JPS63201047A - Minute material with characterized coating layer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] "Industrial Application Field" This invention relates to a micromaterial having a characteristic-imparting coating layer that can be used as a filler/composite material for resins and metals, a ceramic molding material, etc. .

"Prior Art and Problems" In recent years, with the development of the electronics field, aerospace field, etc., different demands than before have been placed on industrial materials. The material properties required in such situations include electrical properties such as insulation, conductivity, dielectricity, and magnetism, high strength,
Mechanical and thermal properties such as high toughness, wear resistance, heat resistance, heat insulation, thermal conductivity, and low thermal expansion, biocompatibility, biochemical properties such as catalysts, optical properties, etc. , and that have several of these characteristics are needed, and the level of demand is becoming more sophisticated year by year.

Therefore, recently, many attempts have been made to create materials with functions and strength that cannot be obtained from the base material alone by filling resins and metals with various particles, whiskers, and flakes and creating composites. For example, by mixing ceramic or metal particles, whiskers, or flakes into resin, which is an organic material, it is possible to improve the disadvantages of resin such as poor moisture resistance and high coefficient of thermal expansion, or to improve the disadvantages of resin, which is originally an insulating material. They can be made to have electrical conductivity, or conversely, they can be made to have even higher insulating properties, or they can have increased mechanical strength.

Alternatively, it is also possible to fill a metal with the particles or the like to form a composite, thereby strengthening the base metal or increasing its wear resistance.

Therefore, as an example, a case of a resin for semiconductor encapsulation, which is one of the typical examples of resin filled with ceramic particles, will be described. As can be seen from the fact that semiconductor encapsulation originally began with ceramics, ceramics have better properties for semiconductor encapsulation than resins, but their moldability is poor, making them easier to mold, lower cost, and less expensive. Resins that are suitable for mass production have gradually come into use, and now 90% of semiconductor encapsulation is done using resin. However, although it is called resin, 70% of its constituent material is ceramic filler, and it can be said to be a composite material of resin, which is an organic material, and ceramic, which is an inorganic material. Semiconductor encapsulation resins are required to have excellent moisture resistance, low thermal expansion, high purity, and high thermal conductivity, and to achieve these properties, ceramic particles are mixed into the resin. be.

By the way, although there are many ceramics that satisfy the characteristics required for mixing with resin, only silica is actually used. The reason for this is that it is very compatible with resin materials such as silica or epoxy resin, and research and development of technology for incorporating coupling agents, etc. is also progressing. This is also to ensure that strength and other properties are not adversely affected.

Furthermore, silica or a natural product of high purity can be obtained, and when fused and vitrified, it has a very low coefficient of thermal expansion.

Resin encapsulation has become so popular because of the function of silica, but recently there has been a strong demand for high thermal conductivity for semiconductor encapsulation resins, and in response to this, silica has become more popular than silica. There is a movement toward using silicon carbide and silicon nitride as fillers, which have good conductivity.

However, both of them have poor compatibility with conventional epoxy resins, and their properties cannot be improved by surface treatment.Kneading them with resins has an adverse effect on the hardening of the resin, and the resin may not harden or its mechanical strength may deteriorate even after hardening. In addition, if a special resin that is compatible with silicon carbide or silicon nitride is used, it would be very expensive, and silicon carbide may have poor insulation properties. , these could not be used, or even if they could be used, the expected properties could not be obtained. Furthermore, although metal materials are optimal in terms of high thermal conductivity, they cannot be used as insulating materials because of their electrical conductivity. These are just a few examples, but there are many other fields in which a material is used as a material because it has excellent properties but other properties are contrary to the desired properties of the material. There are many cases where it cannot be used, narrowing the range of material selection. This is something that all materials researchers have experienced, and if we can solve this problem, we will be able to obtain excellent materials with a wide variety of properties.

"Means for Solving the Problems" The present invention forms at least one coating layer on the surface of a micromaterial main body whose external shape is a particle, whisker, or flake using a substance having characteristics that the micromaterial main body does not have. It is a microscopic material made of , and the unique structure of this microscopic material solves the problems of conventional Fuki.

The function of the microscopic material according to the present invention will first be described using the semiconductor encapsulating resin as an example. Among the micromaterials of the present invention, when the coating layer is silica and the micromaterials are silicon carbide or silicon nitride, when used as a filler for semiconductor encapsulation resin, the surface is silica, so it is difficult to use conventionally used epoxy resin. It has very good compatibility with silica, can be handled in the same way as silica, and can yield good resin moldings without any adverse effects on the resin.

