JP2023084306A - Method for producing composite pigment comprising cellulose - Google Patents

Abstract

To provide a low-cost and efficient production method that enables composite pigment fine particles comprising an inorganic pigment and cellulose or a cellulose derivative to be produced stably with fixed quality.SOLUTION: A production method for composite pigment fine particles comprising an inorganic pigment and cellulose or a cellulose derivative is provided, including the steps of: preparing a liquid composition that comprises cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and has a viscosity of 5,000 mPa s or less; and spray-drying the resultant liquid composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing composite pigment fine particles containing cellulose or a cellulose derivative and an inorganic pigment, a liquid composition that can be used in the production method, composite pigment particles obtained by the production method, and cosmetics containing the particles.

Inorganic pigments refer to inorganic substances that are practically insoluble in water and organic solvents used for coloring. Inorganic pigments are inferior to organic pigments in terms of vividness of color, but are excellent in light resistance, heat resistance, and hiding properties. However, while inorganic pigments are excellent in solvent resistance, aggregation may occur in cosmetic base materials. Agglomeration of inorganic pigments causes a decrease in the feeling of use and a dull color in cosmetics to be blended.

The inventors of the present invention conducted intensive studies with the aim of suppressing the aggregation of inorganic pigments, which causes deterioration of the feeling of use of cosmetics containing inorganic pigments and dullness of colors. As a result, pigment particles containing an inorganic pigment and cellulose or a cellulose derivative are excellent in dispersibility in cosmetic base materials, improve dullness of color, suppress aggregation of pigments, and suppress cellulose on the particle surface. It has been found and reported that it is softer and has an excellent feeling of use (see, for example, Patent Document 1).

WO2021/020560

An object of the present invention is to provide an inexpensive and efficient production method capable of stably producing composite pigment fine particles containing an inorganic pigment and cellulose or a cellulose derivative with constant quality.

Particles containing an inorganic pigment and cellulose or a cellulose derivative can be obtained, for example, by spray-drying a dispersion in which they are dispersed. However, inorganic pigments and cellulose are generally insoluble in water and general-purpose organic solvents, and poor dispersion can lead to clogging of spray nozzles during spray drying and poor homogeneity of the resulting particles. and other problems. Such a problem can be avoided by subjecting the cellulose or pigment in the dispersion to a sufficient defibration/pulverization process, or by reducing the solid content concentration in the dispersion, but the energy cost associated with fibrillation/pulverization can be avoided. Also, there is a drawback that waste liquid treatment costs increase due to a decrease in solid content concentration.

The present inventors have extensively studied a method for producing composite pigment fine particles containing an inorganic pigment and cellulose or a cellulose derivative. By using a liquid composition, it is possible to stably produce composite pigment fine particles with constant quality by spray drying without spending time on the fibrillation/pulverization process or lowering the solid content concentration in the dispersion liquid. I found that it can be done, and completed the present invention.

The present invention is as follows.
[1] A step of obtaining a liquid composition containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa s or less, and a step of spray-drying the obtained liquid composition. A method for producing composite pigment fine particles containing cellulose or a cellulose derivative and an inorganic pigment.
[2] The production method according to [1], wherein the concentration of solids containing cellulose or a cellulose derivative and an inorganic pigment in the liquid composition is 1 to 50% by mass.
[3] The production method according to [1] or [2], wherein the cellulose is crystalline cellulose.
[4] The production method according to any one of [1] to [3], wherein the inorganic pigment is at least one selected from the group consisting of white pigments, colored pigments, pearlescent pigments and functional pigments.
[5] The inorganic pigment is selected from the group consisting of red iron oxide, yellow iron oxide, black iron oxide, chromium oxide, ultramarine blue, Prussian blue, manganese purple, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, barium sulfate, and boron nitride. The manufacturing method according to any one of [1] to [4].
[6] The production method according to any one of [1] to [5], wherein the ratio (weight) of cellulose or cellulose derivative to inorganic pigment is in the range of 1:1 to 1:20.
[7] The production method according to any one of [1] to [6], wherein the dispersant has an acid functional group, its salt or ester.
[8] The dispersant comprises glycerin fatty acid ester, polyglycerin fatty acid ester, alkyl ether carboxylate, glycyrrhizinate, higher fatty acid salt, polyacrylate, polyphosphate, phosphonate, and acid mucopolysaccharide salt. The production method according to any one of [1] to [7], which is selected from the group consisting of
[9] The dispersant is polyglyceryl laurate, polyglyceryl isostearate, polyglyceryl monostearate, sodium polyoxyethylene lauryl ether acetate, dipotassium glycyrrhizinate, sodium oleate, sodium polyacrylate, sodium tripolyphosphate, 1-hydroxyethylidene- The production method according to any one of [1] to [8], which is selected from the group consisting of disodium 1,1-diphosphonate, tetrasodium 1-hydroxyethylidene-1,1-diphosphonate, and sodium hyaluronate.
[10] The production method according to any one of [1] to [9], wherein the dispersant is dipotassium glycyrrhizinate.
[11] A liquid composition containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa·s or less.
[12] Composite pigment fine particles containing cellulose or a cellulose derivative, an inorganic pigment and a dispersant, obtained by the production method according to any one of [1] to [10].
[13] The fine composite pigment particles according to [12], having a particle size in the range of 0.1 to 500 μm.
[14] The composite pigment fine particles according to [12] or [13], which are used for cosmetics.
[15] Cosmetics comprising the composite pigment particles according to any one of [12] to [14].

In the production method of the present invention, a dispersant is added to a dispersion containing an inorganic pigment and cellulose or a cellulose derivative, and a liquid composition having a predetermined viscosity or less is used for spray drying. As a result, the energy cost can be suppressed without taking excessive time for the pulverization and fibrillation process for the inorganic pigment and cellulose or cellulose derivative. Moreover, since the solid content concentration in the dispersion liquid is not lowered, the waste liquid treatment cost can be suppressed. Furthermore, it is also excellent in that clogging of the spray nozzle during spray drying can be prevented and uniform particles can be stably produced.

4 is a scanning electron microscope image of particles prepared in Example 27. FIG. 4 is a scanning electron microscope image of particles prepared in Example 28. FIG. 4 is a scanning electron microscope image of particles prepared in Example 29. FIG. 10 is a field emission scanning electron microscope image of particles prepared in Example 27. FIG. 10 is a field emission scanning electron microscope image of particles prepared in Example 27. FIG. FIG. 10 is a particle size distribution diagram obtained by measuring the particles prepared in Example 27 with a scattering particle size distribution analyzer.

<Manufacturing method>
The present invention includes a step of obtaining a liquid composition containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa·s or less, and a step of spray-drying the obtained liquid composition. , a method for producing composite pigment particulates comprising cellulose or a cellulose derivative and an inorganic pigment.

(Step of preparing liquid composition)
The "liquid composition" used in the production method of the present invention is characterized by containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa·s or less.

The cellulose or cellulose derivative used in the present invention includes natural fibers such as wool, cotton, silk, hemp, and pulp; Cellulose derived from fibers or produced by bacteria. It may also be derived from cellulose composite fibers of cellulose fibers and synthetic fibers (for example, polyolefin fibers such as polyethylene and polypropylene). For example, cellulose such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and salts thereof such as sodium, methylhydroxypropylcellulose, sodium cellulose sulfate, cellulose dialkyldimethylammonium sulfate, crystalline cellulose, cellulose powder, etc. Derivatives thereof can be mentioned.

The cellulose or cellulose derivative used in the present invention includes those derived from natural fibers, such as those derived from plants such as wood, bamboo, hemp, jute, kenaf, cotton, beet, and agricultural waste. , hardwoods, conifers or bamboo. In addition, it is preferable to use crystalline cellulose obtained by partially depolymerizing α-cellulose obtained from such fibrous plants with an acid and purifying it, and more preferable to use microcrystalline cellulose.

Moreover, in the present invention, cellulose nanofibers may be used as cellulose or cellulose derivatives. “Cellulose nanofiber (CNF)” is a fiber obtained by defibrating cellulose fiber to a nano-size level, and generally has a fiber width of about 4 to 200 nm and a fiber length of about 5 μm or more. Such cellulose nanofibers can be prepared by a known method and are commercially available. For example, it can be obtained from suppliers such as Daio Paper Co., Ltd. and Chuetsu Pulp Industry Co., Ltd.

The inorganic pigment used in the present invention means an inorganic pigment capable of imparting coloring properties, coating properties, concealing properties, lubricating properties, etc. to target products (eg, cosmetics). Typically, it is a coloring pigment for adjusting the color tone of the product, a white pigment for controlling coverage and hiding properties, a pearl luster pigment that imparts a so-called pearly feel, or multiple functions such as hiding properties and slipperiness. It is a functional pigment with Examples include red iron oxide, yellow iron oxide, black iron oxide, chromium oxide, ultramarine blue, Prussian blue, manganese purple, carbon black, and other coloring pigments; titanium oxide (titanium dioxide), zinc oxide (zinc white), White pigments such as aluminum oxide (alumina), zirconium oxide, and barium sulfate; mica), photochromic pigments, and functional pigments such as UV-absorbing mica. Among them, from the viewpoint of combination with cellulose or cellulose derivatives and application of particles to cosmetics, coloring pigments and white pigments, specifically red iron oxide, yellow iron oxide, black iron oxide, chromium oxide, ultramarine blue, Prussian blue, manganese purple, At least one selected from the group consisting of titanium oxide, zinc oxide, aluminum oxide, zirconium oxide and barium sulfate is preferred. Alternatively, functional pigments, specifically boron nitride, are preferred. These inorganic pigments are available from suppliers as pharmaceutical, food or cosmetic additives.

