JPH0676602B2 - Manufacturing method of germanium molding granules that impart bioactivity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Germanium is said to be effective not only as a semiconductor material but also as a bioactive substance. Not to mention organic germanium,
It has come to be generally said that the germanium element alone is effective when brought into contact with a living body. Therefore, germanium molding particles have come to be marketed. However, since germanium is an extremely brittle substance,
It has the drawback of being crushed and broken when subjected to a strong impact. If the price of germanium is low, it is possible to use new molding particles, but since germanium powder is a very expensive material, breakage of germanium powder is a great loss to the user. The present invention has been made to eliminate such a danger.

That is, an object of the present invention is to provide a manufacturing method capable of supplying germanium compacted particles which impart physiological activity without fear of breakage.

The biological activation effect of germanium is said to be due to the kinetic peculiarity of the electrons outside the germanium atom, and since it is a substance that is non-toxic to the human body, it is taken internally as an organic salt or as mineral water, but it can also be used on skin. It is used in anticipation of the action of the motion singularity of the outer electrons of the atom. Therefore, if one expects such an effect on germanium particles, the germanium in the molded particles should be present only in the surface layer, and the germanium should be present only in the surface layer of the molded particles of other substances. It will be. And so is the fact.

However, although the coating of germanium is performed by sputtering or vacuum evaporation, it is rather difficult to obtain a completely coated one because of the brittleness of germanium, and from the standpoint of the user of the germanium grain, it is much better that the whole grain is germanium. It is also plausible that there will be a desirable psychology.

On the other hand, if the grains of germanium are used alone, they are not only expensive, but as described above, germanium is extremely brittle and easily crushed into powder. The present invention is intended to solve such a contradiction.

The germanium powder used in the present invention is preferably about 200 mesh, and if too fine one is used, the germanium particles in the particles after molding may be separated from each other. This point and the mixing of large powders are not obstacles.

A wide variety of heat-fusible binder materials can be used in the first and second inventions, but the melting point must be lower than the melting point of germanium (958.5 ° C), and the particle size should be as small as possible. It is desirable that the diameter is in the small micron range. From the viewpoint of ease of molding, it is preferable that the melting point be as low as possible, preferably about 600 ° C or lower.

As the heat-fusible binder substance, many inorganic and organic substances can be used. As the metal in the inorganic substance, tin (melting point 231.9 ° C) or its alloy, or zinc (melting point 419)
C.) and its alloys, etc., and fine powders such as low-melting-point glass frit and low-melting-point ceramic powder (such as glaze component) can be used in addition to metals. Further, as the organic binder substance, it is possible to use various thermoplastic polymer powders obtained by emulsion polymerization or fine powders of precondensates of thermosetting resins such as phenol resins.

The amount of the hot-melt binder material used is preferably about 5 to 50% by volume. If it is less than 5%, the germanium particles are not sufficiently bound to each other, and if it is 50% or more, the germanium particles may not contact each other.

In this case, the germanium molded particles can be molded by compressing a raw material heated to a temperature close to the melting point of the binder substance (in some cases, high) with an ordinary pelletizer,
Depending on the case, the raw material is extruded into a rod shape and pelletized,
The pellets may be repressed. Separately from these means, the raw material may be first press-molded and then the molded product may be heated to the melting point of the binder. In any case, as the molding means itself, any means may be adopted. The shape of the molding particles is arbitrary, but it is generally desirable that the shape is a medium-high disk shape having a diameter of 3 to 10 mm.

The molded product obtained as described above can be commercialized as a germanium molded particle as it is, but it is desirable that the molded particle is used as a base and further coated with germanium. The germanium coating may be formed by sputtering or vapor deposition by a usual vacuum vapor deposition means.

Next, the third invention will be described. Fine powder of noble metal having a melting point higher than that of germanium used in this case is a metal such as platinum, palladium, gold, silver, and copper, which is relatively soft and rich in viscosity, and is a metal having excellent electric conductivity,
Of these, silver is the most preferable. The particle size of such a noble metal fine powder may be the same as or smaller than the particle size of the germanium powder. The mixing ratio is about 3 to 30% by volume with respect to the germanium powder, but in reality it is preferably about 8 to 15%. The pressure molding may be carried out at 1-10 t / cm ² by putting the mixed powder in a metal mold.

