KR101715777B1 - Silicone particle and method for manufacturing thereof - Google Patents

Abstract

(A) preparing a dispersion containing seed particles; And (b) mixing the dispersion with a silicon precursor followed by hydrolysis and condensation to produce silicone particles. In step (b), the particle size distribution of the silicone particles is 50 % Cumulative mass particle size distribution diameter is D50, D50? 10 占 퐉 and a method for producing the same.

Description

[0001] SILICONE PARTICLE AND METHOD FOR MANUFACTURING THEREOF [0002]

The present invention relates to silicon particles and a process for their preparation.

Silicone oligomers, polymers, or resins are widely used in cosmetics and various industrial coatings. They are insoluble particles, soluble particles, highly soluble viscous liquids, or oligomeric forms with a low viscosity of hundreds to thousands of molecular weight Manufactured and sold. That is, the silicone compound is classified into a solid or a liquid according to its physical form, and can be classified into an insoluble and a soluble substance depending on its solubility.

Of the silicon in the solid form, silicon particles in particular have been applied to various applications. Most of the particles applied to existing cosmetics have a diameter of less than about 10 탆 and, when they are applied to a product using free-flowing particles, they may cause harm to the human body as fine particles. Particularly, in the case of polymethylsilsesquioxane particles used in cosmetics, various grades of particles are commercially available, and products having a diameter of about 5 μm are mainly used.

On the other hand, in order to produce particles having a diameter of about 10 mu m or more, a method of largely reducing the amount of the medium is most widely used. However, when such a method is used, the size of the particles increases, but the oligomers produced during the reaction are clumped together, resulting in generation of a large number of by-products, resulting in a very low yield.

(A) preparing a dispersion containing seed particles; And (b) mixing the dispersion with a silicon precursor followed by hydrolysis and condensation to produce silicone particles. In step (b), the particle size distribution of the silicone particles is 50 And a cumulative mass particle size distribution diameter of D50 is D50? 10 占 퐉.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

(A) preparing a dispersion containing seed particles; And (b) mixing the dispersion with a silicon precursor followed by hydrolysis and condensation to produce silicone particles. In step (b), the particle size distribution of the silicone particles is 50 % Cumulative mass particle size distribution diameter is D50, D50 > = 10 mu m.

In the step (a), the seed particle may include at least one selected from the group consisting of hydrophilic or hydrophobic silica, hydrophilic or hydrophobic silicon, metal oxide, metal oxide surface-coated with hydrophilic or hydrophobic, talc and starch.

The metal oxide may be at least one selected from the group consisting of titanium dioxide, zinc oxide, iron oxide and aluminum oxide.

In step (a), the seed particles may be contained in an amount of 0.1 wt% to 10 wt% of the silicon precursor in the step (b).

In the step (b), the silicon precursor may include a chlorosilane or an organic alkoxysilane represented by the following formula (1)

[Chemical Formula 1]

_{A a} -B _4-a -Si

In this formula,

A is an alkyl group having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms whose terminal hydrogen is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group; Or an aryl group having 5 to 10 carbon atoms,

B is an alkoxy group having 1 to 10 carbon atoms; Or an alkoxy group having 1 to 10 carbon atoms in which hydrogen at the terminal is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group,

a is an integer of 1 to 3;

After the hydrolysis and condensation reaction in the step (b), the reaction may be further aged at 100 ° C to 150 ° C.

In the step (b), the silicon particles may form a particle distribution of 10 μm ≦ D 50 ≦ 20 μm.

(D90-D10) / D50? 3, where 90%, 50%, and 10% cumulative mass particle size distribution diameters of the silicone particles in the step (b) are respectively D90, D50 and D10 .

In the step (b), the yield of the silicon particles may be 60% or more.

In one embodiment of the present invention, a silicon particle formed from a dispersion liquid containing seed particles and a silicon precursor, wherein a 50% cumulative mass particle size distribution diameter in the particle distribution of the silicon particles is D50, Silicon particles characterized in that they provide silicon particles.

(D90-D10) / D50? 3 where 90%, 50%, and 10% cumulative mass particle size distribution diameters in the particle distribution of the silicon particles are D90, D50, and D10, respectively.