The dispersant used in the present invention is not particularly limited as long as it is a dispersant capable of dispersing cellulose or a cellulose derivative and an inorganic pigment in water, and has an acid functional group or derivative thereof (e.g., salt or ester thereof). Dispersants are preferred. Examples include glycerin fatty acid esters such as glycerin monolaurate and glycerin monostearate; fatty acid esters; alkyl ether carboxylates such as polyoxyethylene lauryl ether sodium acetate; glycyrrhizinates such as dipotassium glycyrrhizinate; higher fatty acid salts such as sodium laurate, sodium stearate and sodium oleate; Polyacrylates; Polyphosphates such as sodium tripolyphosphate; disodium 1-hydroxyethylidene-1,1-diphosphonate (diNa etidronate; HEDP2Na), tetrasodium 1-hydroxyethylidene-1,1-diphosphonate (ethidrone Phosphonates such as acid 4Na; HEDP4Na); and salts of acidic mucopolysaccharides such as sodium hyaluronate. Among them, at least one selected from the group consisting of glycyrrhizinate such as dipotassium glycyrrhizinate; polyacrylate such as sodium polyacrylate; and polyphosphate such as sodium tripolyphosphate is preferred, and dipotassium glycyrrhizinate is particularly preferred. .

In the liquid composition of the present invention, the concentration of solids containing cellulose or cellulose derivatives and inorganic pigments is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass. It can be as above. The concentration of solid content is, for example, 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

In the present invention, the blending ratio (by mass) of the cellulose or cellulose derivative and the inorganic pigment in the liquid composition is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, of the inorganic pigment per 1 part by mass of cellulose or cellulose derivative. parts, more preferably 3 to 5 parts by mass.

In the present invention, the concentration of the dispersant in the liquid composition is particularly within a range that allows the viscosity of the liquid composition containing cellulose or a cellulose derivative and an inorganic pigment having the above solid content concentration to be 5,000 mPa s or less. Although not limited, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and for example, 10% by mass or less, preferably 5% by mass or less, more preferably It is 2% by mass or less.

In the present invention, the viscosity of the dispersant in the liquid composition is 5,000 mPa s or less, preferably 2,000 mPa s or less, more preferably 1,500 mPa s or less, and still more preferably It is 1,000 mPa·s or less, more preferably 500 mPa·s or less, and particularly preferably 300 mPa·s or less. In addition, in this invention, the viscosity refers to what was measured using the Brookfield viscometer.

The liquid composition according to the present invention contains cellulose or a cellulose derivative and an inorganic pigment as main components. In the present invention, "containing cellulose or a cellulose derivative and an inorganic pigment as main components" means that the ratio (mass basis) of the cellulose or cellulose derivative and the inorganic pigment to the solid content in the liquid composition is more than 50% by mass. means The ratio of cellulose or cellulose derivative to inorganic pigment (based on mass) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

Components other than cellulose or cellulose derivatives, inorganic pigments and dispersants contained in the liquid composition according to the present invention include, for example, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, Strontium silicate, metal tungstate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (e.g. zinc myristate, calcium palmitate, aluminum stearate), silica, fumed silica (ultrafine particles) Inorganic powders of various sizes and shapes such as silicic anhydride), and these are treated with silicones such as hydrogen silicone, cyclic hydrogen silicone, other silanes, or various surface treatment agents such as titanium coupling agents. Examples thereof include powders that have been subjected to hydrophobization or hydrophilization.

The liquid composition according to the present invention can be prepared by any method using the above cellulose or cellulose derivative, inorganic pigment, dispersant and water. For example, it can be obtained by appropriately mixing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water in an arbitrary order and pulverizing the mixture as necessary. The order of addition and mixing of cellulose or cellulose derivative, inorganic pigment, dispersant and water is not particularly limited. , This may be pulverized to obtain a dispersion liquid, and then the remaining solids may be added and mixed in any order, for example, by stirring at 10 to 80 ° C. for 0.01 to 24 hours. can. Examples of embodiments include: cellulose or cellulose derivative, water, inorganic pigment, dispersant in that order/cellulose or cellulose derivative, water, dispersant, inorganic pigment in that order/cellulose or cellulose derivative, inorganic pigment, water, dispersion In order of agent/cellulose or cellulose derivative, dispersant, water, inorganic pigment in order/cellulose or cellulose derivative, inorganic pigment, dispersant, in order of water/cellulose or cellulose derivative, dispersant, inorganic pigment, water In order: water, cellulose or cellulose derivative, inorganic pigment, dispersant; in order: water, cellulose or cellulose derivative, dispersant, inorganic pigment; in order: inorganic pigment, cellulose or cellulose derivative, water, dispersant / Dispersant, cellulose or cellulose derivative, water, inorganic pigment in order / Inorganic pigment, cellulose or cellulose derivative, dispersant, water in order / Dispersant, cellulose or cellulose derivative, inorganic pigment, water in order / Water , inorganic pigment, cellulose or cellulose derivative, in order of dispersant/water, dispersant, cellulose or cellulose derivative, inorganic pigment in order/inorganic pigment, water, cellulose or cellulose derivative, in order of dispersant/dispersant, Water, cellulose or cellulose derivative, in order of inorganic pigment/inorganic pigment, dispersant, cellulose or cellulose derivative, in order of water/dispersant, inorganic pigment, cellulose or cellulose derivative, in order of water/water, inorganic pigment, In the order of dispersant, cellulose or cellulose derivative/Water, dispersant, inorganic pigment, cellulose or cellulose derivative in order/Inorganic pigment, water, dispersant, cellulose or cellulose derivative in order/Dispersant, water, inorganic pigment , in the order of cellulose or cellulose derivative/in the order of inorganic pigment, dispersant, water, cellulose or cellulose derivative/in the order of dispersant, inorganic pigment, water, cellulose or cellulose derivative, and added and mixed according to the present invention. Liquid compositions can be prepared.

The liquid composition according to the present invention may contain a dispersion medium other than water. Such dispersion media are water-miscible organic solvents. Examples of water-miscible organic solvents include alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, nitriles such as acetonitrile, N-methylpyrrolidone and N-cyclohexylpyrrolidone. , N,N-dimethylacetamide and N,N-dimethylformamide, lactones such as γ-butyrolactone, and ethers such as tetrahydrofuran. In the most preferred embodiment, the dispersion medium is water or a mixture of water and alcohols having 1 to 4 carbon atoms.

Pulverization treatment in the present invention preferably means physical pulverization. Physical pulverization means that a mixture containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and/or water is subjected to a stirring device such as a magnetic stirrer or stirring blade, a homogenizer such as Polytron, or an ultrasonic wave such as an ultrasonic crusher. It is carried out by applying a physical external force using a pulverizer such as a generator or a wet pulverizer (for example, Starburst; Sugino Machine Co., Ltd.). However, if commercially available cellulose or cellulose derivatives and/or inorganic pigments are sufficiently pulverized, a dispersion may be obtained without the pulverization treatment. Therefore, in the production method of the present invention, instead of the step of obtaining a cellulose or cellulose derivative (or inorganic pigment) dispersion, a commercially available cellulose dispersion (or a commercially available inorganic pigment dispersion), for example, a commercially available dispersion of cellulose nanofibers may be used.

(Spray drying process)
Composite pigment fine particles containing cellulose or a cellulose derivative and an inorganic pigment as main components can be obtained by spray-drying the liquid composition according to the present invention thus obtained. Spray-drying is performed using a known spray-drying device such as an atomizer, a spray dryer, a micro-mist spray dryer, and the like. The spray drying conditions are appropriately set according to the type of dispersion medium in the dispersion liquid, the type or concentration of cellulose or cellulose derivative, etc. For example, the inlet temperature is 150 to 300° C. and the outlet temperature is 0 to 150° C. .

<Composite Pigment Fine Particles>
The composite pigment fine particles of the present invention are obtained by the above production method. The composite pigment fine particles of the present invention contain cellulose or a cellulose derivative and an inorganic pigment as main components.

The particle size of the particles of the present invention can be appropriately set according to the desired use of the particles. It is distributed in the range of ~80 µm, and the average particle size is, for example, in the range of 5 to 40 µm, preferably in the range of 5 to 30 µm. In the present invention, the particle size means a value measured by a scattering type particle size distribution analyzer, and the average particle size means an arithmetic mean diameter calculated from the obtained particle size distribution.

