KR101822557B1 - Metal-doped UV-protective inorganic pigment and mill base comprising the same - Google Patents

Abstract

The present invention uses titanium dioxide and zinc oxide, which are not nano-sized, as a base material to be doped with a divalent or trivalent metal element, and by doping copper or iron element within a range that does not affect the change of crystal form of titanium dioxide or zinc oxide , The UV-B and UV-A all over the area can be fully demonstrated, as well as titanium dioxide or zinc oxide, the main disadvantage of the existing mill base, Pigments and mill bases comprising them.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a UV-protective inorganic pigment and a mill base,

The present invention relates to an inorganic pigment for protecting ultraviolet rays doped with a metal element and a method for producing a mill base comprising the metallic element. More particularly, the present invention relates to an inorganic pigment for protecting ultraviolet rays, which is one of functional cosmetics, A metal element-doped ultraviolet-shielding inorganic pigment prepared by doping a metal element of the metal element and amplifying the ultraviolet blocking range and capability thereof and further coating the metal oxide and the surface treatment agent, And a method of manufacturing a mill base which makes it easy to manufacture an ultraviolet screening cosmetic.

The sunlight, the source of the life activity of the earth's creatures, is the energy generated by fusion in the sun reaching the Earth in the form of electromagnetic waves. The sunlight reaching the Earth can be divided into the shortest wavelength to the longest in the order of Gamma-ray, X-ray, Ultraviolet (UV), Visible, Infrared, wave.

Among them, ultraviolet rays can be subdivided into UV-C (200 to 290 nm), UV-B (290 to 320 nm) and UV-A (320 to 400 nm) depending on the wavelength range. Visible light is generally in the wavelength range of 400 ~ 800nm, and it is recognized as various colors from violet to red in our eyes.

The shorter the wavelength of sunlight is, the higher the energy is, and when it is irradiated on living organisms, it destroys or transforms the protoplasm, constituent organs and DNA of the cell. Sunlight in the UV-C wavelength range from the gamma rays, which correspond to high-energy light, is blocked by the ozone layer in the upper atmosphere before reaching the surface. Thanks to the ozone layer, UV-B and UV-A, visible light, infrared and radio waves are only reaching the earth's surface.

However, UV-B and UV-A, which are relatively high-energy light through the ozone layer and reaching the surface, are harmful to most living organisms except for helping humans to synthesize and sterilize vitamin D .

Especially, UV-B in the range of 290 ~ 320nm belongs to high-energy light with the shortest wavelength among the sunlight reaching the earth's surface. It penetrates into human epidermis and upper part of dermis, Blisters, rashes, etc., and after a few days it increases melanin pigment causing skin suntan.

UV-A in the range of 320 to 400 nm is relatively weak in energy compared to UV-B, but penetrates deep into the dermis of the human dermis because it can pass through objects such as glass. Converts pigment into deep melanin pigment to make skin darker. It is also known that it modifies collagen and elastin in skin tissue to reduce skin elasticity, promote skin aging, cause photosensitivity dermatosis, and become a major cause of skin cancer.

Therefore, ultraviolet rays should be blocked because of these hazards. In particular, photoaging is a photo-aging phenomenon in which the skin of a person exposed to sunlight for a long time is wrinkled and aged more rapidly than a person who is not exposed to sunlight for a long time. Photoaging is a representative example of ultraviolet ray harmfulness.

The traditional way to block harmful ultraviolet rays is to put a cloth on the face, to wear a hat, or to use tea and sunshine. The beauty method known from ancient times was to put olive oil, rice extract and jasmine on the primitive level.

The company responded to UV rays in earnest from the 1930s when L'Oreal, a French company, started selling cosmetics containing organic sunscreens, which were artificially synthesized. Since then, through the Second World War, to the present day, a variety of ultraviolet screening agents have been developed and new cosmetic formulations have been developed, as well as new organic UV blocking agents. In the 1970s, the formulations that impart water repellency to water-repellent foundations and the surface treatment technology of raw materials were introduced in the 1970s. However, since the skin irritation of organic-based ultraviolet screening agents and the safety concerns over time were not fundamentally solved, Was not complete.

UV blocking agents are often classified into organic and inorganic types. Organic blocking agents, depending on their type and chemical structure, disappear when the safety or harmfulness of the human body is exposed after they are used in cosmetics. It is also replaced. On the other hand, the inorganic blockers are zinc oxide (zinc oxide), which is an inorganic pigment used for shielding ultraviolet rays from the ancient times, and titanium dioxide, which is the most widely used white inorganic pigment since the 18th century, It has been certified and used until now.

On the other hand, the prior art relating to an inorganic ultraviolet screening agent or a combination thereof has been widely used in various fields such as an ultraviolet screening cream and a recent BB lotion, Or a method of imparting water repellency by treating an inorganic pigment with a metal soap, a silicone-based or fluorine-containing dispersant or a reactive polymer. Also, in order to improve the whitening phenomenon which is a disadvantage of titanium dioxide and zinc oxide, an example of the prior art is to use ultrafine particles of nano-size for transmitting visible light, and the ultraviolet screening composition Patent No. 10-0758819, Korean Patent No. 10-1006343, and Korean Patent No. 10-1210371.

Both titanium dioxide and zinc oxide used in the prior art have a common point of being nanoparticles. On the other hand, controversy has persisted since the SCCP (European Union Consumer Products Committee) filed an official opinion in 2009 that nanoparticles could be harmful to the environment and the human body. The controversial nanomaterials are specified to have a size of 1 to 100 nm, and the titanium dioxide and zinc oxide used in the prior art correspond to nanomaterials, so there is a great concern about harmfulness.

The hazard of cosmetics containing nanomaterials is the point of controversy that nanotoxicity caused by nanosized particle size and harmful effects that nanomaterials penetrate into the dermis layer through the skin stratum corneum. However, there is still a lack of accumulation of evidence that the expressed nanotoxicity and the content of nanomaterials that penetrate into the dermal layer are at a worrisome level. However, it is true that nano-aerosol products are regulated because nanomaterials are approved for inhalation toxicity by entering into the respiratory tract.

On the other hand, attempts have been made to solve the problems inherent in inorganic sunscreens by mixing titanium oxide and zinc oxide, which are inorganic ultraviolet screening agents, with metal oxides and sintering the mixture. For example, Korean Patent No. 10-0101125 and Korean Patent No. 10-1359458 disclose a method of mixing and sintering a considerable amount of metal oxide in titanium dioxide or zinc oxide. Separately, Korean Patent Laid-Open Publication No. 10-2005-0088216 discloses a photocatalytic activity of titanium dioxide and zinc oxide in photocatalytic activity of an organic ultraviolet screening agent in a composition for ultraviolet shielding in which titanium dioxide, zinc oxide and organic ultraviolet ray are present together. An example of doping metals such as manganese, vanadium, chromium, iron and the like is proposed to reduce UV absorption loss ratio to 5% or less of the same composition.

However, the ultraviolet screening cosmetics made from the inorganic ultraviolet screening agents exemplified in the prior art or the mill base using the ultraviolet screening agents still have the following problems.

Specifically, it was found that the physical properties of titanium dioxide and zinc oxide used as inorganic UV blocking agents were not extended to the UV-B range in the ultraviolet blocking range limited to UV-A, and in particular, As a result of the sintering treatment, there is a disadvantage that the ultraviolet ray blocking efficiency is adversely affected. The photocatalytic activity of titanium dioxide and zinc oxide can not be removed unless an inert metal oxide and a surface treatment agent are additionally treated on the surface of the inorganic pigment, And it is impossible to completely solve the phenomenon.

