JPS5911627B2 - Surface treated inorganic powder and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface-treated product of inorganic powder and ten methods for producing the same.

Among inorganic substances, inorganic compounds and inorganic mineral substances are generally made into powder by pulverization treatment, and necessary surface treatment is performed depending on the purpose of use. Examples of inorganic compounds used as fillers such as thermoplastic resins and thermosetting resin rubbers or as pigments include calcium carbonate, calcium oxide, calcium hydroxide, aluminum and magnesium-zinc oxides or hydroxides, and carbonates. , silicic anhydride and Ca
, silicates such as Al, M9, and Zn, other titanium oxides, iron oxides, compounds that become various pigments, and inorganic minerals such as marble powder, shell powder, talc, clay, silica, mica,
There are alumina, etc.

They are used according to their respective uses, and pearlite, pumice, dolomite, sintered mud, and other ore powders are used as oil adsorbents after being surface-treated to make them oleophilic. Conventional methods for surface treatment of inorganic substances include, for example, for ultrafine powder calcium carbonate, the surface is treated by coexisting with an aqueous solution of a surface treatment agent when producing lime carbonate by absorbing carbon dioxide gas in an aqueous solution of milky lime. After the lime carbonate is precipitated, it is dried. Alternatively, surface-treated fine powder calcium carbonate is produced by pulverizing and sifting the calcium carbonate. Other untreated powders are impregnated in an aqueous solution of a surface treatment agent and then filtered or dehydrated and dried to produce treated products. 3
5. For surface treatment agents that are poorly soluble in water, the surface treatment agent can be applied to the surface of the inorganic substance by dissolving it in an organic solvent, stirring the powder of the inorganic substance, sprinkling it on the mixture at the same time, or by subsequently removing the solvent by volatilization and drying. Processed products are made by adhering, coating, adsorbing, or bonding.

Further, the patent publication also describes a method of surface treatment by adding and mixing a surface treatment agent during heating using a pen shell mixer or the like for forced mixing. (Special Public Interest Publication 51-12
39). The present inventor has discovered that such inorganic compounds or inorganic mineral substances (
As a result of various studies on surface treatment methods for powders (hereinafter referred to collectively as inorganic substances), it was unexpectedly possible to treat various inorganic substances by adding a surface treatment agent under certain conditions during pulverization and mixing using a pulverizer such as a ball mill. The present invention was achieved by discovering that surface treatment can be carried out simultaneously with pulverization.

In known methods, inorganic substances are subjected to surface treatment after being dried and ground after purification or production, but when a surface treatment agent is mixed under the conditions of impact grinding using a ball mill or the like used in such grinding, the agent is simply We conceived of the possibility of producing so-called surface-treated powder that penetrates into the microscopic voids of the powder, rather than just mixing it, and as a result of painstaking research, we found that, in principle, 0.1 to several percent By adding and mixing a surface treatment agent during the pulverization, the present invention has been completed by arriving at a method in which an inorganic compound to be treated similar to that obtained when the surface is treated separately can be obtained.

In general, the purpose of surface treatment for inorganic substances is 4. In the case of inorganic compounds, the characteristic of hydrophilicity is improved, and the surface that is easily soluble in water or exhibits hygroscopicity is coated with an organic compound to make it hydrophobic. By doing so, it prevents it from dissolving quickly in water and reduces its hygroscopicity.

On the other hand, due to the pulverization of inorganic substances, the fine powders stick to each other due to the secondary cohesive force of the material particles, resulting in deterioration of fluidity such that the fine powders form agglomerates. Surface treatment is performed to prevent a phenomenon in which an aggregate of fine particles is not dispersed into individual particles during use, causing poor dispersion. In addition to the purpose of 4. above, the surface treatment is also carried out to improve the dispersibility of the organic solvent or organic substance that is mixed with the fine powder when the θ fine powder is used.

Furthermore, in addition to improving the dispersibility, various surface treatment agents are being investigated in order to improve the affinity for organic substances. For example, when an inorganic powder is used as a filler to be added to a thermosetting substance such as an epoxy compound or an unsaturated polyester resin as an organic substance, a substance that interferes with the reaction of the cured composition must not be used. However, it is preferable to treat the filler with a type of surface treatment agent that strengthens the bond between the filler and the resin. It is preferable to treat with stearic acid, which is used as a surfactant, but since stearic acid is only partially soluble in polyolefins such as polypropylene, even if it is a thermoplastic resin, it is a surfactant that dissolves in polyolefins. It will be necessary to process it.