The pressure molded product is then heated and sintered. The sintering temperature must be lower than the melting point of germanium, and when silver powder is used, it is preferably in the range of 600 to 800 ° C. When the temperature is close to the melting point of germanium, that is, above 900 ° C., the melting point of the alloy portion between the two metals is lowered, so that the molded product is liquefied and developed, and the molten metal may drop. This sintering is usually carried out in a furnace (continuous furnace) after molding, but when the molding pressure is high, it is sufficient to heat the mold itself and then mold at high pressure. Especially when gold or platinum is used, these metals are quite soft, so this method is preferable.

Examples will be shown below.

Example 1 0.2% in 100 parts by volume of germanium powder passing through 150 mesh
A small amount (2 parts by volume) of the alginic acid aqueous solution was sprayed to wet the powder, and 25 parts by volume of tin fine powder obtained by the distillation method was immediately added to and mixed with the powder, followed by press molding with a mold having a diameter of 5 mm and a thickness of 2 mm. This molded product was fired in a furnace maintained at 400 ° C. for 30 minutes and then taken out. The appearance of the obtained molded product was the same as that of the germanium alone, and it had the same degree of viscosity as metallic tin and was difficult to crush. The alginic acid aqueous solution was used as a temporary binder at room temperature,
Moisture was completely volatilized during the firing step, and even if a small amount of carbon was generated during decomposition, carbon did not interfere with the action and effect of the germanium particles because the carbon was electrically conductive.

Example 2 100 parts of the same germanium powder as in the previous example was wetted with a mist, and
Vinyl acetate-polyvinyl alcohol copolymer resin powder obtained by emulsion polymerization of 0 parts by volume was uniformly mixed, and
It was press-molded with the same mold as the previous example heated to 0 ° C. and taken out. The molded product was slightly inferior to the germanium single particle, but the toughness was very large and it was difficult to crush. In this example, the heating need only reach the softening temperature of the resin used, and it is not necessary to melt the resin. Water is added to make the mixing uniform.

Example 3 The same germanium powder as in the previous two examples was added with 15 parts by volume of fine glass powder having a melting point of 560 ° C. and molded in the same manner as in Example 1. This molded product was placed in a furnace and baked at 600 ° C. for 10 minutes. Appearance is Example 1
Although it was better than that obtained in step 1, the crush resistance was slightly inferior. However, the crush resistance is much higher than that of germanium alone.

Example 4 The surface of the one obtained in the above three examples was coated with germanium by vacuum deposition according to a conventional method. The appearance of each of the obtained grains was the same, and there was no difference from the grains of germanium alone.

Example 5 To 100 parts by volume of germanium powder passing through 150 mesh, 8% by volume of silver powder passing through 200 mesh was added and mixed, and this metal mixture powder was put into a mold having a diameter of 6 mm and press-molded at a pressure of 1 ton. Then, a molded product having a diameter of 6 mm and a thickness of 2 mm was obtained. The molded product was taken out and heated and sintered at 730 ° C. in a continuous heating furnace, and the product obtained was extremely tough and hard, and its appearance was completely similar to that of germanium alone. Further, since this molded product had good conductivity, it was felt at the time of use that the properties peculiar to germanium were better exhibited than those using other binders.

Example 6 Germanium particles were produced according to the previous example using gold powder instead of the silver powder of the previous example. In this case, the product had no difference from the previous example in effect, except that the product had a slightly golden luster.

Claims (3)

[Claims] 1. A physiological activity characterized in that fine powder of a heat-fusible binder substance having a melting point lower than that of germanium is added to germanium powder in an amount of 5 to 50% by volume ratio and mixed to heat-mold. Method of manufacturing germanium molding particles to be imparted. 2. A fine powder of a heat-fusible binder substance having a melting point lower than that of germanium is added to germanium powder in an amount of 5 to 50% by volume ratio and mixed, and the mixture is heat-molded. A method for producing germanium molded particles which imparts physiological activity, characterized by vapor deposition. 3. Physiology, characterized in that fine powder of noble metal having a melting point higher than that of germanium is added to germanium powder in a volume ratio of 3 to 30%, mixed, pressure-molded and sintered. A method for producing germanium that imparts activity.