In order to understand the root cause of the problem of lowering the blocking efficiency of the inorganic ultraviolet screening agent, it has been found that in a composition composed of rutile type titanium dioxide, ferrous oxide (FeO) and ferric oxide (Fe ₂ O ₃ ) It is necessary to understand the phase diagram of Fig. 1 (a), which shows that a crystalline iron-titanium double oxide is produced. http://www.tulane.edu/~sanelson/eens211/tectosilictes&others.pdf,Tectosilicates, Carbonates, Oxides, & Accessory Minerals, Tulane University, Prof. Stephen A. Nelson., Updated on 02-Dec-2014]

As shown in the Iron-Titanium Oxide phase diagram of FIG. 1 (a), in the three-component system of titanium dioxide-ferric oxide-ferric oxide, Ilmenite (FeTiO ₃ ) and Ulvospinel Fe ₂ TiO ₄ ) is easily formed, so that the unique ultraviolet shielding ability of pure titanium dioxide is reduced.

In more detail, the crystal form of titanium dioxide is tetragonal system anatase and rutile, and orthorhombic system brookite. Among them, anatase and rutile are pure titanium dioxide with white color, but brookite is red because it contains iron (Fe), tantalum (Ta) and niobium (Nb) as a common impurity. Therefore, rutile, which is thermally stable and has a refractive index of 2.72, has the best ultraviolet shielding ability, has anatase with a refractive index of 2.52, and has the lowest blocking ability of broucite.

However, it is often the case that a titanium dioxide double oxide of completely different crystal is produced by mixing an external impurity element into titanium dioxide of pure crystal. For example, as shown in FIG. 1 (a), iron-titanium double oxide is produced by mixing rutile titanium dioxide with black ferrous oxide (FeO) and sintering at a high temperature to form rhombohedral ) Structure is easily produced, and when the content of iron oxide is further increased, a nickel-spinel type iron-titanium double oxide having a spinel structure is produced. In addition, iron-titanium double oxides of pseudobrookite (Fe ₂ TiO ₅ ) structure are easily produced by mixing red oxide ferric oxide (Fe ₂ O ₃ ) with brookite type titanium dioxide and sintering at high temperature. Such a crystalline iron-titanium double oxide is generally a black-red inorganic pigment, which may reduce the whitening phenomenon, which is a disadvantage of rutile titanium dioxide. However, the ultraviolet blocking effect is adversely affected as compared with the conventional rutile titanium dioxide .

In the case of zinc oxide, various double oxides are produced by mixing and sintering ferric oxide and ferric oxide. Pure wurtzite crystal type zinc oxide shows the best ultraviolet ray shielding ability. However, if a large amount of different metal oxides are mixed into zinc oxide and a double oxide is formed, the ultraviolet ray blocking effect is drastically reduced. FIG. 1 (b) shows a phase diagram illustrating the formation of a double oxide of a zinc oxide-iron compound. R. Hansson, PC Hayes, and E. Jak, Phase equilibria in the Fe-Zn-O system at related conditions to zinc sintering and smelting, VII International Conference on Molten Slags Fluxes and Salts, The South African Institute of Mining and Metallurgy, 2004]

Therefore, in the conventional method of mixing and sintering a large amount of various metal oxides with titanium dioxide and zinc oxide, which are the base materials, the metal oxides mixed into the crystal lattice of titanium dioxide and zinc oxide as base materials are excessively solidified, Type double oxides are produced, and accordingly, the ultraviolet shielding ability inherently possessed by pure crystalline titanium dioxide and zinc oxide is undesirably reduced.

The present inventors have studied methods for solving various conventional problems while maintaining intrinsic ultraviolet shielding properties of titanium dioxide and zinc oxide, which are inorganic pigments used as cosmetics for ultraviolet screening agents, and have found that nanotoxicity is expressed Without using nano-sized titanium dioxide or zinc oxide that is likely to penetrate into the dermal layer of the skin, the divalent or trivalent metal element is doped into the shallow crystal lattice of the base material without changing the crystal form of the ultraviolet- The wavelength range for blocking ultraviolet rays is expanded and at the same time, the ultraviolet blocking efficiency is improved. In addition, it is confirmed that the cause of the whitening phenomenon, which is the biggest problem in the related art, is fundamentally eliminated. The mill base was completed.

The present invention relates to an ultraviolet-shielding inorganic pigment, wherein the inorganic pigment is titanium dioxide, zinc oxide, or a mixture thereof, the surface of the crystal lattice of the inorganic pigment is doped with a divalent or trivalent metal element, There is provided an inorganic pigment for protecting ultraviolet rays, characterized in that the inorganic pigment is coated with a metal oxide and a surface treating agent.

Further, the present invention provides an inorganic pigment for ultraviolet protection, wherein the inorganic pigment is a mixture of titanium dioxide and zinc oxide in a weight ratio of 2: 8 to 8: 2.

In the present invention, the bivalent or trivalent metal element is used for doping with copper or iron. Unlike the bivalent or trivalent metal elements other than copper and iron, the safety of the human body is secured, Therefore, it is most preferable. The precursor used for doping copper or iron is preferably at least one selected from copper sulfate, copper nitrate, copper chloride, ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous chloride and ferric chloride. At this time, the precursor is preferably used in a doping range of 10 to 10000 ppm based on 100 parts by weight of the ultraviolet shielding inorganic pigment based on the metal element.

In the present invention, the metal oxide for coating the ultraviolet shielding inorganic pigment may be selected from the group consisting of sodium silicate, potassium silicate and teos (TEOS). The coating amount of the metal oxide is preferably 0.05 to 3.0 parts by weight based on 100 parts by weight of the ultraviolet blocking inorganic pigment.

Further, in the present invention, the surface treating agent may be at least one selected from the group consisting of casein, casein sodium, casein potassium, ammonium caseinate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, sodium palmitate, sodium palmitate, At least one selected from the group consisting of potassium stearate, lecithin, reactive silicon, silicone-based coupling agents and fluorine-based coupling agents. The coating amount of the surface treatment agent is preferably 0.5 to 10.0 parts by weight based on 100 parts by weight of the ultraviolet-shielding inorganic pigment.

On the other hand, the present invention provides a method for producing a mill base in which an inorganic pigment doped with a metal element is dispersed. In the above manufacturing method,

A first step;

(1-a) dissolving a precursor of a divalent or trivalent metal element to be doped in purified water and making a first water phase to which a nonionic surfactant is added;

(1-b) preparing a second aqueous phase in which a precursor of a metal oxide to be coated on a mixture of purified water, ethanol or purified water and ethanol is dissolved in a separate vessel;

(1-c) preparing a third aqueous phase in which a basic compound is dissolved in purified water in a separate vessel;

A second step; Adding the ultraviolet shielding inorganic pigment to the first aqueous phase at room temperature, stirring the mixture continuously to disperse the mixture, gradually adding the second aqueous phase to the first aqueous phase, 3 < / RTI > aqueous phase until the viscosity of the aqueous phase increases sharply;

A third step;

(3-a) maintaining the mixture of the second step at room temperature until the sol-gel reaction and the coprecipitation reaction are completed on the surface of the inorganic pigment for ultraviolet shielding;

(3-b) washing the unreacted material with filtration by adding purified water after the step (3-1) is completed;

(3-c) pulverizing the dried material with a pulverizer and sintering the same in an electric furnace;

Step 4; Pulverizing the sintered product with a pulverizer, and coating with a surface treating agent to obtain an ultraviolet blocking inorganic pigment; And

Step 5; Preparing an ultraviolet screening mill base by dispersing the ultraviolet screening inorganic pigment in a circulating disperser together with a cosmetic medium, a surfactant or a dispersant, a stabilizer and an additive, for a predetermined time;

And a control unit.

