Patent Application
20250206632
The present invention relates to a titanium (IV) oxide powder composed of particles characterized by a peanut-like twin shape and a method for producing the same.
The present invention also relates to a cosmetic containing the titanium (IV) oxide powder. Cosmetics containing the titanium (IV) oxide have easy spreadability, soft focus properties, and appropriate hiding power, so that a cosmetic film with excellent uniformity can be produced to exhibit a natural bare skin feel.
Conventionally, makeup cosmetics such as foundations that contain a pigment having a large coloring power such as titanium (IV) oxide and a coloring agent such as other inorganic pigments and organic pigments have been used as cosmetics that change the color tone of the skin to cover rubicund face, dullness, age spots, freckles, etc. in the skin, and to exhibit a uniform and beautiful skin in appearance.
Regarding the titanium oxide described above, pigments with high coloring power and hiding power as represented by titanium (IV) oxide are generally used to cover rubicund face, dullness, etc., and to erase unevenness of the skin. In JP S61-118311 A (Patent Literature 1), spherical titanium oxide having a particle size of 0.1 μm to 50 μm is used.
However, in the case of applying makeup to the skin using the foundation containing the titanium oxide, a creaky feel may be caused or a smooth feel of the skin may be lost. Furthermore, under sunlight, a problem that the finish of makeup looks pale and unnatural, which is generally referred to as white cast, due to high reflectance of bluish colors may occur. In order to solve the problem, attempts have been made to set the primary particle diameter to a smaller value.
For example, in JP H09-221411 A (Patent Literature 2) a cosmetic containing titanium dioxide having an average particle size of more than 0.10 μm and 0.14 μm or less is disclosed. Further, in JP HI 1-158035 (Patent Literature 3), a cosmetic containing titanium oxide having an anatase crystal form with a primary particle size of 0.001 μm or more and 0.15 μm or less and a secondary particle size of 0.6 μm or more and 2.0 μm or less is proposed.
Further, in JP 2000-191325 A (Patent Literature 4), use of aggregates of spherical titanium dioxide as cosmetic is proposed, wherein the aggregates have an apparent average particle diameter of 0.1 μm or more and 3 μm or less, and the aggregates are formed of small spherical particles of titanium dioxide having an average primary particle diameter of 0.01 μm or more and 0.07 μm or less as measured by X-ray diffraction method. Further, it is disclosed that the cosmetic is expected to impart good slipperiness and excellent light stability that conventional titanium dioxide does not have.
In JP 2008-56535 A (Patent Literature 5), the present applicant has proposed rutile-type titanium oxide agglomerated particles with a particle diameter of 0.1 μm or more and 5.0 μm or less formed by aggregating rod-shaped primary particles of titanium oxide to form a fan-shaped titanium oxide, and further agglomerating the fan-shaped titanium oxide, and a cosmetic made of the agglomerated particles. Further, the present applicant has reported that the cosmetic can be applied smoothly to the skin, gives no creaky feel and no rough feel to the skin, and exhibits a natural bare skin feel without white cast, due to moderate coloring power and hiding power.
However, the cosmetic described in Patent Literature 2 has insufficient spreadability and slippery when applying makeup.
Further, the cosmetic described in Patent Literature 3 has high activity and a strong bluish color due to anatase-type crystal form, as well as insufficient dispersion when compounded into cosmetics.
Further, the cosmetic described in Patent Literature 4 requires use of hydrogen peroxide and an autoclave in production, and production safety and production efficiency were not necessarily satisfied.
The cosmetic described in Patent Literature 5 leaves a slightly pale impression, and there is still room for improvement in hiding power. The present inventors believed that it is important to have an appropriate hiding power in order to stably obtain cosmetics that are free from bluishness without white cast.
In addition to relying on hiding power, the present inventors have focused on means of blurring to make age spots or the like on the skin less noticeable. In other words, the present inventors believed that a titanium oxide pigment with soft focus properties is able to give a natural impression with less occurrence of white cast, without need to increase the hiding power excessively.
Accordingly, an object of the present invention is to provide titanium (IV) oxide particles from which a uniform cosmetic film is formed when used in cosmetics, being capable of exhibiting a natural bare skin feel due to soft focus properties and appropriate hiding power in addition to easy spreadability, and to provide a cosmetic containing the particles.
