JP7038452B1 - Method for manufacturing surface-treated particles and surface-treated particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide surface-treated particles capable of achieving excellent water repellency.
SOLUTION: The surface-treated particles of the present invention are an inorganic particle, a first modifier supported by the inorganic particle, and a second modification supported by the inorganic particle supporting the first modifier. The first modifier includes a fatty acid having a carbon atom number of 18 or more and a melting point of 50 ° C. or more, a fatty acid metal salt having a carbon atom number of 12 or more, and a full ester ester wax. The second modifier is one or more selected from the group consisting of, and the second modifier is one or more of fatty acid metal salts having 12 or more carbon atoms.
[Selection diagram] FIG. 4

Description

The present invention relates to surface treated particles.

As the inorganic particles used in cosmetics and the like, in order to improve properties such as water repellency, inorganic powder such as silica coated with a surface treatment agent, that is, surface treatment particles may be used.

As the surface-treated particles, for example, Patent Document 1 describes hydrophobicized plate-shaped inorganic particles in which the surface of the plate-shaped inorganic particles is coated with a cured product of a room temperature curable silicone composition.

Japanese Patent Application Laid-Open No. 2021-104906

An object of the present invention is to provide surface-treated particles capable of achieving excellent water repellency.

According to one aspect of the present invention, it is composed of inorganic particles, a first modifier supported by the inorganic particles, and a second modifier supported by the inorganic particles supporting the first modifier. The first modifier is one or more selected from the group consisting of a fatty acid having 18 or more carbon atoms and a melting point of 50 ° C. or more and a fatty acid metal salt having 12 or more carbon atoms. When the second modifier is one or more of the fatty acid metal salts having 12 or more carbon atoms and the first modifier is a fatty acid metal salt, the first modifier and the first modifier are used. 2 Surface-treated particles different from the modifier are provided.

According to still another aspect of the present invention, the inorganic particles, the first modifier supported by the inorganic particles, and the second modifier supported by the inorganic particles supporting the first modifier. A method for producing surface-treated particles comprising the above, which is a first step of heating and mixing the first modifier and the inorganic particles to obtain a first treated product, wherein the first modifier is carbon. The first step and the second modification selected from the group consisting of a fatty acid having 18 or more atoms and a melting point of 50 ° C. or more and a fatty acid metal salt having 12 or more carbon atoms. In the second step of mixing the agent and the first treated product to obtain a second treated product, the second modifier is one or more of fatty acid metal salts having 12 or more carbon atoms. When the first modifier is a fatty acid metal salt, a method for producing surface-treated particles different from the first modifier and the second modifier is provided.

According to the present invention, surface-treated particles capable of achieving excellent water repellency are provided.

A photomicrograph obtained by imaging inorganic particles with a scanning microscope. A micrograph obtained by imaging the first processed object with a scanning microscope. A photomicrograph obtained by imaging a processed product obtained by mixing the first processed product and the first component shown in FIG. 2 with a scanning microscope. A micrograph obtained by imaging the surface-treated particles according to Example 2-71 with a scanning microscope. A photomicrograph obtained by imaging Zn laurate with a scanning microscope. A photomicrograph obtained by imaging Mg stearate with a scanning microscope.

Hereinafter, embodiments of the present invention will be described.
<Surface-treated particles>
The surface-treated particles according to the embodiment of the present invention include inorganic particles, a first modifier supported by the inorganic particles, and a second modifier supported by the inorganic particles supporting the first modifier. It is equipped with.
According to one example, the surface treated particles can be used in cosmetics such as foundations and emulsions. According to another example, the surface-treated particles can be used for quasi-drugs such as antiperspirants. According to yet another example, the surface-treated particles can be used as additives such as resins and paints.

Inorganic particles consist of, for example, silicate minerals, silicic acid compounds, calcium compounds, barium compounds, titanium compounds, zinc compounds, or two or more of these. Silicate minerals are, for example, sericite, talc, mica or zeolite. The mica may be synthetic mica or natural mica. The silicic acid compound is, for example, silica. Silica may be spherical or amorphous. The calcium compound is, for example, calcium carbonate. Calcium carbonate is, for example, light calcium carbonate. The light calcium carbonate may be spherical or spindle-shaped. The barium compound is, for example, barium sulfate. The titanium compound is, for example, titanium oxide. The zinc compound is, for example, zinc oxide.