Moreover, after being kneaded with resin and molded, it imparts the characteristics of internal particles (high thermal conductivity), and since silica is a material with good insulation, the electrical insulation properties of silicon carbide are also improved, resulting in high thermal conductivity. A resin molded body for semiconductor encapsulation was obtained. In addition, as a filler having higher thermal conductivity than silica, among the products of the present invention, particles having a coating layer of silica and an interior of boron nitride, magnesia, or beryllia can be used, and good results have been obtained. Furthermore, if it is desired to obtain a resin molded article under high heat, it is also possible to use particles of the present invention in which the coating layer is made of silica and the interior is made of aluminum. this is,
This is because aluminum, which is a metal, can also be used satisfactorily as a resin for semiconductor sealing, which is an insulating material, due to the insulating effect of the silica layer. As another example of the use of the product of the present invention, by using particles whose coating layer is glassy silica and whose interior is crystalline silica, a filler with less mold wear than crystalline silica can be obtained. Furthermore, in order to obtain a filler with less mold wear, this becomes possible by using particles whose coating layer is a cured resin.

As mentioned above, the present invention relates to a micromaterial characterized by having at least one coating layer on its surface, and the feature of the product of the present invention is that each micromaterial main body has at least one coating layer. By having layers, it has the characteristics of microscopic materials or several types of substances. In the past, it has been common practice to form a film on the surface of a molded object, but the present invention is the first to provide a material in which each microscopic material has a film on its surface.

In addition, the product of the present invention has a coating made of polymer that allows the internal substances to seep out due to its osmotic effect, or protects the internal substances for a certain period of time, and then prevents the internal substances from flowing out due to the destruction of the coating. It is essentially different from microcapsules,
Each microscopic material is a kind of functional composite material that has both the physical properties of the internal substance and the physical properties of the material forming the external film at each microscopic material level. Of course, this is completely different from minute materials such as particles, which are simply a mixture of two or more types of substances. As a result of intensive research, we were able to produce microscopic materials characterized by having at least one coating layer on the surface in a monodisperse state without agglomeration in each of the following combinations. That is, first, the micromaterial main body (internal substance) is silicon (Si),
Titanium (Ti), zirconium (Zr), germanium (Ge), iron (Fe), aluminum (Ari), magnesium (Mg), calcium (Ca), sodium (Na), boron (B), tin ( Sn), barium (Ba
), gallium (Ga), zinc (Zn), indium (I
n), tantalum (Ta), yttrium (Y), thorium (Th), beryllium (Be), copper (Cu), lead (Pb), oxides of each of the above elements, nitrides of each of the above elements,
Carbide of each of the above elements, calcium carbonate (CaCO3),
Mullite (3Al2O3" 25tOt), mica, Schinel (MgO-Al2O6), carbon (C), barium carbonate (BaCOs), barium titanate (BaTiOa)
, Ba1TiO4), polyethylene, polypropylene,
Polystyrene, polyvinyl chloride, ABS resin, AS resin, methacrylic resin, polyamide, polyacetal, polycarbonate, PET resin, PBT resin, polyphenylene ether, fluororesin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, At least one member selected from the group consisting of silicone resin, polyurethane, natural rubber, natural rubber derivatives, butadiene-based synthetic rubber, olefin-based synthetic rubber, polysulfide-based synthetic rubber, and chlorosulfonated polyethylene; Silicon (S i), titanium (T i),
Zirconium (Zr), germanium (Ge), iron (F
e), aluminum (A12), magnesium (Mg)
, calcium (Ca), sodium (Na), boron (
B), tin (Sn), barium (B a), gallium (G
a), zinc (Zn), indium (In), tantalum (Ta), yttrium (Y), thorium (Th),
Beryllium (Be), copper (Cu), lead (Pb), oxides of the above elements, nitrides of the above elements, carbides of the above elements, carbon (C), polystyrene, ABS resin, methacrylic resin, vinyl acetate resins, cellulose resins, polycarbonates, polysulfones, silicone resins, natural rubber derivatives, butadiene synthetic rubbers, olefin synthetic rubbers, chlorosulfonated polyethylene, phenolic resins,
This combination is at least one selected from the group consisting of urea resin, melamine resin, xylene resin, polyester resin, epoxy resin, polyurethane resin, polyimide, and ASA resin.