In the production method of the present invention, the non-ionic surfactant in the first step is selected from the group consisting of polyoxyethylene glycol alkyl ether, polyoxypropylene glycol alkyl ether, glucoside alkyl ether, polyoxyethylene glycol octylphenol ether, glycerol alkyl ester, polyoxyethylene At least one selected from the group consisting of glycerol fatty acid alkyl esters, glycol sorbitan alkyl esters, sorbitan alkyl esters, flocamers, cocamide monoethanolamines, and cocamide diethanolamines, and 0.05 to 5.0 wt% Is preferably used.

The present invention also provides a method for producing a basic compound, wherein the basic compound in the first step is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, ethanolamine, triethanolamine, sodium phosphate monobasic, Wherein at least one member selected from the group consisting of calcium, sodium, dibasic potassium phosphate, potassium dibasic and potassium polyphosphate is selected and 0.1 to 20.0 parts by weight is used per 100 parts by weight of the third aqueous phase. do.

In the second step, the mixing ratio of the first to third water phase is 30 to 200 parts by weight of the first water phase, 10 to 200 parts by weight of the second water phase and 5 to 50 parts by weight of the third water phase in the second step The present invention provides a manufacturing method characterized by:

In the present invention, it is preferable that the sintering treatment conditions to be performed in the third step are sintering for 1 to 4 hours at a temperature of 500 to 900 캜.

In the fourth step, the additive for coating the surface treatment agent on the ultraviolet-shielding inorganic pigment is selected from the group consisting of malic acid, maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, citric acid, magnesium chloride, aluminum chloride, Magnesium sulfate, aluminum sulfate and zinc sulfate, and treating the resulting mixture with 0.5 to 10 parts by weight per 100 parts by weight of the product obtained in the third step.

In the fifth step, the ultraviolet ray blocking inorganic pigment is contained in an amount of 20 to 70% by weight, the cosmetic medium is 20 to 50% by weight, the surfactant or dispersant is 1 to 20% by weight, the viscosity adjuster is 1 to 10% By weight, and 0.5 to 5% by weight of an additive.

In another aspect, the present invention provides a cosmetic composition comprising a mill base in which the ultraviolet-shielding inorganic pigment is dispersed.

For example, the present invention provides a cosmetic composition comprising 1 to 50 wt% of the mill base described above.

The mill base of the present invention can be produced by using titanium dioxide or zinc oxide which is not a nano-sized material as a base material doped with a divalent or trivalent metal element, and by using a copper or iron element It is possible to sufficiently exhibit the blocking effect in all of the UV-B and UV-A regions and fundamentally solve the cause of the whitening phenomenon which is the biggest disadvantage of the conventional mill base containing titanium dioxide or zinc oxide .

Therefore, the mill base in which the iron or copper-doped titanium dioxide or zinc oxide of the present invention is mixed with and dispersed therein can be easily applied to various formulations in UV-blocking cosmetics.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a phase diagram showing a double oxide produced when an iron compound is incorporated into titanium dioxide and zinc oxide. FIG. (a) is a phase diagram showing a crystalline region of various double oxides produced when black iron oxide (FeO) and red iron oxide (Fe ₂ O ₃ ) are mixed with rutile type titanium dioxide and sintered, and (b) Fig. 3 is a phase diagram showing a crystalline region of a double oxide produced when black iron oxide or red iron oxide is mixed and sintered. Fig.
2 is a cross-sectional schematic diagram of an inorganic pigment for protecting a metal element-doped ultraviolet ray of the present invention.
FIG. 3 is a flow chart showing an inorganic pigment for ultraviolet-shielding metal-doped ultraviolet rays according to the present invention and a method for producing the mill base in which the inorganic pigment is dispersed.
4 is an X-ray diffraction (XRD) result of the iron-doped rutile titanium dioxide of the present invention. (a) is a diffraction pattern (black peak) of the third step obtained in Example 1, which is matched with the diffraction peak position (red bar) of the synthesized standard rutile titanium dioxide. (b) is the diffraction peak position (red bar) of the standard rutile titanium dioxide synthesized from the diffraction pattern (black peak) of the third step obtained in Example 3.
5 is an absorbance spectroscopy spectrum in an ultraviolet-visible light region obtained by measuring the third step product of Example 1 by a tape method. (a) is the UV-Vis spectrum of the transparent tape, (b) is the UV-Vis spectrum of the untreated rutile titanium dioxide, and (c) is the UV-Vis spectrum of the third step product of Example 1.
6 is an electron micrograph showing the result of the third step of Example 1. Fig.
7 is a result of measurement of the ultraviolet barrier index of the mill base and the conventional mill base obtained in Example 2 with an SPF290 analyzer. (a) is the SPF measurement result of the mill base obtained in Example 2, and (b) is the SPF measurement result of the mill base manufactured by the prior art No. 10-0758819.
8 is a photograph of the dispersion state of the mill base obtained in Example 2 of the present invention observed by an optical microscope.
9 is a photograph taken in order to compare the appearance color of the untreated rutile titanium dioxide with the appearance color of iron-doped titanium dioxide which is the third step obtained in Example 1 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In order to accomplish the above object, the present invention provides a method for preparing a titanium oxide, a zinc oxide or a mixture thereof, which is used as an ultraviolet shielding inorganic pigment according to the present invention, as a base material to be doped with a divalent or trivalent metal element, Is doped into a crystal lattice of the base material to form a new doping type ultraviolet shielding inorganic pigment and then the resulting dispersion is added to a cosmetic medium in a stable manner with a dispersant in advance And a dispersed mill base is obtained.

In the present invention, the optical effect obtained by doping titanium dioxide and zinc oxide, which are inorganic ultraviolet screening agents, with a divalent or trivalent metal element is that the free photoelectrons in titanium dioxide and zinc oxide produced by the absorption of light move with each other A difference in energy level between a conductive band and a valence band is changed by a doping effect of an impurity element and a new band gap E _g is formed. For this reason, the absorptive capacity is extended to the wavelength region of the light corresponding to the new bandgap.

This phenomenon can be explained by overcoming the Schottky barrier between metal and semiconductor. The titanium dioxide and zinc oxide used in the present invention are typical optical semiconductor materials. The band gaps of titanium dioxide and zinc oxide are 3.2 eV and 3.3 eV, respectively, capable of absorbing short wavelength light, that is, UV-A and UV-A, corresponding to an energy of 370 to 380 nm or more, UV-A up to a long 400 nm wavelength range still lacks the ability to block. This problem is caused by the fact that the metal element is hetero-bonded to the interface of the crystal lattice existing on the shallow surface of the inorganic pigment serving as a semiconductor by doping to narrow the bandgap of the inorganic pigment corresponding to the overcome of the Schottky barrier, The ability to block the light in the wavelength region is generated.

Of course, the precondition here is that a very small amount of the metal element should be doped into the inorganic pigment, and the metal element should not be solidified into the inorganic pigment, which is the base, to form a double oxide.

As a result, the ultraviolet shielding inorganic pigment of the present invention satisfying the above-mentioned conditions is doped with a very small amount of metal element, thereby reducing the Schottky barrier, thereby adjusting the band gap. By adjusting the band gap energy, -A, and at the same time, the whitening phenomenon is eliminated by the coloring effect by doping. Therefore, an inorganic pigment for ultraviolet shielding which can achieve the object of the present invention and a mill base dispersed with the inorganic pigment are provided .

