KR102747619B1 - Pigment particle, Apparatus and method for manufacturing thereof - Google Patents

Abstract

Pigment particles and a manufacturing device and manufacturing method thereof are disclosed. The pigment particles according to the present invention include a substrate; a coating portion formed by stepwise coating at least two different metal oxides on the surface of the substrate, wherein the substrate is a spherical glass bead; and the coating portion includes a first metal oxide layer coated on the surface of the substrate and being tin oxide (SnO) having a rutile crystal structure; a second metal oxide layer coated on the surface of the first metal oxide layer and being titanium dioxide (TiO ₂ ) having a rutile crystal structure; and a protective layer coated on the surface of the second metal oxide layer and being formed of sodium silicate (Na ₂ SiO ₃ ), wherein the thickness of the second metal oxide layer is controlled by a titration method. According to the present invention, since titanium dioxide (Ti0 ₂ ) having a rutile crystal structure can be easily formed, the solvent resistance is excellent, so that the usage of the pigment can be widely expanded, and in particular, when applied to cosmetics, cosmetics having improved texture and moisturizing power as well as spreadability and spreadability can be manufactured.

Description

Pigment particle, Apparatus and method for manufacturing thereof {Pigment particle, Apparatus and method for manufacturing thereof}

The present invention relates to pigment particles. More specifically, it relates to pigment particles that improve spreadability and applicability on the skin, improve expressed color and gloss, and improve heat stability, as well as a manufacturing device and a manufacturing method thereof.

Pigments are fine powders that do not dissolve in water or organic solvents and give color to other substances. Organic pigments include phthalocyanine, diketopyrrolopyrrole, azo pigments, and quinacridone, while inorganic pigments include various types of iron oxide or ultramarine.

Meanwhile, pigments are also widely used in cosmetics. When pigments are used in cosmetics, plastic beads have been used as a base material.

And, metal oxides used in pigments include _Ti02 , _Si02 , ZnO, _W03 , etc. Meanwhile, CdS and ZnS can also be used instead of metal oxides. In terms of refractive index, the refractive index of _Ti02 is 2.84 at 500 to 600 nm, the refractive index of _Si02 is 1.457, the refractive index of ZnO is 2.0, the refractive index of _W03 is 1.67, the refractive index of CdS is 2.384, and the refractive index of ZnS is 2.355.

Accordingly, a pigment having a predetermined refractive index can be produced by coating the surface of a plastic bead, which is a substrate, with a metal oxide material that exhibits a desired refractive index.

The representative metal oxide used in pigments is titanium dioxide (Ti0 ₂ ), and the crystal structures of titanium dioxide (Ti0 ₂ ) can be divided into rutile, anatase, and brookite. Of these, brookite is very unstable and it is difficult to synthesize a pure crystal, so it is not used industrially. Titanium dioxide (Ti0 ₂ ) with rutile and anatase crystal structures is used industrially.

In the case of the anatase crystal structure, it is mainly used as a photocatalyst because of its excellent photoactivity and has recently been widely used in air purification. In comparison, the rutile crystal structure has excellent light and heat resistance and is generally used as a white pigment. Meanwhile, the anatase crystal structure has a characteristic that a phase transition occurs and the crystal structure changes to rutile when heat is applied during the process of coating titanium dioxide (Ti0 ₂ ). In terms of the physical properties of the pigment, titanium dioxide (Ti0 ₂ ) with a rutile crystal structure has excellent light resistance, heat resistance, and weather resistance, and has good color and hiding power, and a high refractive index compared to the anatase crystal structure, so it is advantageous to use titanium dioxide (Ti0 ₂ ) with a rutile crystal structure as a pigment.

In addition, titanium dioxide (Ti0 ₂ ) is known to have excellent optical properties and to be harmless to the human body, as well as having excellent corrosion resistance and mechanical durability. In addition, since it has a refractive index of 1.9 to 2.6 depending on the deposition form, it can achieve a high refractive index when coated on a plastic bead. In particular, titanium dioxide (Ti0 ₂ ) with a rutile crystal structure is transparent and birefringent, so it is advantageous to form a rutile crystal structure when used as a pigment. However, titanium dioxide (Ti0 ₂ ) has a disadvantage in that it is coated with an anatase crystal structure when coated on a plastic bead under general coating process conditions.

Meanwhile, the methods for coating titanium dioxide (Ti0 ₂ ) on substrates such as plastic beads are mainly using fluidized bed chemical vapor deposition and uniform deposition.

First, fluidized bed chemical vapor deposition is a method of coating a gaseous raw material onto a plastic bead to be coated.

When titanium dioxide (Ti0 ₂ ) is coated on a plastic bead using the chemical vapor deposition method, a reaction as shown in the following chemical formula 1 occurs.

TiCl ₄ + 2H ₂ O + Plastic bead → TiO ₂ -Plastic bead + 4HCl … [Chemical Formula 1]

However, when using the fluidized bed chemical vapor deposition method, since the TiO ₂ coated on the substrate is formed in an anatase crystal structure, SnO ₂ must be added during the coating process in order to transform the anatase crystal structure of TiO ₂ into a rutile crystal structure. However, in order to induce the phase transition of TiO ₂ by adding SnO _2, titanium chloride (TiCl ₄ ) must be heated to a high temperature, which limits the commercial use of the fluidized bed chemical vapor deposition method.

And, the homogeneous precipitation method is a method in which precipitation occurs by releasing OH- ions through solution reactions such as hydrolysis without adding a precipitant from the outside to the solution when the precipitate is formed.

When titanium dioxide (Ti0 ₂ ) is coated on plastic beads using the homogeneous precipitation method, a reaction as shown in the following chemical formula 2 occurs.