Preferably, the inorganic particles consist of one or more selected from the group consisting of silicate minerals, silicic acid compounds, calcium compounds, barium compounds, titanium compounds and zinc compounds.
More preferably, the inorganic particles consist of one or more selected from the group consisting of sericite, talc, mica, zeolite, silica, calcium carbonate, barium sulfate, titanium oxide and zinc oxide.

The diameter of the inorganic particles is not limited to a range from fine particles of 0.1 μm to flakes and granular products of several mm.

The first modifier is selected from the group consisting of fatty acids having 18 or more carbon atoms and a melting point of 50 ° C. or more, fatty acid metal salts having 12 or more carbon atoms, and full ester ester waxes. Is 1 or more. The first modifier includes fatty acids having 18 to 22 carbon atoms, a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, and a metal salt of oleic acid. It is preferably one or more of a metal salt of stearic acid, a metal salt of behenic acid, a triglyceride, and a full ester of pentaerythritol. According to one example, the first modifier is a fatty acid having 18 or more carbon atoms and a melting point of 50 ° C. or higher. According to another example, the first modifier is a fatty acid metal salt having 12 or more carbon atoms. According to yet another example, the first modifier is a full ester ester wax.

The fatty acid preferably has 28 or less carbon atoms, and more preferably 22 or less. According to one example, fatty acids have carbon atoms in the range of 18 to 22.

The melting point of the fatty acid is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. The fatty acid preferably has a melting point of 50 ° C. or higher, more preferably 60 ° C. or higher.

The fatty acid is preferably a linear fatty acid. The surface-treated particles provided with the linear fatty acid as the first modifier can realize particularly excellent water repellency. Further, the fatty acid is preferably a saturated fatty acid. Surface-treated particles containing saturated fatty acids as the first modifier can achieve particularly excellent water repellency.

The fatty acid is, for example, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid or two or more of them. The fatty acid is preferably stearic acid or behenic acid.

The fatty acid metal salt is, for example, lauric acid metal salt, myristic acid metal salt, palmitic acid metal salt, stearic acid metal salt, oleic acid metal salt, 12-hydroxystearic acid metal salt, behenic acid metal. A salt or a metal salt of montanic acid, or two or more of these. The fatty acid metal salt is preferably at least one of lauric acid metal salt, myristic acid metal salt, palmitic acid metal salt, stearic acid metal salt, oleic acid metal salt, and behenic acid metal salt. .. Further, unlike the fatty acid, the fatty acid metal salt may be a metal salt of an unsaturated fatty acid.

The fatty acid metal salt is, for example, fatty acid zinc, fatty acid calcium, fatty acid magnesium, fatty acid aluminum, fatty acid sodium, fatty acid lithium, fatty acid potassium or two or more of them.

The fatty acid metal salt preferably has 28 or less carbon atoms, and more preferably 22 or less. The fatty acid metal salt preferably has 12 or more carbon atoms.

The fatty acid metal salt preferably has a melting point of 300 ° C. or lower, and more preferably 260 ° C. or lower. The fatty acid metal salt preferably has a melting point of 60 ° C. or higher, more preferably 80 ° C. or higher.

Fatty acid metal salts include, for example, zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc oleate, zinc behenate, aluminum stearate, potassium stearate, calcium stearate, sodium stearate, magnesium stearate, etc. Lithium stearate, or two or more of these. Fatty acid metal salts include zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc oleate, zinc behenate, aluminum stearate, potassium stearate, calcium stearate, sodium stearate, magnesium stearate and stearic acid. It is preferably 1 or more selected from the group consisting of lithium.

The ester wax of a full ester is an ester obtained by reacting 80% or more of the hydroxyl groups of a polyhydric alcohol with the carboxyl group of a carboxylic acid.

Multivalent alcohols are divalent or higher alcohols. The polyhydric alcohol is, for example, a trihydric, tetravalent or hexavalent alcohol.
The polyhydric alcohol is, for example, glycerin or pentaerythritol.

The carboxylic acid is, for example, a monovalent or divalent carboxylic acid.
The carboxylic acid is, for example, stearic acid or 12-hydroxystearic acid, or two or more of them.

Preferably, the ester wax of the full ester is at least one of the triglyceride and the full ester of pentaerythritol.

The triglyceride is, for example, glycerin tri 12-hydroxystearate.
The full ester of pentaerythritol is, for example, pentaerythritol tetrastearate.