As a result of intensive study on the problem, the present inventors have found that a cosmetic that spreads easily, having soft focus properties and appropriate hiding power, capable of exhibiting a natural-looking bare skin feel can be provided with use of a titanium (IV) oxide powder composed of peanut-like twin shaped particles having a major axis diameter, which is the longest part of a single particle, of 300 nm or more and 700 nm or less, a minor axis diameter, which is the maximum part in the direction perpendicular to the major axis, of 100 nm or more and 400 nm or less, a constriction diameter, which is the length in the direction perpendicular to the major axis at the central position of the major axis, of 80 nm or more and 200 nm or less, and a ratio of constriction diameter/minor axis diameter of 0.9 or less. The present invention includes, but is not limited to, the following:
The titanium (IV) oxide particles of the present invention blended in a cosmetic, particularly in a makeup cosmetic, allows a uniform cosmetic film to be formed, so that a natural bare skin feel can be exhibited. Further, a coating film including the titanium (IV) oxide particles of the present invention has soft focus properties and appropriate hiding power.
According to the present invention, a powder composed of titanium (IV) oxide particles having a peanut-like twin shape with a major axis diameter and a minor axis diameter in specific ranges and a constriction part at the center, is provided. Since the particles have an appropriate size, the particles blended in a cosmetic allows the cosmetic to spread easily. Further, due to the shape, smoothness, soft focus properties and appropriate hiding power are provided, and when made into a cosmetic film, excellent uniformity can be obtained. Thus, a cosmetic capable of exhibiting a natural-looking bare skin feel can be produced. Also, excellent dispersion is achieved when blended into a cosmetic, and a cosmetic with excellent feel can be provided.
The titanium (IV) oxide particles that constitute the powder of the present invention have a major axis diameter, which is the longest part of a particle, of 300 nm or more and 700 nm or less, a minor axis diameter, which is the maximum part in the direction perpendicular to the major axis, of 100 nm or more and 400 nm or less, a constriction diameter, which is the length in the direction perpendicular to the major axis at the central position of the major axis, of 80 nm or more and 200 nm or less, and a ratio of constriction diameter/minor axis diameter obtained by dividing the constriction diameter by the minor axis diameter, of 0.9 or less. As described above, the particles constituting the powder of the present invention have a peanut-like twin shape with a constriction at the center. In order to obtain a peanut-like twin shape, the diameter of the second largest portion in the direction perpendicular to the long axis direction is preferably larger than the constriction diameter. Within the range, the larger the long axis diameter is, the more transparent cosmetic with natural bare skin feel can be obtained. However, with a major axis diameter of more than 700 nm, the hiding power becomes too small, so that age spots or the like cannot be hidden. Also, with a ratio of constriction diameter/minor axis diameter of more than 0.9, the soft focus properties are lowered. The lower limit of the major axis diameter is more preferably 350 nm or more, still more preferably 400 nm or more, and the upper limit is more preferably 650 nm or less. The lower limit of the minor axis diameter is more preferably 110 nm or more, still more preferably 150 nm or more, and the upper limit is more preferably 360 nm or less. The lower limit of the constriction diameter is more preferably 85 nm or more, still more preferably 100 nm or more, and the upper limit is more preferably 195 nm or less, still more preferably 180 nm or less. The ratio of constriction diameter/minor axis diameter is more preferably 0.80 or less, still more preferably 0.60 or less. The lower limit of the constriction diameter/minor axis diameter ratio is not particularly limited, and presumed to be about 0.40.
The major axis diameter, minor axis diameter, and constriction diameter of the particles may be measured by the following method.
Approximately 300 particles are observed with a transmission electron microscope to measure the major axis diameters, minor axis diameters, and constriction diameters defined above, and the respective average values are calculated.
Further, the ratio of constriction diameter/minor axis diameter of particles may be obtained by the following method.
Approximately 300 particles are observed with a transmission electron microscope to calculate the values of the ratio of constriction diameter/minor axis diameter from the minor axis diameter and constriction diameter values defined above for each particle, and the ratio is obtained by averaging the values.
As described above, the titanium (IV) oxide powder of the present invention blended in a cosmetic allows the cosmetic to spread easily and to have soft focus properties and appropriate hiding power. The reason is presumed as follows, though not being clear. The particles constituting the titanium (IV) oxide powder of the present invention have a shape in which two particles with a particle size of 100 nm to 400 nm are connected, so that the optical properties as an aggregate are similar to those of particles with a particle size of 100 nm to 400 nm. However, since the number of times that an incident light passes through the particle surface decreases, so that scattering and reflection are suppressed. On the other hand, in the titanium (IV) oxide powder of the present invention, due to the shape of the particles constituting the powder, many spaces are left inside the powder, and the light that enters the powder is scattered at the interface between the space and the particle. It is presumed that these effects compete against each other, resulting in the soft focus properties and appropriate hiding power. Further, the powder of the present invention has a smaller specific surface area and smaller contact points between particles in comparison with an aggregate of particles having a particle size of 100 nm to 400 nm, so that it is presumed that the powder spreads easily.