TiOSO ₄ + Plastic bead + H ₂ O → TiO ₂ -Plastic bead + H ₂ SO ₄ … [Chemical Formula 2]

When using the homogeneous precipitation method, a titanium salt solution is added to ultrapure water containing plastic beads at a certain temperature and stirred. The titanium salt is hydrolyzed to form a titanium hydrate precipitate, which coats the surface of the plastic beads. However, since the homogeneous precipitation method exhibits strong acidity during the reaction process, the pH must be neutralized for safety. In addition, when using the homogeneous precipitation method, the titanium dioxide (Ti0 ₂ ) that is precipitated has an irregular oval shape, which causes light to scatter due to the shape, which reduces the gloss effect.

In this way, when plastic beads are used as a base material, due to the nature of plastic, there are disadvantages such as the inability to be stable to heat and the need for additional neutralization processes during the manufacturing process. In addition, when plastic beads are used as a base material for cosmetics, there are problems such as the deterioration of the texture and moisturizing power of the cosmetics, or the deterioration of the color and gloss due to the aforementioned reasons.

The content described as background technology above is only for understanding the background of the present invention, and should not be taken as an acknowledgment that it corresponds to prior art already known to those skilled in the art.

Literature 1. Korean Intellectual Property Office Patent Registration No. 10-2149688, “Pearl luster pigment particles and their manufacturing method”

Accordingly, the present invention has been made to solve the problems of the above-mentioned prior art, and an object of the present invention is to provide pigment particles and a manufacturing device and a manufacturing method thereof, which can improve heat stability by using glass beads as a substrate, thereby facilitating the process, and can improve the color and gloss expressed by coating titanium dioxide (Ti0 ₂ ) on the glass beads, and can improve not only the texture and moisturizing power but also the spreadability and application properties when the pigment is applied to cosmetics.

The pigment particles of the present invention for achieving the above purpose preferably include a substrate; and a coating portion formed by stepwise coating at least two different metal oxides on the surface of the substrate;

The above description is a spherical glass bead,

The above coating portion includes a first metal oxide layer coated on the surface of the substrate and being tin oxide (SnO) having a rutile crystal structure; a second metal oxide layer coated on the surface of the first metal oxide layer and being titanium dioxide (Ti0 ₂ ) having a rutile crystal structure; and a protective layer coated on the surface of the second metal oxide layer and being formed of sodium silicate (Na ₂ SiO ₃ ).

The second metal oxide layer is characterized in that its thickness is controlled by a titration method.

At this time, the coating portion is formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the protective layer, and a third metal oxide layer formed with a thickness different from that of the second metal oxide layer may be further formed.

Additionally, it is preferable that the thicknesses of the second metal oxide layer and the third metal oxide layer are each formed to be 10 to 150 nm.

And, when the pigment particles are applied to a combination of cosmetics, the pigment particles can be used as a tracer or filler, or for the production of a pigment preparation or a dry preparation.

Meanwhile, the present invention is a device for manufacturing pigment particles in which at least one layer among the coating portions formed in multiple layers on the surface of a substrate has a thickness controlled through a titration method.

It may include a plurality of tanks each storing raw materials for coating the above-mentioned substrate; a reactor in which coating is performed by introducing the above-mentioned substrate and raw materials; a supply control valve formed between the reactor and each tank to selectively control the supply of the above-mentioned substrate and raw materials; and a control unit controlling each supply control valve.

At this time, the reactor may include a stirrer for stirring the materials and raw materials introduced into the reactor, and a motor for rotating the stirrer.

In addition, the tank may include a substrate tank for storing the substrate, a first tank for storing a titanium dioxide (Ti0 ₂ ) precursor, a second tank for storing a tin oxide (SnO) precursor, a third tank for storing sodium hydroxide (NaOH), and a fourth tank for storing sodium silicate (Na ₂ SiO ₃ ).

In addition, the supply control valve may include a substrate supply control valve that controls the supply of the substrate, a first supply control valve that controls the supply of the titanium dioxide (Ti0 ₂ ) precursor, a second supply control valve that controls the supply of the tin oxide (SnO) precursor, a third supply control valve that controls the supply of sodium hydroxide (NaOH), and a fourth supply control valve that controls the supply of sodium silicate (Na ₂ SiO ₃ ).

In addition, in order to check and process the coating process in real time, the reactor may further include a thermometer for measuring the temperature inside the reactor, a pH meter for measuring the pH inside the reactor, and a heater for heating the inside of the reactor.

And, the control unit may include a motor controller for controlling the rotational speed of the motor when the process is performed according to the selective control of the first to fourth supply control valves, a process time control unit for controlling the process time according to the selective control of the first to fourth supply control valves, a temperature control unit for controlling the temperature inside the reactor in response to the selective control of the first to fourth supply control valves, a pH control unit for controlling the third supply control valve in response to the selective control of the first, second, and fourth supply control valves to control the pH inside the reactor in real time, and a raw material supply speed control unit for controlling the first to fourth supply control valves in response to the control of the temperature control unit and the pH control unit to control the input speed of the raw material.

Meanwhile, as a method for manufacturing pigment particles using the pigment particle manufacturing device of the present invention,

A first step of preparing a substrate; a second step of preparing a precursor for forming a coating portion; and a third step of forming a coating portion on the surface of the substrate, wherein at least one of the plurality of layers forming the coating portion is formed of a metal oxide while controlling its thickness using a titration method.

In the above first step, the substrate is prepared into a sphere having a diameter of 0.1 to 20 μm using glass beads,

In the second step, the precursor includes a tin oxide (SnO) precursor forming a first metal oxide layer and a titanium dioxide (Ti0 ₂ ) precursor forming a second metal oxide layer.