In addition, a metal oxide is coated together to protect the metal element doping layer, and a surface treatment agent is coated for the purpose of improving dispersibility and imparting water repellency when dispersed in a medium to obtain a mill base for blocking ultraviolet rays.

2 is a schematic cross-sectional view for explaining the constitutional concept of the ultraviolet-shielding inorganic pigment of the present invention in which a divalent or trivalent metal element is doped and a metal oxide and a surface treatment agent are coated together.

Fig. 2 (a) shows the base material of the doping. In the present invention, titanium dioxide, zinc oxide, or a mixture thereof can be used as a base material for doping, and the base material represented in the cross-sectional view of FIG. 2 represents rutile titanium dioxide. The rutile titanium dioxide used in the present invention has an average particle diameter (D ₅₀ ) of 0.2 μm, which corresponds to 200 nm.

FIG. 2 (b) is a quadrangular pyramid shape of the rutile titanium dioxide in a simplified plan view.

2 (c) shows a doping layer doped with iron (Fe) in a crystal lattice of a shallow depth of the rutile titanium dioxide. The doped layer (c) doped with iron corresponds to a Schottky barrier (layer) which explains the phenomenon of band gap migration due to heterojunction between metal and semiconductor. Since the iron-doped layer (c) of the present invention is formed only on the very shallow crystal lattice of the rutile titanium dioxide surface, its doping depth is on the order of several angstroms (A). On the other hand, if the doping amount of iron is greatly increased, various double oxides of iron-titanium dioxide described in FIG. 1 (a) are produced, and ultraviolet shielding ability is greatly reduced.

2 (d) shows a metal oxide coating layer which is coated together when doping a metal element. The metal oxide coating layer protects the metal element doping layer and transmits the incident light almost directly to the doping layer, so that the metal oxide is transparent and has the lowest refractive index. The most preferred metal oxide is the index of refraction of approximately 1.45, silica (SiO _2). The coating thickness of this metal oxide coating layer is usually several nm.

On the other hand, ultimately, in order to produce the ultraviolet shielding mill base of the present invention, the ultraviolet shielding inorganic pigment must be dispersed in a liquid medium for various cosmetics. In order to stably disperse in a cosmetic medium, it is necessary to coat a surface treatment agent which forms a double layer on colloid particles to impart stability.

Fig. 2 (e) shows the coating layer of the surface treatment agent described above. In general, the surface treating agent means a surfactant or a dispersing agent. As the surface treatment agent, a surfactant mainly used in the production of a hydrophilic mill base is mainly used, and a metal soap, lecithin, a silicone or a fluorine-based dispersant is used in the production of a lipophilic mill base. The coating thickness of the surface treatment agent coating layer is usually several nm, but it varies slightly depending on the length of the surface treatment agent used and the coating density.

Hereinafter, the structure and the solution of the present invention will be described in detail.

In order to achieve the object of the present invention, the inorganic ultraviolet screening agent used for doping a divalent or trivalent metal element may be titanium dioxide or zinc oxide, or a mixture of titanium dioxide and zinc oxide in a weight ratio of 2: 8 to 8: 2 Can be used.

It is preferable to select copper (Cu) or iron (Fe) as the divalent or trivalent metal element used as a doping agent. They not only allow titanium dioxide and zinc oxide to be colored in a beige color so as to efficiently move the ultraviolet blocking region of titanium dioxide and zinc oxide to the UV-A side and remove the whitening phenomenon, Unlike metal elements, it is most suitable because it is safe for human body and can be used in cosmetics.

In order to dope these metal elements, it is preferable to use a precursor for doping, which is more preferably used in the form of an aqueous solution. Thus, the precursor to create a water-soluble compound containing copper and iron element is copper sulfate (CuSO _4), copper nitrate _{(Cu (NO 3) 2)} , copper chloride (CuCl _2), ferrous sulfate (FeSO _4), ferric sulfate (Fe ₂ (SO _{4) 3),} nitric acid, ferrous _{(Fe (NO 3) 3)} , nitric acid, ferric _{(Fe (NO 3) 3)} , ferrous chloride (FeCl _2), used to select one or more of ferric chloride (FeCl ₃₎ .

The amount of the water soluble compound precursor to be doped is preferably 10 to 10000 ppm based on pure copper or iron element contained in the precursor with respect to 100 parts by weight of the ultraviolet blocking inorganic pigment. If the doping amount is less than 10 ppm, the doping effect is not sufficient. If the doping amount is more than 10,000 ppm, various double oxides as illustrated in the diagrams (a) and (b) of FIG. 1 may occur depending on the sintering treatment conditions.

When the copper or iron element is doped in the ultraviolet-shielding inorganic pigment, the metal element serves to diffuse into the shallow crystal lattice of the base material and protects the doping layer of the metal element shown in Fig. 2 (c) It is necessary to form a metal oxide coating layer together. These metal oxides lower the sintering temperature during the sintering process performed after the doping process and prevent the particles of the base material from aggregating. The most preferred metal oxide is silica.

As a precursor for forming the metal oxide coating layer, it is preferable to use at least one selected from sodium silicate, potassium silicate, and tetraethyl orthosilicate (TEOS). These metal oxide precursors are preferably used in an amount of 0.05 to 3.0 parts by weight based on 100 parts by weight of the ultraviolet blocking inorganic pigment.

The inorganic pigment doping type ultraviolet blocking inorganic pigment of the present invention and the method of producing the mill base containing the same are schematically shown in the manufacturing process flow chart of FIG. 3, and the detailed manufacturing process will be described below.

First, in the first step of the manufacturing process, the precursor of copper or iron element to be doped is dissolved in purified water and a small amount of nonionic surfactant is added to make a first water phase, and another vessel is charged with purified water or ethanol or a mixture of purified water and ethanol A second water phase is prepared by dissolving a different additive and a third water phase is obtained by dissolving a basic compound in purified water in another vessel.

In the second step, the ultraviolet shielding inorganic pigment is added to the first aqueous phase at room temperature and stirring is continued while the second aqueous phase is gradually added thereto while being continuously dispersed so as to be uniformly dispersed. Thereafter, the first aqueous phase and the second aqueous phase The third water phase is gradually added to the combined water phase. If the viscosity of the water phase increases sharply, the third water phase is stopped at the proper end point, and then the mixture is stirred for a sufficient time.

In the third step, the product obtained in the second step process is allowed to stand at room temperature for at least a certain period of time, so that the adsorption on the surface of the doped base material by the sol-gel reaction or coprecipitation reaction in the dispersion system of the ultraviolet- . After completion of the reaction, purified water is added to the mixture to wash the unreacted material, which is then filtered and dried, and then pulverized by a pulverizer to obtain a fine powder, which is sintered in an electric furnace. The sintering atmosphere is preferably a reducing atmosphere.

In the fourth step, the product obtained in the three-step process is pulverized again with a pulverizer to prepare a fine powder, and then surface treatment is performed to change the surface properties of the obtained product. That is, when the surface treatment is performed with a metallic soap, a silicone, a fluorine compound and a surfactant that imparts water repellency and dispersibility to the ultraviolet shielding inorganic pigment doped with a metal element, the water resistance of the doped ultraviolet shielding inorganic pigment is improved The mill base dispersion performed in the next process step becomes easy.