Furthermore, by treating with an organic surface treatment agent, the surface of the inorganic powder to be treated becomes easily wetted by other organic solvents, and as a result, it becomes a kind of lipophilic or organophilic solvent.

As a result, when the inorganic powder of the present invention is added to an organic substance, it is rapidly dispersed, and the secondary cohesive force between the dispersed particles is hindered. In general, inorganic suspensions dispersed in organic solvents aggregate and become difficult to settle, but in the case of inorganic blocks to be treated, by measuring the apparent sedimentation volume in the organic solvent, , the degree of lipophilicity improvement can be confirmed. As is clear from the above description, the first aspect of the present invention
The purpose is to provide a surface-treated product with improved performance compared to known surface-treated products of inorganic powder, and the second purpose is to develop a new pulverization method and surface treatment that provides the surface-treated product more simply and quickly. Provide processing methods. Other purposes will become clear from the description below.

That is, the present invention (1) mixes an inorganic granule or powder selected from the following (a) with a surface treatment agent selected from the following (b), and uses a pulverizer selected from the following (c). A surface-treated inorganic powder, which is obtained by surface-treating an inorganic powder while pulverizing it or mixing it with a pulverizer, and a method for producing the same.

(a) The inorganic lumps, granules or powders consist of calcium carbonate, quicklime, gypsum, talc, clay, bentonite, silica, silica, alumina, perlite, titanium oxide or ammonium salts of inorganic acids.

(b) The surface treatment agent is a higher fatty acid, a combination of a higher fatty acid and a petroleum resin, solid paraffin or sulfur, or
Consists of a combination of dotesylsuccinic anhydride and petroleum resin.

(c) The crusher is a crusher, ball mill, colloid mill, or roll mill.

(2) Grinding with a ball mill at 0 to 200°C;
The method according to (1) above, which takes 10 minutes to 20 hours.

It is.

Hereinafter, the structure and effects of the present invention will be explained in detail.

First, the inorganic granules and powders (hereinafter collectively referred to as "inorganic powders, etc.") used in the present invention are inorganic materials that can be pulverized into fine particles, and are mainly water-soluble. This refers to inorganic or water-insoluble inorganic compounds or mineral materials, but it also includes metal materials, glassy materials, or materials that are mostly inorganic materials and contain a small amount of organic matter, as long as they can be crushed using a crusher, etc. as described below. These inorganic powders include calcium monocarbonate, quicklime, gypsum, cement, talc, bentonite, silica, silica, mica, diatomaceous earth, alumina, pumice, perlite, titanium oxide,
There are natural or artificial materials that are insoluble or sparingly soluble in water, react with water, or are hydraulic, such as iron oxide, magnesia, barium oxide, and barium carbonate.

Also, ammonium diphosphate, ammonium sulfate,
There are water-soluble ammonium salts such as ammonium chloride. Furthermore, the surface treatment agent used in the present invention refers to a treatment agent that has a hardness lower than that of the inorganic powder, etc., and can substantially coat the powder, etc. in a powdered state. Regardless of whether it is an organic substance, whether water-soluble or oil-soluble, it may be solid and pulverizable, semi-solid or liquid. However, it does not matter whether or not the powder can be pulverized.

Such surface treatment agents include various animal, vegetable, mineral oils and fats, waxes, resin acids, oleic acids, stearic acids,
Examples include higher fatty acids such as palmitic acid, sulfur, etc., but the present invention is not limited to these as long as the implementation and purpose of the present invention can be achieved. The surface treatment of the present invention is carried out by placing inorganic powder, etc. in a pulverizer, mixing pulverizer, etc., and supplying the surface treatment agent used in the present invention all at once, in portions, or continuously within a certain period of time. Grinding and simultaneous surface treatment are carried out at 200° C., usually from 15° C. to 100° C., for 10 minutes to 20 hours, often for 1 hour to 6 hours.

