KR100508961B1 - a composition powder with surface treatment and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a surface-treated composite powder and a production method thereof.

This is characterized by coating the surface of the composite powder with an organosilicon compound and the like while coating the titanium dioxide in the particulate state with a plate mineral such as kaolin.

Accordingly, since the particles of the powder are plate-like, skin adhesion and malleability are improved, and the coated ultra-fine titanium dioxide brings light shielding and light scattering effects, and hydrophilicity and hydrophobicity can be controlled by the surface modification method. To improve usability.

Description

Surface treatment composite powder and its manufacturing method {a composition powder with surface treatment and manufacturing method

The present invention relates to a surface-treated composite powder, and to a method for producing the same. More specifically, the surface of the composite powder is coated with an organic silicon compound or the like while the fine particulate titanium dioxide is coated with a plate mineral such as kaolin. The present invention relates to a surface-treated composite powder and a method for producing the same, which have a good dispersibility of powders and thus can be usefully used as pigments and additives blended in cosmetics, inks, paints, resins, toners, and the like.

Generally, particulate powders such as titanium oxide and zinc oxide are known to have the ability to shield ultraviolet rays harmful to the skin. However, these particles have a problem of being agglomerated and difficult to disperse in cosmetics and the like.

As described above, various attempts have been made to improve the dispersibility of the fine particle powder.

For example, in the manufacturing method of the composite powder for color cosmetics of Patent No. 283124, and in the color cosmetics containing the composite powder produced by this, the fine powder is fixed in a sieving pigment to make a composite powder to improve the dispersibility of the fine powder. It is proposed to let.

However, even in the case of the above method, it was not possible to sufficiently improve the dispersibility of the fine particle powder.

That is, in order to improve the dispersibility of the fine particle powder in the same way as described above, the most important factor is to disperse the fine particle powder to a state close to the primary particles when producing the composite powder. This is because a simple mixing level does not provide a high degree of dispersion.

As a method of mechanically wet grinding or wet pulverizing the powder, there is generally known a method of grinding or pulverizing the powder by a powder machine using a medium bead, a mill with an orifice, an ultrasonic disperser, or the like.

For example, Japanese Patent Laid-Open No. 7-108156 discloses a method for wet grinding with a sand grind mill.

That is, such a method is to surface-treat microparticle powder with an organic compound, powdering microparticle powder, and to improve the dispersibility of microparticle powder.

However, if the bead that is normally used for media stirring mills, such as sand grind mills, is made of ceramics, the particles having a particle size of about 0.2 mm are the smallest, and the primary particle size for disintegrating dispersion is 0.1 μm or less. In this case, the reality is that it cannot be sufficiently disintegrated in a short time.

In order to solve this problem, it is inevitable to increase the number of times of milling or to carry out a cyclic treatment for a long time, thereby causing a problem such as mixing of foreign matter in the media agitating mill or deterioration in productivity.

In addition, in order to disintegrate the fine particle powder with high efficiency by using a medium stirring mill, it is necessary to use as fine a medium beads as possible, and to give the kinetic energy necessary for disintegration to the beads, it is important to use beads having a higher specific gravity as the beads are smaller. If not, there is a problem in that the kinetic energy of one bead becomes smaller and the disintegration force is relatively lowered.

In addition, it is difficult to automatically separate the dispersion from the slurry in fine beads having a particle size of 0.2 mm or less that are currently available, and even if the fine powder is crushed by such a medium stirring mill, it is often reaggregated after crushing. The reality is that sufficient effects corresponding to the disintegration energy cannot be obtained.

An object of the present invention for solving the above problems is to disintegrate the fine particle powder to the primary particles or a state close to the primary particles, and to have the same characteristics as the fine particle powder is dispersed in the state of the primary particles To provide a surface-treated composite powder and a method for preparing the powder composition to have a high efficiency in a very short time, and to have characteristics such as high UV shielding ability, photodegradation ability, antibacterial activity, deodorizing ability, adsorption capacity, etc. for the same amount. have.