The titanium (IV) oxide in the powder of the present invention is preferably rutile-type titanium (IV) oxide. Rutile-type titanium oxide has a weaker blue color and lower activity in comparison with anatase-type titanium oxide. Further, compared with titanium (IV) oxide in crystal phases other than rutile-type and anatase-type, better productivity and stability can be obtained. The crystal phase of titanium (IV) oxide may be determined by confirming the main peak of each crystal phase (for example, the diffraction intensity of the (110) plane of rutile-type titanium (IV) oxide) using an X-ray diffraction device.
Each particle constituting the titanium (IV) oxide powder of the present invention may be composed of fine rod-like particles with a long axis diameter of 30 nm or more and 350 nm or less and a short axis diameter of 3 nm or more and 12 nm or less, and the fine rod-like particles aggregate into a particle having a peanut-like twin shape. In the case where the particles having a peanut-like twin shape formed from aggregation of fine rod-like particles are blended into a cosmetic, the makeup durability of the cosmetic can be improved. Although the reason for this is not clear, it is presumed that in the case wthere each of the peanut-like twin shaped particles is formed from aggregation of rod-shaped particles, many fine voids are created on the surface of the particles, allowing excess sebum and sweat to be gradually absorbed into the fine voids to improve the makeup durability. The fine rod-like particles have a lower limit of the long axis of preferably 150 nm or more, more preferably 200 nm or more, and an upper limit of preferably 325 nm, more preferably 300 nm or less, and have a lower limit of the short axis of preferably 8 nm or more, and an upper limit of 11 nm or less.
The long axis diameter and short axis diameter of the fine rod-like particles are the respective average values of the long axis diameter and short axis diameter of about 300 fine rod-like particles observed with a transmission electron microscope.
Incidentally, particles having a peanut-like twin shape may be formed by firing particles having a form in which fine rod-like particles are aggregated into a peanut-like twin shape so as to fuse the fine rod-like particles with each other. The particles constituting the powder of the present invention include both of those in which fine rod-shaped particles aggregate (without fusing) to form an apparently single particle, and those in which fine rod-shaped particles are fused to form a single particle. In the former case, as described above, when blended into a cosmetic, the effect of improving makeup durability can be obtained. In the latter case, a cosmetic more excellent in hiding power can be obtained.
The titanium (IV) oxide powder of the present invention preferably has a total light transmittance of 45.0% or more and 60.0% or less, and a haze value of 90.0% or more. The powder having such a total light transmittance and haze value blended into a cosmetic has soft focus properties and appropriate hiding power, so that a natural bare skin feel can be exhibited. Preferably, the total light transmittance has a lower limit of 50.0% or more and an upper limit of 60.0% or less, and the haze value has a lower limit of 91.0% or more. The upper limit of the haze value is not particularly limited, and may be 100.0%. The measurement method of total light transmittance and haze value is as follows.
The powder is added to a 1:1 mixture of trimethylsiloxysilicic acid and cyclopentane siloxane and stirred at 2000 rpm to prepare a coating material at a powder concentration of 100 g/kg. The coating material is formed into a coating film with a bar coater having a film thickness of 18.4 μm, and the total light transmittance and haze value of the coating film are measured with irradiation of C-light, which is light having a color temperature of 6774 K, by a double beam method.
The entire surface or at least a portion of the surface of the particles constituting the powder of the present invention may be coated with a layer of inorganic and/or organic substance. Examples of the inorganic substance may include one or more of aluminum, silicon, zinc, titanium, zirconium, iron, cerium, and tin, which are preferably an oxide, hydroxide, or oxyhydroxide thereof. Preferred examples of the organic substance include one or more of silicone-based compounds such as dimethylpolysiloxane and methyl hydrogen polysiloxane; coupling agents such as silane-based, aluminum-based, titanium-based and zirconium-based coupling agents; fluorine compounds such as perfluoroalkyl phosphoric acid compounds, and fatty acids including lauric acid and stearic acid. In addition, hydrocarbons, lecithin, amino acids, polyethylene, wax, etc. may also be used.
The titanium (IV) oxide powder of the present invention may be blended in cosmetics. The amount of titanium (IV) oxide powder blended in cosmetics varies depending on the form of the cosmetics, and in general, being preferably 1 g/kg or more and 500 g/kg or less, more preferably 10 g/kg or more and 450 g/kg or less.