Pressure is increased or reduced as necessary, and the process is carried out in an inert gas atmosphere if necessary.

The mixing and grinding machines used are usually ball mills, roll mills,
In addition to fine pulverizers such as colloid mills and vibration mills, various types of coarse grinders such as crushers may be used depending on the physical properties of the inorganic powder used, the surface treatment agent used in the present invention, and the degree of treatment required. A crusher can also be used, and the aforementioned crusher, coarse crusher or mixer can also be used in combination. If the surface treatment agent that is generally used is in large quantities or in solid form, it is best to mix it all at once or in portions relatively early in the pulverization of the inorganic powder. When the amount is small or in liquid form, it is effective to mix continuously at a relatively late stage of the pulverization. The surface treatment of the present invention is essentially different from known surface treatment methods in that it is carried out simultaneously while the object to be treated is being pulverized.

Therefore, the effects of the present invention cannot be obtained by mere mixing unrelated to pulverization. Therefore, the characteristics of the surface treatment of the present invention are as follows: 4. As a result of the surface treatment agent being immediately applied to the fresh cross section of the object to be crushed, adsorption or bonding is considered to be extremely good in many cases; ◎It is presumed that the impact pressure applied during pulverization causes the surface treatment agent to penetrate deep into the fine pores of the porous object after being treated. Therefore, if the ratio of the surface treatment agent to the inorganic powder used in the present invention is 0.2% or less, especially 0.1% or less, the effect is ineffective or extremely insufficient. It's hot,
It is preferably 0.3% or more, preferably 0.75% or more. Also,
When the amount used exceeds 1%, an amount of 1% or more and 50% or less, preferably 2% or more and 30% or less can be adopted depending on the intended degree of imparting hydrophobicity or lipophilicity. Furthermore, two or more types of surface treatment agents may be used independently, or the two or more types may be uniformly mixed in advance or mixed and melted before use. The effects of surface treatment confirmed by experimental examples of the present invention will be explained.

Regarding the method for determining the strength or degree of surface treatment, if the surface of the inorganic powder object to be treated is hydrophobic, the following is attached when the surface of the inorganic powder object is made hydrophobic using stearic acid as a surface treatment agent. do. When the surface treatment rate or intensity is low, when the treated object is put into water, it absorbs into the water relatively quickly and dissolves or settles. On the other hand, when the surface treatment of the present invention is carried out to an extent exceeding the necessary and sufficient proportion, the surface of the powder produced from the inorganic powder becomes hydrophobic, and as a result, the powder produced from the inorganic powder, which originally has a higher specific gravity than water, It is immiscible with water, and as a result of its surface not being wet by water, it does not sink in water and exhibits the property of floating on top of water. As described above, the method of the present invention provides powders of inorganic substances with various degrees of surface treatment.

For example, using pulverized calcium carbonate with an average particle size of 1.8μ, 0.1, 0.2, 0.5, 0.75
, 1, 2, 5, 10% by weight of stearic acid and pulverized and mixed in a ball mill to perform the surface treatment of the present invention.
When added to a large amount of water, the 1 and 0.2% treated products float on the water for about 1 to 3 minutes, but when stirred, they settle like untreated calcium carbonate powder, but the 0.5% treated products 1%, 2%, 5%, 10 within 5-10 minutes until settling
As the percentage and amount of treatment increases, the time it takes for the treated calcium carbonate to settle becomes longer, and products treated with 5% and 10% float on the water and do not sink in the water even after one hour. On the other hand, the treated calcium carbonate powder of the present invention adsorbs dioctyl phthalate DOP, but in order to examine its adsorption power, it was first immersed in excess DOP, and then the excess DOP was removed by 40%.
The amount of DOP adsorbed on the treated calcium carbonate powder was measured by removing it with a centrifuge at 00 rpm width D rotation, as shown in Figure 1. is less, 0.75
% stearic acid treatment, it can be seen that approximately half of the surface exhibiting adsorption properties for calcium carbonate was surface treated (adsorbed) with stearic acid.