In order to achieve the above object, the mixing ratio of the fine particle powder having an average particle diameter of 0.01 to 0.1 μm and the platelet powder having an average particle diameter of 0.5 to 100 μm is set to a weight ratio of 1: 9 to 9: 1, and thus 1 to 10 of the powder filling weight. There is provided a surface-treated composite powder in which a solvent is mixed so that a solid content concentration is 10 to 50% by weight by adding a weight-% surface treatment agent.

In another aspect, the present invention, the step of pre-treating the flaky inorganic ore to form a plate-like powder having an average particle diameter of 0.5 ~ 100㎛;

Wet-pulverizing and coating the fine powder having an average particle diameter of 0.01 to 0.1 μm on the plate-shaped powder;

Provided is a method for producing a surface-treated composite powder, wherein the particulate powder is coated with a plate powder to produce a composite powder.

Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

In order to increase the dispersibility of the fine particle powder in a short time, the present invention utilizes a phenomenon in which the fine particle powder is dispersed and fixed in kaolin as a carrier when the fine particle powder is dispersed in the primary particle size.

Referring to the present invention, as shown in Figs. 1 and 2, a medium stirring mill using beads having an average particle diameter of 0.2 to 2 mm as the disintegrating medium is used when disintegrating the fine particle powder.

In addition, an inorganic powder such as kaolin having an average particle diameter of 0.5 to 100 µm can be used as a carrier for fixing particulate powder such as titanium dioxide having 0.01 to 0.1 µm, and a highly dispersed powder composition can be produced in a short time with high productivity. I would have to.

That is, the present invention uses a surface treatment agent and a solvent in a weight ratio of from 1: 9 to 9: 1 in the mixing ratio of the average primary particle diameter of 0.01 to 0.1 µm fine particle powder and kaolin which is a plate-shaped inorganic powder having an average particle diameter of 0.5 to 50 µm. The wet pulverization treatment is performed by a medium stirring mill filled with beads having an average particle diameter of 0.2 to 3 mm.

The powder of the present invention having the composition as described above and a manufacturing method thereof will be described.

As shown in Fig. 1 and Fig. 2, the powder composition produced according to the present invention can obtain the same effect as the fine powder is pulverized to a state substantially close to the primary particle size.

As a result, the ultraviolet shielding ability by the fine particle powder can be exerted highly, and since the said plate composition has a plate-like inorganic powder like kaolin to serve as a carrier of the fine particle powder, the dispersibility of the fine particle powder is improved.

In addition, according to the present invention, since the powder composition can be produced in a short time with high productivity, the incorporation of foreign matter into the powder composition from a media stirring mill or the like is prevented.

In addition, the media stirring mill used in the present invention comprises a medium bead, a device for transmitting kinetic energy thereto, and a container having the same, and the device for delivering kinetic energy to the beads includes a disk form, a rod form, There are anura types, and any of them can be used.

In addition, the beads have a particle diameter of 0.2 mm to several mm and are available on the market, but any one of them can be used to disintegrate aggregates of fine powder, and the beads are preferably as small as possible and have a high specific gravity. As the agent or zirconia, an average particle diameter of about 0.2 to 2 mm is preferable.

The beads are usually filled with an apparent volume of about 50 to 85% of the effective contents of the media stirring mill. However, the beads are not limited thereto and can be appropriately adjusted according to the amount of powder to be processed.

Moreover, the average primary particle diameter of the fine particle powder used in this invention is less than 0.1 micrometer in 0.01 micrometer or more, and the preferable fine powder of 0.01-0.05 micrometer is suitable.

In general, the fine particles form agglomerated particles of several micrometers to several tens of micrometers, and it is preferable to use titanium oxide, zinc oxide, cerium oxide, or the like which is excellent in UV shielding ability, regardless of the shape of the particles.