The ester wax of the full ester is preferably at least one of glycerintri 12-hydroxystearate and pentaerythritol tetrastearate.

The amount of the first modifier is preferably in the range of 0.01 parts by mass to 100 parts by mass, preferably 0.1 parts by mass to 45 parts by mass, when the amount of the inorganic particles is 100 parts by mass. It is more preferable to be within the range. When the amount of the first modifier is within the above range, particularly excellent water repellency can be realized.

The second modifier is one or more of fatty acid metal salts having 12 or more carbon atoms. As the second modifier, the above-mentioned fatty acid metal salt which is the first modifier can be used.

When the first modifier is a fatty acid metal salt, the first modifier and the second modifier are different.

Preferably, the second modifier is one or more of a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, a metal salt of stearic acid, a metal salt of oleic acid and a metal salt of behenic acid. .. More preferably, the second modifier is zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc oleate, zinc behenate, aluminum stearate, potassium stearate, calcium stearate, sodium stearate, One or more selected from the group consisting of magnesium stearate and lithium stearate.

The median diameter of the fatty acid metal salt as the second modifier is preferably in the range of 0.1 μm to 50 μm, and more preferably in the range of 0.1 μm to 20 μm. The median diameter described here and later is a median diameter obtained by using a laser diffraction type particle size distribution measuring device.

The amount of the second modifier is preferably in the range of 0.1 part by mass to 45 parts by mass, and is 0.1 part by mass to 25 parts by mass, when the amount of the inorganic particles is 100 parts by mass. It is more preferable to be within the range. When the amount of the second modifier is within the above range, a particularly excellent tactile sensation can be realized.

The second modifier may contain two or more fatty acid metal salts having 12 or more carbon atoms.

In the above surface-treated particles, the first modifier forms a continuous layer on the surface of the inorganic particles, but a partially discontinuous layer may be formed. The second modifier can be present in various forms.
For example, one or more of the second modifiers may form a layer. This layer may be a continuous film or a discontinuous film. If it is a discontinuous film, it may be a granular layer of aggregates of particles. In the granular layer, the particles constituting the granular layer may or may not be bonded to each other. Further, when the second modifier is a combination of a plurality of compounds, each of the plurality of compounds may form a layer.

One or more of the second modifiers may not form a layer. For example, the particles made of a certain modifier may be attached to the inorganic particles without forming a layer, and the particles made of another modifier directly or indirectly supported by the inorganic particles or It may be attached to the layers or to both of them.

According to one example, the first modifier forms a layer supported by the inorganic particles, and the second modifier forms a supported granular layer on top of the layer of the first modifier. According to another example, the first modifier forms a layer supported by the inorganic particles, and the second modifier is the particles supported on the layer of the first modifier.

<Manufacturing method of surface-treated particles>
Hereinafter, an example of a method for producing surface-treated particles will be described.

First, a first step, that is, a step of heating and mixing the above-mentioned first modifier and the above-mentioned inorganic particles to obtain a first treated product is performed. Mixing is carried out by a dry method. A high speed mixer can be used for mixing. The high-speed mixer is, for example, a Henschel mixer (manufactured by Nippon Coke Industries) or a super mixer (manufactured by Kawata Co., Ltd.).

According to one example, the first step is performed by mixing the inorganic particles and the first modifier without using a solvent. This mixing is performed while heating. This heating is performed at a temperature equal to or higher than the melting point of the first modifier.

When the first modifier is heated at a temperature equal to or higher than the melting point, the heating temperature is preferably + 10 ° C. or lower, more preferably + 5 ° C. or lower with respect to the melting point of the first modifier. Increasing the heating temperature tends to cause particle agglomeration. The heating time is preferably in the range of 1 minute to 30 minutes, more preferably in the range of 5 minutes to 15 minutes. After heating, the first treated product is preferably cooled to a temperature below the melting point of the first modifier, for example, −10 ° C. or lower with respect to the melting point of the first modifier.

When the first step is performed as described above, when the first modifier contains a fatty acid metal salt, the median diameter of the fatty acid metal salt particles is preferably in the range of 0.1 μm to 50 μm, preferably 0.1 μm. It is more preferably in the range of to 20 μm. When the first modifier contains a fatty acid, the diameter of the fatty acid particles is preferably in the range of 0.01 mm to 30 mm, more preferably in the range of 0.05 mm to 15 mm. When the first modifier contains ester wax, the diameter of the ester wax particles is preferably in the range of 0.01 mm to 30 mm, more preferably in the range of 0.01 mm to 1 mm. The diameters described here and later are diameters obtained by using a dry sieve.