The silicon particles according to the present invention are formed from a dispersion liquid containing seed particles and a silicon precursor, wherein a 50% cumulative mass particle size distribution diameter in the particle distribution of the silicon particles is D50, It is harmless to the human body even when it is inhaled, and it is possible to exert excellent performance in improving the touch feeling.

In addition, the silicon particles have a narrow particle size distribution by inhibiting the aggregation during the production process, and the production of a large amount of by-products is suppressed and the yield is also high.

FIG. 1 is a graph showing the particle size distribution of polymethylsilsesquioxane particles prepared according to Example 1. FIG.
2 is a scanning electron microscope (SEM) photograph of the polymethylsilsesquioxane particles prepared according to Example 1. Fig.

The inventors of the present invention have found that when seed particles are introduced into the silicon particle production, formation of aggregate by-products is suppressed to reduce the amount of the medium, and thus the silicon particle having a narrow particle size distribution and a large diameter can be formed at a high yield And completed the present invention.

(A) preparing a dispersion containing seed particles; And (b) mixing the dispersion with a silicon precursor followed by hydrolysis and condensation to produce silicone particles. In step (b), the particle size distribution of the silicone particles is 50 % Cumulative mass particle size distribution diameter is D50, D50 > = 10 mu m.

In the present invention, the term " silicone particle " refers to a polymer in which an organosilicone containing an organic group and oxygen are chemically bonded to each other. The silicon particles may be, for example, polymethylsilsesquioxane particles, polyphenylsilsesquioxane particles, or mixtures thereof. These silicon particles are unique chemical materials with both organic and inorganic properties and can be applied in many forms and are positioned as high-function materials essential in most industrial fields.

In particular, in the case of the silicone particles having a large particle size and a narrow particle size distribution according to the present invention, they are harmless to the human body and can exhibit excellent performance for improving the feel and can be used in the field of cosmetics or medicine, , Leather, and the like.

First, in order to produce the silicon particles according to the present invention, a dispersion containing the seed particles is prepared (step (a)).

The seed particles are used as a starting material for producing silicon particles. The seed particles preferably have an average particle size of less than 10 mu m and preferably 10 nm to 8 mu m, but are not limited thereto. At this time, when the average particle size of the seed particles is out of the above range, mixing with the silicon precursor, hydrolysis and condensation reaction are difficult to occur smoothly or it is difficult to act as a starting material for producing silicon particles.

The seed particles may include at least one selected from the group consisting of silica, hydrophilic or hydrophobic silicon, metal oxide, metal oxide surface-coated with hydrophilic or hydrophobic, talc and starch.

Specifically, the silica seed particles refer to silica-seed particles which have not been surface-modified, and are characterized by having a hydrophilic property as a chemical bond of silicon and oxygen.

The hydrophilic silicone seed particles have a property of having a strong affinity to water, and specifically comprise polymethylsilsesquioxane and silica. In this case, the oil absorption is 60 g / 100 g to 80 g / 100 g, the refractive index is about 1.40 to 1.50, and the bulk density is about 8.4 g / in ³ .

The hydrophobic silicon seed particles have a property of lacking affinity for water, and specifically comprise polymethylsilsesquioxane. In this case, the oil absorption is 35g / 100g to 55g / 100g, the refractive index is about 1.40 to 1.50, and the bulk density is about 8.8g / in ³ .

The metal oxide particles may be at least one selected from the group consisting of titanium dioxide, zinc oxide, iron oxide and aluminum oxide, and may be a combination of iron oxide and titanium dioxide, , But is not limited thereto.

At this time, the surface of the metal oxide may be coated with a hydrophilic or hydrophobic polymer.

The seed particles preferably include 0.1 wt% to 10 wt% of the silicon precursor, but the present invention is not limited thereto. At this time, when the seed particles are less than the above-mentioned weight range, there is a problem that it is difficult to act as a starting material for preparing silicon particles. When the seed particles exceed the above weight range, there is a problem that mixing with the silicon precursor is not smooth .