Furthermore, in the case of stearic acid treatment of 1 to 2 (L), it is determined that the DOP adsorption capacity has decreased to A because the surface that exhibits adsorption capacity adsorbs stearic acid. In other words, the surface of calcium carbonate is By pulverizing and mixing using a ball mill or the like in the presence of the surface treating agent according to the invention, the surface treating agent is adsorbed not only by mixing but also by crushing or impact onto a new surface or the surface of a conventional powder. As a result, the DOP adsorption capacity is thought to have decreased depending on the degree of surface treatment.Stearic acid, which is a surface treatment agent, is a long-chain fatty acid, and in extreme cases it forms a monomolecular film on the surface of inorganic materials. is formed and covers the surface of inorganic substances, and has the property of becoming watery. However, when treated with 1 to 5% stearic acid, the stearic acid adsorbed on the surface of calcium carbonate becomes It is thought that as a result of making the surface water repellent, when added to water, it does not sink in water but floats.

Furthermore, when we measured the angle of repose, which is a factor that measures the fluidity of powder based on the cohesive force between particles, it was found that calcium carbonate without surface treatment had an angle of repose of 51 (average particle diameter 1.8μ pulverized amount). However, the amount of calcium carbonate that was surface-treated with 2% stearic acid decreased to 49 squares, and the fluidity of the powder was improved.

FIG. 2 shows the results of measuring the dispersion sedimentation rate in DOP of the surface-treated calcium carbonate powder of the present invention using the aforementioned calcium carbonate powder having an average particle size of 1.8 μm and stearic acid. In general, the finer the particles, the better they are dispersed in organic solvents, and therefore the dispersion and sedimentation rate in organic solvents is lower. The dispersion sedimentation rate has the property of becoming slower. As the amount of stearic acid used as the surface treatment agent of the present invention increases from O to 0.1% and 0.2%, the sedimentation rate becomes slower, and after leaving it for one day, no clear difference appears in the amount treated. However, the difference becomes more pronounced as it is left for 2 to 4 days, and after 4 days, the untreated product has almost completely settled.

In addition, the apparent sedimentation volume of the 0.75% treated product is 95%.
It was confirmed that the greater the amount of the surface treatment agent, the more the lipophilicity of the calcium carbonate powder was significantly improved depending on the surface treatment and its degree. As described above, the present invention is characterized by adding a surface treatment agent during pulverization and mixing using a ball mill, etc.
This relates to a method for treating the surface of an inorganic substance powder and an object to be treated, which makes the surface of an inorganic substance powder water repellent, and as a result of using a surface treatment agent of a certain percentage or more, the inorganic compound is submerged in water. It has the effect of allowing inorganic compounds with heavy specific gravity to float on water without getting wet when added.

At the same time, by improving water absorption and hygroscopicity, improving the flow characteristics of inorganic fine powder, and making it lipophilic,
Mixing of various organic solvents and oils can be done quickly. As a result, the materials treated according to the invention can not only be used as oil absorbers, but also as fillers or additives with improved mixing and dispersibility due to the improved wetting properties of many other plastic processing raw materials. This makes manufacturing possible. As described above, the method of the present invention enables surface treatment of inorganic powder at the same time as pulverization or by mixing using a pulverizer, which simplifies the manufacturing method of surface-treated powder. be converted into

Furthermore, the product of the present invention is a surface-treated product that is used as an oil-absorbing filler or additive, and the degree of oil-absorbing dispersibility, etc. thereof is adjusted depending on the purpose of use. The present invention will be described below with reference to Examples.

Examples 1 to 7 2.5 kg of commercially available heavy calcium carbonate with an average particle diameter of 1.8 μm was placed in a insect ball mill with an outer diameter of 20 crn0, and at the same time 15 12u1 porcelain balls and 20 8 mm porcelain balls were placed. 2.5g of each (1) stearic acid,
(2) 5.09, (3) 12.59, (4) 18.29
(5) 259, (6) 509, and (7) 1259 were added, and the mixture was placed in a rotating machine and subjected to ball milling at room temperature for 6 hours.

After 1 hour, scrape off the calcium carbonate adhering to the wall of the ball mill to ensure sufficient mixing during pulverization.
After a period of time, the balls were removed to obtain surface-treated calcium carbonate powders (Examples 1 to 8). When each of the 59 powders of the samples in Examples 1 and 2 was poured into a 100 ml beaker containing 50 ml of water, the powders of Examples 1 and 2 floated on the water immediately after being added, but when stirred gently with a glass rod, they floated after 1 to 3 minutes. It settled and dispersed in the water.