The third step includes: a first process of introducing deionized water (DI water) and a substrate into a reactor in which current flows between a stirring rod and an inner wall; a second process of introducing HCl and the tin oxide (SnO) precursor into the reactor and stirring the reactor to form a first metal oxide layer formed of tin oxide (SnO) having a rutile crystal structure on the surface of the substrate; a third process of introducing HCl and the titanium dioxide (TiO ₂ ) precursor into the reactor and stirring the reactor to form a second metal oxide layer formed of titanium dioxide (TiO ₂ ) having a rutile crystal structure on the surface of the first metal oxide layer; a fourth process of performing dehydration in the reactor and then washing the substrate on which the first metal oxide layer and the second metal oxide layer are formed using deionized water; It may include a fifth process of drying the substrate on which the first metal oxide layer and the second metal oxide layer are formed to recover pigment particles.

At this time, the third step may further include a sixth step of forming a protective layer by coating sodium silicate (Na ₂ SiO ₃ ) on the surface of the pigment particles after the fifth step.

In addition, after the sixth process, the method may further include a seventh process of adding deionized water and pigment particles on which the protective layer is formed to a reactor in which current flows between the stirring rod and the inner wall; and an eighth process of adding HCl and the titanium dioxide (Ti0 ₂ ) precursor to the reactor and stirring to form a third metal oxide layer formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the protective layer.

In addition, it is preferable to control the thickness of the formation of the second metal oxide layer and the third metal oxide layer by controlling the time for adding and stirring the titanium dioxide (Ti0 ₂ ) precursor in the third and eighth processes.

In addition, it is preferable to stir the third and eighth processes for 3 to 12 hours under conditions of pH 1.6 and a temperature of 70 to 80°C.

In addition, it is desirable to maintain the coating speed of the third and eighth processes at 20 to 30 nm/hr.

As described above, according to the pigment particles and the manufacturing apparatus and manufacturing method thereof according to the present invention, when coating titanium dioxide (Ti0 ₂ ) on a substrate, it is expected that the effect of easily forming titanium dioxide (Ti0 ₂ ) having a rutile crystal structure even at a low temperature can be expected by utilizing SnO.

In addition, by coating using the titration method, it is expected that the thickness of the coating layer can be easily controlled.

In addition, it is superior to conventional fluidized bed chemical vapor deposition or uniform precipitation methods in terms of production time and production volume, and can produce high-quality pigments at low manufacturing costs.

In addition, according to an embodiment of the present invention, the coating portion can be formed as a composite layer of three or more layers to form an excellent refractive index, and accordingly, it can exhibit color anisotropy, dichroism, and double refraction in which direct color and indirect color change depending on the angle.

And, since it is easy to form titanium dioxide (Ti0 ₂ ) with a rutile crystal structure, it is expected to have the effect of broadly expanding the use of pigments due to its excellent content resistance. In particular, when applied to cosmetics, it is possible to manufacture cosmetics with improved texture and moisturizing power as well as spreadability and spreadability.

In addition, by coating two or more metal oxides, the light absorption rate can be reduced and the reflectance can be increased more effectively than before, thereby expressing gloss more effectively.

And, since all processes take place inside the reactor, rapid process processing is possible.

FIG. 1 is a cross-sectional view showing pigment particles according to one embodiment of the present invention.
FIG. 2 is a cross-sectional view showing pigment particles according to another embodiment of the present invention.
Figure 3 is a configuration diagram of a pigment particle manufacturing device according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention and the accompanying drawings, on the premise that like reference numerals in the drawings indicate like components.

When it is said in the detailed description of the invention or in the claims that one component "includes" another component, this is not to be construed as being limited to consisting of only that component unless otherwise specifically stated, but should be understood to mean that it may further include other components.

In addition, components named as “means,” “part,” “module,” or “block” in the detailed description of the invention or the patent claims mean units that process at least one function or operation, and each of these can be implemented by software or hardware, or a combination thereof.

Hereinafter, an example in which the pigment particles of the present invention and the manufacturing device and manufacturing method thereof are implemented will be described through specific examples.

First, for easy explanation of the present invention, the refractive index will be explained first.

The refractive index is the rate at which the speed of light decreases when traveling through different media. Optically, light has wave-particle duality, being both a particle and a wave. The speed of light waves differs in media with different properties. In other words, the speed of light traveling through air or a vacuum is different from that of light traveling through titanium dioxide (Ti0 ₂ ) and being divided into reflected light and refracted light. The degree to which light bends when passing through the boundary of different media is called the refractive index.

Meanwhile, when the standard medium is air and the corresponding medium is titanium dioxide (Ti0 ₂ ), if the crystal structure of titanium dioxide (Ti0 ₂ ) is the rutile phase, the relative refractive index is approximately 2.84, which is known to be higher than that of other metal oxides. This relative refractive index can be explained by Snell's law.

FIG. 1 is a cross-sectional view showing pigment particles according to one embodiment of the present invention.

As illustrated in FIG. 1, a pigment particle according to one embodiment of the present invention includes a substrate (100) and a coating portion (200) formed by stepwise coating at least two different metal oxides on the surface of the substrate (100).

A spherical glass bead may be used as the substrate (100). Here, the glass bead may be composed of 72.5 wt% of silicon dioxide (Si0 ₂ ), 0.2 wt% of iron oxide (Fe ₂ 0 ₃ ), 0.6 wt% of aluminum oxide (Al ₂ 0 ₃ ), 9.1 wt% of calcium oxide (Ca0 ), 3.8 wt% of magnesium oxide (Mg0 ), 13.3 wt% of sodium oxide (Na ₂ 0), 0.3 wt% of potassium oxide (K ₂ 0), and 0.2 wt% of water (H ₂ 0). In addition, the pH of the glass bead used in this embodiment is 9.8, and the specific gravity is 2.40. Meanwhile, a silica bead may be used as the substrate (100).

For example, the substrate (100) may use a spherical glass bead having a refractive index of about 1.6 and a diameter of 0.1 to 20 ㎛, more specifically, a diameter of 0.1729 to 19.904 ㎛. Preferably, the substrate (100) uses a glass bead having a diameter of 0.5122 to 8.816 ㎛. In this case, it is preferable to use a glass bead that is white in color and has an even surface.