The composite pigment fine particles of the present invention may be porous particles. The term "porous" as used in the present invention means that the surface of the pigment particles is uneven and has a plurality of pores. Specifically, the porous pigment particles of the present invention have groove-like streaks (concavo-convex structure) that have a wrinkled or pleated appearance when an enlarged image of the particles is observed. The porous particles have a porosity within a predetermined range to be described later, or have a porosity of 0.1 m ² /g or more, preferably 1 m ² /g or more, more preferably 5 m ^{2 /g} or more, as determined by mercury porosimetry. g and less than 100 m ² /g, preferably less than 50 m ² /g, more preferably less than 30 m ² /g.

The porosity of the particles of the present invention can be appropriately set according to the desired use of the particles, and is, for example, in the range of 5 to 50%, preferably in the range of 5 to 40%, more preferably in the range of 5 to 30%. It is preferably in the range of 10-30%. In the present invention, the porosity refers to the void area (particle cross-sectional image The sum of the areas of the void portions in the area) is expressed as a percentage, and the average porosity means the arithmetic average value of the obtained porosities. When the porosity of the particles of the present invention is within such a range, the softness of the particles can be maintained and excellent optical properties can be exhibited even in the formulation of foundation.

The particles of the present invention preferably have a light scattering rate represented by the following formula (1) in the range of 50 to 230%.

｛式（１）中、角度２０°、７０°及び５°での反射強度は、粒子に対して法線方向を０°として、粒子に－３０°の角度から光を入射した時の受光器の感度を任意の値（感度調整値と呼ぶ）に設定した後、ある角度から光を入射した時の受光器の角度が２０°、７０°及び５°における反射光の強度を意味する。｝

{In formula (1), the reflection intensity at angles of 20°, 70° and 5° is the light receiver when the normal direction to the particle is 0° and the light is incident on the particle at an angle of -30° After setting the sensitivity to an arbitrary value (called a sensitivity adjustment value), it means the intensity of the reflected light at the angles of 20°, 70° and 5° of the light receiver when the light is incident from a certain angle. }

Here, the light scattering rate is calculated according to the above formula (1) described in International Publication No. 2010/092890. For example, when calculating the light scattering rate at a light incident angle of -30°, first, the normal direction of the surface on which the sample is pressed is assumed to be 0°, and the light is incident on the sample at an angle of -30°. After setting the sensitivity of the photodetector to an arbitrary value (called a sensitivity adjustment value), the intensity of the reflected light is measured at the photodetector angles of 20°, 70° and 5°. Next, while maintaining the initial sensitivity adjustment value, the intensity of the reflected light is measured at the light receiver angles of 20°, 70° and 5° when light is incident on the same sample at an angle of −45°. In the case of an incident angle of −60°, the relative intensity is measured in the same manner, and finally the light scattering rate is calculated.

When the light scattering rate represented by the above formula (1) reaches 100%, the graph showing the reflection intensity becomes circular, which means that the incident light is diffused uniformly. If this light scattering rate exceeds 100%, it means that the graph showing the reflection intensity becomes a horizontally long ellipse, and if it is less than 100%, it means that it becomes a vertically long ellipse.

The particles of the present invention have a more uniform reflected light intensity even if they have a wrinkled or pleated uneven structure on their surface. The particles of the present invention preferably have a light scattering rate in the range of 50 to 230%. When observing light incident angles of −30°, −45° and −60°, the light scattering rate is preferably in the range of 50 to 230% at any one incident angle, more preferably any The light scattering rate is in the range of 50 to 230% at the two incident angles, and more preferably the light scattering rate is in the range of 50 to 230% at both incident angles. The light scattering rate of the particles of the present invention is more preferably in the range of 70-230%, more preferably in the range of 90-230%. This means that the particles of the present invention can achieve more uniform omnidirectional reflection. For example, when the particles of the present invention are used as a cosmetic additive, a defocusing effect can be expected.

In particular, in the measurement of the reflected light distribution, the maximum intensity of the reflected light near the specular reflection of the incident light (for example, the angle of specular reflection within ± 10 °, preferably within the angle of specular reflection ± 5 °) near the incident light ( For example, the ratio of the maximum intensity of the reflected light within ±10° of the incident light angle, preferably within ±5° of the incident light angle, is preferably in the range of 0.5:1 to 2:1, and 0 It is preferably in the range of 0.5:1 to 1.8:1. When the specular reflection intensity is within such a range, excellent optical properties, particularly when the particles of the present invention are used as an additive for cosmetics (especially an additive for foundation), manifestation of a defocusing effect can be achieved. I can expect it.

<Cosmetics>
Since the composite pigment fine particles of the present invention are suppressed in aggregation and excellent in dispersibility in a base material, they can improve the dullness of colors. Suitable for adding to products. In addition, the particles of the present invention contain cellulose, preferably have a wrinkled or pleated uneven structure on the surface, and have appropriate pores and voids inside, so that they are soft and have excellent usability. , suitable for addition to cosmetics that come in direct contact with the skin. Since the particles of the present invention also have excellent optical properties (light scattering properties) that incident light is uniformly scattered, they can be added to cosmetics that come into direct contact with the skin and require optical properties such as defocusing effects. is particularly suitable for Examples of such cosmetics include skin care products such as lotions, gels, and emulsions; toiletry products such as facial cleansing foams, facial cleansing powders and body cleansers; hair care products such as shampoos and conditioners; oral care products such as toothpaste; Makeup cosmetics such as bases, powder foundations, liquid foundations, BB creams, concealers, lipsticks, and sunscreens, etc., can be used as inorganic pigments or as light scattering agents for expressing defocusing effects in these.

When the composite pigment fine particles of the present invention are added to cosmetics or quasi-drugs, they can be surface-treated with a surface treatment agent that is commonly used in cosmetics, as long as the effects are not impaired. Specifically, the surface can be treated using one or more of the hydrophobizing agents listed below.
(1) Methylhydrogenpolysiloxane (KF99P, manufactured by Shin-Etsu Chemical Co., Ltd.), methylhydrodienepolysiloxane/dimethylpolysiloxane copolymer (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.), dimethylpolysiloxane, branched silicone Treatment using silicones such as (ethoxy-functional) treating agents (KF9908, KF9909, manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic silicone treating agents (KP574, manufactured by Shin-Etsu Chemical Co., Ltd.).
(2) Treatment with an alkylalkoxysilane compound such as octyltriethoxysilane (DYNASILAN OCTEO manufactured by EVONIK DEGUSSA), hexyltrimethoxysilane, octadecyltriethoxysilane.
(3) Treatment with fatty acids such as palmitic acid and stearic acid.
(4) Treatment with alkylated saccharides such as dextrin palmitate obtained by alkyl-esterifying a part of hydroxyl groups of dextrin; treatment with metal soap using alkali metal salt or alkaline earth metal salt of fatty acid.
(5) Treatment of amino acids such as N-lauroyl-L-lysine, glutamic acid or its alkali salts, and acylated amino acids.
(6) perfluoroalkyl phosphate diethanolamine salt, perfluoroalkyl phosphate, perfluorohexylethyltriethoxysilane, perfluorooctylethyltriethoxysilane, copolymers containing functional groups with perfluoroalkyl chain length of C4 to C6, etc. Fluorine treatment using
(7) Treatment with a quaternary ammonium salt such as distearyldimethylammonium chloride.

Surface treatment methods other than the above include, for example, higher alcohol treatment, lecithin treatment, hydrogenated lecithin treatment, amino acid treatment, collagen treatment, elastin treatment, ester treatment, wax wax treatment, surfactant treatment, and moisturizing treatment. is also possible.

The composite pigment fine particles of the present invention can also be used as additives for cosmetic container (package) resins. Examples of such resins include
- Synthetic resins such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, derivatives thereof, and composite materials thereof;
- biodegradable resin;
- A composite material of a synthetic resin and a biodegradable resin can be mentioned.

Examples of biodegradable resins include polylactic acid, polyvinyl alcohol, poly(butylene adipate/terephthalate), polybutylene succinate, polyhydroxyalkanoate, (polylactic acid/polybutylene succinate) block copolymer, polycaprolactone, poly( caprolactone/butylene succinate), poly(butylene succinate/adipate), poly(butylene succinate/carbonate), poly(ethylene terephthalate/succinate), poly(tetramethylene adipate/terephthalate), polyethylene succinate, polyglycolic acid modified starch; casein plastic;

The composite pigment fine particles of the present invention can be used in combination with various additives that can be used as additives for cosmetics and additives for quasi-drugs, if necessary.

Additives such as physiologically active substances and functional substances that are blended in external skin preparations such as cosmetics or quasi-drugs include, for example, oily bases, moisturizing agents, texture improvers, surfactants, polymers, and thickeners.・Gelling agents, solvents, propellants, antioxidants, reducing agents, oxidizing agents, preservatives, antibacterial agents, bactericidal agents, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts, UV absorbers, Whitening agents, vitamins and their derivatives, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cooling agents, warming agents, wound healing accelerators, irritation relief pain relievers, cell activators, plant/animal/microorganism extracts, antipruritic agents, exfoliating/dissolving agents, antiperspirants, cooling agents, astringents, enzymes, nucleic acids, fragrances, pigments, colorants, dyes, pigments, anti-inflammatory agents, anti-inflammatory agents, anti-asthma agents, anti-chronic obstructive pulmonary disease agents, anti-allergic agents, immunomodulators, anti-infective agents, anti-fungal agents and the like.