Example 3 (0.5% treated product) sedimented and dispersed in water after 5 to 10 minutes, but Examples 4, 5, 6, and 7 all floated on water, and Example 4 did so after 10 to 30 minutes. In Examples 5 to 7, the floating state was maintained on the water for more than 1 hour. Also, Examples 1 to 6
Figure 1 shows the results of measuring the amount of dioctyl phthalate DOP absorbed in the treated products. Even in the 0.1% treated product, the amount of DOP absorbed is smaller than that of the untreated product, indicating that the amount treated is large. The amount of DOP absorbed decreased as the amount increased, and at 0475%, the amount of DOP absorbed was halved, and when it reached 2% or more, the amount of DOP absorbed decreased to approximately A. Measurement of DOP absorption was done using cylindrical paper (constant weight) with '50f! After adding 200 m of 10D0P to the top and letting it adsorb to calcium carbonate and leaving it for a day to remove most of the DOP,
Centrifuged for 30 minutes in a 00rpn1 rotary centrifuge, powder 1
The increased amount of DOP attached per 009 was taken as the respective DOP absorption amount. If stearic acid, which is a surface treatment agent, is simply mixed with powder, stearic acid is
It was thought that the DOP absorption amount of calcium carbonate that was treated with stearic acid rather than being separated with P would not change, or that the DOP absorption amount would increase due to the increased surface area due to the pulverization process. The above results are considered to be due to the fact that stearic acid is adsorbed on the surface of the pulverized material, resulting in a decrease in the apparent amount of adsorption. 1 each in a 50ml graduated cylinder
．． Figure 2 shows the results of measuring the apparent volume of calcium carbonate after 24 hours (A), 48 hours (03), and 96 hours (C) when each of the 59 samples was added and stirred. DOP
(sedimentation rate of treated calcium carbonate).

From the results, the amount of stearic acid used is 0.1% to 0.7
The sedimentation rate in DOP, which is a polar organic solvent, gradually became slower as the concentration increased to 5%, and reached a maximum value at 0.75%. It has been found that the surface treatment of the present invention significantly improves the lipophilicity of finely ground calcium carbonate with respect to organic liquids as a result of the surface treatment of the present invention.

On the other hand, untreated fine powder heavy calcium carbonate has poor fluidity due to the secondary cohesive force between the fine particles, but the 2% surface-treated product obtained in Example 6 clearly improved the fluidity of the powder. The angle of repose of calcium carbonate powder without surface treatment is 5.
1 theory, whereas the angle of repose obtained in Example 6 is 4
9 It was hot Example 8 Exactly the same as Example 6 2
.

5kg of heavy calcium carbonate with an average particle size of 1.8μ
Calcium carbonate, which had been surface-treated by adding stearic acid (No. After mixing, when press molding was performed for 170' ClO, the molded product had a shore hardness D of 87, an isot impact notched strength of 4.1 kg/CTll, and the resulting molded product had gloss. Surface-treated commercially available precipitated calcium carbonate (trade name,
The appearance was similar to that in the case of using Shiroenka).

O Example 9 500c of quicklime 3009 with 309 stearic acid
E capacity porcelain ball mill and 100m 1 diameter porcelain ball mill 2
The powder was placed in a rotary machine together with 15 ball mills having a diameter of 0 and 6111, and pulverized using a ball mill for 6 hours in the same manner as in Examples 1 to 7.

When the resulting quicklime powder was added to a large amount of water, the entire amount floated up, the quicklime did not react with water, and no heat was generated even after 6 hours.

Also, when water was added to the powder, it became water droplets and did not react with the quicklime. Therefore, when 100 cc of an aqueous solution containing 5% of a surfactant (commercial product Emar) is added to the surface-treated quicklime of 509, the powder becomes a mixed slurry that can be wetted with water and mixed, and after 15 minutes it heats up to 50°C. Quicklime reacted and became milk of lime. Example 10 2.5kg of quicklime was placed in a 31 volume ball mill with 50f of stearic acid! At the same time, ball milling was performed for 6 hours in a Shiji ball mill.