In addition, the inorganic carrier powder can be formed by maintaining the particle size in an intermediate state between the average primary particle diameter of the fine particle powder and the particle diameter of the beads used as the medium stirring mill. Specifically, the average primary particle size is 0.5 to 100 µm, and the average is particularly average. It is preferable that the primary particle diameter is 0.5-10 micrometers.

At this time, when the average primary particle size of the inorganic carrier powder is smaller than 0.5 µm, the aggregate of the fine particle powder is not sufficiently disintegrated since the particle size is substantially smaller than that of the aggregated particles of the fine particle powder.

In addition, when the average primary particle diameter of the inorganic powder is larger than 100 µm, the number of particles of the pulverized fine powder as a carrier is less preferable, and the inorganic powder is pulverized by beads, so that the pulverized energy is consumed and the pulverized effect is lowered. Not.

On the other hand, although the particle shape of the said inorganic support powder may be flaky, spherical, rod-like, or needle-shaped, it is preferable that it is satisfactory for the purpose of use.

As the flaky inorganic powder, it can be selected and used as a sieving pigment such as kaolin, talc, mica and mica, and the mixing ratio of the functional fine powder and the inorganic carrier powder is 1: 9 to 9: 1 in weight ratio, in particular 2: 8-7: 3 are preferable.

At this time, when the mixing ratio of the fine particle powder is less than the above range, the productivity of the surface-treated powder is lowered, and when the mixing ratio of the functional fine particle powder is larger than the above range, it becomes impossible to fully serve as a carrier of the disintegrated fine particle carrier powder. The dispersibility of the fine powder falls.

In addition, as said surface treating agent, what kind of thing to add may be selected according to the characteristic to be shown when processing powder with a medium stirring mill, and separating and powdering a solvent, ie surface property, surface charge, etc.

For example, in the case of using particulate titanium dioxide as shown in the examples, the surface of the primary particles of titanium dioxide is covered with a surface treating agent to reduce the cohesion between primary particles of the particulate titanium dioxide, and the surface treating agent is functional particulate dioxide. It becomes a fixing agent which connects titanium and kaolin which is a support | carrier.

In addition, the affinity for the dispersant is improved in the preparation of the surface-treated powder application products.

The surface treatment agent, hydrophilic, hydrophobic or neutral surface treatment agent may be applied according to the use of the application, and as the silicon compound, in addition to the siloxane, such as methyl polysiloxane, methylhydrogen polysiloxane, modified siloxane, alkyl silane, silane coupling agent, syrah The fatty acid or fatty acid salt is selected and used, and stearic acid, aluminum stearate, magnesium stearate, and the like are preferably used. The addition amount of the surface treatment agent is preferably about 1 to 10% by weight of the total weight of the powder.

In addition, a solvent is used in order to make a slurry form when mix | blending the mixed powder composition to cosmetics etc. As said solvent, water, an organic solvent, oil, etc. can be used according to the kind etc. of surface treatment agents.

At this time, the solid content concentration of the said slurry can be selected freely in the range which can be processed with a medium stirring mill substantially, and about 10-50 weight% is preferable.

When the solid content concentration of the slurry is lower than 10% by weight, the treatment efficiency becomes poor, and when the solid content concentration of the slurry is higher than 50% by weight, the viscosity of the slurry becomes so high that sufficient kinetic energy cannot be delivered to the beads, so that the disintegration ability is increased. There is a risk of falling.

At this time, the slurry injecting method of the medium stirring mill can be used in any of batch type, circulation type and continuous type, and the pulverization treatment number of the slurry in the case of processing speed or continuous processing may be appropriately set as necessary.

In addition, the treatment temperature is usually suitable about 20 ~ 40 ℃, the temperature is not limited and can be appropriately adjusted according to the use conditions.

Hereinafter, the surface-treated composite powder of the present invention and a manufacturing method thereof will be described in more detail with reference to Examples.