Examples of these additive components include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol, jojoba alcohol, chimyl alcohol, selachyl alcohol, and batyl alcohol. Higher (polyhydric) alcohols such as alcohol, hexyldecanol, isostearyl alcohol, 2-octyldodecanol, dimer diol; aralkyl alcohols such as benzyl alcohol and derivatives thereof; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid , behenic acid, undecylenic acid, 12-hydroxystearic acid, palmitoleic acid, oleic acid, linoleic acid, linoleic acid, erucic acid, docosahexaenoic acid, eicosapentaenoic acid, isohexadecanoic acid, anteisohenicosanoic acid, long chain Higher fatty acids such as branched fatty acids, dimer acids and hydrogenated dimer acids, metal soaps such as aluminum salts, calcium salts, magnesium salts, zinc salts, potassium salts and sodium salts thereof, and nitrogen-containing derivatives such as amides; Hydrocarbons such as liquid paraffin (mineral oil), heavy liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalene, petrolatum, solid paraffin; candelilla wax , carnauba wax, rice wax, Japan wax, beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolatum, Fischer-Tropsch wax, polyethylene wax, ethylene/propylene copolymer waxes; coconut oil, palm oil , palm kernel oil, safflower oil, olive oil, castor oil, avocado oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rosehip oil, meadowfoam oil, persic oil, tea tree Oil, peppermint oil, corn oil, rapeseed oil, sunflower oil, wheat germ oil, linseed oil, cottonseed oil, soybean oil, peanut oil, rice bran oil, cocoa butter, shea butter, hydrogenated coconut oil, hydrogenated castor oil, jojoba oil , Hydrogenated jojoba oil and other vegetable oils; Beef tallow, milk fat, horse fat, egg yolk oil, mink oil, turtle oil and other animal oils; Animal waxes such as whale wax, lanolin, and orange roughy oil; Lanolins such as lanolin, reduced lanolin, adsorbed and purified lanolin, lanolin acetate, acetic acid liquid lanolin, hydroxyl lanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, lanolin acetate alcohol, acetic acid (cetyl/lanolyl) ester; Lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids such as sphingomyelin, phosphatidic acid, phospholipids such as lysolecithin; hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogenated Phospholipid derivatives such as egg yolk phospholipids and partially hydrogenated egg yolk phospholipids; sterols such as cholesterol, dihydrocholesterol, lanosterol, dihydrolanosterol, phytosterol, and cholic acid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, stearin cholesteryl acid, cholesteryl isostearate, cholesteryl oleate, di(cholesteryl/behenyl/octyldodecyl) N-lauroyl-L-glutamate, di(cholesteryl/octyldodecyl) N-lauroyl-L-glutamate, N-lauroyl-L-glutamic acid Acylsarcosine alkyl esters such as di(phytosteryl/behenyl/octyldodecyl), N-lauroyl-L-glutamic acid di(phytosteryl/octyldodecyl), N-lauroylsarcosine isopropyl, cholesteryl 12-hydroxystearate, macadamia nut oil fatty acid cholesteryl, macadamia nuts Sterol esters such as phytosteryl oil fatty acid, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long-chain branched fatty acid cholesteryl, long-chain α-hydroxy fatty acid cholesteryl; phospholipid-cholesterol complex, phospholipid-phytosterol complex lipid complexes such as; , isotridecyl isononanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neodecanoate, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanolin fatty acid, hexyldecyl dimethyloctanoate, erucic acid Octyldodecyl, Hydrogenated Castor Oil Isostearate, Ethyl Oleate, Avocado Oil Fatty Acid Ethyl, Isopropyl Myristate, Isopropyl Palmitate, Octyl Palmitate, Isopropyl Isostearate, Isopropyl Lanolin Fatty Acid, Diethyl Sebacate, Diisopropyl Sebacate, Dioctyl Sebacate, Monoalcohol carboxylic acid esters such as diisopropyl adipate, dibutyloctyl sebacate, diisobutyl adipate, dioctyl succinate, and triethyl citrate; oxyacid esters such as cetyl lactate, diisostearyl malate, and hydrogenated castor oil monoisostearate Glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate, caprylic/capric triglyceryl, caprylic/capric/myristic/stearic triglyceride, hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), eicosanedioic acid glyceryl behenate, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, dioctanoic acid 2- Butyl-2-ethyl-1,3-propanediol, propylene glycol dioleate, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, ditrimethylolpropane triethylhexanoate, ditrimethylolpropane (isostearate/sebacate), Pentaerythrityl triethylhexanoate, (hydroxystearic acid/stearic acid/rosin acid) dipentaerythrityl, diglyceryl diisostearate, polyglyceryl tetraisostearate, polyglyceryl nonaisostearate, deca (erucic acid/isostearic acid/ricinoleic acid) polyglyceryl- 8, (hexyldecanoic acid/sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate), 3-methyl-1,5-pentanediol dinopentanoate, 2,4-diethyl-1,5-pentane dinopentanoate Polyhydric alcohol fatty acid esters such as diols; diisopropyl dimer dilinoleate, diisostearyl dimer dilinoleate, di(isostearyl/phytosteryl) dimer dilinoleate, dimer dilinoleic acid (phytosteryl/behenyl), dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl), dimer dilinoleyl dimer dilinoleate, dimer dilinoleyl diisostearate, hydrogenated rosin condensate of dimer dilinoleate, hydrogenated castor oil of dimer dilinoleate, hydroxyalkyl dye Dimer acid such as dilinoleyl ether or derivative of dimer diol; Lauramide DEA), lauric acid monoisopropanolamide (Lauramide MIPA), palmitic acid monoethanolamide (Partamide MEA), palmitic acid diethanolamide (Partamide DEA), fatty acid alkanolamides such as coconut oil fatty acid methylethanolamide (cocamide methyl MEA); Dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone, diphenyldimethicone, phenyldimethicone, stearoxypropyldimethylamine, (amino Ethylaminopropyl methicone/dimethicone) copolymer, dimethiconol, dimethiconol crosspolymer, silicone resin, silicone rubber, amino-modified silicone such as aminopropyl dimethicone and amodimethicone, cation-modified silicone, polyether-modified silicone such as dimethicone copolyol, polyglycerin-modified Silicone, sugar-modified silicone, carboxylic acid-modified silicone, phosphoric acid-modified silicone, sulfate-modified silicone, alkyl-modified silicone, fatty acid-modified silicone, alkyl ether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cation-modified and polyether Silicones such as modified silicone, amino-modified and polyether-modified silicone, alkyl-modified and polyether-modified silicone, and polysiloxane/oxyalkylene copolymer; fluorinated oils such as perfluorodecane, perfluorooctane, and perfluoropolyether are preferred.

Moisturizers and texture improvers include glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Polyols such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol/propylene glycol copolymer, and polymers thereof; diethylene glycol monoethyl ether Glycol alkyl ethers such as (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol dibutyl ether; Esters; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, maltitol; glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid , glucuronic acid, cyclodextrins (α-, β-, γ-cyclodextrins and modified cyclodextrins such as maltosylation and hydroxyalkylation), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabino Sugars and their derivatives such as galactan, dextrin, dextran, glycogen, ethylglucoside, glucosylethyl methacrylate polymer or copolymer; hyaluronic acid, sodium hyaluronate; sodium chondroitin sulfate; mucoitin sulfate, caronin sulfate, keratosulfate, dermatan Sulfuric acid; Tremella fungus extract, Tremella fungus polysaccharide; Fucoidan; Tuberose polysaccharide or naturally occurring polysaccharide; Citric acid, tartaric acid, lactic acid and other organic acids and salts thereof; Salts such as sodium; betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cysteine, methionine , leucine, isoleucine, valine, tryptophan, histidine, taurine and other amino acids and salts thereof; Peptide, keratinolytic peptide, hydrolyzed keratin, conchiolinolytic peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean proteolytic peptide, wheat proteolytic peptide, hydrolyzed wheat protein, caseinolysis Protein peptides such as peptides and acylated peptides and their derivatives; Palmitoyl oligopeptides, palmitoyl pentapeptides, palmitoyl tetrapeptides and other acylated peptides; Silylated peptides; Submandibular gland mucin, hypotaurine, sesame lignan glycoside, glutathione, albumin, whey; choline chloride, phosphorylcholine; placenta extract, aerastin, collagen, aloe extract, hamamelis water, loofah water, chamomile extract, licorice extract, comfrey Animal and plant extract ingredients such as extract, silk extract, rose rose extract, yarrow extract, eucalyptus extract, melilot extract, natural ceramide (type 1, 2, 3, 4, 5, 6), hydroxyceramide, pseudoceramide, sphingo Glycolipids, ceramides, and ceramides such as sugar-ceramide-containing extracts are preferred.