The fifth step is a step of making a mill base so that the metal-element-doped inorganic pigment, which is a product obtained in the four-step process, can be easily used in cosmetics. In the present invention, the composition constituting the mill base is prepared by dispersing a liquid raw material such as an ultraviolet shielding inorganic pigment doped with a metal element, alcohol such as ethanol, polyol such as glycerin, silicone oil and ester oil, ), And various nonionic surfactants, silicone and fluorinated surfactants and the like are used as a dispersing agent, and high molecular materials such as gum arabic, xanthan gum, and carbomer are used as a viscosity modifier, and ionic blocking agents, antioxidants, whitening agents And the like as an additive.

The mill base may be prepared by dispersing all of these compositions together in a batch or circulating milling machine for a predetermined time or by using a dispersing machine such as a three-roll mill in which a strong shearing force is generated, Followed by successive steps to obtain an ultraviolet shielding mill base.

The nonionic surfactant serving to uniformly disperse titanium dioxide or zinc oxide by being added to the first aqueous phase of the first step is polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers polyoxyethylene glycol ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, polyoxyethylene glycol octylphenol ethers, glycerol alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, sorbitan alkyl esters, poloxamers, cocamide monoethanolamine, and cocamide diethanolamine may be selected and used A suitable amount of the first filler is 100 parts by weight About it is preferred to use 0.05 to 5.0 parts by weight.

The basic compounds used to titrate the metal oxide doping layer with the metal element doping layer used in the third phase of the first step process include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide Ca (OH) ₂ ), ammonia water (NH ₄ OH), ethanolamine, triethanolamine, sodium phosphate NaH ₂ PO ₄ , Na ₂ HPO ₄ , sodium phosphate (Na ₃ PO _4), sodium polyphosphate _{(Na 5 P 3 O 10)} , dipotassium hydrogen phosphate (K ₂ HPO _4), the third potassium phosphate (K ₃ PO _4), polyphosphoric acid potassium (K ₅ P ₃ O ₁₀ ). It is preferable that the amount is 0.1 to 20.0 parts by weight based on 100 parts by weight of the third water phase. These easily adsorb the metal elements in the aqueous solution of the metal element doping precursor to the surface of the base material.

The amount of each aqueous phase used in the first step is 30.0 to 200.0 parts by weight for the first water phase, 10.0 to 200.0 parts by weight for the second water phase, 5.0 to 50.0 parts by weight for the third water phase, .

The sintering treatment conditions in the third step are preferably sintered at a temperature of 500 to 900 DEG C for 1 to 4 hours. The sintering temperature is not sufficient for the doping effect at a temperature of 500 ° C or below, and at 900 ° C or higher, the doping metal diffuses too deeply into the crystal lattice of the base material, which is not preferable. If possible, it is desirable to keep the electric furnace in a reducing atmosphere.

The surface treatment agent constituting the coating layer shown in FIG. 2 (e) which is the outermost coating layer of the metal element-doped inorganic pigment to be carried out in the fourth step is casein, sodium caseinate, potassium caseinate, Sodium laurate, sodium laurate, sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium laurate, sodium citrate, At least one selected from the group consisting of sodium stearate, potassium stearate, lecithin, reactive silicone, silicone-based coupling agent and fluorine-based coupling agent is selected and used. The coating amount of the surface- 0.5 to 10.0 parts by weight based on 100 parts by weight of the total weight of the composition.

The additive for coating the surface treatment agent may be selected from the group consisting of malic acid, maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, Citric acid, magnesium chloride, aluminum chloride, calcium chloride, zinc chloride, magnesium sulfate, aluminum sulfate, zinc sulfate zinc sulfate is selected and dissolved in purified water. The additive is preferably used in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the third step dispersion product dispersed together with the surface treatment agent.

The fifth step is a final step of obtaining the mill base by mixing the resultant obtained in the previous step with a dispersing medium and a dispersing agent, and then dispersing the mixture in a strong mill.

The mill base composition obtained in the final step is such that the metal element-doped inorganic pigment as a result of the fourth step is 20.0-70.0 wt% or more, the dispersion medium is 20.0-50.0 wt%, the surfactant or dispersant is 1.0-20.0 wt% The viscosity adjusting agent is in the range of 1.0 to 10.0% by weight, and the additive is in the range of 0.5 to 5.0% by weight.

The ultraviolet shielding mill base of the present invention obtained by the above-described production method can be incorporated in cosmetics of various formulations such as bibby cream, sunscreen, liquid foundation, makeup base, compact, etc., .

The present invention will be described in detail as follows.

The manufacturing method of the present invention, which is obtained by an earnest research to solve the problems of the conventional mill base and the object of the present invention, is the same as the flow chart shown in Fig.

(First water) or a metal oxide precursor body fluid (second water) or a treatment solution (second water) used for coating a metal oxide with copper or iron, which is a bivalent or trivalent metal element, 3 water phase) in which an inorganic pigment is dispersed in a first water phase and a metal element doped precursor fluid of a first water phase is doped in a sol-gel or coprecipitation process with a second water phase or a third water phase, A third step of washing, filtering, drying and pulverizing the resulting product, and then sintering the product at a high temperature; a fourth step of further modifying the physical properties of the inorganic pigment to a lipophilic property from the hydrophilic property, And a five-step process for producing a mill base by combining the components and raw materials necessary for cosmetics for ultraviolet shielding by using the obtained product.

In the above manufacturing process, titanium dioxide and zinc oxide used as an ultraviolet shielding inorganic pigment are used as a base material for doping, and a precursor containing a small amount of a divalent or trivalent metal element is selected as a doping agent and injected into a shallow crystal lattice of the base material a surface treatment for changing the surface properties is performed to prepare an inorganic pigment for ultraviolet shielding doped with a new metal element. The inorganic pigment is combined with various dispersants in various cosmetic media and dispersed in a stable manner, It is characterized by obtaining a mill base.

Hereinafter, the present invention will be described in detail by way of examples, comparative examples, test examples, and formulation examples in which a mill base is blended. These examples and formulations are provided to further illustrate the present invention, and the scope of the present invention is not limited by these examples.

Example 1

To prepare a precursor solution doped with a metal element in the first step, 500 ml of purified water is added to a 1000 ml beaker, and 7.25 g of ferrous chloride (FeCl ₃ ) (2.5 g in terms of Fe) is added to dissolve. Then, 0.5 g of sorbitan sesquioleate, a nonionic surfactant, is added and dissolved to prepare a first water phase. 30 ml of purified water, 15 ml of ethanol and 5 ml of TEOS are added to another 100 ml beaker and mixed with each other to prepare a second water phase for silica coating. 8.0 g of sodium hydroxide (NaOH) is added to another 300 ml beaker and purified water is added to make a 200 ml aqueous 2N NaOH solution.

In the two-step process, 500 g of rutile titanium dioxide having an average particle diameter of 0.2 탆 was slowly added to the first water phase and dispersed for 30 minutes with a stirrer. The stirring is continued carefully while dropping the second water phase, and further dispersed for 10 minutes after the completion of the addition. The third aqueous phase, which is a 2N NaOH solution, is titrated by adding it to a mixed solution of the first aqueous phase and the second aqueous phase in which titanium dioxide is dispersed. And carefully stirred while observing the change of the titanium dioxide dispersion system according to the titration of the third water phase. The amount of the third aqueous phase is stopped at a point where the pH becomes 8 or so as the viscosity of the dispersed system increases sharply.

In the three-step process, the product obtained in the two-step process contained in the 1000 ml beaker is kept for 1 hour, and the supernatant is separated and removed, and 500 ml of purified water is poured therein to be washed, filtered and dried in a drier. This was pulverized by a pulverizer, put in a ceramic crucible and sintered in an electric furnace at 800 ° C for 1 hour to obtain 500 g of titanium dioxide doped with 5000 ppm of iron element.