The titanium (IV) oxide particles having a peanut-like twin shape constituting the powder of the present invention may be obtained by a method including step 1 of adding hydrochloric acid to a slurry containing an acid-soluble titanium compound, and holding the mixture with a hydrochloric acid concentration of 60 g/L or more and 130 g/L or less at a temperature of 25° C. or more and 60° C. or less, for 1 hour or more to perform thermal hydrolysis, and a step 2 of holding the mixture with the hydrochloric acid concentration and/or the temperature higher than those in step 1 for 1 hour or more to perform thermal hydrolysis.
The acid-soluble titanium compound for use in the present invention may be any titanium compound soluble in hydrochloric acid, such as titanium hydroxide and sodium titanate. Among the acid-soluble titanium compounds, sodium titanate is particularly preferred.
In the hydrolysis reaction in step 1, as described above, the hydrochloric acid concentration is controlled and maintained at 60 g/L or more and 130 g/L or less, and the temperature is controlled and maintained at 25° C. or more and 60° C. or less. The lower limit of the hydrochloric acid concentration is more preferably 70 g/L or more, still more preferably 80 g/L or more. The lower limit of the temperature is more preferably 30° C. or more, still more preferably 35° C. or more, and the upper limit is more preferably 50° C. or less, even more preferably 45° C. or less. The holding time is not particularly limited as long as it is one hour or more, and from the viewpoint of energy efficiency, a short holding time is preferred. The holding time is preferably one hour or more and ten hours or less, and more preferably two hours or more and five hours or less.
In the hydrolysis reaction in step 2, at least one of the hydrochloric acid concentration and the temperature is made higher than in step 1. In step 2, it is more preferable to control both the hydrochloric acid concentration and the temperature higher than those in step 1. Further, in step 2, the upper limit of the hydrochloric acid concentration is controlled to 180 g/L or less, and the upper limit of the temperature is controlled to 100° C. or less. The upper limit of the hydrochloric acid concentration is preferably 170 g/L or less, more preferably 160 g/L or less, and the temperature is preferably 70° C. or less, still more preferably 65° C. or less. The lower limits of both the hydrochloric acid concentration and the temperature are not particularly limited, but is preferably 60 g/L or more and 25° C. or more, respectively, since it is preferred not to be less than step 1. The holding time in step 2 is not particularly limited as long as it is 1 hour or more, being preferably 1 hour or more and 30 hours or less, and more preferably 10 hours or more and 20 hours or less.
The hydrolysis reaction may be performed three or more times. The conditions for the third times and later are not particularly limited, and it is desirable that the hydrolysis reaction is performed under conditions similar to those for the first and second times, considering the equipment necessary for the hydrolysis.
It is desirable that the sample after hydrolysis is collected through holding the solution at a constant temperature to precipitate titanium (IV) oxide, and then through cooling, filtering, and washing the precipitate. Although the conditions for precipitation are not limited, it is desirable to maintain the temperature at 60° C. or more and 100° C. or less for 1 hour or more. The upper limit of the holding time during precipitation is not particularly limited, being preferably 8 hours or less. The cooling, filtration and washing methods are not particularly limited. It is preferable that conventional procedures in the field be employed.
The titanium (IV) oxide obtained through the steps 1 and 2 may be further fired (step 3). The titanium (IV) oxide particles having a peanut-like twin shape of the present invention may be fired to further improve the hiding power of a cosmetic when blended into the cosmetic, as needed. The firing temperature is preferably 700° C. or less. In the case where the firing is performed at a temperature more than 700° C., sintering proceeds excessively, so that the particles having the peanut-like twin shape in the scope of the present invention may not be obtained, and the natural-looking bare skin cannot be obtained when the particles are used in a cosmetic. The lower limit of the firing temperature is not particularly limited. In one embodiment, it is preferably 300° C. or more. In the case where the firing temperature is less than 300° C., the change in performance is small similarly to the case where no firing is performed, so that the value of firing is small from an industrial perspective. The holding time is preferably 10 minutes or more and 60 minutes or less. With a holding time of more than 60 minutes, sintering may proceed excessively and the particles having the peanut-like twin shape in the scope of the present invention may not be obtained. With a holding time of less than 10 minutes, uneven heat distribution may occur within the powder to cause non-uniform quality, which is industrially undesirable. The holding time is more preferably 20 minutes or more and 50 minutes or less.