Kaolin Pretreatment

Since the kaolin ore used contains about 15% by weight of water, it is dried enough to have about 3% by weight of water in the air circulation dryer at 100 ± 5 ℃, and then used by using jaw crusher and cone crusher. It was crushed to mm or less.

In addition, since ore ore contains a significant amount of impurity minerals, it is necessary to grind for separation of these and kaolin for quality improvement.

Therefore, the crushed sample was ground using an impact mill (fine-impact mill, 100 UPZ, Alpine, German) for the single separation of kaolin and impurities. In order to control the production rate of the product (-325 mesh) it was pulverized while adjusting the number of revolutions of the grinding media.

Then, in the classification precision test for separating and sorting of mineral impurities and the kaolin in the pulverized product it was used as the German company Alpine air classifier (air classifier, 100MZR, German), the maximum particle size classifier (D ₉₇₎ 10㎛ Purified kaolin was prepared and used as a basis.

< Example 1>

A slurry having a solid content of 25% by weight by mixing 500 g of chiolin having an average primary particle size of 10 μm, 500 g of fine particle titanium dioxide having an average primary particle size of 0.03 μm, 30 g of methylhydrogen polysiloxane as a surface treatment agent, and 3000 g of toluene as a solvent. Was prepared.

Subsequently, the slurry was mixed with a stirrer for 30 minutes, and then 80% (but the apparent volume) of the effective content was supplied to the ultra-biscomill filled with zirconia beads having an average particle diameter of 0.5 mm, and wetted at a temperature of 35 ± 5 ° C. Disintegration was carried out, and the residence time in the mill was about 5 minutes.

In the slurry obtained by wet pulverization treatment as described above, toluene was separated by distillation under reduced pressure (vessel temperature: 110 ° C, product temperature: 30 to 60 ° C, reduced pressure: about 100 Torr) using a reactor, and 150 ° C. The thermal treatment of the surface treatment agent was carried out for 2 hours.

Subsequently, the powder after the heat adhesion treatment was gradually cooled to room temperature, and then ground using a pin mill to obtain a composite powder.

< Comparative Example 1>

According to the conventional proposal, the same amount of particulate titanium dioxide, kaolin and surface treatment agent as in Example 1 were added to the Hansel mixer using toluene as a solvent and mixed for 30 minutes at a rotational speed of 1800 rpm. did.

At this time, the mixed slurry was distilled under reduced pressure to separate the solvent, and the subsequent steps were treated in the same manner as in Example 1.

< Comparative Example 2>

According to the conventional proposal, the same amount of particulate titanium dioxide, kaolin and surface treatment agent as in Example 1 were added to the wet medium mill using toluene as a solvent and mixed for 30 minutes at a rotational speed of 600 rpm. did.

At this time, the mixed slurry was distilled under reduced pressure to separate the solvent, and the subsequent steps were treated in the same manner as in Example 1.

< Comparative Example 3>

1000 g of fine particle titanium dioxide having an average primary particle diameter of 0.03 µm, 50 g of methylhydrogen polysiloxane as a surface treatment agent, and 3000 g of toluene were mixed as a solvent to prepare a slurry having a solid content of 25% by weight.

That is, as in Example 1, except that the amount of titanium dioxide, surface treatment agent and toluene is the same, but kaolin was not used, and the amount of particulate titanium dioxide was increased by that amount. Treatment was carried out to obtain powder.

< Example 2>

Powders were obtained in the same manner as in Example 1 except that the amounts of the particulate titanium dioxide and kaolin as in Example 1 were adjusted and tested in the same manner as in the blending ratios shown in Table 1.

Furtherance(%) Titanium dioxide kaoline Sample 1 10 90 Sample 2 30 70 Sample 3 50 50 Sample 4 70 30 Sample 5 90 10

Test Methods

Optical Properties of Composite Powders

< Test Example 1>

Using the powder obtained in Example 1 and Comparative Examples 1-3 above as a measurement sample, polyvinylpyrrolidone was dissolved in isopropyl alcohol at 1:10 to prepare a film forming agent, and then in the process of Example 1 After dispersing the composite powder of the prepared example, the dispersion was applied to the polyflopropylene film to a thickness of 70㎛ using a film applicator.