The seed particles are dispersed in a dispersion medium and prepared in the form of a dispersion. Examples of the dispersion medium include water, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF) It is preferable to use at least one selected from the group consisting of ethanol, methanol, cyclohexanol, cyclohexanone, methyl ethyl ketone, acetone, ethylene glycol, octane, diethyl carbonate, dimethyl sulfoxide (DMSO) But is not limited thereto. These types of dispersants can help seed particles be well dispersed and mixed with the silicon precursor.

Next, in order to produce the silicon particles according to the present invention, the dispersion is mixed with the silicon precursor, and then silicone particles are prepared through hydrolysis and condensation (step (b)).

The silicon precursor refers to a pre-stage material to become silicon particles through hydrolysis and condensation reaction.

The silicon precursor may comprise a chlorosilane or an organoalkoxysilane represented by the following formula:

[Chemical Formula 1]

_{A a} -B _4-a -Si

In this formula,

A is an alkyl group having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms whose terminal hydrogen is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group; Or an aryl group having 5 to 10 carbon atoms,

B is an alkoxy group having 1 to 10 carbon atoms; Or an alkoxy group having 1 to 10 carbon atoms in which hydrogen at the terminal is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group,

a is an integer of 1 to 3;

Specifically, the chlorinated silane refers to a compound represented by SiH _n Cl _{4 -n} (n = 1, 2, 3), which may be monochlorosilane, dichlorosilane, trichlorosilane or silicon tetrachloride.

The organic alkoxysilane represented by the above formula (1) may be at least one selected from the group consisting of methyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane , Methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane and N - (2-aminoethyl) aminopropyltriethoxysilane.

The silicon precursor as described above undergoes hydrolysis and condensation reactions by adjusting pH conditions. At this time, the hydrolysis reaction becomes the main reaction under the acidic condition, and the condensation reaction can be the main reaction under the basic condition.

In order to use the silicone particles produced through the hydrolysis and condensation reaction as raw materials in the field of cosmetics, it is preferable to adjust the final pH to 6 to 8.

After the hydrolysis and condensation reaction, it may be further aged at 100 ° C to 150 ° C. Through this aging process, an additional condensation reaction of the unconjugated residual oligomer can be induced, and the final yield can be further increased.

The silicon particles finally produced through the above hydrolysis and condensation reaction can be measured through a particle size analyzer or a scanning electron microscope (SEM), and the 50% cumulative mass particle size distribution diameter in the particle distribution of silicone particles D50, D50? 10 占 퐉. That is, even if it is inhaled, it is harmless to the human body, and there is an advantage that excellent performance can be exerted to improve touch feeling.

More preferably, the silicon particles can form a particle distribution of 10 占 퐉? D50? 20 占 퐉.

When 90%, 50%, and 10% cumulative mass particle size distribution diameters of the silicon particles finally obtained through the hydrolysis and condensation reaction are D90, D50, and DO10, respectively, (D90-D10) / D50? 3, and it can be confirmed that the particle size distribution is narrow.

In this case, (D90-D10) / D50 is an index for measuring the particle size distribution width, and it is considered that the particle size distribution width is narrower toward 0.

The yield of the silicon particles is preferably 60% or more, but is not limited thereto. In the present invention, when silicon particles are formed from seed particles as a starting material, a large amount of by-products produced by the oligomers generated during the reaction are suppressed, thereby increasing the yield.

Further, the present invention is a silicon particle formed from a dispersion liquid containing a seed particle and a silicon precursor, wherein a 50% cumulative mass particle size distribution diameter in the particle distribution of the silicon particles is D50, Silicon particles.

(D90-D10) / D50? 3 where 90%, 50%, and 10% cumulative mass particle size distribution diameters in the particle distribution of the silicon particles are D90, D50, and DO10, respectively.

The silicon particles according to the present invention are formed from a dispersion liquid containing seed particles and a silicon precursor, wherein a 50% cumulative mass particle size distribution diameter in the particle distribution of the silicon particles is D50, It is harmless to the human body even when it is inhaled, and it is possible to exert excellent performance in improving the touch feeling.