According to another example, the first step is carried out using a solution obtained by dissolving the first modifier in a solvent. For example, a powder composed of inorganic particles is flowed, and the above solution is added little by little to the powder. The above solution is added so that the inorganic particles maintain the powder state. The solvent may be volatilized at normal temperature and pressure, or may be volatilized by at least one of heating and depressurization. When heating is performed, the heating temperature may be lower than the melting point of the first modifier and may be higher than the melting point of the first modifier.

The solvent is, for example, water or alcohol. The amount of the solvent is preferably in the range of 100 parts by mass to 10000 parts by mass, and preferably in the range of 400 parts by mass to 1900 parts by mass, when the amount of the first modifier is 100 parts by mass. Is more preferable.

Next, a second step, that is, a step of mixing the first treated product and the above-mentioned second modifier to obtain a second treated product is performed. Mixing is carried out by a dry method. Further, the above-mentioned high-speed mixer can be used for mixing. The second step is performed, for example, at a temperature below the melting point of the second modifier, for example, at room temperature.

When the second modifier is a combination of a plurality of compounds, the compounds may be mixed with the first treated product at the same time. Alternatively, one of these compounds may be mixed with the first treated product, and then the treated product obtained thereby may be mixed with the other one of the above compounds, and so on.

The above is an example of a method for producing surface-treated particles.

<Effect>
The surface-treated particles described above can achieve excellent water repellency. The present inventors consider that one of the reasons why the surface-treated particles can realize excellent water repellency is as follows. All of the above-mentioned first modifiers have a polar group. In the surface-treated particles, the first modifier is oriented so that these polar groups face the inorganic particles. In this structure, the hydrocarbon group, which is a non-polar group, is located outside the polar group to enhance water repellency. Further, the second modifier also has a non-polar group, and for example, by being present on the first modifier or in the discontinuity of the layer made of the first modifier, the water repellency is further improved. Increase. Therefore, the above-mentioned surface-treated particles can realize excellent water repellency.

In addition, the above-mentioned surface-treated particles can realize an excellent tactile sensation. The tactile sensation is, for example, a stretchy sensation, a moist sensation, or a silky sensation. The present inventors consider that one of the reasons why the surface-treated particles can realize an excellent spreading feeling, smooth feeling or moist feeling is as follows. The above-mentioned second modifier has high crystallinity. According to one example, when surface-treated particles using a modifier having a flat or similar particle shape of the second modifier are placed on the skin, friction between the surface-treated particles against each other is generated. It is small and easily spreads on the surface of the skin. Therefore, the above-mentioned surface-treated particles can realize an excellent spreading feeling or a smooth feeling. On the other hand, when surface-treated particles using a modifier having a plate-like or similar shape are placed on the skin, the friction between the surface-treated particles is large. Therefore, the above-mentioned surface-treated particles can realize an excellent moist feeling.

By the way, as described above, as the surface-treated particles, those in which the inorganic particles are coated with a composition containing silicone are known. However, since silicone is a highly moisturizing oil, it is resistant to sebum and water, and the remaining silicone that cannot be washed completely blocks the pores, which may cause rough skin and hair loss. On the other hand, the surface-treated particles described above do not have silicone on their surface, that is, the first and second modifiers. Therefore, rough skin derived from silicone cannot occur.

On the other side, it is known to use plastic particles. However, since plastic particles are not decomposed in nature, pollution spreads throughout the ecosystem through the food chain, and there is concern that it will have harmful effects on living organisms. On the other hand, since the above-mentioned surface-treated particles do not contain plastic particles, the harmful effects caused by the above-mentioned plastic particles cannot occur.

Examples are described below.
<Preparation of surface-treated particles>
<Example 1-1>
First, 100 parts by mass of inorganic particles and 6 parts by mass of the first modifier were mixed while heating to obtain a first treated product. Sericite was used as the inorganic particles. Sericite has a median diameter of 13 μm. Stearic acid was used as the first modifier. Stearic acid has 18 carbon atoms and a melting point of 70 ° C. The diameter is about 0.5 mm. Heating was performed at 75 ° C. for 10 minutes.

Next, the obtained first treated product and 6 parts by mass of the second modifier were mixed at room temperature to obtain a second treated product. Magnesium stearate was used as the second modifier. Magnesium stearate has 18 carbon atoms. It has a melting point of 135 ° C. and a median diameter of 10 μm.
The obtained second treated product was used as the surface-treated particles according to Example 1-1.