In addition, the transmittance in the ultraviolet and visible wavelength range of the film was measured using a spectrophotometer Cary5E (manufacturer: Varian), and the results are shown in Table 2.

Measurement Sample Transmittance Difference from Example 1 300 nm 700 nm Example 1 20.0 93.2 Comparative Example 1 53.7 92.5 2 hours mixing by Hansel mixer Comparative Example 2 43.7 92.5 1 hour mixing by wet media mill Comparative Example 3 33.9 92.7 Kaolin free

As a result, as shown in Table 2, in Example 1, the transmittance at a wavelength of 700 nm in the visible light region was almost similar to that of Comparative Examples 1 and 2, while the transmittance at a wavelength of 300 nm in the ultraviolet region was higher than that of Comparative Examples 1 and 2. Remarkably small.

That is, it was confirmed from the results shown in Table 2 that the powder composition prepared according to Example 1 of the present invention retains transparency to visible light and excellent shielding to ultraviolet light.

In addition, Comparative Example 1, which had been mixed for a long time by a Hansel mixer and Comparative Example 2, which was not subjected to the wet disintegration treatment using a medium stirring mill, had a low absorbance at a wavelength of 300 nm compared with Example 1 and did not have sufficient ultraviolet shielding ability. .

That is, even if the mixing treatment by the hand mixer, which is a general wet mixing method as in the case of Comparative Examples 1 and 2, for a long time did not reach the ultraviolet shielding ability of the powder composition prepared in a short time by the present invention.

In addition, even when the wet pulverization treatment by the medium stirring mill was not performed, as in Comparative Example 2, sufficient ultraviolet shielding ability was not obtained. I could not get it.

Subsequently, except for changing the amounts of the particulate titanium dioxide and kaolin used in Example 2 as shown in Table 3, the powder obtained by treatment in the same manner as in Example 1 was prepared in the same manner as in Example 1. The transmittance | permeability in wavelength 700nm and 300nm was measured as density | concentration 2.3weight%. The results are shown in Table 3.

Furtherance (%) Transmittance Titanium dioxide kaoline 300 nm 700 nm Sample 1 10 90 23.8 89.1 Sample 2 30 70 16.2 93.2 Sample 3 50 50 20.0 94.2 Sample 4 70 30 25.1 93.3 Sample 5 90 10 30.9 92.5

As a result, as shown in Table 3, the measurement samples 1 to 4 of the present invention had a small transmittance at a wavelength of 300 nm and were excellent in ultraviolet shielding ability.

That is, from the result shown in Table 3, when the mixing ratio of the fine particle titanium dioxide of the first base material and the kaolin base material of the first base material is in the range of 1: 9 to 9: 1 by weight ratio, the transmittance at the wavelength of 300 nm is small and the ultraviolet ray shielding ability is excellent. It was clear.

It is considered that the above results can be obtained by the following mechanism. Particle titanium dioxide having ultraviolet shielding ability is disintegrated to a size close to the primary particles by the wet disintegration treatment using a medium stirring mill. When kaolin, which is a carrier, is not blended as shown in Fig. 4, the ultraviolet ray shielding ability is not improved because it is reaggregated as soon as agitation is completed or disintegration is insufficiently completed.

However, if kaolin in the middle of the beads and particulate titanium dioxide is added, kaolin acts as a carrier for fixation of particulate titanium dioxide, and finely divided particulate titanium dioxide to a size close to the primary particles adheres to the surface of kaolin. .

At this time, it is believed that the kaolin acted as a disintegration medium for the particulate titanium dioxide.

From these results, the plate-shaped composite powder coated with the ultrafine titanium dioxide of the present invention transmits light in the visible light region (380 to 780 nm), which is the central wavelength of the skin color, thereby improving the saturation of the skin color to express a bright and healthy skin color. .