The coating portion (200) can be implemented as multiple layers by stepwise coating different metal oxides to have various refractive indices.

For example, the coating portion (200) may include a first metal oxide layer (210) coated on the surface of the substrate; a second metal oxide layer (220) coated on the surface of the first metal oxide layer (210); and a protective layer (230) coated on the surface of the second metal oxide layer (220). Meanwhile, in the present embodiment, a case of coating the first metal oxide layer (210) and the second metal oxide layer (220) is described, but only one of them may be coated.

At this time, the first metal oxide layer (210) may be formed of tin oxide (SnO) having a rutile crystal structure, the second metal oxide layer (220) may be formed of titanium dioxide ( _Ti02 ) having a rutile crystal structure, and the protective layer (230) may be formed of sodium _silicate ( _Na2SiO3 ). In this embodiment, the case where titanium dioxide (Ti02) is formed as the second metal oxide layer (220) is described, but iron oxide ( _Fe203 ) may be used for coating. In addition, the case where sodium _silicate ( _Na2SiO3 ) is formed as the protective layer ( ₂₃₀ ) is described, but aluminum oxide ( _{Al203 )} , silane, etc. may be used for coating. Meanwhile, as described above, a coating layer can be formed using only the second metal oxide layer (220) and the protective layer (230) without coating the first metal oxide layer (210).

Of course, the first metal oxide layer (210) and the second metal oxide layer (220) form different high refractive indices, so that the color expression is distinct, and the direct color and indirect color are clear, so that a pigment with high brightness can be implemented.

Meanwhile, the first metal oxide layer (210) is formed of tin oxide (SnO) having a rutile crystal structure, and the tin oxide (SnO) having a rutile crystal structure induces a phase transition of titanium dioxide (TiO ₂ ) from an anatase crystal structure to a rutile crystal structure even at a low temperature when the second metal oxide layer (220) is formed on the surface of the first metal oxide layer (210).

Tin oxide (SnO) forming the first metal oxide layer (210) has the characteristic of reducing the absorption rate of light, and since the absorption and reflection of light have a complementary color effect, a pigment with excellent refractive index can be implemented by forming the first metal oxide layer (210) with tin oxide (SnO).

The second metal oxide layer (220) is formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure. Since the first metal oxide layer (210) is formed of tin oxide (SnO) having a rutile crystal structure, it is easy to implement by inducing a phase transition of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure at a low temperature. At this time, the second metal oxide layer (220) can be formed while controlling its thickness using a titration method. At this time, it is preferable that the thickness of the second metal oxide layer (220) is formed to be 10 to 150 nm.

Titanium dioxide (Ti0 ₂ ) forming the second metal oxide layer (220) has a very high refractive index, is anisotropic and non-toxic, and has a high hiding power, so it does not dissolve in any solvent. In addition, titanium hydroxide is synthesized by titrating a strong base such as NaOH and titanium, and this titanium hydroxide has an excellent color development reaction (or color reaction), so it is advantageous in synthesizing a pigment from matte to glossy, and it can realize a pigment of better quality than conventional pigments due to its excellent color development and coloring power.

It is preferable that the protective layer (230) be formed of sodium silicate (Na ₂ SiO ₃ ), which is an inorganic adhesive.

Sodium silicate (Na ₂ SiO ₃ ) forming the protective layer (230) is an inorganic adhesive having content resistance, and can further enhance the content resistance of the second metal oxide layer (220).

Meanwhile, the present invention can further form a metal oxide layer on the coating portion in order to implement a more diverse refractive index.

Meanwhile, when the pigment particles of the present invention are applied to a combination of cosmetics, the pigment particles can be used as a tracer or filler, or for the production of a pigment preparation or a dry preparation.

FIG. 2 is a cross-sectional view showing pigment particles according to another embodiment of the present invention.

As illustrated in FIG. 2, pigment particles according to another embodiment of the present invention include, similarly to the above-described embodiment, a substrate (100); and a coating portion (200) formed by stepwise coating at least two different metal oxides on the surface of the substrate (100). In addition, the coating portion (200) includes a first metal oxide layer (210) coated on the surface of the substrate (100); a second metal oxide layer (220) coated on the surface of the first metal oxide layer (210); and a protective layer (230) coated on the surface of the second metal oxide layer (220). However, in the present embodiment, a third metal oxide layer (240) formed of titanium dioxide (TiO ₂ ) having a rutile crystal structure and having a different thickness from that of the second metal oxide layer (220) is further formed on the surface of the protective layer (230).

At this time, it is preferable that the third metal oxide layer (240) be formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure, similar to the second metal oxide layer (220).

At this time, the third metal oxide layer (240) can also be formed by controlling its thickness using the titration method, similar to the second metal oxide layer (220). Therefore, it is preferable that the thickness of the third metal oxide layer (240) is also formed to be 10 to 150 nm.

However, it is preferable that the thickness of the third metal oxide layer be formed to a different thickness from the thickness of the second metal oxide layer (220).

Therefore, it is possible to implement various colors of the pigment by creating a difference between direct and indirect colors through the second metal oxide layer (220) and the third metal oxide layer (240) exposed at the outermost layer.

Figure 3 is a configuration diagram of a pigment particle manufacturing device according to one embodiment of the present invention.

As illustrated in FIG. 3, a device for manufacturing pigment particles according to one embodiment of the present invention includes a plurality of tanks (300) in which raw materials for coating a substrate are each stored, a reactor (400) in which the substrate and raw materials are introduced and coating is performed, a supply control valve (500) formed between the reactor (400) and each tank (300) to selectively control the supply of the substrate and raw materials, and a control unit (600) that controls each supply control valve (500).

The reactor (400) includes a stirrer (410) that stirs the materials and raw materials introduced into the reactor (400) and a motor (420) that rotates the stirrer (410). Here, the stirrer (410) may be a stirring rod.