The obtained quicklime to be treated floated when added to water, did not cause irritation when touched by hand like normal lime, and was easy to handle.

1f! in water obtained by adding 0.5g of soybean oil to 1j of water and stirring! When the quicklime to be treated was added, the oil was adsorbed to the quicklime, and the oil-adsorbed lime adhered to the vessel wall and a portion sank into the water.

After standing overnight, the aqueous layer was removed, the oil was extracted with hexane, and the hexane extract was determined from the distillation residue, yielding 0.0049.

On the other hand, the quicklime that adhered to the wall of the vessel and settled out easily dried when left to stand and became a lump that could be powdered. It can be used as an oil absorbent or an oil scavenger on water. Example 11 Natural rubber 3009, zinc amount 1.59, stearic acid 0.
59, vulcanization accelerator DMl. 29 Similarly, the accelerator Dl. 29
, Sulfur 7.51 The 300% modulus of the test piece obtained by heating sample 3009 of Example 10 at 141°C for 40 minutes using a Banbury mixer and press molding was 6.6.
It exhibited k9/Cl tensile strength of 160 kg/d and elongation of 650%.

Example 12 25g of talc (commercially available average particle size 7μ) powder 2.5k9
of stearic acid and saturated petroleum resin 259 were added and ball milled in a 31 volume ball mill at room temperature for 6 hours.

After mixing 2 kg of talc surface-treated with the obtained stearic acid and petroleum resin with 8 kg of polypropylene resin pellets (melt index 4 to 6) in a rotary mixer (tumbler), L/D2O was 30 m. After melt extrusion using a diameter extruder, a test piece molded product was again created using a 5-ounce injection molding machine.The resulting product was a glossy filler molded product, with talc uniformly mixed with the polypropylene, indicating that it had not been processed. No phenomena such as flaking or stickiness were observed on the surface even after being left to warm.

For comparison, when talc without surface treatment is used, it is 201! Even when extruded using an extruder, the polypropylene and talc did not mix sufficiently, and the talc and polypropylene came out separately, making it impossible to mold using the molding machine used in this experiment. Furthermore, the surface-treated talc in this experiment had the property of floating on water.

Example 13 As a lipophilic example, alumina (average particle size 40-60
μ Showa Denko H-10) 20kg of 209 stearic acid, saturated petroleum resin (argon) 20f! At the same time, ball milling was performed for 6 hours in a 31-volume ball mill.

The resulting powder floated on the water when added to a large amount of water.

The alumina to be treated was treated in the same manner as in Example 12, and was then treated with medium-low pressure polyethylene (MI5, Chitsuso Co., Ltd. product M8O5).
After mixing 8 kg with the polyethylene in a tumbler and extruding it into pellets using a 30 mm diameter extruder, a test piece was made again using a 5 oz injection molding material. Obtained. Example 14 Alumina (Showa Denko product H-10), reagent S! 02. Sintered clay (clay baked at 300℃ for 6 hours in an electric furnace)
1 each for iron oxide, titanium oxide, and antimony oxide
Ball milling was carried out with 0% stearic acid and porcelain balls in a 500 cc ball mill.

All of the obtained inorganic substance powders to be treated floated when added to a large amount of water and were water repellent.

Example 15 α-gypsum CasO4・IH2O (Chitsuso Co., Ltd. product KP
a) 2.5 kg was milled with stearic acid 509 (2%) in a 32 volume ball mill for 6 hours.

The resulting gypsum is water-repellent and does not sink when added to water.
When the surface-treated gypsum powder is placed in 50 cc containing a surfactant (Emano (Ha) 2f, manufactured by Kao Soap Co., Ltd.), it becomes wet with water and becomes a slurry. 2CII of this slurry
A molded product was made by putting it into a mold of L x 2 cm x 8 cm and curing it. The bending strength of the obtained molded product was 63 kg/Cd, which was somewhat lower than that of a regular product, but it was dipped in an acrylic acid ester emulsion 20 (:Ff) solution for about 1 minute and then dried. In the water permeability test (water resistance test when the lower part 5mm is immersed in water), the water absorption amount for 2 hours was 0.8%, and the water immersion bending strength was 45k9/CIL, making it a gypsum product with improved water resistance. I was able to make it. Example 16 Commercially available cement 2.5k9 was pulverized with stearic acid 509 in a 31 volume ball mill for 6 hours.