In addition, as shown in FIG. 2, it can be seen that the UV-shielding effect of the surface-modified powder is excellent in the ultraviolet shielding effect in the ultraviolet region around 300 nm, which is applied when the composite particles have a spherical shape. This is because the layer is not dense and the occupied area of the titanium dioxide coated surface is small. However, when the composite particles are in the form of a plate, the coated layer of the composite particles becomes dense and the occupied area of the titanium dioxide coated surface is very large.

Thus, according to the present invention, the particulate powder is disintegrated to the primary particles or the state close to the primary particles and then subjected to surface treatment, and the particulate powder is uniformly attached to the surface of the inorganic powder and dispersed in the state of primary particles. As a result, the powder composition is produced in a very short time and with high efficiency.

In addition, when the powder composition prepared by the present invention is blended into cosmetics, paints, inks, resins, toners, and the like, the fine particles are easily dispersed in substantially the state close to the primary particles or primary particles, and thus the same amount as in the conventional formulation. Even if it is used, it exhibits characteristics such as ultraviolet ray shielding ability, photodegradation ability, antibacterial activity, deodorizing ability and adsorption ability depending on the particulate powder and surface treatment agent used.

While the invention has been shown and described with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention as provided by the following claims. I would like to clarify that those who have knowledge of this can easily know.

1 is a manufacturing process chart of the surface-modified composite powder according to the present invention.

Figure 2 is a graph showing the transmittance in the ultraviolet and visible light region of the surface-modified composite powder according to the present invention.

Claims (8)

After mixing the fine particle powder (a) of an average particle diameter of 0.01-0.1 micrometer of a primary particle, and the plate-shaped powder (b) of an average particle diameter of 0.5-100 micrometers by weight ratio 1: 9-9: 1, One of a group of silicon compounds comprising a silicon compound siloxane, a modified siloxane, an alkyl silane, a silane coupling agent, sirazane, or a fatty acid and fatty acid group containing stearic acid, aluminum stearate, magnesium stearate in the mixture of the particulate powder and the plate powder Is added in an amount of 1 to 10% by weight of the powder filling weight, Surface-treated composite powder, characterized by mixing the solvent (d) to maintain a solid concentration of 10 to 50% by weight. The surface-treated composite powder according to claim 1, wherein the plate-like powder is one of a group containing kaolin, talc, mica, and mica. The surface-treated composite powder according to claim 1, wherein the fine particle powder is one of a group containing fine particles of titanium dioxide, zinc oxide, and cerium oxide. delete Pre-processing the flaky inorganic ore to form a plate powder having an average particle diameter of 0.5 to 100 µm, and then adding and stirring the fine particle powder having a mean particle size of 0.01 to 0.1 µm, a surface treating agent, and a solvent; Wet-pulverizing and coating the fine powder on the plate-shaped powder; Method for producing a surface-treated composite powder to heat-process the plate-like powder coated with the fine particle powder The method of claim 5, wherein the preliminary processing of the flaky mineral ore is carried out by drying and pulverizing / polishing and classifying and calcining the ore of one of the groups including kaolin, talc, mica and mica. Method for producing a surface-treated composite powder, characterized in that it is formed. 6. The method of claim 5, wherein the coating of the fine powder on the plate-shaped powder comprises one of titanium dioxide, zinc oxide, and cerium oxide, wherein the fine powder is pulverized to an average particle diameter of 0.01 to 0.1 µm. A method for producing a surface-treated composite powder, which is mixed in a range of from 9 to 1: 1 and wet-crushed by a medium stirring mill filled with beads having an average particle diameter of 0.2 to 3 mm. The method of claim 5, wherein the heat treatment of the plate-like powder coated with the fine particle powder is heated at a temperature of 120 to 150 ° C for at least 2 hours, and then cooled slowly to room temperature.