The tank (300) includes a substrate tank (310) for storing substrate, a first tank (320) for storing a titanium dioxide (Ti0 ₂ ) precursor, a second tank (330) for storing a tin oxide (SnO) precursor, a third tank (340) for storing sodium hydroxide (NaOH), and a fourth tank (350) for storing sodium silicate (Na ₂ SiO ₃ ).

Here, 15 to 25 ℓ of HCl, 15 to 25 kg of D.I Water, and 0.5 to 2.5 kg of tin oxide (SnO) may be injected into the second tank (330) to form a tin oxide (SnO) precursor. Meanwhile, the second tank (330) may be formed by subdividing each of the three tanks, and each of the subdivided tanks may be directly supplied to the reactor (400) through each valve. That is, HCl, D.I Water, and tin oxide (Tin Oxide) may be directly supplied to the reactor (400) to form a tin oxide (SnO) precursor within the reactor (400), or HCl and D.I Water required for other processes may be directly supplied to the reactor (400) when the relevant process is in progress.

The supply control valve (500) includes a substrate supply control valve (510) that controls the supply of the substrate, a first supply control valve (520) that controls the supply of the titanium dioxide (Ti0 ₂ ) precursor, a second supply control valve (530) that controls the supply of the tin oxide (SnO) precursor, a third supply control valve (540) that controls the supply of sodium hydroxide (NaOH), and a fourth supply control valve (550) that controls the supply of sodium silicate (Na ₂ SiO ₃ ). In this way, the supply control valves (500) can be formed in each supply pipe connected to each tank.

Meanwhile, in order to check and process the coating process in real time, the reactor (400) is further configured with a thermometer (430) for measuring the temperature inside the reactor (400), a pH meter (440) for measuring the pH inside the reactor (400), and a heater (450) for heating the inside of the reactor (400).

The control unit (600) comprises a motor controller (610) for controlling the rotation speed of the motor (420) when the process is performed according to the selective control of the first supply control valve (520) to the fourth supply control valve (550), a process time control unit (620) for controlling the process time according to the selective control of the first supply control valve (520) to the fourth supply control valve (550), a temperature control unit (630) for controlling the temperature inside the reactor (400) in response to the selective control of the first supply control valve (520) to the fourth supply control valve (550), a pH control unit (640) for controlling the pH inside the reactor (400) in real time by controlling the third supply control valve (540) in response to the selective control of the first supply control valve (520), the second supply control valve (530), and the fourth supply control valve (550), and a temperature control unit (630) and pH It includes a raw material supply speed control unit (650) that controls the first supply control valve (520) to the fourth supply control valve (550) in response to the control of the control unit (640) to control the raw material input speed.

Here, the motor controller (610) is connected to the motor (420) to control the speed of the motor (420) for each process, the process time control unit (620) is connected to the motor controller (610), the temperature control unit (630), the pH control unit (640), and the raw material supply speed control unit (650) to control the process time in real time, the temperature control unit (630) is connected to the thermometer (430) and the heater (450) to control the temperature of the heater for each process in response to the temperature sensing value, the pH control unit (640) is connected to the pH meter (440) to control the pH for each process, and the raw material supply speed control unit (650) is connected to the supply control valve (500) to control the real-time supply amount of each supply control valve (510, 520, 530, 540, 550).

Meanwhile, in order to discharge the raw material introduced into the reactor (400) after each process is completed, an outlet (not shown) is formed in the reactor (400), and the outlet is connected to a discharge pipe (not shown) in which a discharge valve (not shown) is formed.

The manufacturing device for pigment particles configured in this manner controls the substrate supply control valve (510) to input the substrate into the reactor (400), and selectively controls the first supply control valve (520) to the fourth supply control valve (550) to form a coating portion (200) on the substrate.

Here, as an example, a process of forming a coating portion (200) on a substrate using a pigment particle manufacturing device is described.

First, the control unit (600) controls the substrate supply control valve (510) to feed the substrate into the reactor (400), and then controls the second supply control valve (530) to feed the tin oxide (SnO) precursor into the reactor (400) and stir. Accordingly, a first metal oxide layer formed of tin oxide (SnO) having a rutile crystal structure is formed on the surface of the substrate. At this time, it is preferable to feed 15 to 25 ℓ of HCl, 15 to 25 kg of D.I. Water, and 0.5 to 2.5 kg of tin oxide (SnO) precursor into the second tank (330) and stir in advance before supplying the tin oxide (SnO) precursor to the reactor (400). Of course, if the second tank (330) is divided into three, it is possible to supply directly from each tank to the reactor (400).

Next, the control unit (600) controls the first supply control valve (520) to inject and stir a titanium dioxide (Ti0 ₂ ) precursor to form a second metal oxide layer formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the first metal oxide layer.

Here, when forming the first metal oxide layer and the second metal oxide layer, the control unit (600) controls the third supply control valve (540) to supply sodium hydroxide (NaOH) into the reactor (400) so that the pH inside the reactor (400) can be controlled in real time within the range of 1.6 to 7.5. In addition, the temperature inside the reactor (400) can be controlled in real time. In this way, by controlling the pH and temperature inside the reactor (400) in real time in conjunction with the supply speed of the raw material, it is possible to obtain not only the desired gloss but also various glosses. In addition, since each supply control valve is controlled by the control unit (600), not only the application of the titration method is easy, but also the thickness of the second metal oxide layer can be easily controlled.

Meanwhile, when the process of forming the second metal oxide layer is completed, the control unit (600) controls the fourth supply control valve (550) to inject sodium silicate (Na ₂ SiO ₃ ) into the reactor (400) to form a protective layer on the surface of the second metal oxide layer.

In addition, when the process of forming a protective layer is completed, the control unit (600) controls the first supply control valve (520) to inject and stir a titanium dioxide (Ti0 ₂ ) precursor to form a third metal oxide layer formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the protective layer.