Preferred surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymeric surfactants, and the like. Examples of preferred surfactants include anionic surfactants such as fatty acid salts such as potassium laurate and potassium myristate; alkyl sulfate salts such as sodium lauryl sulfate, triethanolamine lauryl sulfate and ammonium lauryl sulfate; Polyoxyethylene alkyl sulfates such as sodium laureth sulfate and triethanolamine laureth sulfate; sodium cocoyl methyl taurate, potassium cocoyl methyl taurate, sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, sodium lauroyl methyl alanine, sodium lauroyl sarcosinate, lauroyl sarcosyntriate Ethanolamine, acyl N-methyl amino acid salts such as sodium methylalanine lauroyl glutamate; sodium cocoyl glutamate, triethanolamine cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium stearoyl glutamate, ditriethanolamine palmitoyl aspartate, cocoyl alanine triethanol Acyl amino acid salts such as amines; polyoxyethylene alkyl ether acetates such as sodium laureth acetate; succinic acid ester salts such as sodium lauroyl monoethanolamide succinate; fatty acid alkanolamide ether carboxylates; Amine sulfates; fatty acid alkanolamide sulfates; fatty acid glyceride sulfates such as hydrogenated coconut oil fatty acid sodium glycerol sulfate; alkylbenzene polyoxyethylene sulfates; olefin sulfonates such as sodium α-olefin sulfonate; Alkyl sulfosuccinates such as dioctyl sodium sulfosuccinate; Alkyl ether sulfosuccinates such as disodium laureth sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate; sodium tetradecylbenzene sulfonate, Alkylbenzenesulfonates such as tetradecylbenzenesulfonate triethanolamine; Alkylnaphthalenesulfonates; Alkanesulfonates; α-sulfo fatty acid methyl ester salts; Acyl isethionates; Alkyl ether phosphate salts such as sodium laureth phosphate, sodium dilaureth phosphate, sodium trilaureth phosphate, sodium monooleth phosphate; alkyl phosphate salts such as potassium lauryl phosphate; sodium caseinate; alkyl aryl ether phosphates; fatty acid amides Ether phosphate; Phospholipids such as phosphatidylglycerol, phosphatidylinositol, and phosphatidic acid; Silicone-based anionic surfactants such as carboxylic acid-modified silicone, phosphoric acid-modified silicone, and sulfuric acid-modified silicone; is laureth (polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steareth (polyoxyethylene stearyl ether), beheneth (polyoxyethylene behenyl ether), isosteareth (polyoxyethylene isostearyl ether) ), polyoxyethylene alkyl ethers with various polyoxyethylene addition numbers such as octyldodeceth (polyoxyethylene octyldodecyl ether), etc.; polyoxyethylene alkylphenyl ether; polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil monoisostearate, polyoxyethylene hydrogenated castor oil triisostearate, polyoxyethylene hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene hydrogenated castor oil Castor oil and hydrogenation such as maleic acid Castor oil derivatives; Polyoxyethylene phytosterol; Polyoxyethylene cholesterol; Polyoxyethylene cholestanol; Polyoxyethylene lanolin; Polyoxyethylene reduced lanolin; Polyoxyethylene/polyoxypropylene alkyl ethers such as decyltetradecyl ether, polyoxyethylene/polyoxypropylene monobutyl ether, polyoxyethylene/polyoxypropylene hydrogenated lanolin, and polyoxyethylene/polyoxypropylene glycerin ether;
Polyoxyethylene/polyoxypropylene glycol; (poly)glycerin polyoxypropylene glycol such as PPG-9 diglyceryl; glyceryl stearate, glyceryl isostearate, glyceryl palmitate, glyceryl myristate, glyceryl oleate, glyceryl coconut oil fatty acid, Glycerin fatty acid partial esters such as mono-cottonseed fatty acid glycerin, glycerin monoerucate, glycerin sesquioleate, α,α'-pyroglutamic acid glyceryl monostearate, glyceryl monostearate malic acid; polyglyceryl-2, 3, 4 stearate , 5, 6, 8, 10, polyglyceryl-6, 10 distearate, polyglyceryl-2 tristearate, polyglyceryl-10 destearate, polyglyceryl-2 isostearate, 3, 4, 5 , 6, 8, 10, polyglyceryl-2 diisostearate (diglyceryl diisostearate), 3, 10, polyglyceryl-2 triisostearate, polyglyceryl-2 tetraisostearate, polyglyceryl-10 decaisostearate, olein Polyglycerin fatty acid esters such as polyglyceryl-2, 3, 4, 5, 6, 8, 10, polyglyceryl-6 dioleate, polyglyceryl-2 trioleate, polyglyceryl-10 decooleate; monostearin ethylene glycol mono fatty acid esters such as ethylene glycol; propylene glycol mono fatty acid esters such as propylene glycol monostearate; pentaerythritol partial fatty acid esters; sorbitol partial fatty acid esters; maltitol partial fatty acid esters; Sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc. sorbitan fatty acid esters; sucrose fatty acid esters, methylglucoside fatty acid esters, sugar derivative partial esters such as trehalose undecylenate; alkyl glucosides such as caprylyl glucoside; alkyl polyglycosides; lanolin alcohol; Polyoxyethylene fatty acid mono- and diesters such as polyethylene glycol diisostearate, polyoxyethylene monooleate, polyoxyethylene dioleate; polyoxyethylene/propylene glycol fatty acid esters; polyoxyethylene glycerin monostearate, polyoxyethylene Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monooleates such as ethylene glycerin monoisostearate and polyoxyethylene glycerin triisostearate; polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene Polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monooleate and polyoxyethylene sorbitan tetraoleate; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monooleate, polyoxyethylene sorbitol pentaoleate, polyoxyethylene sorbitol mono Polyoxyethylene sorbitol fatty acid esters such as stearates; polyoxyethylene methyl glucoside fatty acid esters; polyoxyethylene alkyl ether fatty acid esters; polyoxyethylene animal and vegetable oils and fats such as polyoxyethylene sorbitol beeswax; Alkyl glyceryl ethers such as selachyl alcohol and batyl alcohol; polyhydric alcohol alkyl ethers; polyoxyethylene alkylamines; tetrapolyoxyethylene/tetrapolyoxypropylene-ethylenediamine condensates; natural surfactants such as saponin and sophorolipid ; Polyoxyethylene fatty acid amide; coconut oil fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (Lauramide MEA), lauric acid diethanolamide (Lauramide DEA), monolauric acid Fatty acid alkanolamides such as isopropanolamide (lauramide MIPA), palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamide methyl MEA); lauramine oxide, cocamine oxide , Stearamine oxide, Alkyldimethylamine oxide such as behenamine oxide; Alkylethoxydimethylamine oxide; Polyoxyethylene alkylmercaptan; silicone-based nonionic surfactants such as silicones and sugar-modified silicones; cationic surfactants such as alkyltrimethylammonium chlorides such as behentrimonium chloride, steartrimonium chloride, cetrimonium chloride and lauryltrimonium chloride; Alkyltrimethylammonium bromide such as stearyltrimonium bromide; Dialkyldimethylammonium chloride such as distearyldimonium chloride and dicocodimonium chloride; Alkyl ether amines such as dimethylamine and their salts or quaternary salts; Fatty acid amide type quaternary ammonium salts such as ethyl sulfate long-chain branched fatty acid (12-31) aminopropylethyldimethylammonium, ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium Alkylamine salts; Fatty acid amide guanidinium salts; Alkyletheraminemonium salts; Alkyltrialkyleneglycol ammonium salts; Benzalkonium salts; Benzethonium salts; pyridinium salt of;
imidazolinium salts; alkylisoquinolinium salts; dialkylmorphonium salts; polyamine fatty acid derivatives; silicone-based cationic surfactants such as ether-modified silicone; amphoteric surfactants such as N-alkyl-N,N-dimethylamino acid betaines such as lauryl betaine (lauryldimethylaminoacetic acid betaine); cocamidopropyl betaine; Fatty acid amide alkyl-N,N-dimethyl amino acid betaines such as lauramidopropyl betaine; imidazoline-type betaines such as sodium cocoamphoacetate and sodium lauroamphoacetate; alkylsulfobetaines such as alkyldimethyltaurine; Betaine; Phosphate type betaine such as alkyldimethylaminoethanol phosphate ester; Phospholipids such as egg yolk phospholipids, partially hydrogenated egg yolk phospholipids, and hydroxylated lecithin; silicone-based amphoteric surfactants; Alkyl methacrylate copolymers; and various silicone-based surfactants are preferred.