The resulting titanium (IV) oxide particles (including fired products and non-fired products) may have at least a portion of the particle surface coated with an inorganic and/or organic layer. The method of applying the coating is not particularly limited, and conventional methods may be used. Coating at least a portion of the particle surface with an inorganic layer allows, for example, dispersion stability and durability in the dispersion medium to be improved. Examples of the inorganic substance that may be used include one or more metals such as aluminum, silicon, zinc, titanium, zirconium, iron, cerium, and tin. Oxides, hydroxides or oxyhydroxides thereof are preferred. There are no restrictions on the type of a salt of the metal.
Further, depending on the intended use of the cosmetic, at least a portion of the particle surface may be coated with a layer of an organic substance, to perform water and/or oil repellent treatment in the particles. Examples of the organic substance include silicone-based compounds such as dimethylpolysiloxane and methyl hydrogen polysiloxane; coupling agents such as silane-based, aluminum-based, titanium-based, and zirconium-based coupling agents; fluorine compounds such as perfluoroalkyl phosphoric acid compounds; hydrocarbons; lecithin; amino acids; polyethylene; wax; and fatty acids such as lauric acid and stearic acid.
The application of the titanium (IV) oxide powder of the present invention is not particularly limited, being particularly suitable for blending into cosmetics. The powder of the present invention allows cosmetics to be imparted with properties such as soft focus properties, appropriate hiding power, and non-stickiness.
In the case of using the titanium (IV) oxide powder of the present invention in cosmetics, the powder may be mixed with other cosmetic raw materials according to known methods. It is preferable that the surface of the powder be coated in advance as described above. In mixing with other cosmetic raw materials, the powder may be directly mixed with the other raw materials, or the powder may be dispersed in a dispersion medium to prepare a dispersion, and then the dispersion may be mixed with other raw materials. In the present invention, the term “cosmetics containing titanium (IV) oxide powder” refers to not only cosmetics containing titanium (IV) oxide powder as it is (in powder form), but also cosmetics containing the powder dispersed in a dispersion medium to form a dispersion and then blended into the cosmetics. The content of the titanium (IV) oxide powder of the present invention in cosmetics may be optionally set depending on the required characteristics of various cosmetics, being preferably 1 g/kg or more and 500 g/kg or less, more preferably 10 g/kg or more and 450 g/kg or less. A mixture of two or more types of titanium (IV) oxide powder composed of particles having a peanut-like twin shape according to the present invention, with one or more of the major axis diameter, minor axis diameter, and constriction diameter being different, may be used. Alternatively, into a cosmetic containing the powder of the present invention, titanium oxide having a different particle size and/or shape may be further blended depending on the purpose.
In preparation of a cosmetic containing the titanium (IV) oxide powder of the present invention, various components such as inorganic pigments and organic pigments used in ordinary cosmetics may be used in combination on an as needed basis. Examples of the inorganic pigments usable in combination include titanium oxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, brown iron oxide, ultramarine, Prussian blue, cerium oxide, talc, muscovite, synthetic mica, phlogopite, biotite, synthetic fluorophlogopite, mica titanium, micaceous iron oxide, sericite, zeolite, kaolin, bentonite, clay, silicic acid, silicic anhydride, magnesium silicate, aluminum silicate, calcium silicate, barium sulfate, magnesium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, boron nitride, bismuth oxychloride, alumina, zirconium oxide, magnesium oxide, chromium oxide, calamine, hydroxyapatite, and complexes thereof. Examples of the organic pigments usable in combination include silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, nylon powder, urethane powder, silk powder, polymethyl methacrylate (PMMA) powder, starch, polyethylene powder, polystyrene powder, carbon black, tar pigments, natural pigments, metal soaps such as zinc stearate, and complexes thereof.
Cosmetics containing the titanium (IV) oxide powder of the present invention may contain other components in addition to the components described above depending on the purpose, within a quantitative and qualitative range that does not impair the effects of the present invention. For example, oily components, pigments, pH adjusters, moisturizers, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, sequestering agent, astringents, anti-inflammatory agents, ultraviolet absorber, fragrances, etc. in an appropriate amount may be blended within a range not impairing the effects of the present invention.
A cosmetic containing the titanium (IV) oxide powder of the present invention may be produced by a known method. The cosmetic may be in any dosage form such as powder, powder solid, cream, emulsion, lotion, oily liquid, oily solid, and paste. For example, makeup cosmetics, skin care cosmetics, and hair care cosmetics, which include makeup bases, foundations, concealers, face powder, control colors, sunscreen cosmetics, lipsticks, lip balms, eye shadows, eyeliners, mascaras, cheek colors, nail polishes, body powder, perfume powder, baby powder, etc. may be produced.