Meanwhile, after each process is completed, a dehydration and washing process can be performed, and the dehydration and washing process can use ultrapure water and is performed in real time inside the reactor (400). That is, when each process is completed, the stirrer (410) and heater (450) formed in the reactor (400) are operated to perform the dehydration and washing process inside the reactor (400). In this way, in the present invention, since all processes are processed inside the reactor (400), rapid process processing is possible. That is, in the existing method, manual work to take out the substrate for the dehydration and washing process performed after each process was required, but by preventing such manual work, process automation and rapid process processing are possible.

Then, a method for manufacturing pigment particles of the present invention using a manufacturing device for pigment particles configured as described above will be described.

A method for manufacturing a pigment according to one embodiment of the present invention comprises: a first step of preparing a substrate; a second step of preparing a precursor for forming a coating portion; and a third step of forming a coating portion on a surface of the substrate, wherein at least one of a plurality of layers forming the coating portion is formed of a metal oxide while controlling its thickness using a titration method.

At this time, in the first stage, the substrate is prepared into a spherical shape with a diameter of 0.1 to 20 μm using glass beads.

And, in the second step, a tin oxide (SnO) precursor that forms the first metal oxide layer and a titanium dioxide (Ti0 ₂ ) precursor that forms the second metal oxide layer are prepared separately.

Here, the tin oxide (SnO) precursor uses a tin oxide (Tin Oxide)-based material, and the titanium dioxide (Ti0 ₂ ) precursor uses TiOCl ₂ .

When the substrate, tin oxide (SnO) precursor, and titanium dioxide (Ti0 ₂ ) precursor are prepared in this manner, multiple layers of coating parts are sequentially coated on the substrate.

Therefore, the third step comprises: a first process of introducing deionized water (DI Water) and a substrate into a reactor (400) in which current flows between a stirring rod and an inner wall; a second process of introducing HCl and the tin oxide (SnO) precursor into the (400) and stirring to form a first metal oxide layer formed of tin oxide (SnO) having a rutile crystal structure on the surface of the substrate; a third process of introducing HCl and the titanium dioxide (TiO ₂ ) precursor into the reactor (400) and stirring to form a second metal oxide layer formed of titanium dioxide (TiO ₂ ) having a rutile crystal structure on the surface of the first metal oxide layer; a fourth process of performing dehydration in the reactor (400) and then washing the substrate on which the first metal oxide layer and the second metal oxide layer are formed using deionized water; It includes a fifth process of drying the substrate on which the first metal oxide layer and the second metal oxide layer are formed to recover pigment particles.

Meanwhile, the third process of forming the second metal oxide layer can control the thickness of the second metal oxide layer using the titration method.

In the third process, when titanium dioxide (Ti0 ₂ ) is coated on the surface of a substrate, preferably the surface of a substrate on which a first metal oxide layer is formed, using a titration method, a reaction as shown in the following chemical formula 3 occurs.

TiOCl ₂ + 2NaOH + Glass bead → TiO ₂ -Glass bead + 2NaCl + H ₂ O … [Chemical Formula 3]

The above titration method is one of the important operations in quantitative analysis, which is a method of obtaining the amount of a reagent of known concentration required to react with a certain amount of a test material solution in volumetric analysis, calculating the concentration of the test material, and dropping it one drop at a time to coat it. This can be achieved through real-time control of the supply control valve (500) by the control unit (600). Therefore, it is easy to productively control the thickness of the coating layer by precipitating titanium dioxide (Ti0 ₂ ) generated by neutralizing titanium chloride (TiOCl ₂ ) with ammonia or sodium hydroxide (2NaOH) and coating it on glass beads.

And, after the fifth process, a sixth process is further performed to form a protective layer on the surface of the second metal oxide layer by coating the surface of the pigment particles with sodium silicate (Na ₂ SiO ₃ ).

Meanwhile, in order to further form a third metal oxide layer on the surface of the protective layer as in the other embodiments described above, after the sixth process, a seventh process of introducing deionized water (DI water) and pigment particles on which the protective layer is formed into a reactor (400) in which current flows between the stirring rod and the inner wall; and an eighth process of introducing HCl and the titanium dioxide (Ti0 ₂ ) precursor into the reactor (400) and stirring the mixture to form a third metal oxide layer formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the protective layer can be further performed.

The method for manufacturing the pigment as described above is explained through specific examples.

In order to control the thickness of the formation of the second metal oxide layer using the titration method of the present invention, it is preferable to control the time for adding and stirring the titanium dioxide (Ti0 ₂ ) precursor in the third process described above.

Add 15 to 30 ℓ of D.I water and 1.5 to 3.5 ㎏ of 0.1 to 20 ㎛ glass beads to a 50 ℓ reactor (400) and stir while maintaining the temperature at 70 to 80 ℃. At this time, the stirring rod is made of stainless steel (Stainlee steel) made of SU316L material with Mo synthesized, and stirring is started by the motor stirrer.

In addition to the substrate tank (310), four tanks are prepared for feeding raw materials into the reactor (400).

Therefore, a titanium dioxide (Ti0 ₂ ) precursor, i.e., TiOCl ₂ , is prepared in the first tank (320), and 15 to 25 ℓ of HCl, 15 to 25 kg of DI water, and 0.5 to 2.5 kg of tin oxide (SnO) precursor, tin oxide (Tin Oxide), are prepared by stirring in the second tank (330).

And, in the third tank (340), NaOH is prepared for pH adjustment, and in the fourth tank (350), a sodium silicate (Na ₂ SiO ₃ ) aqueous solution is prepared for forming a protective layer.

Once the raw materials are prepared in this way, the raw materials prepared in the first tank (320) to the fourth tank (350) are fed into the reactor (400) in a set order to perform coating.