In a four-step process, 1,000 ml of purified water and 15.0 g of sodium caseinate are placed in a 2000 ml beaker, and the mixture is heated to 60 ° C and dissolved slowly while stirring. 500 g of the product obtained in the third step is added and dispersed. To this, 10% aqueous solution of calcium chloride (CaCl ₂ ) is added dropwise while stirring and titration. The titration of the aqueous solution of calcium chloride is stopped with the end point of the point at which phase separation occurs as the viscosity of the dispersion rapidly increases. Discard the supernatant from the separated upper and lower layers, wash with 500 ml of purified water, filter and dry. This is dried in a dryer at 110 DEG C to obtain 515 g of iron-doped titanium dioxide coated with sodium caseinate.

In the 5-step process, a mixture of 70 g of lauryl glucoside, 10 g of propylene glycol, 10 g of 1,2-hexanediol, 5 g of polysorbate 80, 3 g of xanthan gum and 387 g of purified water were dispersed in a 2 L vessel and dispersed in a circulating basket mill for 30 minutes to obtain 1,000 g of a mill base for blocking ultraviolet rays.

Examples 2 to 5

The raw materials and compositions shown in the following Table 1 were subjected to the same processes as in Example 1 to obtain metallic elements-doped ultraviolet blocking inorganic pigments of the present invention and a mill base dispersed therein.

Stage input composition and manufacturing conditions of each process

Example
Process step Example 2 Example 3 Example 4 Example 5 Doping target
Inorganic pigments Titanium dioxide 500 g Titanium dioxide 500 g Titanium dioxide 300 g
Zinc oxide 200g Zinc oxide 500 g One
only
system 1 Award Purified water 500ml
Fe ₂ (SO ₄ ) ₃ 8.9 g
Polysolvate 1.0 g Purified water 500ml
CuCl ₂ 2H ₂ O 13.5g
Flocamer 0.5 g Purified water 400ml
Fe (NO ₃ ) ₃ 8.9 g
Polysorbate 1.0 g Purified water 500ml
FeCl ₃ 10.0 g
Flocamer 0.3 g 2 Awards Same as Example 1 Purified water 50ml
Sodium silicate 5.0 g Purified water 50ml
Potassium silicate 5.0 g Same as in Example 3 3 Awards Purified water 100ml
Triethanolamine 10.0 g Purified water 80ml
35% ammonia 20ml Purified water 90ml
Sodium Phosphate 10.0 g Same as Example 1 Step 2
Doping course Same as Example 1 Same as Example 1 Same as Example 1 Same as Example 1 Step 3
Sintering condition 800 ° C, 2 hours 600 ° C, 3 hours 700 ° C, 1.5 hours 550 ° C, 2 hours Step 4
Surface treatment Sodium stearate 15g
10% AlCl ₃ 50 ml Casein potassium 20g
10% citric acid 50ml Lecithin 20g
10% MgCl ₂ 50 ml Sodium stearate 15g
10% AlCl ₃ 50 ml 5
only
system wheat
Base
Furtherance 500 g of the 4-step product
Cyclopentasiloxane 260 g
Cyclohexasiloxane 140 g
PEG-10 dimethicone 100 g

Same as Example 1 Four-step yield 400 g
Cyclopentasiloxane 260 g
Cyclohexasiloxane 140 g
PEG-10 dimethicone 100 g
Decyl olivate 100 g
550g < tb >
Purified water 330g
Decyl glucoside 80g
Glycerin 20g
15 g of 1,2-hexanediol
Arabian Sword 5g Dispersion method Same as Example 1 Same as Example 1 Same as Example 1 Same as Example 1 Mill base
Yield 1000g 1000g 1000g 1000g

Comparative Example 1

A commercially available wheat base product (trade name: Tinoply SE50T) manufactured by the prior art Korean Patent No. 10-0758819 was purchased and used as a sample of a comparative example.

Tests were conducted to compare the physical properties of the stepwise yields of the above examples or the ultimately obtained mill base for shielding of the present invention and the mill base of the comparative example as follows.

Test Example 1: X-ray diffraction (XRD) pattern

Crystalline changes of the iron-doped titanium dioxide obtained in the step 3 of Example 1 were confirmed by an x-ray diffractometer (PANalytical B.V, EMPYREAN, The Netherlands). The results are shown in the graphs of (a) and (b) of FIG.

The X-ray incident on the three-step product of Example 1, which is the analytical sample, differs in the position and intensity of the diffraction line depending on the reflection plane and crystal form of the rutile titanium dioxide crystal. The diffracted ray having the strongest intensity in the rutile type surface index 110 appears at the position of 27.5 DEG (2-Theta), the second strong diffraction ray at the surface index 211 shows the diffraction line at the position of 54.3 DEG, The third strong diffraction line appears at the 36.2 ° position and the fourth strong diffraction line at the plane index (111) appears at the 41.2 ° position. Subsequently, diffraction lines appear at various positions and intensities on the crystal planes of several surface indices. By analyzing the position and intensity of the diffraction line of the surface index, it can be seen whether the crystalline form of the sample material is pure, or whether the crystal distortion or change of its own is caused by the external invading element.

The x-ray diffraction pattern obtained by measuring the three-step product of Example 1 of the present invention is shown in Fig. 4 (a), and the x-ray diffraction pattern obtained by measuring the three-step product of Example 3 is shown in Fig. 4 (b) Respectively. 4 (a) and 4 (b), the diffraction peak indicated by black in FIG. 4 (a) is a diffraction pattern of iron-doped titanium dioxide which is the three-step product of Example 1, The diffraction line position and the relative intensity of the synthesized rutile type titanium dioxide (standard sample) exactly coincide with each other.

Also in FIG. 4 (b), the diffraction pattern of the copper-doped titanium dioxide, which is also the three-step product of Example 3 shown in black, is also the diffraction pattern of the synthesized rutile titanium dioxide (standard sample) Relative strengths exactly match each other.

Therefore, the obtained product according to the embodiment of the present invention shows that the crystal of the rutile titanium dioxide is maintained as it is despite the process of doping the metal element. This means that the iron and copper elements used in the doping do not change the interplanar spacing by distorting the surface index of the rutile crystal of titanium dioxide.

Finally, it was found that the iron-doped titanium dioxide obtained in Examples 1 and 3 of the present invention did not form any double oxides as shown in the TiO ₂ -FeO-Fe ₂ O ₃ 3 component shown in FIG. 1 (a) .

Test Example 2: Absorption spectrum of ultraviolet-visible light (UV-Vis)

The absorbance of the untreated rutile titanium dioxide standard sample and the three-step yield of Example 1 was measured with an ultraviolet-visible spectrophotometer (Perkin-Elmer, Lamda 35, USA). Since the measurement sample is a powder, it was measured by a tape method. In the control of the spectrometer, the cellophane tape was attached as it was to set the baseline, and the untreated rutile-type titanium dioxide and the three-step product of Example 1 were adhered to the cellophane tape in a certain amount thinly, After that, the absorbance was measured in a wavelength range of 290 to 800 nm including ultraviolet light and visible light. The results are shown in Fig.

5 (a) is an absorption spectrum of a cellophane tape used for attaching a sample powder, which is set as a blank, (b) is an absorption spectrum of untreated rutile titanium dioxide, and (c) 1 < / RTI > of iron-doped titanium dioxide. The absorbance spectrum of FIG. 5 (c) showed higher absorbance in the wavelength range of 290 to 380 nm in the ultraviolet ray region and 420 to 550 nm in the blue visible ray region, as compared with the spectrum of (b). It is considered that a red shift occurred in the absorption spectrum of iron-doped rutile-type titanium dioxide.