In addition, the silicon particles have a narrow particle size distribution by inhibiting the aggregation during the production process, and the production of a large amount of by-products is suppressed and the yield is also high.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

[ Example ]

Example  One

10 g of tetraethoxysilane and 10 ml of water were mixed, 10 ml of a 10% NaOH aqueous solution was added, and the mixture was stirred for about 10 to 12 hours to prepare a solution containing silica seed particles having an average particle diameter of about 1 탆. The supernatant was removed by centrifugation and the silica seed particles were recovered.

2 g of the silica seed particles having an average particle size of 3 탆 was dispersed in 1000 ml of water, and then 200 g of methyltrimethoxysilane was mixed. The oily layer was removed by adding 0.5 ml of concentrated hydrochloric acid to the mixture, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred for about 10 to 12 hours. The particles were precipitated by a dipping method, and the supernatant was removed. The particles were washed with water and adjusted to pH 6-8 using dilute hydrochloric acid. The particles were recovered by centrifugation and dried at 120 ° C to obtain polymethylsilsesquioxane The particles were finally prepared (final yield = 70%).

The final polymethylsilsesquioxane particles were analyzed by a particle size analyzer (HELOS / RODOS, OASIS). As a result, D50 = 10.5 占 퐉 and (D90-D10) / D50 = 2.3 as shown in Fig.

As shown in FIG. 2, SEM photographs showed that the polymethylsilsesquioxane particles had a spherical shape with a high roundness and an average particle size of about 10 μm.

Example  2

1 g of hydrophilic silicon seed particles having an average particle size of 5 to 6 탆 (SESQ-MH5, ENM Technologies, Inc.) was dispersed in 1000 ml of water, followed by mixing 200 g of methyltrimethoxysilane. The oily layer was removed by adding 0.5 ml of concentrated hydrochloric acid to the mixture, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred for about 10 to 12 hours. The particles were precipitated by a dipping method, and the supernatant was removed. The particles were washed with water and adjusted to pH 6-8 using dilute hydrochloric acid. The particles were recovered by centrifugation and dried at 120 ° C to obtain polymethylsilsesquioxane The particles were finally prepared (final yield = 65%).

The final polymethylsilsesquioxane particles were analyzed by a particle size analyzer (HELOS / RODOS, OASIS). As a result, D50 = 10 μm and (D90-D10) / D50 = 3.

Example  3

1 g of hydrophobic silicon seed particles having an average particle size of 5 to 6 占 퐉 (SESQ-ML5, EN-M Technologies) was dispersed in 5 ml of ethanol and 1000 ml of water, and then 250 g of methyltrimethoxysilane was mixed. The oily layer was removed by adding 0.5 ml of concentrated hydrochloric acid to the mixture, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred for about 10 to 12 hours. The particles were precipitated by a dipping method, and the supernatant was removed. The particles were washed with water and adjusted to pH 6-8 using dilute hydrochloric acid. The particles were recovered by centrifugation and dried at 120 ° C to obtain polymethylsilsesquioxane The particles were finally prepared (final yield = 75%).

The final polymethylsilsesquioxane particles were analyzed by means of a particle size analyzer (HELOS / RODOS, OASIS). As a result, D50 = 12 占 퐉 and (D90-D10) /D50=2.5.

Example  4

0.1 g of the iron oxide seed particles having an average particle size of 0.4 탆 and 0.9 g of the iron oxide seed particles having an average particle size of 0.12 탆 were dispersed in 1000 ml of water and then 150 g of methyltrimethoxysilane and 50 g of phenyl trimethoxysilane were mixed. The oily layer was removed by adding 2 ml of concentrated hydrochloric acid to the mixture, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred for about 10 to 12 hours. The particles were precipitated by a dipping method and the supernatant was removed. The particles were washed with water and adjusted to pH 6-8 using dilute hydrochloric acid. The particles were recovered by centrifugation and dried at 120 ° C to finally produce silicon particles (Final yield = 73%).

The final silicon particles were analyzed by a particle size analyzer (HELOS / RODOS, OASIS). As a result, D50 = 10 占 퐉 and (D90-D10) / D50 = 2.