At this time, the supply speed of raw materials fed into the reactor (400) from the first tank (320) to the fourth tank (350) is maintained at a speed of 5±3 ml/min.

Then, the pH inside the reactor (400) is adjusted to 1.6 and then coating is started. Of course, the pH can be adjusted to obtain the desired gloss.

First, raw materials are supplied from the second tank (330) and the third tank (340) to the reactor (400), and stirred at 35±5 RPM for 30 minutes. Then, inside the reactor (400), tin oxide (Tin Oxide), which is a tin oxide (SnO) precursor, reacts, forming a first metal oxide layer on the surface of the substrate.

Then, raw materials are supplied from the first tank (320) and the third tank (340) to the reactor (400), and stirred at 45±5 RPM while maintaining for 3 to 4 hours. Then, inside the reactor (400), a second metal oxide layer is formed while being coated on the surface of the first metal oxide layer at a rate of 20 to 30 nm/hr.

Next, the substrate on which the first metal oxide layer and the second metal oxide layer are formed is dehydrated within the reactor (400) and washed four times using D.I Water. At this time, the stirrer (410) and heater (450) formed within the reactor (400) are operated to perform the dehydration and washing process within the reactor (400).

Then, the substrate on which the first metal oxide layer and the second metal oxide layer are formed is placed again in the reactor (400) and stirred at 45±5 RPM while maintaining it for 1 hour. Then, a protective layer is formed on the surface of the second metal oxide layer.

Next, the substrate on which the protective layer is formed is dehydrated within the reactor (400) and washed four times using D.I Water. At this time, the stirrer (410) and heater (450) formed within the reactor (400) are operated to perform the dehydration and washing process within the reactor (400).

After washing, dry at 350℃ for 24 hours.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) having a rutile crystal structure with a thickness of 40 to 60 nm formed the second metal layer. The recovered pigment realized a white color with a very high refractive index.

It can be used as a filler for cosmetic formulations, such as compact powder, lipstick, and pure white emulsion and cream, and a white powder having a very smooth skin feel can be obtained.

Example 2 supplied raw materials from the first tank (320) and the third tank (340) to the reactor (400), which is the process for forming the second metal oxide layer, and maintained the stirring time for 5 to 7 hours at 45±5 RPM, and manufactured a pigment under the same conditions as Example 1.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) having a rutile crystal structure with a thickness of 60 to 80 nm formed the second metal layer. The recovered pigment exhibited a yellow color with a very high refractive index.

It can be used as a filler for cosmetic formulations, such as compact powder, lipstick and pure white emulsion and cream, and a yellow powder having a very smooth skin feel can be obtained.

Example 3 supplied raw materials from the first tank (320) and the third tank (340) to the reactor (400), which is the process for forming the second metal oxide layer, and maintained the stirring time for 8 to 9 hours at 45±5 RPM, and manufactured a pigment under the same conditions as Example 1.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) with a rutile crystal structure of 80 to 100 nm in thickness formed the second metal layer. The recovered pigment realized a red color with a very high refractive index.

It can be used as a filler for cosmetic formulations, such as compact powder, lipstick and pure white emulsion and cream, and a red powder having a very smooth skin feel can be obtained.

Example 4 supplied raw materials from the first tank (320) and the third tank (340) to the reactor (400), which is the process for forming the second metal oxide layer, and maintained the stirring time for 10 to 11 hours at 45±5 RPM, and manufactured a pigment under the same conditions as Example 1.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) having a rutile crystal structure with a thickness of 100 to 140 nm formed the second metal layer. The recovered pigment realized a blue color with a very high refractive index.

It can be used as a filler for cosmetic formulations, such as compact powder, lipstick and pure white emulsion and cream, and a blue powder having a very smooth skin feel can be obtained.

Example 5 supplied raw materials from the first tank (320) and the third tank (340) to the reactor (400), which is the process for forming the second metal oxide layer, and maintained the stirring time for 11 to 12 hours at 45±5 RPM, and manufactured a pigment under the same conditions as Example 1.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) having a rutile crystal structure with a thickness of 140 to 160 nm formed the second metal layer. The recovered pigment realized a green color with a very high refractive index.

It can be used as a filler for cosmetic formulations, such as compact powder, lipstick and pure white emulsion and cream, and a green powder having a very smooth skin feel can be obtained.

[Comparative example]

A comparative example was prepared by manufacturing a pigment under the same conditions as Example 1, except that the process of supplying raw materials from the second tank (330) and the third tank (340) to the reactor (400) in the process of forming the first metal oxide layer and maintaining it for 30 minutes while stirring at 35±5 RPM was not performed.

Thus, a pigment was recovered in which titanium dioxide (Ti0 ₂ ) having an anatase crystal structure with a thickness of 40 to 60 nm formed the second metal layer. The color of the recovered pigment was implemented as white, similar to that of the first embodiment.

As can be seen from the above Examples 1 to 5, it was confirmed that the thickness of the second metal oxide layer can be controlled to a desired level by controlling the time at which the second metal oxide layer is coated using the titration method, and it was confirmed that the color implemented can be controlled depending on the thickness of the second metal oxide layer.

In addition, as can be seen from the comparison of the examples and comparative examples, when the first metal oxide layer is formed before the second metal oxide layer and SnO is used together when forming the second metal oxide layer, it was confirmed that even at a relatively low temperature of 70 to 80°C, a phase transition of titanium dioxide (Ti0 ₂ ) from an anatase crystal structure to a rutile crystal structure can occur, thereby forming a second metal oxide layer having a rutile crystal structure.

Meanwhile, as can be seen from Examples 1 to 5, while forming the first metal oxide layer and the second metal oxide layer, the pH inside the reactor (400) is controlled by supplying NaOH to the third tank (340) for pH control. It is preferable that the hydrolysis reaction conditions for forming the first metal oxide layer or the second metal oxide layer be maintained at a temperature of 70 to 80° C. and a pH of 1.6 to 7.5.