Guar gum, locust bean gum, queen's seed, carrageenan, galactan, gum arabic, tara gum, tamarind, furcelleran, karaya gum, tororo mallow, cara gum, tragacanth gum, pectin, pectic acid and sodium are used as polymers, thickeners and gelling agents. Salts such as salts, salts such as alginic acid and sodium salts, mannan; starches such as rice, corn, potato, wheat; xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid and its salts, xanthan gum, pullulan, gellan gum, chitin , chitosan, agar, cassava extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and salts thereof such as sodium, methylhydroxypropylcellulose, cellulose sulfate Cellulose and its derivatives such as sodium, dialkyldimethylammonium sulfate cellulose, crystalline cellulose, and cellulose powder; starch-based polymers such as soluble starch, carboxymethyl starch, methylhydroxypropyl starch, methyl starch, hydroxypropyltrimonium chloride starch, octenylsuccinic acid Starch derivatives such as corn starch aluminum; alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyrididone (PVP), polyvinyl alcohol (PVA), vinylpyridone-vinyl alcohol copolymer, polyvinyl methyl ether; , polyoxyethylene / polyoxypropylene copolymer; (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, amphoteric methacrylic acid ester copolymer such as (acrylates / stearyl acrylate / methacrylate ethylamine oxide) copolymer; (dimethicone / vinyl dimethicone) crosspolymer, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / diacetone acrylamide) copolymer AMP; partially saponified polyvinyl acetate, maleic acid copolymer; vinylpyrrolidone-dialkylamino methacrylate Alkyl copolymer; acrylic resin alkanolamine; polyester, water-dispersible polyester; polyacrylamide; Acid/methacrylic ester copolymer; acrylic acid/methacrylate alkyl copolymer; cationized cellulose such as polyquaternium-10, diallyldimethylammonium chloride/acrylamide copolymer such as polyquaternium-7, polyquaternium-22 and the like Acrylic acid/diallyldimethylammonium chloride copolymer, acrylic acid/diallyldimethylammonium chloride/acrylamide copolymer such as polyquaternium-39, acrylic acid/cationized methacrylate copolymer, acrylic acid/cationized methacrylic acid Amide copolymer, acrylic acid/methyl acrylate/methacrylamidopropyltrimethylammonium chloride copolymer such as polyquaternium-47, chlorinated methacrylic acid choline ester polymer; cationized oligosaccharide, cationized dextran, guar hydroxypropyltrimonium chloride Cationic polysaccharides such as polyethyleneimine; cationic polymers; polymers of 2-methacryloyloxyethylphosphorylcholine such as polyquaternium-51 and copolymers with butyl methacrylate copolymers; acrylic resin emulsions, polyethyl acrylate emulsions , polyacryl alkyl ester emulsion, polyvinyl acetate resin emulsion, natural rubber latex, synthetic latex and other polymer emulsions; nitrocellulose; polyurethanes and various copolymers; various silicones; silicones such as acrylic-silicone graft copolymers various fluorine-based polymers; 12-hydroxystearic acid and its salts; dextrin fatty acid esters such as dextrin palmitate and dextrin myristate; silicic anhydride, fumed silica (ultrafine silicic anhydride), silica Preferred are magnesium aluminum phosphate, magnesium sodium silicate, metal soap, metal dialkyl phosphate, bentonite, hectorite, organically modified clay mineral, sucrose fatty acid ester, and fructo-oligosaccharide fatty acid ester. Among the above examples, cellulose and its derivatives, alginic acid and its salts, polyvinyl alcohol, hyaluronic acid and its salts, or collagen are preferred.

Solvents and propellants include lower alcohols such as ethanol, 2-propanol (isopropyl alcohol), butanol and isobutyl alcohol; glycols such as propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol and isopentyldiol. Classes: Diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Glycol ethers such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate and other glycol ether esters; Diethoxyethyl succinate, ethylene glycol disuccinate and other glycol esters; Benzyl Propellants such as alcohol, benzyloxyethanol, propylene carbonate, dialkyl carbonate, acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbons, next-generation freon; LPG, dimethyl ether, and carbon dioxide are preferred.

Antioxidants include tocopherol (vitamin E), tocopherol derivatives such as tocopherol acetate; BHT, BHA; gallic acid derivatives such as propyl gallate; vitamin C (ascorbic acid) and/or derivatives thereof; erythorbic acid and derivatives thereof; sulfites such as sodium sulfite; bisulfites such as sodium bisulfite; thiosulfates such as sodium thiosulfate; metabisulfite; thiotaurine, hypotaurine; It is mentioned as.

Preferred reducing agents include thioglycolic acid, cysteine, cysteamine, and the like.

Preferred examples of the oxidizing agent include aqueous hydrogen peroxide, ammonium persulfate, sodium bromate, and percarbonate.

Antiseptics, antibacterial agents, and disinfectants include hydroxybenzoic acid and its salts or esters such as methylparaben, ethylparaben, propylparaben, and butylparaben; salicylic acid; sodium benzoate; phenoxyethanol; isothiazolinone derivatives such as linone; imidazolinium urea; dehydroacetic acid and its salts; phenols; halogenated bisphenols such as triclosan, acid amides, quaternary ammonium salts; Benzethonium, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban, hexachlorophene, hinokitiol; other phenols such as phenol, isopropylphenol, cresol, thymol, parachlorophenol, phenylphenol, phenylphenol sodium; phenylethyl alcohol, photosensitizer , antibacterial zeolites, and silver ions are preferred.

Chelating agents include edetate (ethylenediaminetetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediamine triacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytic acid; Phosphonic acid and salts such as its sodium salt; Sodium oxalate; Polyamino acids such as polyaspartic acid and polyglutamic acid; Sodium polyphosphate, sodium metaphosphate, phosphoric acid; Sodium citrate, citric acid, alanine, dihydroxyethylglycine , gluconic acid, ascorbic acid, succinic acid and tartaric acid are preferred.

pH adjusters, acids, and alkalis include citric acid, sodium citrate, lactic acid, sodium lactate, potassium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, and sulfuric acid. , monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine , sodium hydroxide, potassium hydroxide, aqueous ammonia, guanidine carbonate, and ammonium carbonate are preferred.

Powders include mica, talc, kaolin, sericite, montmorillonite, kaolinite, mica, muscovite, phlogopite, synthetic mica, red mica, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, silicic acid. Barium, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, mud, metal Soap (e.g. zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, Prussian blue, carbon black, titanium oxide, fine and ultrafine titanium oxide, zinc oxide, Fine and ultrafine zinc oxide, alumina, silica, fumed silica (ultrafine silicic anhydride), mica titanium, fish scale foil, boron nitride, photochromic pigment, synthetic fluorine phlogopite, fine composite powder, gold, aluminum, etc. Inorganic powders of various sizes and shapes, and these are treated with silicones such as hydrogensilicone and cyclic hydrogensilicone, or various surface treatment agents such as other silanes or titanium coupling agents to make them hydrophobic or hydrophilic. starch, cellulose, nylon powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene/acrylic acid copolymer resin powder, polyester powder, benzoguanamine resin powder, polyethylene terephthalate/polyethylene Methyl methacrylate layered powder, polyethylene terephthalate/aluminum/epoxy layered powder, urethane powder, silicone powder, Teflon (registered trademark) powder, etc. Body is preferred.

Examples of inorganic salts include sodium chloride-containing salts such as common salt, common salt, rock salt, sea salt, and natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, bittern, zinc chloride, ammonium chloride; sodium sulfate, aluminum sulfate, Aluminum/potassium sulfate (alum), aluminum/ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na, 2Na, and 3Na phosphate, phosphoric acid Potassiums, calcium phosphates, and magnesium phosphates are preferred.

UV absorbers include para-aminobenzoic acid, para-aminobenzoic acid monoglycerol ester, N,N-dipropoxy para-aminobenzoic acid ethyl ester, N,N-diethoxy para-aminobenzoic acid ethyl ester, N,N-dimethyl para-aminobenzoic acid ethyl ester. Benzoic acid-based UV absorbers such as esters, N,N-dimethylpara-aminobenzoic acid butyl ester, N,N-dimethylpara-aminobenzoic acid ethyl ester; Anthranilic acid-based UV absorbers such as homomenthyl-N-acetylanthranilate; Salicylic acid and salicylic acid-based ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, p-isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl- 2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate mate, 2-ethylhexyl p-methoxycinnamate (octyl paramethoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate (cinoxate), cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenyl Cinnamic acid-based UV absorbers such as cinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate (octocrine), glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, ferulic acid and derivatives thereof;2 ,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy -4-methoxybenzophenone (oxybenzone-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 Benzophenone UV absorbers such as '-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone; 3-(4'-methylbenzylidene)-d ,l-camphor, 3-benzylidene-d,l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2′-hydroxy-5-methylphenylbenzotriazole; 2-(2′-hydroxy-5′ -t-octylphenyl)benzotriazole; 2-(2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3-pentane-2 -one; dibenzoylmethane derivatives such as 4-t-butylmethoxydibenzoylmethane; octyl triazone; urocanic acid and urocanic acid derivatives such as ethyl urocanate; 2-(2′-hydroxy-5′-methylphenyl)benzo hydantoin derivatives such as triazole, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, 2-ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate, phenylbenzimidasazole sulfonic acid, Preferred are terephthalylidenedicanefursulfonic acid, drometrisol trisiloxane, methyl anthranilate, rutin and its derivatives, oryzanol and its derivatives.

Whitening agents include hydroquinone glycosides such as arbutin and α-arbutin and esters thereof; ascorbic acid, ascorbic acid phosphate salts such as sodium ascorbic acid phosphate and magnesium ascorbic acid phosphate; Ascorbic acid fatty acid esters such as tetraisopalmitate, ascorbic acid alkyl ethers such as ascorbic acid ethyl ether, ascorbic acid glucosides such as ascorbic acid-2-glucoside and their fatty acid esters, ascorbic acid sulfates, tocopheryl ascorbyl phosphate Ascorbic acid derivatives such as; kojic acid, ellagic acid, tranexamic acid and its derivatives, ferulic acid and its derivatives, placenta extract, glutathione, oryzanol, butylresorcinol, oil-soluble chamomilla extract, oil-soluble licorice extract, Nishikawayanagi extract, saxifrage extract and other plant extracts are preferred.