In addition, the thickness of the coating layer in the present invention is from o, oot microns to several tens of microns, and the size of the micromaterial body is 0.
．． It ranges from 0.01 micron to several hundred microns.

Further, the shape of the particles can be either angular (crushed) or spherical.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

"Example Summer" A micromaterial whose main body is silicon carbide (SiC) particles and a coating layer of silica was prepared, and this was blended with a resin etc. according to the blending ratio shown in (Blending Example ■). The mixture was kneaded for 5 minutes using hot rolls to obtain a molding material. Molded products using this material had good mechanical strength. Table 1 shows its physical property values (thermal conductivity, coefficient of thermal expansion).

"Example 2" A micromaterial whose main body is silicon nitride (SiJ4) particles and a coating layer of silica was prepared, and this was compounded according to the compounding ratio shown in (Formulation Example 1), and then heated with a hot roll. using 5
The mixture was kneaded for a minute to obtain a molding material.

Molded products using this material had good mechanical strength. Its physical property values (thermal conductivity, coefficient of thermal expansion) are also shown in Table 1'.

"Example 3" A micromaterial whose main body was boron nitride (BN) particles and a coating layer of silica was prepared, and this was blended according to the blending ratio shown in (Formulation Example 1), and heated with a hot roll. The mixture was kneaded for 5 minutes to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 4" A micromaterial whose main body is magnesia (MyO) particles and a coating layer of silica is prepared, and this is applied to a resin etc. (Formulation Example 1)
) and kneaded for 5 minutes using hot rolls to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 5" A micromaterial whose main body is beryllia (Bed) particles and a coating layer of silica is prepared, and this is made into resin etc. (Formulation Example 1)
The mixture was blended according to the blending ratio shown in , and kneaded for 5 minutes using hot rolls to obtain a molding material.

Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 6" A micromaterial whose main body is zirconia (ZrOt) particles and a coating layer of silica is prepared, and this is blended with resin etc. according to the blending ratio shown in (Blending Example 1), and it is heated. The mixture was kneaded using a roll for 5 minutes to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 7" A micromaterial whose main body is calcium carbonate (CaCO3) particles and a coating layer of silica was prepared, and this was coated with resin etc. (
They were mixed according to the mixing ratio shown in Formulation Example 1) and kneaded for 5 minutes using hot rolls to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 8" A micromaterial whose main body is calcia (Cab) particles and a coating layer of silica is prepared, and this is made into resin etc. (Formulation Example 1)
The mixture was blended according to the blending ratio shown in , and kneaded for 5 minutes using hot rolls to obtain a molding material.

Molded products using this material had good mechanical strength. Its physical properties (thermal conductivity, coefficient of thermal expansion) are the same (
It is shown in Table 1.

"Example 9" The micro material body is mullite (3AI2tO, 2SiOt)
A fine material with a coating layer of silica is prepared from particles, and this is blended with resin etc. according to the blending ratio shown in (Blending Example 1),
This was kneaded for 5 minutes using hot rolls to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 10" A micromaterial whose main body is mica particles and a coating layer is silica is prepared, and this is blended with resin etc. according to the blending ratio shown in (Formulation Example 1), and then it is heated using a hot roll. The mixture was kneaded for 5 minutes to obtain a molding material. Molded products using this material had good mechanical strength. The physical property values (thermal conductivity, thermal expansion coefficient) are also shown in Table 1.

"Example 11" A micromaterial whose main body was spinel (Mli'0-AI2tOJ particles and a coating layer of silica) was prepared, and this was blended with resin etc. according to the blending ratio shown in (Blending Example 1). The mixture was kneaded for 5 minutes using hot rolls to obtain a molding material. Moldings made using this material had good mechanical strength. Its physical properties (thermal conductivity, coefficient of thermal expansion) are also shown in Table I.

"Example (2)" A micromaterial whose main body is carbon particles and a coating layer of silica is prepared, and this is blended with resin etc. according to the blending ratio shown in (Formulation Example 1), and then heated with a hot roll. The material was kneaded for 5 minutes to obtain a molding material.The material was molded into a molded product with good mechanical strength.The physical properties (thermal conductivity, coefficient of thermal expansion) are shown in Table 1. Indicated.