The titanium (IV) oxide powder of the present invention may be used in various fields where titanium oxide is generally used, in addition to cosmetics. Specific examples of the fields include resin compositions, coating materials, inks, external additives to toner, photocatalysts, electrical/electronic materials, ultraviolet blocking materials, heat insulating materials, radio wave blocking materials and ultraviolet blocking materials, though not limited thereto.
For example, the titanium (IV) oxide powder of the present invention has properties that a space between the particles is easily formed due to the particle shape, and accordingly, in the case where the powder is added to a resin, it is considered that an effect of preventing a formation of lumps can be obtained. It is also considered that in the case where the powder is used in an ink or coating material, fluidity can be maintained due to the small contact point between particles. In addition, due to the special shape, it is considered that the titanium (IV) oxide powder of the present invention has electrical and mechanical characteristics not found in conventional titanium (IV) oxide, and the novel characteristics may be applied to the field of electrical and electronic materials. That is, a cosmetic, a resin composition, a coating material, an ink, or an electrical/electronic material containing the titanium (IV) oxide powder of the present invention is an aspect of the present invention. From another point of view, the use of the titanium (IV) oxide powder of the present invention in cosmetics, resin compositions, coating materials, inks, or electrical/electronic materials is also an aspect of the present invention. Further, for example, the use of the titanium (IV) oxide powder of the present invention in production of cosmetics, resin compositions, coating materials, inks, or electrical/electronic materials can also be said to be one aspect of the present invention.
Prior to explaining Examples, the test methods used in the present invention are explained as follows.
Measurement was performed using a transmission electron microscope JEM-1400 plus manufactured by JEOL Ltd. The observation magnification was 50000 times (observation magnification power of transmission electron microscope: 10000, magnification power of print: 5). In each of the particles, a major axis diameter is the longest part, a minor axis diameter is the maximum part in the direction perpendicular to the major axis, and a constriction diameter is the length in the direction perpendicular to the major axis at the central position of the major axis. The major axis diameters, minor axis diameters, and constriction diameters of approximately 300 particles in the observation field were evaluated with an image analysis software ImageJ. The average values of the respective diameters of the about 300 particles were defined as the major axis diameter, minor axis diameter, and constriction diameter. Further, the value of constriction diameter/minor axis diameter was calculated by dividing the constriction diameter by the minor axis diameter for each of about 300 particles, and by calculating the average value thereof, the “Ratio of Constriction diameter/Minor axis diameter” was calculated.
Using an X-ray diffractometer RINT-TTRIII manufactured by Rigaku Corporation under conditions with a target of copper (Cu), a tube voltage of 50 kV, a tube current of 300 mA, a divergent slit ½°, a divergent vertical slit of 10 mm, and a scattering slit of ½°, a light receiving slit of 0.15 mm and a scanning rate of 0.5°/min, a range from 20° to 35° of 2θ was scanned to measure the diffraction intensity of (110) plane of rutile-type titanium dioxide (IV) and (101) plane of anatase-type titanium dioxide (IV).
In a 140-mL mayonnaise bottle, 30.0 g of commercially available acrylic-based clear paint for automobile refinishing, 5.0 g of butyl acetate, and 10.0 g of titanium (IV) oxide powder were weighed and placed in DISPERMATFE/S manufactured by VMA-GETZMANN with an impeller having a diameter of 30 mm attached, so as to be dispersed at a rotation speed of 5000 rpm for 20 minutes, and then a dispersion was obtained. The dispersion in amount of 0.5 g was collected and dispersed by a Hoover Muller with 50 rotations under a load of 150 Lbs. The resulting dispersion was applied to a sheet of hiding ratio test paper Lot. NA220022 manufactured by Motofuji with a 3-mil applicator and then dried. The color tone was measured with an SM-7 type color computer manufactured by Suga Test Instruments Co., Ltd., and the ratio of L value on black background/L value on white background was defined as the hiding ratio.
A sample in an amount of 1 g was added to trimethyl siloxy silicate KF-7312J manufactured by Shin-Etsu Chemical Co., Ltd. (mixture of trimethyl siloxy silicate and cyclopentane siloxane at a mass ratio of 1:1) in an amount of 9.0 times the mass, and the mixture was stirred with a Labolution® manufactured by PRIMIX Corporation at 2000 rpm to obtain a coating material having a powder concentration of 100 g/kg. The coating material was formed into a coating film using a bar coater with a film thickness of 18.4 μm. The resulting coating film was air-dried with cold air from a dryer until the surface was dried. The diffuse transmittance and total light transmittance were measured by a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd., irradiating C-light, which is light having a color temperature of 6774 K, by a double beam method. The haze value was calculated from (Diffuse transmittance/Total light transmittance)×100.