Examples of vitamins and derivatives thereof include vitamin A such as retinol, retinol acetate, and retinol palmitate; flavin adenine dinucleotide, cyanocobalamin, folic acids, nicotinic acids such as nicotinamide and benzyl nicotinate, B vitamins such as choline; vitamin Cs such as ascorbic acid and salts thereof such as sodium; vitamin D; Vitamin E such as β, γ, δ-tocopherol; other vitamins such as pantothenic acid and biotin; ascorbic acid phosphate salts such as ascorbyl phosphate sodium salt and ascorbyl phosphate magnesium salt, ascorbic acid tetra Ascorbic acid fatty acid esters such as isopalmitate, ascorbyl stearate, ascorbyl palmitate, and ascorbyl dipalmitate, ascorbic acid alkyl ethers such as ascorbyl ethyl ether, ascorbic acid glucosides such as ascorbic acid-2-glucoside, and fatty acid esters thereof , ascorbic acid derivatives such as tocopheryl ascorbyl phosphate; vitamin derivatives such as tocopherol nicotinate, tocopheryl acetate, tocopherol linoleate, tocopherol ferulate, tocopherol phosphate, tocotrienols, and other various vitamin derivatives are preferred. It is mentioned as.

Hair growth agents, blood circulation promoters, and stimulants include plant extracts and tinctures such as assembly extract, capsicum tincture, ginger tincture, ginger extract, and cantharis tincture; , borneol, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, γ-oryzanol, vitamin E and derivatives such as tocopherol nicotinate and tocopherol acetate, γ-oryzanol, nicotinic acid and nicotinic acid amide, nicotinic acid benzyl ester, Derivatives such as inositol hexanicotinate, nicotine alcohol, allantoin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, flavanonol derivatives, stigmasterol or stigmastanol and its glycosides, and minoxidil are preferred. be done.

Preferred examples of hormones include estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone, and the like. Other medicinal agents such as anti-wrinkle agents, anti-aging agents, tightening agents, cooling agents, warming agents, wound healing promoting agents, stimulating agents, analgesics, and cell activators include retinols, retinoic acids, and retinoin. tocopheryl acid; lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and derivatives such as glycosides and esters thereof, hydroxycapric acid, long-chain α-hydroxy fatty acids, α- or long-chain α-hydroxy fatty acid cholesteryl β-hydroxy acids and their derivatives; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; carnosine; creatine; ceramides, sphingosines; caffeine, xanthine, etc. and their derivatives; , astaxanthin, lutein, α-lipoic acid, platinum nanocolloids, antioxidants and active oxygen scavengers such as fullerenes; catechins; flavones such as quercetin; isoflavones; gallic acid and ester sugar derivatives; Polyphenols such as anthocyanidins, chlorogenic acid, and apple polyphenols; derivatives such as rutin and glycosides; derivatives such as hesperidin and glycosides; lignan glycosides; shogaol, gingerol; menthol, cedrol and other flavoring substances and their derivatives; capsaicin, vanillin and their derivatives; insect repellents such as diethyltoluamide; .

Plant/animal/microorganism extracts include iris extract, angelica keiskei extract, asunaro extract, asparagus extract, avocado extract, amacha extract, almond extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, and ginkgo biloba extract. , Inchko extract, Fennel extract, Turmeric extract, Oolong tea extract, Arctic extract, Age extract, Echinashi leaf extract, Tripod extract, Scutellaria root extract, Phellodendron bark extract, Coptis extract, Barley extract, Panax ginseng extract, Hypericum extract, Dead nettle extract, Ononis extract , Dutch mustard extract, orange extract, seawater dried matter, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, kakkon extract, chamomile extract, oil-soluble chamomile extract, carrot extract, wormwood extract, oat extract, karkade extract, licorice extract, oil-soluble licorice extract, kiwi extract, kiwi extract, cloud ear extract, cinchona extract, cucumber extract, paulownia leaf extract, guanosine, guava extract, kujin extract, gardenia extract, kumazasa extract, clara extract, walnut Extract, Chestnut extract, Grapefruit extract, Clematis extract, Black rice extract, Brown sugar extract, Black vinegar, Chlorella extract, Mulberry extract, Gentian extract, Gennoshoko extract, Black tea extract, Yeast extract, Koboku extract, Coffee extract, Burdock extract, Rice extract, Rice Fermented extract, rice bran fermented extract, rice germ oil, comfrey extract, collagen, cowberry extract, rhinoceros extract, rhinoceros extract, rhinoceros extract, saffron extract, salvia extract, soapwort extract, bamboo grass extract, hawthorn extract, sansha extract, Japanese pepper extract, shiitake extract, reed extract, licorice extract, perilla extract, linden extract, meadowsweet extract, jatoba extract, peony extract, ginger extract, calamus root extract, white birch extract, white fungus extract, horsetail extract, stevia extract, fermented stevia, Nishikawayanagi extract, Ivy Extract, Hawthorn Extract, Sambucus Extract, Yarrow Extract, Peppermint Extract, Sage Extract, Mallow Extract, Cnidium Extract, Assembly Extract, Rhubarb Extract, Rhubarb Extract, Soybean Extract, Sunflower Extract, Thyme Extract, Dandelion Extract, Ground Clothing extract, tea extract, clove extract, cinnamon extract, chimp extract, tea tree oil, sweet tea extract, capsicum extract, angelica root extract, calendula officinalis extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract, wild rose extract , hibiscus extract, Bakumondou extract, lotus extract, parsley extract, birch extract, honey, hamamelis extract, parietalia extract, hikiokoshi extract, bisabolol, cypress extract, bifidobacterium extract, loquat extract, coltsfoot extract, butterbur extract, sagebrush extract, butcher Bloom extract, Grape extract, Grape seed extract, Propolis, Loofah extract, Safflower extract, Peppermint extract, Bodaiju extract, Botan extract, Hop extract, Mica squid extract, Pine extract, Horse chestnut extract, Asian skunk cabbage extract, Soap extract, Melissa extract, Mozuku extract , peach extract, cornflower extract, eucalyptus extract, saxifrage extract, yuzu extract, lily extract, coix seed extract, mugwort extract, lavender extract, green tea extract, eggshell membrane extract, apple extract, rooibos tea extract, litchi extract, lettuce extract, lemon extract, forsythia extract , astragalus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, burnet extract and the like are preferred.

Antipruritics include diphenhydramine hydrochloride, chlorpheniramine maleate, camphor, substance-P inhibitors and the like.

Examples of exfoliating/dissolving agents include salicylic acid, sulfur, resorcinol, selenium sulfide, pyridoxine, and the like.

Antiperspirants include aluminum chlorohydroxy, aluminum chloride, zinc oxide, zinc paraphenolsulfonate, and the like.

Cooling agents include menthol and methyl salicylate.

Examples of astringents include citric acid, tartaric acid, lactic acid, aluminum/potassium sulfate, and tannic acid.

Enzymes include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease and the like.

Preferred nucleic acids include ribonucleic acid and its salts, deoxyribonucleic acid and its salts, and disodium adenosine triphosphate.

Fragrances include acetylcedrene, amyl cinnamaldehyde, allyl amyl glycolate, β-ionone, iso-e-super, isobutylquinoline, iris oil, iron, indole, ylang-ylang oil, undecanal, undecenal, γ-undecenal, Estragole, eugenol, oakmoss, opoponax resinoid, orange oil, eugenol, aurantiol, galacsolid, carvacrol, L-carvone, camphor, cannon, carrot seed oil, clove oil, methyl cinnamate, geraniol, geranyl nitrile, isobornyl acetate, geranyl acetate, dimethylbenzylcarbyl acetate, styraryl acetate, cedryl acetate, terpinel acetate, p-t-butylcyclohexyl acetate, betiveryl acetate, benzyl acetate, linalyl acetate, isopentyl salicylate, benzyl salicylate, sandalwood oil, santalol, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromyrcenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, citronellal, cinnamon bark oil, 1,8-cineol, cinnamaldehyde , styraxresinoid, cedarwood oil, cedren, cedrol, celery seed oil, thyme oil, damascone, damascenone, thymol, tuberose absolute, decanal, decalactone, terpineol, γ-terpinene, tripral, nerol, nonanal, 2,6-nonadienol, Nonalactone, patchouli alcohol, vanilla absolute, vanillin, basil oil, patchouli oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petitgrain oil, hexylcinnamaldehyde, cis-3-hexenol, peruvian balsam, vetiver Oil, vetiverol, peppermint oil, pepper oil, heliotropine, bergamot oil, benzyl benzoate, borneol, myresinoid, musk ketone, methylnonylacetaldehyde, γ-methylionone, menthol, L-menthol, L-mentone, eucalyptus oil, β-ionone , lime oil, lavender oil, D-limonene, linalool, lyral, lyreal, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, various essential oils, synthetic and natural fragrances, and various compounded fragrances are preferred. mentioned.