"Example 13" A micromaterial whose main body is titanium dioxide (Tidy) particles and a coating layer of silica is prepared, and this is blended with resin etc. (according to the compounding ratio shown in the blending example), and heated. A molding material was obtained by kneading for 5 minutes using a roll.The molded material was molded using this material and had good mechanical strength.The physical properties (thermal conductivity, coefficient of thermal expansion) were the same. It is shown in Table 1.

"Example 14" A micromaterial whose main body is aluminum (A12) particles and a coating layer of silica is prepared, and this is blended with resin etc. according to the blending ratio shown in (Blending Example 1). The mixture was kneaded for 5 minutes using hot rolls to obtain a molding material. Products molded using this material had good mechanical strength, and the physical properties (thermal conductivity, coefficient of thermal expansion) are shown in Table 1.

(Hereinafter, blank spaces) (Blend Example 1) (Comparative Example 1) In the above (Blend Example 1), molded products were obtained in the same manner as in each of the above Examples, using fused silica as the filler and using the same blend ratio. The physical property values of this molded article are also shown in Table 1.

(Comparative Example 2) A molded article was obtained in the same manner as in each of the Examples above using crystalline silica as a filler and the same compounding ratio in the area (composition PII). The physical property values of this molded article are also shown in Table 1.

The dimensions of the microscopic material body of each filler used in each of the above examples are approximately 30 microns in diameter for particles, approximately 2 microns in diameter for whiskers, approximately 30 microns in length, and approximately 30 microns in diameter for flakes. The thickness of the layer was approximately 0.3 microns, and the outer shape was angular (crushed) and spherical. Further, the dimensions of the filler used in each comparative example were approximately the same as the dimensions of the micromaterial main body in each example.

(Hereinafter, blank space) [Table 1] As is clear from Table 1 above, “Example 1, 2.3.4
．． 5.8.11.12.13.14'', a resin molded body with better thermal conductivity than (Comparative Example 2) was obtained. "
In "Example 6.7.9", a resin molded article having better thermal conductivity than (Comparative Example 1) was obtained.

Furthermore, in "Example 10", a resin with high strength was obtained due to the shape of the filler. From these, “Examples 1 to 9
．． It can be seen that the resin molded bodies obtained in Examples 11 to 14 have high thermal conductivity and good insulation, and can be used in various fields including resins for semiconductor encapsulation. In addition, “Example 10
It can also be seen that by mixing the fine material used in Example IJ with other Examples such as Example IJ, it is possible to obtain a resin molded body with good thermal conductivity and high strength.

"Example 15" Among the micromaterials of the present invention, the coating layer is CaO and SiO2, and the micromaterial main body is alumina, but when only the surface part is fired, the surface part is so-called cementitious and the inside is alumina. can get. When this is reacted with water, each particle is bonded by a hydration reaction of the surface layer to obtain a molded body. In this molded body, only the grain boundary portion contains CaO, Sin, and 1
Since it is a three-phase product with most of the remainder being alumina, it becomes a molded product with excellent heat resistance and thermal conductivity, and can be molded into any shape by mixing it with water and pouring it into a mold. Therefore, it is possible to obtain a refractory with better formability and lower cost than conventional alumina refractories.

[Example 16J Among the micromaterials of the present invention, if the coating layer is 5 inches and the micromaterial body is alumina, it will be used as a rubber filler.
The silica phase on the surface blends very well with rubber and imparts the heat resistance, high thermal conductivity, and abrasion resistance of alumina, making it possible to obtain heat-resistant and abrasion-resistant rubber products.

"Example 17" Among the micromaterials of the present invention, if one in which the coating layer is 5 iOz and the micromaterial body is alumina is used as a filler for a fluororesin, the heat resistance of the fluororesin can be further improved.
Since wear resistance is also improved, resin molded products can be used for parts that are exposed to high temperatures and undergo severe wear, such as bearings. Further, in this case, if a spherical minute material is used, the surface of the resulting resin molded product can be made smooth, and it can be made suitable for bearings.

"Example 18" Among the micromaterials of the present invention, if one in which the coating layer is 5 iOz and the micromaterial body is alumina is used as a filler in a paint,
Due to the silica phase on the surface, it is compatible with the resin that is the paint, and a weather-resistant and abrasion-resistant paint can be obtained without adversely affecting its fluidity or hardening condition.