This means that the band gap energy of the untreated rutile titanium dioxide was changed to a lower band gap due to the doping effect of the iron element disclosed in the present invention.

Test Example 3: Electron Microscope (SEM) observation

FIG. 6 is a photograph of the state of the iron-doped titanium dioxide particles obtained in the three-step step of Example 1 under an electron microscope (JEOL, JSM 6510, Japan).

As shown in the photograph of FIG. 6, it can be seen that the particle size of the iron-doped titanium dioxide obtained in the third step of Example 1 of the present invention is in the micron range of about 0.2 μm (that is, 200 nm) rather than the nano region. Therefore, it shows that the particle size of the rutile titanium dioxide is increased or the coagulation does not occur even though the sintering treatment is performed at a high temperature of about 800 ° C or so.

Test Example 4: Comparison of SPF

The test comparing the mill base obtained in the final stage of Example 2 with the UV barrier index of the existing mill base was measured with an SPF290 Analyzer (Optometries LLC, SPF290S, USA). The mill base of the comparative example used for the measurement is a commercially available product (trade name: Tinoply SE50T) manufactured by the method disclosed in Korean Patent No. 10-0758819. The results are shown in Fig.

As shown in FIG. 7, (a) showing the ultraviolet blocking spectrum of the mill base obtained in Example 2 of the present invention shows a high UV blocking index (MPF in the Y axis of the graph) in all regions of ultraviolet rays, (B) showing the ultraviolet blocking spectrum of the mill base was high only in a specific region of the ultraviolet ray. Specifically, the mill base (b) of Comparative Example 1 exhibits a high MPF only in the wavelength region of 290 to 315 nm corresponding to UV-B, and exhibits a maximum MPF at 305 nm, but has a disadvantage of falling rapidly.

In contrast, the millbase (a) of Example 2 has a slightly lower MPF than the millbase (b) of Comparative Example 1 in UV-B but has a much higher MPF in the UV-A region, And UV-A in the whole region of ultraviolet light.

This becomes clearer when comparing the ultraviolet region with an MPF of 30 or more. When comparing the MPF averaged at the four scan points (indicated by the dotted lines), the mill base (a) of Example 2 has a range of 290 to 400 nm in which the MPF is 30 or more, The mill base (b) of Comparative Example 1 is judged to block ultraviolet rays only in the UV-B region because the region having the MPF of 30 or more is 290 to 335 nm.

As a result, the SPF measurement result of the mill base according to the second embodiment of the present invention showing a relatively high ultraviolet shielding ability at UV-A is 110.37 at the top of FIG. 7 (a) The SPF measurement result of the mill base of Comparative Example 1, which is shown in Fig. 7 (b), is 56.35. As a result, the SPF measurement value of the mill base of Comparative Example 1 was about 1/2 of that of the mill base of the present invention.

Therefore, it can be seen that the mill base of the present invention has excellent ultraviolet shielding ability over the entire wavelength range of ultraviolet rays.

Test Example 5: Observation of aging stability and dispersion state of mill base

Table 2 shows the results of the aging stability test by observing whether or not the mill base obtained in the final stage of Example 2 was phase-separated with time, and the dispersion state of the mill base was measured with an optical microscope (Leica, OMLM , Germany). The results are shown in FIG.

The dispersion stability of the mill base obtained in Example 2

Storage period
Observation condition Aging change Test Methods 1 month 2 months 3 months 4 months 5 months 6 months Indoor storage stability stability stability stability stability stability Store in lab shelves Accelerated test stability stability stability stability stability stability Sequential circulation from 15 ° C ↔ 5 ° C ↔ 25 ° C to 45 ° C in a cycling chamber with a relative humidity of 75%

From the results of the dispersion stability test of Table 2, it was found that the mill base of the present invention had excellent dispersion stability in all the room storage and acceleration tests.

8, which shows the dispersion state of the mill base according to the present invention, which is related to the dispersion stability test result, it is confirmed that the mill base of the present invention maintains a uniform state, Could know.

Test Example 6: Observation of cloudiness phenomenon

The main disadvantage of the conventional UV mill base is the occurrence of cloudiness. The whitening phenomenon refers to an excessively whitish appearance of the face when applied to cosmetics containing white inorganic pigments, or to a creepy appearance of a makeup or a pale patient. This opacification is most pronounced in antiseptic cosmetics such as sunscreen formulated with titanium dioxide or zinc oxide for UV protection. This is because titanium dioxide and zinc oxide are high in total reflectivity of visible light rays. However, they are used as the most excellent white inorganic pigments in the field of general industrial coatings. However, in cosmetics field, the reflectance of visible light, .

As a result of intensive research to remove the root cause of white turbidity from titanium dioxide and zinc oxide itself having disadvantages of clouding phenomenon or mill base using them, it has been found that by preparing titanium dioxide or zinc oxide doped with metal, The ultraviolet shielding mill base was completed. Therefore, the three-step product of Example 1 of the present invention is iron-doped titanium dioxide from which the cause of the whitening phenomenon is removed, and a photograph comparing the titanium dioxide with untreated titanium dioxide is shown in FIG.

9, the appearance of the untreated titanium dioxide on the left side of the photograph is white with a high brightness, whereas the iron-doped titanium dioxide on the right side of the photograph has a beige color. That is, the iron-doped titanium dioxide originally shows a change from a high luminance white color to a yellow beige color. This means that the iron-doped titanium dioxide for ultraviolet shielding of the present invention has changed to a state in which the appearance color is changed through the manufacturing process of the present invention so that the whitening phenomenon can not occur.

There is one important prerequisite, however, that iron-doped titanium dioxide should not change its appearance color to such an extent that cloudiness does not occur. That is, the ultraviolet ray shielding titanium dioxide must be changed from a whitish color to a whitish color having a strong appearance color, but it must satisfy the precondition that the ultraviolet ray shielding property should not deteriorate due to iron doping to the original crystal form of titanium dioxide do.

Whether or not the mill base of the present invention satisfies the prerequisite conditions for solving the above-mentioned whitening phenomenon is determined by the X-ray diffraction analysis result of Test Example 1 in which the crystal form of the iron-doped titanium dioxide, which is the three-step product of Example 1 and Example 3, And the results of measuring the ultraviolet barrier index of Test Example 4 are well explained. According to the results of these two test examples, the mill base of the present invention fully satisfies the above-mentioned conditions.

As shown in the X-ray diffraction analysis graph of FIG. 4 (a) and FIG. 4 (b) obtained in Test Example 1, the iron-doped titanium dioxide of the present invention maintains the original rutile crystal well . Also, as shown in FIG. 7 (a) in which the ultraviolet blocking spectrum obtained in Test Example 4 was measured, the mill base in which the iron-doped titanium dioxide of the present invention was dispersed showed excellent ultraviolet shielding ability in the entire ultraviolet region.

Therefore, the metallic element-doped titanium dioxide or zinc oxide obtained by the research of the present invention has the ultraviolet shielding ability even though its crystal form remains unchanged. Moreover, it provides a new mill base which fundamentally eliminates the whitening phenomenon, which is the biggest disadvantage of the existing mill base, which appears when used in cosmetics with UV protection.

Moreover, due to these physical and optical characteristics, the mill base of the present invention does not require the use of nano-sized titanium dioxide or nanosized zinc oxide, which has a difficult manufacturing process and a much higher purchase price of raw materials and transmits visible light, in order to avoid cloudiness, to be.