The present invention is explained in more detail with reference to the following Examples. The Examples are given for illustrative purposes only and the scope of the invention is not limited thereto.
Incidentally, in the stirring operations described in Examples and Comparative Examples, the rotation speed is adjusted appropriately such that the entire liquid is mixed uniformly and droplets are prevented from scattering around, considering properties related to the behavior of the liquid during stirring such as the liquid volume, liquid viscosity, and container shape. In the case where the same effect can be obtained from a commercially available general product manufactured by any company such as sodium hydroxide, the name of the manufacturers and distributors are omitted.
Commercially available sodium titanate was dissolved in a mixture of water and 400 g/L hydrochloric acid to prepare a sodium titanate slurry with a TiO2 concentration of 80 g/L and a hydrochloric acid concentration of 130 g/L. Subsequently, the slurry was heated while stirring using HEIDON® 600G manufactured by SHINTO Scientific Co., Ltd. (hereinafter referred to as the “stirrer”), and the liquid temperature was kept at 40° C. for 3 hours, so that a first hydrolysis was performed. Subsequently, 400 g/L hydrochloric acid was added to the solution, and while adjusting the hydrochloric acid concentration to 150 g/L, the liquid was heated and held at a liquid temperature 45° C. for 17 hours while stirring, so that a second hydrolysis was performed. Then, the liquid temperature was raised and kept at 80° C. for 8 hours, so that titanium (IV) oxide was precipitated, and the precipitate was subjected to cooling, filtering, and washing to obtain a white powder.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 1, except that the hydrochloric acid concentration was adjusted to 120 g/L in the first hydrolysis.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 1, except that the hydrochloric acid concentration was adjusted to 110 g/L in the first hydrolysis.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 1, except that the hydrochloric acid concentration was adjusted to 80 g/L in the first hydrolysis.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 1, except that the hydrochloric acid concentration was adjusted to 160 g/L in the second hydrolysis.
The titanium (IV) oxide powder obtained in Example 5 was fired at 650° C. for 30 minutes with SUPER-C C-2035D manufactured by Motoyama Co., Ltd., and cooled to room temperature to obtain a w % bite powder.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 1, except that the hydrochloric acid concentration was adjusted to 50 g/L in the first hydrolysis.
A white powder of titanium (IV) oxide was obtained in the same manner as in Example 5, except that the hydrochloric acid concentration was adjusted to 140 g/L in the first hydrolysis.
A commercially available rutile-type titanium (IV) oxide powder for use in cosmetics was used. The titanium oxide powder is formed of non-uniform shape particles, having a major axis diameter 340 nm and a minor axis diameter of 240 nm, a constriction diameter of 240 nm, and a constriction diameter/minor axis diameter ratio of 1.00. Measured values of the hiding ratio, total light transmittance, diffuse transmittance, and haze value are shown in Table 3.
In Table 1, production conditions for the titanium (IV) oxide powders in Examples and Comparative Examples are shown, in Table 2, the characteristics of particles constituting the titanium (IV) oxide powders obtained in Examples and Comparative Examples are shown, and in Table 3, the characteristics of the titanium (IV) oxide powders in Examples and Comparative Examples are shown.
As is clear from Table 3, the hiding ratios of the titanium (IV) oxide powders obtained in Examples 1 to 6 are greater than those in Comparative Examples 1 and 2. It is predicted that the titanium (IV) oxide powders of Examples 1 to 6 blended into cosmetics can impart appropriate covering power to the cosmetics. Further, the powders obtained in Examples 1 to 6 have a haze value as large as that of the commercially available titanium oxide in Comparative Example 3, and have a higher total light transmittance than that in Comparative Example 3, so that the cosmetics containing any of the powders in Examples 1 to 6 are expected to have excellent soft focus properties in addition to the covering power.
Hereinafter, cosmetics containing the titanium (IV) oxide powder of the present invention are explained.
Powder foundations were prepared by blending the powders (titanium oxide samples) obtained in Examples and Comparative Examples.
The resulting powder foundation was subjected to sensory tests for spreadability, smoothness, covering power, white cast, and makeup durability.
Powder foundations prepared from the powders in Examples 1 to 6 and Comparative Examples 1 to 3 were used by 10 panelists, and the sensory evaluation items in Table 4 were evaluated on a scale of 1 to 5 and determined based on the average score.