Example  5

1 g of zinc oxide seed particles having an average particle size of 0.3 탆 was dispersed in 5 ml of ethanol and 1000 ml of water, and then 300 g of methyltrimethoxysilane was mixed. The oily layer was removed by adding 0.5 ml of concentrated hydrochloric acid to the mixture, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred for about 10 to 12 hours. The particles were precipitated by a dipping method and the supernatant was removed. The particles were washed with water and adjusted to pH 6-8 using dilute hydrochloric acid. The particles were recovered by centrifugation and dried at 120 ° C to finally produce silicon particles (Final yield = 60%).

The final silicon particles were analyzed by a particle size analyzer (HELOS / RODOS, OASIS). As a result, D50 = 15 占 퐉 and (D90-D10) / D50 = 2.

Comparative Example  One

1000 ml of water and 300 g of methyltrimethoxysilane were mixed. 0.5 ml of concentrated hydrochloric acid was added to the mixture to remove the oily layer, and the mixture was adjusted to pH 10 with 10% aqueous NaOH solution and stirred. A large mass was formed in a state in which agglomerations were formed within 5 minutes after the agitation and no further stirring was possible.

The silicon particles according to Examples 1 to 5 were formed from seed particles as a starting material and had D50 of 10 to 15 占 퐉 and (D90-D10) / D50 of 2 to 3, And the size distribution is narrow. In particular, it was confirmed that when zinc oxide was used as the seed particles as in Example 5, silicon particles having a D50 of 15 mu m or more could be formed.

On the other hand, according to Comparative Example 1, it was confirmed that a large mass was formed due to the intergranular agglomeration due to the omission of the use of the seed particles.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

(a) preparing a dispersion containing zinc oxide-containing seed particles; And
(b) mixing the dispersion with a silicon precursor, and then producing silicone particles through hydrolysis and condensation reaction,
When the 50% cumulative mass particle size distribution diameter in the particle distribution of the silicone particles in the step (b) is D50, D50? 15 占 퐉,
Wherein the silicon precursor comprises an organoalkoxysilane represented by the following formula (1)
Method of producing silicon particles:
[Chemical Formula 1]
_{A a} -B _4-a -Si
In this formula,
A is an alkyl group having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms whose terminal hydrogen is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group; Or an aryl group having 5 to 10 carbon atoms,
B is an alkoxy group having 1 to 10 carbon atoms; Or an alkoxy group having 1 to 10 carbon atoms in which hydrogen at the terminal is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group,
a is an integer of 1 to 3;
delete delete The method according to claim 1,
In the step (a), the seed particles may be contained in an amount of 0.1 wt% to 10 wt% with respect to the silicon precursor in the step (b)
A method for producing silicon particles.
delete The method according to claim 1,
After the hydrolysis and condensation reaction in step (b), further aging is performed at 100 ° C to 150 ° C
A method for producing silicon particles.
The method according to claim 1,
Wherein the silicon particles in the step (b) have a D50 ≤
A method for producing silicon particles.
The method according to claim 1,
(D90-D10) / D50? 3 when the 90%, 50%, and 10% cumulative mass particle size distribution diameters of the silicon particles in the step (b) doing
A method for producing silicon particles.
The method according to claim 1,
In the step (b), the yield of the silicon particles is 60% or more
A method for producing silicon particles.
A dispersion containing zinc oxide-containing seed particles, and a silicon particle formed from a silicon precursor,
And a 50% cumulative mass particle size distribution diameter in the particle distribution of the silicon particles is D50, D50? 15 占 퐉,
Wherein the silicon precursor comprises an organoalkoxysilane represented by the following formula (1)
Silicon particles:
[Chemical Formula 1]
_{A a} -B _4-a -Si
In this formula,
A is an alkyl group having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms whose terminal hydrogen is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group; Or an aryl group having 5 to 10 carbon atoms,
B is an alkoxy group having 1 to 10 carbon atoms; Or an alkoxy group having 1 to 10 carbon atoms in which hydrogen at the terminal is substituted with a halogen atom, a nitro group, a sulfone group, a hydroxyl group, an amine group, an aldehyde group, or a carboxyl group,
a is an integer of 1 to 3;
11. The method of claim 10,
(D90-D10) / D50? 3 where 90%, 50% and 10% cumulative mass particle size distribution diameters in the particle distribution of the silicon particles are D90, D50 and D10, respectively
Silicon particles.

Images