If the temperature inside the reactor (400) is lower than 70°C, the reaction proceeds slowly and the first metal oxide layer and the second metal oxide layer of the desired thickness are not formed. In addition, if the temperature inside the reactor (400) is higher than 80°C, a problem may occur in which hydrolysis occurs in the tank where the raw material is loaded, not in the reactor (400).

And, it is desirable that the pH inside the reactor (400) starts at 1.6 and is maintained between 1.6 and 7.5 during the reaction. If the pH inside the reactor (400) is higher than 7.5, a problem may occur in which the desired gloss is not achieved.

In addition, it is preferable that the coating thickness of the first metal oxide layer or the second metal oxide layer coated on the substrate be formed to be 10 to 150 nm to implement various colors such as white, yellow, red, blue, and green.

In addition, it is preferable that the coating speed of the first metal oxide layer or the second metal oxide layer coated on the substrate be maintained at 20 to 30 nm/hr. If the coating speed is slower than the suggested speed, a problem of slow reaction speed may occur, and if it is faster than the suggested speed, a problem of improper coating may occur.

The technical idea of the present invention has been examined through several examples above.

It is obvious that a person having ordinary skill in the art to which the present invention pertains can make various modifications or changes to the above-described embodiments based on the description of the present invention. In addition, even if not explicitly illustrated or described, it is obvious that a person having ordinary skill in the art to which the present invention pertains can make various modifications including the technical idea of the present invention based on the description of the present invention, and this still falls within the scope of the rights of the present invention. The above-described embodiments described with reference to the attached drawings are described for the purpose of explaining the present invention, and the scope of the rights of the present invention is not limited to these embodiments.

100: Base 200: Coating
210: First metal oxide layer 220: Second metal oxide layer
230: Protective layer 240: Third metal oxide layer
300: Tank 400: Reactor
500: Supply control valve 600: Control unit

Claims (6)

A device for manufacturing pigment particles in which at least one layer among the coating portions formed in multiple layers on the surface of a substrate has a thickness controlled through a titration method,
A plurality of tanks each storing raw materials for coating the substrate, including the above-described materials;
A reactor in which coating is performed by putting in the above-mentioned materials and raw materials;
A supply control valve formed between the reactor and each tank to control the supply of the substrate and the raw material; and
A control unit for selectively controlling each of the above supply control valves;

The above tank includes a substrate tank for storing the substrate, a first tank for storing a titanium dioxide (Ti0 ₂ ) precursor, a second tank for storing a tin oxide (SnO) precursor, a third tank for storing sodium hydroxide (NaOH), and a fourth tank for storing sodium silicate (Na ₂ SiO ₃ ).
The above second tank is formed into three subdivided tanks so that HCl, DI water, and tin oxide can be directly supplied to the reactor, respectively.

The above reactor includes a stirrer for stirring the substrate and raw material introduced into the reactor, and a motor for rotating the stirrer.
The above reactor further comprises a thermometer for measuring the temperature inside the reactor, a pH meter for measuring the pH inside the reactor, and a heater for heating the inside of the reactor.

The above supply control valve includes a substrate supply control valve for controlling the supply of the substrate, a first supply control valve for controlling the supply of the titanium dioxide (Ti0 ₂ ) precursor, a second supply control valve for controlling the supply of the tin oxide (SnO) precursor, a third supply control valve for controlling the supply of the sodium hydroxide (NaOH), and a fourth supply control valve for controlling the supply of the sodium silicate (Na ₂ SiO ₃ ).

The control unit includes a motor controller for controlling the rotational speed of the motor when the process is performed according to the selective control of the first to fourth supply control valves, a process time control unit for controlling the process time according to the selective control of the first to fourth supply control valves, a temperature control unit for controlling the temperature inside the reactor in response to the selective control of the first to fourth supply control valves, a pH control unit for controlling the third supply control valve in response to the selective control of the first, second, and fourth supply control valves to control the pH inside the reactor in real time, and a raw material supply speed control unit for controlling the first to fourth supply control valves in response to the control of the temperature control unit and the pH control unit to control the input speed of the raw material.

The above motor controller is connected to the above motor and controls the speed of the motor for each process.
The above process time control unit is connected to the motor controller, the temperature control unit, the pH control unit, and the raw material supply speed control unit, respectively, to control the process time in real time.
The above temperature control unit is connected to the thermometer and the heater and controls the temperature of the heater for each process in response to the temperature sensing value.
The above pH control unit is connected to the pH meter and controls the pH for each process.
A pigment particle manufacturing device in which the above raw material supply speed control unit is connected to the above supply control valve and controls the real-time supply amount of each supply control valve. In claim 1,
The above description is a device for manufacturing pigment particles, which are spherical glass beads. In claim 2,
The above coating part,
A first metal oxide layer coated on the surface of the glass bead, which is tin oxide (SnO) having a rutile crystal structure;
A second metal oxide layer coated on the surface of the first metal oxide layer, which is titanium dioxide (Ti0 ₂ ) having a rutile crystal structure; and
A device for manufacturing pigment particles, comprising a protective layer formed of sodium silicate (Na ₂ SiO ₃ ) and coated on the surface of the second metal oxide layer. In claim 3,
A pigment particle manufacturing device characterized in that the coating portion is formed of titanium dioxide (Ti0 ₂ ) having a rutile crystal structure on the surface of the protective layer, and a third metal oxide layer formed with a thickness different from that of the second metal oxide layer is further formed. In claim 4,
A pigment particle manufacturing device, characterized in that the second metal oxide layer and the third metal oxide layer each have a thickness of 10 to 150 nm. In claim 5,
A pigment particle manufacturing device characterized in that when the pigment particles are applied to a combination of cosmetics, the pigment particles are used as a tracer or filler, or for manufacturing a pigment preparation or a dry preparation.

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