<Examples 1-2 to 1-35 and Comparative Examples 1-1 to 1-93>
In Examples 1-2 to 1-35 and Comparative Examples 1-1 to 1-93 by the same method as described for Example 1-1 except that the composition was changed as described in Tables 1 to 10. Such surface-treated particles were obtained. However, in Examples 1-16 and 1-24 to 1-27, and Comparative Examples 1-57 to 1-64 and 1-77 to 1-81, while heating the inorganic particles and the first modifier. Instead of mixing to obtain the first treated product, water is volatilized by heating and mixing the solution obtained by dissolving the first modifier in 54 parts by mass of water and the inorganic particles to obtain the first treated product. rice field.

<Example 2-1>
The surface-treated particles according to Example 2-1 were obtained by the following method. In the following method, a combination of the two compounds was used as the second modifier. One compound is used as the first component, and the other compound is used as the second component.

First, 100 parts by mass of inorganic particles and 6 parts by mass of the first modifier were mixed while heating to obtain a first treated product. As the inorganic particles, the same ones as the sericite used in Example 1-1 were used. Stearic acid was used as the first modifier. Heating was performed at 75 ° C. for 10 minutes.

Next, the obtained first treated product and 3 parts by mass of the first component are mixed at room temperature, and then the obtained treated product and the second component are mixed at room temperature to obtain a second treated product. Obtained. Zinc laurate was used as the first component. Zinc laurate has a melting point of 130 ° C. and a median diameter of 16 μm. Zinc stearate was used as the second component. Zinc stearate has a melting point of 130 ° C. and a median diameter of 10 μm.
The obtained second treated product was used as the surface-treated particles according to Example 2-1.

<Examples 2-2 to 2-66 and Comparative Examples 2-1 to 2-89>
Examples 2-2 to 2-66 and Comparative Example 2-by the same method as described for Example 2-1 except that the compositions were changed as described in Tables 11 to 18 and Tables 20 to 29. Surface-treated particles according to 1 to 2-89 were obtained. However, in Examples 2-42 to 2-54, and Comparative Examples 2-33 to 2-45 and 2-62 to 2-73, the inorganic particles and the first modifier are mixed while being heated and first. Instead of obtaining the treated product, water was volatilized by heating and mixing the solution obtained by dissolving the first modifier in 54 parts by mass of water and the inorganic particles to obtain the first treated product.

<Examples 2-67 to 2-74>
As the inorganic particles, the compounds shown in Table 19 were used instead of sericite, behenic acid was used instead of stearic acid as the first modifier, and magnesium stearate was used instead of zinc stearate as the second component. However, by the same method as described in Example 2-1 except that the mass part of the first modifier, the mass part of the first component, and the mass part of the second component were changed as shown in Table 19. Surface-treated particles according to Examples 2-67 to 2-74 were obtained.
For the surface-treated particles according to Example 2-71, scanning micrographs were obtained for each manufacturing process. The acquired scanning micrograph will be described later.

<Comparative Examples 3-1 to 3-28>
As the first modifier, the compounds shown in Tables 30 and 31 were used instead of stearic acid, and the same method as described in Example 1-1 except that the first treated product was obtained as surface-treated particles. Obtained the surface-treated particles according to Comparative Examples 3-1 to 3-28.

<Comparative Example 3-29>
The same sericite as the sericite used in Example 1-1 was used as the inorganic particles according to Comparative Example 3-29.

<Evaluation of water repellency>
Surface-treated particles and comparisons according to Examples 1-1 to 1-35 and 2-1 to 2-74, and Comparative Examples 1-1 to 1-93, 2-1 to 2-89 and 3-1 to 3-28. The water repellency of the inorganic particles of Example 3-29 was evaluated by the following method.

First, a mixture of 20 parts by mass of surface-treated particles and 80 parts by mass of alcohol was applied to a slide glass and then dried. Next, 25 μL of water droplets were dropped on the surface of the slide glass coated with the above mixture. Next, 30 seconds after the water droplet was dropped, the water droplet was photographed with a microscope and the contact angle was measured. Isopropyl alcohol was used as the alcohol.