The obtained cement showed water repellency and floated on water and did not react with water as it was, but by adding a small amount of surfactant (Kao Soap Co., Ltd., Emar 201), it became wettable with water. , it became a hardened cement body. Example 17 Crystalline powders of monoammonium phosphate and diammonium phosphate were each subjected to ball milling with 10% stearic acid.

None of the resulting surface-treated powders dissolved in water even when added to cold water, nor did they settle or dissolve even after 1 hour. When added to a large amount of hot water (90°C), ammonium phosphate would sink in the water, but it would become fluffy particles and be suspended in water, making it possible to control the solubility of ammonium phosphate. Example 1
8 25 kg of perlite and solid paraffin (melting point 70°C) 5
09 was placed in a 32-volume ball mill, and 35 g of porcelain balls were placed in a rotary machine to perform ball milling.

The powdered pearlite thus obtained floated on water and could be used as an oil absorbent. Example 19 2.5 kg of perlite (lightweight aggregate) and 7.5 kg of stearic acid.
59 solid paraffin was placed in a 31 volume ball mill and subjected to ball milling together with a porcelain ball mill.

The resulting powder floated on water and could be used as an oil absorbent. Example 20 Silica 84 containing trace amounts of fulumina, magnesia and iron oxide
Stearic acid 6f11 solid paraffin 149 was added to 2 kg of slag containing % to 95%, and rotary pulverization mixing was performed for 6 hours with 35 porcelain balls in a 31 volume ball mill.

The obtained mineral surface treatment floated on the water when added to a large amount of water.

This product can be used as an oil remover on water surfaces. Example 21 Clay was placed in an electric furnace at 300°C and dehydrated and sintered.
After 2 hours, let it cool and then weigh 2.5 kg and add palmitic acid 6.
9 solid paraffin 14f! and pulverized and mixed for 6 hours with 35 magnetic balls in a 31-volume ball mill.

When the resulting fine powder clay was added to a large amount of water, it floated to the surface and did not sink even after one day. Example 22 7.5f of stearic acid in 2.5kg of calcium carbonate with an average particle size of 1.8μ! was added and rotary pulverized and mixed for 2 hours with 35 porcelain balls in a 31-volume ball mill, and then sulfur 509 was added and pulverized and mixed again for 6 hours.

The obtained calcium carbonate is surface treated with sulfur,
It was a water-repellent, lipophilic calcium carbonate that floated like water for over an hour. This product can also be used as an oil remover on water surfaces. Example 23 A solid powder obtained by melting and cooling 10 g of dodecenyl succinic anhydride in saturated petroleum resin 259 was added to 2.5 kg of calcium carbonate with an average particle size of 1.8 μm in a 31-volume ball mill. Magnetic ball 35
The calcium carbonate obtained from step 1, which was rotary pulverized and mixed for 6 hours, was water-repellent and lipophilic calcium carbonate that floated on water for more than 1 hour.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between the amount of surface treatment agent and the amount of DOP absorbed in the surface-treated calcium carbonate powder of the present invention.

Claims (1)

[Scope of Claims] 1. Inorganic granules or powder selected from the following (a) are mixed with a surface treatment agent selected from the following (b) to produce the following (
A method for surface treatment of inorganic powder, characterized in that the surface treatment is performed while pulverizing with a pulverizer selected from c) or mixing with a pulverizer. (a) The inorganic granules or powder are calcium carbonate,
Consists of quicklime, gypsum, perlite, talc, bentonite, silica, silica, alumina, titanium oxide or ammonium salts of inorganic acids. (b) The surface treatment agent consists of a combination of a higher fatty acid, a higher fatty acid and a petroleum resin, a higher fatty acid and solid paraffin, a higher fatty acid and sulfur or dodecyl succinic anhydride, and a petroleum resin. (c) The crusher is a crusher, ball mill, colloid mill, or roll mill. 2 Grinding with a ball mill at 0°C to 200°C, 1
2. A method according to claim 1, wherein the duration is 0 minutes to 20 hours.