerated particles by the particle size distribution measurement, and it is not possible to judge whether or not they are single particles only by the specific surface area S. Also, with only SEM photographs,
Hard to judge.

However, according to the study by the present inventor, it is possible to evaluate the single particle state of all particles by the above ratio S ₁ / S ₂ regardless of the particle size of the aluminum nitride powder. It was found to be. That is, the ratio S ₁ /
It was found that the larger S ₂ is, the closer the particles are to a single particle state, and that when this ratio is 0.3 or more, particularly 0.4 or more, excellent properties are exhibited as a heat radiation filling material. Was issued. On the other hand, when the ratio S ₁ / S ₂ is less than 0.3 as seen in the existing aluminum nitride powder, a large amount of agglomerated particles are contained, so that the flowability and the filling property are poor, and the filling is poor. The density and thermal conductivity of the resin molding are reduced.

If necessary, the aluminum nitride powder according to the present invention can be subjected to a surface treatment by forming an aluminum oxide film, forming a phosphoric acid type film, or applying a silicon type organic coupling agent. Such a surface treatment achieves the effect that the water resistance of the aluminum nitride powder can be stably maintained even under high temperature and high humidity conditions.

[0028]

According to the present invention, it is possible to mass-produce an aluminum nitride powder having a large average particle size and sphericity (S ₁ / S ₂ ) and excellent fluidity and filling properties at a low price.

When the large-diameter aluminum nitride powder according to the present invention is used as a heat radiation filling material, a heat radiation component having higher density and higher thermal conductivity can be easily obtained.

Further, the large-diameter aluminum nitride powder according to the present invention has a high thermal conductivity, and therefore, it can be advantageously used as an insulating material for sheath heaters and the like.

[0031]

EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention. It goes without saying that the present invention is not limited by such Examples and Comparative Examples.

The physical properties below were measured by the following methods.

(1) The average particle size (D ₅₀ ; μm) is determined by a laser diffraction method using a laser diffractometer (“A-500 type” manufactured by Horiba Ltd.) after ultrasonic dispersion according to a conventional method. It was That is, the particle diameter of particles corresponding to 50% of the total number of particles in the particle size distribution curve is defined as D ₅₀ .

(2) The specific surface area (S ₁ ; m ² / g) was calculated from the following formula.

S ₁ = 6 / (D ₅₀ × 3.26) where 6 is a constant and 3.26 (g / cm ³ ) is the true density of aluminum nitride.

(3) The specific surface area (S ₂ ; m ² / g) is B
Using an ET specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd.), measurement was carried out under the conditions of one-point method and nitrogen exhaust flow rate of 700 ml / min. (4) The density of the molded body (g / cm ³ ) was determined by the Archimedes method using a densitometer (“JL-180 type” manufactured by Nagaseiki Seisakusho Co., Ltd.).

(5) The thermal conductivity (W / mK) of the molded product is
Thermal conductivity measuring device (manufactured by Rigaku Corporation "PCM-FA85"
10B type ") was used to determine by the laser flash method.

Example 1 60 parts by weight of atomized aluminum powder having an average particle size of 26.2 μm was added to 4 parts of aluminum nitride having an average particle size of 6.5 μm.
After adding 0 parts by weight and mixing, the mixture was granulated into pellets having a thickness of about 1 mm. Then, the granulated body is filled in a graphite crucible,
It was fired at 1000 ° C. for 1 hour in a nitrogen atmosphere.

The reaction product obtained was stirred by a vibrating mill for 20 minutes.
After crushing for minutes, turbo classification was performed. As a result of subjecting the obtained powder to X-ray diffraction, it was confirmed that it consisted of an AlN single phase. A SEM photograph showing the particle structure of the obtained AlN powder is shown in FIG. 1, and its characteristics are shown in Table 1.

Then, 80 parts by weight of the powder obtained after classification and an imide-modified epoxy resin powder (trade name "Bestlex"
LS "and 20 parts by weight of Sumitomo Chemical Co., Ltd. were thoroughly mixed by stirring with a ball mill. The obtained mixed sample 0.3
g was heated at 180 ° C. for 25 minutes by a heat molding press machine to obtain a molded body having a diameter of 10 mm × height of 2 mm, and then further heat treated at 200 ° C. for 2 hours to cure. Table 1 also shows the density and thermal conductivity of the obtained molded and cured product.

The density of the imide-modified epoxy resin used was 1.23 g / cm ³ , and the thermal conductivity was 0.23.
It was W / mK.