<Evaluation of tactile sensation>
Surface-treated particles and comparisons according to Examples 1-1 to 1-35 and 2-1 to 2-74, and Comparative Examples 1-1 to 1-93, 2-1 to 2-89 and 3-1 to 3-28. With respect to the inorganic particles of Example 3-29, the tactile sensation, specifically, the moist sensation, the silky sensation and the spread sensation were evaluated by the following methods.

Regarding the moist feeling, first, each of the 10 evaluators evaluated each surface-treated particle on a scale of 1 to 5 by pinching an appropriate amount of the surface-treated particles with their fingers and rubbing the fingers together. Evaluation 1 indicates that the moist feeling was the weakest, and evaluation 5 indicates that the moist feeling was the strongest.
When all the evaluations obtained were confirmed, some of the surface-treated particles had differences in the scoring method among the evaluators, but the surface-treated particles were different among the evaluators. There was no contradiction in the order of evaluation.

Next, the average value of the obtained evaluations was calculated for each surface-treated particle, and the value obtained by rounding off the first decimal place of the calculated average value was obtained as the evaluation value of the moist feeling.

As for the smooth feeling, the evaluation value of the smooth feeling was obtained by the same method as the evaluation method of the moist feeling.
For the feeling of spread, instead of pinching an appropriate amount of surface-treated particles with fingers and evaluating the sensuality when rubbing the fingers together, pinching an appropriate amount of surface-treated particles with fingers and rubbing the pinched surface-treated particles against the back of the hand. Except for the evaluation of the sensuality, the evaluation value of the stretch feeling was obtained by the same method as the evaluation method of the moist feeling.
As for the feeling of smoothness and the feeling of spreading, there were some differences in the way of scoring among the evaluators, as in the case of the moist feeling, but there was no contradiction in the order of evaluation.

The results of the evaluation of water repellency and the evaluation of tactile sensation are summarized in Tables 1 to 32 below.

In the above table, in the column described as "evaluation" of "water repellency", "x" indicates that the contact angle could not be measured, or the contact angle was 90 ° or less, and "△" indicates that the contact angle was 90 ° or less. , Indicates that the contact angle was in the range of 91 ° to 120 °, and “◯” indicates that the contact angle was 121 ° or more.

In the above table, in the column described as "evaluation" of "tactile sensation", "x" indicates that the evaluation values of the stretchy feeling, the moist feeling and the smooth feeling are all 3 or less, and all the items are not 3. Indicating, "△" indicates that the evaluation values of the stretchy feeling, the moist feeling and the smooth feeling are all 3, and "○" indicates that the stretchable feeling is 3 or more and the evaluation values of the stretchy feeling, the moist feeling and the smooth feeling are all 3. It shows that at least one of them was 4 or more. It should be noted that the evaluation value of the stretched feeling was 2 or less, and none of the moist feeling and the silky feeling was 4 or more.

In the above table, in the column described as "comprehensive evaluation", "x" indicates that at least one of the evaluation of water repellency and the evaluation of tactile sensation was x, and "Δ" is the evaluation of water repellency. And, at least one of the evaluations of tactile sensation was Δ, and “◯” indicates that both the evaluation of water repellency and the evaluation of tactile sensation were 〇.

In the table, "silicone (A)" is dimethicone. "Silicone (B)" is methicon.

Further, "capric acid" in the table has 10 carbon atoms and a melting point of 32 ° C. "Lauric acid" has 12 carbon atoms and a melting point of 43 ° C. The diameter is about 1 mm. "Behenic acid" has 22 carbon atoms and a melting point of 80 ° C. The diameter is about 5 mm. "Montanic acid" has 28 carbon atoms and a melting point of 91 ° C. The diameter is about 1 mm. "Oleic acid" has 18 carbon atoms and a melting point of 13 ° C. "Isostearic acid" has 18 carbon atoms and a melting point of 7 ° C. "12-Hydroxystearic acid" has 18 carbon atoms and a melting point of 75 ° C. The diameter is about 1 mm.

Further, "Zn stearate" in the table has a melting point of 130 ° C. and a median diameter of 10 μm. "Ca stearate" has a melting point of 150 ° C. and a median diameter of 5 μm. "Na stearate" has a melting point of 220 ° C. and a median diameter of 14 μm. "Al stearate" has a melting point of 160 ° C. and a median diameter of 15 μm. "Li stearate" has a melting point of 220 ° C. and a median diameter of 7 μm. "K stearic acid" has a melting point of 240 ° C. and a median diameter of 15 μm. "Zn capric acid" has a melting point of 135 ° C. and a median diameter of 14 μm. "Zn myristic acid" has a melting point of 130 ° C. and a median diameter of 10 μm. "Zn palmitic acid" has a melting point of 130 ° C. and a median diameter of 11 μm. "Zn oleate" has a melting point of 80 ° C. and a median diameter of 18 μm. "Zn behenic acid" has a melting point of 130 ° C. and a median diameter of 13 μm.