As a result of the sensory test, the powder foundations containing the powders obtained in Examples 1 to 6 were excellent in spreadability, smoothness, covering power, and makeup durability, and all of them had rare occurrence of white cast. The titanium (V) oxide powder of the present invention composed of particles having a peanut-like twin shape blended into a cosmetic imparted easy spreadability, soft focus properties, and appropriate hiding power to the cosmetic. As a result, a cosmetic that has an excellent cosmetic film uniformity, blurs age spots and pores, and exhibits a natural-looking bare skin feel was provided.
A W/O emulsion-type foundation was prepared using the powder obtained in Example.
The resulting W/O emulsion-type foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate hiding power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
A W/O emulsion-type sunscreen was prepared using the powder obtained in Example.
The resulting W/O emulsion sunscreen was very easily spread without stickiness, and excellent in adhesion.
The resulting pressed powder foundation was excellent in spreadability, and afler application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
A pressed powder foundation was prepared using the powder obtained in Example.
The resulting pressed powder foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
The resulting 2-way cake foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
The resulting oil-based cake foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
The resulting stick foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
An O/W emulsion-type foundation was prepared using the powder obtained in Example.
The resulting O/W emulsion-type foundation was excellent in spreadability, and after application, due to the soft focus properties and appropriate covering power, no white cast occurred, with a finish blurring age spots and pores to exhibit a natural-looking bare skin feel.
The resulting moisturizing O/W cream was easily spread, and was smooth without stickiness or greasiness and creaky feel, with refreshing feel, and excellent in stability.
An O/W cream was as prepared using the powder obtained in Example.
C. While stirring. B was gradually added to A to be emulsified, and aftercooling, component 14 was added thereto, so that an O/W cream was obtained.
The resulting O/W cream was easily spread, and was smooth without stickiness or greasiness and creaky feel, with refreshing feel, excellent in stability.
A body lotion was prepared using the powder obtained in Example.
The resulting body lotion was easily spread, and was smooth without stickiness or greasiness and creaky feel, with refreshing feel, and excellent in stability.
A sun-block cream was prepared using the powder obtained in the example.
The resulting sun-block cream was very easily spread without stickiness, and was excellent in adhesion.
A pressed cheek color was prepared using the powder obtained in Example.
The resulting pressed cheek color was easily spread without greasiness or powderiness, and was excellent in adhesion to the skin with a natural finish.
A loose powder was prepared using the powder obtained in Example.
The resulting loose powder was excellent in spreadability, and after application, excellent in transparency. Due to the appropriate covering power, no white cast occurred, with a finish exhibiting a natural-looking bare skin feel.
The resulting eyeliner had uniform color tone, and was excellent in spreadability and adhesion.
A mascara was prepared using the powder obtained in Example.
C Components 12 to 20 were heated and dissolved in another container.
D. C was added to B. and after emulsification, the mixture was cooled to 40° C., component 21 was added, and the mixture was cooled to room temperature to obtain a mascara.
The resulting mascara had a uniform color tone, moderate gloss, and excellent adhesion to eyebrows.
A cream eyeshadow was prepared using the powder obtained in Example.
The resulting cream eyeshadow was easily spread without greasiness or powderiness, and was excellent in adhesion to the skin.
An eyeshadow was prepared using the powder obtained in Example.
The resulting eyeshadow had a uniform color tone, and was excellent in spreadability and adhesion to the skin.
A nail enamel was prepared using the powder obtained in Example.
The resulting nail enamel had an apparent color equivalent to the applied color, a uniform color tone, and excellent spreadability.
A polyhydric-alcohol-in-oil-emulsion blusher in solid form was prepared using the powder obtained in Example.
The resulting polyhydric-alcohol-in-oil-emulsion blusher in solid form was easily spread without stickiness or greasiness, and was excellent in adhesion to the skin with natural finish.
A blusher was prepared using the powder obtained in Example.
The resulting blusher was easily spread without greasiness or powerderiness, and was excellent in adhesion to the skin with natural finish.
A creamy lipstick was prepared using the powder obtained in Example.
The resulting creamy lipstick was easily spread without stickiness or greasiness, and was moist with no-feeling of dryness.
A facial cleansing foam was prepared using the powder obtained in Example.
The resulting facial cleansing foam had an appearance with beautiful white color, and was excellent in foaming and foam retention without impairment of the cleansing properties.
A lipstick was prepared using the powder obtained in Example.
The resulting lipstick had an apparent color equivalent to the applied color, and excellent spreadability
A lip gloss was prepared using the powder obtained in the example.
The resulting lip gloss had an apparent color equivalent to the applied color, and excellent spreadability and adhesion.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-060113 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/011099 | 3/22/2023 | WO |