Example 2 40 parts by weight of atomized aluminum powder having an average particle size of 25.8 μm was added to aluminum nitride 6 having an average particle size of 6.8 μm.
Table 1 shows the powder characteristics of the aluminum nitride powder obtained by adding 0 parts by weight and mixing, and then granulating, firing, crushing and classifying in the same manner as in Example 1.

The powder obtained after the classification was mixed with the resin in the same manner as in Example 1 to obtain a molded body. Table 1 also shows the density and thermal conductivity of the molded and cured product.

Example 3 60 parts by weight of atomized aluminum powder having an average particle size of 26.0 μm was added to 4 parts of aluminum nitride having an average particle size of 6.6 μm.
Powder characteristics of aluminum nitride powder obtained by adding 0 parts by weight and 2 parts by weight of yttria powder having an average particle size of about 1 μm, mixing, and then granulating, firing, crushing and classifying in the same manner as in Example 1. Is shown in Table 1.

The powder obtained after the classification was mixed with the resin in the same manner as in Example 1 to obtain a molded body. Table 1 also shows the density and thermal conductivity of the molded and cured product.

Comparative Example 1 40 parts by weight of atomized aluminum powder having an average particle size of 25.3 μm was added to aluminum nitride 6 having an average particle size of 6.4 μm.
A graphite crucible was filled with a mixed powder to which 0 part by weight was added, and the mixture was baked at 1000 ° C. for 1 hour in a nitrogen atmosphere.

The reaction product obtained was subjected to a vibration mill to 20
After crushing for minutes, turbo classification was performed, and the mixture was mixed with the resin in the same manner as in Example 1 to obtain a molded body. Table 1 also shows the density and thermal conductivity of the molded and cured product.

Comparative Examples 2 to 3 25 parts by weight of atomized aluminum powder having an average particle size of 25.5 μm was added to aluminum nitride 7 having an average particle size of 6.4 μm.
A mixed powder containing 5 parts by weight was filled in a graphite crucible and fired at 1000 ° C. for 1 hour in a nitrogen atmosphere.

The obtained reaction product was crushed in a vibration mill for 20 minutes (Comparative Example 2) and 120 minutes (Comparative Example 3) to obtain an aluminum nitride powder. The powder characteristics of these powders are shown in Table 1.

Further, each of the two kinds of powders obtained above was kneaded into a resin in the same manner as in Example 1 to obtain a molded body. Table 1 also shows the density and thermal conductivity of the molded and cured product.

[0051]

[Table 1] From the results shown in Table 1, when the raw material mixture was not granulated in advance (Comparative Examples 1 to 3), even if the average particle diameter of the obtained aluminum nitride was 4 μm or more (Comparative Examples 1 and 2). ,
The value of S ₁ / S ₂ is less than 0.3, and it is clear that the resin molded body has low density and low thermal conductivity. Further, even if the value of S ₁ / S ₂ is 0.3 or more, the relative density of the resin molded article is low when the average particle diameter of the obtained aluminum nitride is less than 3 μm (Comparative Example 3), The thermal conductivity is also low.

The average particle diameter of the powder used in Comparative Examples 1 to 3 is the aggregate particle diameter.

[Brief description of drawings]

FIG. 1 is an SEM photograph showing a particle structure of an AlN powder obtained according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masatoshi Uenishi 3-6-8, Kutaro-cho, Chuo-ku, Osaka-shi, Osaka Toyo Aluminum Co., Ltd. (56) Reference JP-A-5-270809 (JP, A) JP-A-3-23206 (JP, A) JP-A-5-279002 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C01B 21/072 CA (STN)

Claims (3)

(57) [Claims] 1. A total of 100: 30 to 80 parts by weight of metallic aluminum powder and 70 to 20 parts by weight of aluminum nitride powder.
A large particle size aluminum nitride powder characterized by being crushed and classified after firing a mixed granulated product obtained by press granulating a mixed powder consisting of parts by weight in a non-oxidizing atmosphere containing nitrogen at 800 to 1200 ° C. Manufacturing method. 2. An average particle size measured by a laser diffraction method.
(D ₅₀ ) is 4 μm or more, and the specific surface calculated from D ₅₀
Product (S ₁ ) and specific surface area (S ₂ ) measured by BET method
Ratio = S ₁ / S ₂ is 0.3 or more
A method for obtaining an aluminum nitride powder having a particle size according to claim 1.
Manufacturing method . 3. An average particle diameter measured by a laser diffraction method.
The (D ₅₀ ) is in the range of 10 to 50 μm.
Manufacturing method .