Further, "ester WAX (A)" in the table is glycerintri 12-hydroxystearate, and glycerintri 12-hydroxystearate has a melting point of 85 ° C. and a diameter of about 3 mm. "Ester WAX (B)" is pentaerythritol tetrastearate, which has a melting point of 55 ° C. and a diameter of about 0.5 mm. "Ester WAX (C)" is pentaerythritol monostearate, and pentaerythritol monostearate has a melting point of 62 ° C. "Ester WAX (D)" is a glycerin monostearate, and the glycerin monostearate has a melting point of 65 ° C. "Paraffin wax" is a hydrocarbon compound having a melting point of 65 ° C. "Glycerin" has a melting point of 20 ° C. The paraffin WAX, glycerin, and the ester WAX (C) and (D) are not full ester ester waxes.

As shown in Tables 1 to 3 and Tables 11 to 19, the surface-treated particles according to Examples 1-1 to 1-35 and 2-1 to 2-74 realized excellent water repellency and tactile sensation.

On the other hand, the surface-treated particles according to Comparative Examples 1-1 to 1-93, 2-1 to 2-89 and 3-3 to 3-28 and the inorganic particles of Comparative Example 3-29 all have excellent water repellency and excellent water repellency. At least one of the excellent tactile sensations could not be achieved.

The contact angles of the surface-treated particles according to Comparative Examples 1-3, 1-4, and 3-3 and the inorganic particles of Comparative Example 3-29 could not be measured because the contact angles were too small.
<Scanning micrograph>
As described above, scanning micrographs of the surface-treated particles according to Example 2-71 were obtained for each manufacturing process. Hereinafter, the acquired scanning micrographs will be described.
FIG. 1 is a photomicrograph obtained by imaging inorganic particles with a scanning microscope. FIG. 2 is a photomicrograph obtained by imaging a mixture of the inorganic particles shown in FIG. 1 and the first modifier, that is, the first treated product with a scanning microscope. FIG. 3 is a photomicrograph obtained by imaging a processed product obtained by mixing the first processed product and the first component shown in FIG. 2 with a scanning microscope. FIG. 4 is a photomicrograph obtained by photographing a processed product obtained by mixing the processed product shown in FIG. 3 and the second component, that is, the surface-treated particles according to Example 2-71 with a scanning microscope.

According to the comparison between FIGS. 1 and 2, the first modifier covers the entire surface of the inorganic particles. Further, as shown in FIGS. 3 and 4, the second modifier is supported on a layer made of the first modifier.
The scanning micrographs obtained in the process of manufacturing the surface-treated particles according to Example 2-71 have been described above.