"Example 19" Among the micromaterials of the present invention, one in which the coating layer was vitreous silica and the micromaterial main body was crystalline silica was used as a filler for an epoxy resin. As a result, the mold wear during molding was reduced to 273 when using crystalline silica, and the thermal conductivity of the molded product was almost the same as when using crystalline silica.

"Example 20" Among the micromaterials of the present invention, the coating layer is a cured epoxy resin,
A micromaterial whose main body was crystalline silica was used as a filler for epoxy resin. As a result, mold wear during molding was further reduced than in "Example 19".

“Example 21” Conventionally, when sintering silicon nitride, MipO, Y, 0
3°A (!203) is mixed as an additive to improve the difficulty of sintering silicon nitride. However, in this case, a problem occurs that the additive is not mixed uniformly. Therefore, the present invention Among these fine materials, the coating layer is MgO and the fine material body is Si, N, or the coating layer is Y2O3 and A.
If hO3 whose main body is Si3N+ is used as a raw material for sintering, a very good sintered body can be obtained.

"Example 22" 100 pieces of crushed epoxy resin cured product with average particle size of 20μ
9 and a tin alkoxide hydrolysis solution containing 10% by weight of Sn02 and a hydrolysis rate of 100%, and drying the mixture at 150°C with a spray dryer to form a coating layer of S.
No. 2, particles with epoxy resin inside were obtained. At this time, the thickness of the coating layer was 0.6 microns.

"Effects of the Invention" As described above, the micromaterial having the characteristic-imparting coating layer according to the present invention has both the characteristics of the surface coating layer and the properties of the micromaterial itself, and the coating layer and the micromaterial By changing the combination of constituent materials of the main body, it is possible to simultaneously satisfy the required characteristics of 2M or more, and it can be applied to various uses such as fillers, composite materials, and ceramic molding materials.

Claims (3)

[Claims] (1) Characteristics characterized in that at least one coating layer is formed on the surface of a micromaterial main body whose external shape is a particle, whisker, or flake using a substance having characteristics different from those of the micromaterial main body. A micromaterial with an applied coating layer. (2) The coating layer is made of silicon (Si), titanium (Ti)
, zirconium (Zr), germanium (Ge), iron (
Fe), aluminum (Al), magnesium (Mg)
, calcium (Ca), sodium (Na), boron (
B), tin (Sn), barium (Ba), gallium (Ga
), zinc (Zn), indium (In), tantalum (T
a), yttrium (Y), thorium (Th), beryllium (Be), copper (Cu), lead (Pb), oxides of the above elements, nitrides of the above elements, carbides of the above elements, carbon ( C), polystyrene, ABS resin, methacrylic resin, vinyl acetate resin, cellulose resin, polycarbonate, polysulfone, silicone resin, natural rubber derivative, butadiene synthetic rubber, olefin synthetic rubber, chlorosulfonated polyethylene, phenolic resin, urea Resin, melamine resin, xylene resin, polyester resin, epoxy resin, polyurethane resin, polyimide, AS
A micromaterial having a characteristic-imparting coating layer according to claim 1, which is at least one selected from the group consisting of A resins. (3) The fine material main body is made of silicon (Si), titanium (T),
i), zirconium (Zr), germanium (Ge),
Iron (Fe), aluminum (Al), magnesium (M
g), calcium (Ca), sodium (Na), boron (B), tin (Sn), barium (Ba), gallium (
oxides of each of the above elements, Nitride of each of the above elements, carbide of each of the above elements, calcium carbonate (CaCO_3), mullite (3Al
_2O_3・2SiO_2), mica, spinel (Mg
O・Al_2O_3), carbon (C), barium carbonate (B
aCO_3), barium titanate (BaTiO_3, B
a_2TiO_4), polyethylene, polypropylene,
Polystyrene, polyvinyl chloride, ABS resin, AS resin, methacrylic resin, polyamide, polyacetal, polycarbonate, PET resin, PBT resin, polyphenylene ether, fluororesin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, Claim 1: At least one member selected from the group consisting of silicone resin, polyurethane, natural rubber, derivatives of natural rubber, butadiene-based synthetic rubber, olefin-based synthetic rubber, polysulfide-based synthetic rubber, and chlorosulfonated polyethylene. A micromaterial having a characteristic-imparting coating layer as described in .