In addition, the use of a mill base containing nano-sized titanium dioxide or nano-sized zinc oxide is advantageous in that there is no fear of nano-toxicity or inhalation toxicity that can be manifested in the use of cosmetics containing a large amount of nanomaterials.

Formulation Examples 1 to 3

A cosmetic composition containing the mill base of the present invention was prepared as shown in the following Table-2.

(Cosmetic composition for protecting ultraviolet rays) (unit: parts by weight)

division
Raw material name Formulation Example 1
(BB cream) Formulation Example 2
(Sun cream) Formulation Example 3
(foundation) The mill base of Example 1
The mill base of Example 2
Butylene glycol
glycerin
1,2-hexanediol
Caprylic / capric triglyceride
Adenosine
Sodium chloride
Cetyl ethyl hexanoate
Cyclomethicone
Dimethicone copolyol
Sorbitan isostearate
Sodium stearate
Beads wax
Tocopheryl acetate
Silicone-treated red iron oxide
Silicone-treated black iron oxide
Spices
Purified water 10.0
-
5.0
3.0
2.0
2.0
0.04
1.0
2.5
10.0
2.0
0.5
1.0
0.5
0.1
Suitable amount
Suitable amount
Suitable amount
to 100 -
30.0
5.0
3.0
2.0
2.0
0.04
1.5
4.0
10.0
2.0
0.5
1.0
1.0
0.1
-
-
Suitable amount
to 100 -
18.0
5.0
3.0
2.0
2.0
0.04
1.5
4.0
10.0
2.0
0.5
1.0
1.0
0.1
Suitable amount
Suitable amount
Suitable amount
to 100

The cosmetic having the ultraviolet shielding function obtained in the above-mentioned formulation example not only has a sufficient effect of ultraviolet ray shielding without containing any organic ultraviolet screening agent but also has excellent cosmetic effect without whitening.

At this time, the content of the mill base of the present invention in the prescription of the ultraviolet screening cosmetic product may vary depending on the cosmetic formulation to be selected, the intended use and the feeling of use to be designed, but it is preferable that the content is 1.0 to 50.0% by weight.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Therefore, the embodiments disclosed in the present specification are intended to illustrate rather than limit the present invention, and the scope and spirit of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (17)

In the inorganic pigment for ultraviolet shielding, the inorganic pigment is titanium dioxide, zinc oxide or a mixture thereof. The surface of the crystal lattice of the inorganic pigment is doped with a copper or iron metal element, An ultraviolet blocking inorganic pigment coated with an oxide and a surface treatment agent,
Wherein the inorganic pigment is a mixture of titanium dioxide and zinc oxide in a weight ratio of 2: 8 to 8: 2,
The coating amount of the metal oxide is 0.05 to 3.0 parts by weight based on 100 parts by weight of the ultraviolet-shielding inorganic pigment,
Wherein the surface treatment agent is at least one selected from the group consisting of casein, casein sodium, potassium caseinate, ammonium caseinate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate, And at least one selected from the group consisting of fluorine-based coupling agents,
Wherein the coating amount of the surface treatment agent is 0.5 to 10.0 parts by weight based on 100 parts by weight of the ultraviolet shielding inorganic pigment.
delete delete The ultraviolet blocking inorganic pigment according to claim 1, wherein the precursor of the metal element is used in a doping range of 10 to 10000 ppm in terms of a metal element based on 100 parts by weight of the ultraviolet blocking inorganic pigment.
The ultraviolet blocking inorganic pigment according to claim 1, wherein the metal oxide is at least one selected from the group consisting of sodium silicate, potassium silicate, and teos (TEOS).
delete delete delete 1. A method for producing a mill base in which an inorganic pigment doped with a metal element is dispersed,
A first step;
(1-a) dissolving a precursor of a divalent or trivalent metal element to be doped in purified water and making a first water phase to which a nonionic surfactant is added;
(1-b) preparing a second aqueous phase in which a precursor of a metal oxide to be coated on a mixture of purified water, ethanol or purified water and ethanol is dissolved in a separate vessel;
(1-c) preparing a third aqueous phase in which a basic compound is dissolved in purified water in a separate vessel;
A second step; Adding the ultraviolet shielding inorganic pigment to the first aqueous phase at room temperature, stirring the mixture continuously to disperse the mixture, gradually adding the second aqueous phase to the first aqueous phase, 3 < / RTI > aqueous phase until the viscosity of the aqueous phase increases sharply;
A third step;
(3-a) maintaining the mixture of the second step at room temperature until the sol-gel reaction and the coprecipitation reaction are completed on the surface of the inorganic pigment for ultraviolet shielding;
(3-b) after completion of the step (3-a), adding purified water to wash the unreacted material, followed by filtration and drying;
(3-c) pulverizing the dried material with a pulverizer and sintering the same in an electric furnace;
Step 4; Pulverizing the sintered product with a pulverizer, and coating with a surface treating agent to obtain an ultraviolet blocking inorganic pigment; And
Step 5; Preparing an ultraviolet screening mill base by dispersing the ultraviolet screening inorganic pigment in a circulating disperser together with a cosmetic medium, a surfactant or a dispersant, a stabilizer and an additive, for a predetermined time;
A method for producing a mill base in which an inorganic pigment for ultraviolet-shielding doped with a metal element is dispersed
10. The method of claim 9, wherein the non-ionic surfactant in the first step is selected from the group consisting of polyoxyethylene glycol alkyl ether, polyoxypropylene glycol alkyl ether, glucoside alkyl ether, polyoxyethylene glycol octylphenol ether, glycerol alkyl ester, polyoxyethylene At least one selected from the group consisting of glycerol fatty acid alkyl esters, glycol sorbitan alkyl esters, sorbitan alkyl esters, flocamers, cocamide monoethanolamines, and cocamide diethanolamines, and 0.05 to 5.0 wt% A method for producing a mill base in which an inorganic pigment doped with a metal element is dispersed
delete The method according to claim 9, wherein the mixing ratio of the first water to the third water in the second step is 30 to 200 parts by weight of the first water phase, 10 to 200 parts by weight of the second water phase and 5 to 50 parts by weight of the third water phase A method of producing a mill base in which an inorganic pigment doped with a metal element is dispersed
The method according to claim 9, wherein the sintering treatment in the third step is carried out at a temperature in the range of 500 ° C to 900 ° C for 1 hour to 4 hours. The metal element-doped ultraviolet blocking inorganic pigment is dispersed Method of manufacturing a mill base.
The method of claim 9, wherein the additive for coating the surface treatment agent on the ultraviolet-shielding inorganic pigment in the fourth step is selected from the group consisting of malic acid, maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, citric acid, At least one member selected from the group consisting of zinc chloride, calcium chloride, zinc chloride, magnesium sulfate, aluminum sulfate and zinc sulfate, and 0.5 to 10 parts by weight based on 100 parts by weight of the product obtained in the third step (3-c) Wherein the ultraviolet-shielding inorganic pigment is doped with a metal element.
[12] The method of claim 9, wherein in the fifth step, 20 to 70% by weight of the ultraviolet shielding inorganic pigment, 20 to 50% by weight of a cosmetic material, 1 to 20% by weight of a surfactant or a dispersant, %, And 0.5 to 5 wt% of an additive.
A cosmetic composition comprising a mill base dispersed with an ultraviolet shielding inorganic pigment according to claim 1 The cosmetic composition according to claim 16, wherein the mill base comprises 1 to 50 wt%.

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