Scanning micrographs were also obtained for Zn laurate and Mg stearate. FIG. 5 is a photomicrograph obtained by imaging Zn laurate with a scanning microscope. FIG. 6 is a photomicrograph obtained by imaging Mg stearate with a scanning microscope. As shown in FIG. 5, Zn laurate is a plate-shaped particle. As shown in FIG. 6, Mg stearate is a flat particle.
The inventions described in the original claims are described below.
[1]
It comprises an inorganic particle, a first modifier supported by the inorganic particles, and a second modifier supported by the inorganic particles supporting the first modifier.
The first modifier is composed of a fatty acid having a carbon atom number of 18 or more and a melting point of 50 ° C. or more, a fatty acid metal salt having a carbon atom number of 12 or more, and a full ester ester wax. One or more to be chosen,
The second modifier is a surface-treated particle having 1 or more of a fatty acid metal salt having 12 or more carbon atoms.
[2]
Item 2. The surface-treated particle according to Item 1, wherein the inorganic particle is one or more selected from the group consisting of silicate minerals, silicic acid compounds, calcium compounds, barium compounds, titanium compounds and zinc compounds.
[3]
The first modifier includes fatty acids having 18 to 22 carbon atoms, a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, and a metal salt of oleic acid. Item 3. The surface-treated particle according to Item 1 or 2, wherein the metal salt of stearic acid, the metal salt of behenic acid, the triglyceride, and the full ester of pentaerythritol is one or more.
[4]
Item 2. The amount of the first modifier is described in any one of Items 1 to 3, which is in the range of 0.01 parts by mass to 100 parts by mass when the amount of the inorganic particles is 100 parts by mass. Surface treated particles.
[5]
Item 2. The surface-treated particle according to any one of Items 1 to 4, wherein the second modifier contains 2 or more fatty acid metal salts having 12 or more carbon atoms.
[6]
The second modifier is one or more of a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, a metal salt of oleic acid, a metal salt of stearic acid, and a metal salt of behenic acid. The surface-treated particle according to any one of 5 to 5.
[7]
Item 2. The amount of the second modifier is described in any one of Items 1 to 6, which is in the range of 0.5 parts by mass to 45 parts by mass when the amount of the inorganic particles is 100 parts by mass. Surface treated particles.
[8]
In the first step of heating and mixing the first modifier and the inorganic particles to obtain the first treated product, the first modifier has a carbon atom number of 18 or more and a melting point of 50 ° C. or more. The first step, which is one or more selected from the group consisting of a certain fatty acid, a fatty acid metal salt having 12 or more carbon atoms, and an ester wax of a full ester.
In the second step of mixing the second modifier and the first treated product to obtain the second treated product, the second modifier is one of fatty acid metal salts having 12 or more carbon atoms. With the second step above
A method for producing surface-treated particles containing.
[9]
Item 8. The method for producing surface-treated particles according to Item 8, wherein the second modifier contains a plurality of compounds, and in the second step, the plurality of compounds are sequentially mixed with the first treated product.

Claims (9)

It is composed of inorganic particles, a first modifier supported by the inorganic particles, and a second modifier supported by the inorganic particles supporting the first modifier.
The first modifier is one or more selected from the group consisting of a fatty acid having 18 or more carbon atoms and a melting point of 50 ° C. or more and a fatty acid metal salt having 12 or more carbon atoms.
The second modifier is one or more of fatty acid metal salts having 12 or more carbon atoms .
When the first modifier is a fatty acid metal salt, the surface-treated particles are different from the first modifier and the second modifier . The surface-treated particle according to claim 1, wherein the inorganic particle is one or more selected from the group consisting of a silicate mineral, a silicic acid compound, a calcium compound, a barium compound, a titanium compound and a zinc compound. The first modifier includes fatty acids having 18 to 22 carbon atoms, a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, and a metal salt of oleic acid. The surface-treated particle according to claim 1 or 2, which is one or more selected from the group consisting of a metal salt of stearic acid and a metal salt of behenic acid. The amount of the first modifier is according to any one of claims 1 to 3, which is in the range of 0.01 parts by mass to 100 parts by mass when the amount of the inorganic particles is 100 parts by mass. Surface treated particles. The surface-treated particle according to any one of claims 1 to 4, wherein the second modifier contains two or more fatty acid metal salts having 12 or more carbon atoms. The second modifier is selected from the group consisting of a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, a metal salt of oleic acid, a metal salt of stearic acid and a metal salt of behenic acid1. The surface-treated particle according to any one of claims 1 to 5 as described above. The amount of the second modifier is according to any one of claims 1 to 6, which is in the range of 0.5 parts by mass to 45 parts by mass when the amount of the inorganic particles is 100 parts by mass. Surface treated particles. A method for producing surface-treated particles, which comprises inorganic particles, a first modifier supported by the inorganic particles, and a second modifier supported by the inorganic particles supporting the first modifier. hand,
In the first step of heating and mixing the first modifier and the inorganic particles to obtain a first treated product, the first modifier has 18 or more carbon atoms and a melting point of 50 ° C. The first step, which is 1 or more selected from the group consisting of the above fatty acids and the fatty acid metal salts having 12 or more carbon atoms.
In the second step of mixing the second modifier and the first treated product to obtain the second treated product, the second modifier is a fatty acid metal salt having 12 or more carbon atoms. Including the second step which is 1 or more
When the first modifier is a fatty acid metal salt, a method for producing surface-treated particles different from the first modifier and the second modifier . The second modifier contains two or more types of fatty acid metal salts having 12 or more carbon atoms, and in the second step, the two or more types of fatty acid metal salts having 12 or more carbon atoms are used. The method for producing surface-treated particles according to claim 8, wherein the surface-treated particles are sequentially mixed with the first treated product.

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