Colorants/colorants/dyes/pigments include Brown No. 201, Black No. 401, Purple No. 201, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 202, Blue No. 203 and Blue No. 204. , Blue No. 205, Blue No. 403, Blue No. 404, Green No. 201, Green No. 202, Green No. 204, Green No. 205, Green No. 3, Green No. 401, Green No. 402, Red No. 102, Red No. 104-1 , Red No. 105-1, Red No. 106, Red No. 2, Red No. 201, Red No. 202, Red No. 203, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 208, Red No. 213 , Red No. 214, Red No. 215, Red No. 218, Red No. 219, Red No. 220, Red No. 221, Red No. 223, Red No. 225, Red No. 226, Red No. 227, Red No. 228, Red No. 230-1 , Red No. 230-2, Red No. 231, Red No. 232, Red No. 3, Red No. 401, Red No. 404, Red No. 405, Red No. 501, Red No. 502, Red No. 503, Red No. 504, Red No. 505 , Red No. 506, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Yellow No. 201, Yellow No. 202-1 , Yellow No. 202-2, Yellow No. 203, Yellow No. 204, Yellow No. 205, Yellow No. 4, Yellow No. 401, Yellow No. 402, Yellow No. 403-1, Yellow No. 404, Yellow No. 405, Yellow No. 406, Yellow Legal dyes such as No. 407 and Yellow No. 5; Other acid dyes such as Acid Red 14; Basic dyes such as Arianor Sienna Brown, Arianor Madder Red, Arianor Steel Blue, and Arianor Straw Yellow; HC Yellow 2, HC Yellow 5, HC Red Nitro dyes such as 3,4-hydroxypropylamino-3-nitrophenol, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, HC Blue 2, Basic Blue 26; disperse dyes; titanium dioxide, zinc oxide Inorganic red pigments such as iron oxide (red iron oxide) and iron titanate; Inorganic brown pigments such as γ-iron oxide; Inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic black pigments such as titanium suboxide; Inorganic purple pigments such as mango violet and cobalt violet; Inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; Inorganic blue pigments such as ultramarine blue and Prussian blue; Titanium-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, bismuth oxychloride, pearl pigments such as fish scale foil; metal powder pigments such as aluminum powder, copper powder, and gold; surface-treated inorganic and Metal powder pigments; organic pigments such as zirconium, barium or aluminum lakes; surface-treated organic pigments; Naphthoquinones such as cochineal and shikonin, bixin, flavones, betacyanidin, henna, hemoglobin, lycopene, riboflavin, natural pigments and dyes such as rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m- , or oxidation dye intermediates and couplers such as p-aminophenol, m-phenylenediamine, 5-amino-2-methylphenol, resorcinol, 1-naphthol, 2,6-diaminopyridine, etc. and salts thereof; Oxidative dye; dihydroxyacetone is preferred.

Antiphlogistic agents and anti-inflammatory agents include glycyrrhizic acid and its derivatives, glycyrrhizic acid derivatives, salicylic acid derivatives, hinokitiol, guaiazulene, allantoin, indomethacin, ketoprofen, ibuprofen, diclofenac, loxoprofen, celecoxib, infliximab, etanercept, zinc oxide, and hydrocortisone acetate. , prednisone, diphedramine hydrochloride, chlorpheniramine maleate; plant extracts such as peach leaf extract and mugwort leaf extract.

Anti-asthma, anti-chronic obstructive pulmonary disease, anti-allergic, and immunomodulators include aminophylline, theophylline, steroids (fluticasone, beclomethasone, etc.), leukotriene antagonists, thromboxane inhibitors, intal, and β2 agonists. (formoterol, salmeterol, albuterol, tulobuterol, clenbuterol, epinephrine, etc.), tiotropium, ipratropium, dextromethorphan, dimemorphan, bromhexine, tranilast, ketotifen, azelastine, cetirizine, chlorpheniramine, mequitazine, tacrolimus, cyclosporine, sirolimus, methotrexate , cytokine modulators, interferon, omalizumab, protein/antibody preparations are preferred.

Preferred anti-infective agents and anti-fungal agents include oseltamivir, zanamivir and itraconazole. In addition to these, the Standards for Cosmetic Ingredients, Standards for Ingredients by Cosmetic Type, List of Ingredient Labels of the Japan Cosmetic Industry Association, INCI Dictionary (The International Cosmetic Ingredient Dictionary and Handbook), Standards for Quasi-drug Ingredients, Japanese Pharmacopoeia, Pharmaceutical Additives Standards , Ingredients listed in the Official Code of Food Additives, etc., and listed in Japanese and foreign patent publications and patent publications (including publications and republications) that belong to the classification of A61K7 and A61K8 in the international patent classification IPC It is possible to contain known cosmetic ingredients, pharmaceutical ingredients, food ingredients, and the like in known combinations, compounding ratios, and compounding amounts.

[Reference Synthesis Example 1: 5% by mass microcrystalline cellulose dispersion]
After dispersing 4.0 kg of microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) in 76.0 kg of ion-exchanged water, it is subjected to wet atomization equipment Starburst (manufactured by Sugino Machine Co., Ltd.) at 150 MPa. The pulverization treatment was carried out five times to obtain the titled 5% by mass microcrystalline cellulose dispersion.

[Reference Synthesis Example 2: 8% by mass microcrystalline cellulose dispersion]
After dispersing 8.0 kg of microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) in 92.0 kg of ion-exchanged water, it was subjected to wet atomization equipment Starburst (manufactured by Sugino Machine Co., Ltd.) at 150 MPa. The pulverization treatment was carried out five times to obtain the titled 8% by mass microcrystalline cellulose dispersion.

[Examples 1 to 4, Comparative Example 1: Preparation of liquid composition]
According to Table 1, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 5 mass% microcrystalline cellulose dispersion obtained in Reference Synthesis Example 1 (described as 5% cellulose dispersion in the table), a dispersant, and purified water. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. Thereafter, yellow iron oxide was slowly added so as to form lumps, and the liquid composition of Examples 1 to 4 or Comparative Example 1 was obtained by heating and stirring at 600 rpm for 3 hours in a water bath at 50°C. rice field.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A liquid composition with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 1, 2, 3 and 4 were confirmed to have viscosities of 300 mPa·s or less, and liquid compositions that were stable cellulose/pigment/dispersant slurries could be prepared.

[Examples 5 to 10, Comparative Example 1: Preparation of liquid composition]
According to Table 2, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 5% by mass microcrystalline cellulose dispersion obtained in Reference Synthesis Example 1 (described as 5% cellulose dispersion in the table), a dispersant, and purified water. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. Thereafter, yellow iron oxide was slowly added so as to form lumps, and the liquid composition of Examples 5 to 10 or Comparative Example 1 was prepared by heating and stirring in a water bath at 50° C. for 3 hours at 600 rpm. Obtained.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 5, 6, 7, 8, 9 and 10 were confirmed to have viscosities of 900 mPa s or less, and liquid compositions that were stable cellulose/pigment/dispersant slurries were obtained by controlling the amount of dispersant. was prepared.

[Examples 11 to 14, Comparative Example 2: Preparation of liquid composition]
According to Table 3, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 8% by mass microcrystalline cellulose dispersion obtained in Reference Synthesis Example 2 (described as 8% cellulose dispersion in the table), a dispersant, and purified water. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. Thereafter, yellow iron oxide was slowly added so as to form lumps, and the liquid composition of Examples 11 to 14 or Comparative Example 2 was prepared by heating and stirring in a water bath at 50° C. for 3 hours at 600 rpm. Obtained.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 11, 12, 13 and 14 were confirmed to have viscosities of 1,300 mPa s or less, and liquid compositions that were stable cellulose/pigment/dispersant slurries were obtained by controlling the amount and molecular weight of the dispersant. was prepared.

[Examples 15 to 18, Comparative Example 2: Preparation of liquid composition]
According to Table 4, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 8% by mass microcrystalline cellulose dispersion obtained in Reference Synthesis Example 2 (described as 8% cellulose dispersion in the table), a dispersant, and purified water. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. Thereafter, yellow iron oxide was slowly added so as to form lumps, and the liquid composition of Examples 15 to 18 or Comparative Example 2 was prepared by heating and stirring in a water bath at 50° C. for 3 hours at 600 rpm. Obtained.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 15, 16, 17 and 18 were confirmed to have viscosities of 1000 mPa s or less, and a stable cellulose/pigment/dispersant slurry was obtained by using a carboxylate as a dispersant and controlling the amount of the liquid. A composition was prepared.

[Examples 19 to 26, Comparative Example 1: Preparation of liquid composition]
According to Table 5, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 5% by mass microcrystalline cellulose dispersion obtained in Reference Synthesis Example 1 (described as 5% cellulose dispersion in the table), a dispersant, and purified water. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. Thereafter, yellow iron oxide was slowly added so as to form lumps, and the liquid composition of Examples 19 to 26 or Comparative Example 1 was obtained by heating and stirring in a water bath at 50° C. for 3 hours at 600 rpm. Obtained.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 19, 20, 21, 22, 23, 24, 25 and 26 were confirmed to have a viscosity of 350 mPa s (mPa s) or less, and by controlling the structure, molecular weight, and addition amount of the dispersant A liquid composition could be prepared which was a stable cellulose/pigment/dispersant slurry.

[Example 27: Composite pigment fine particles of cellulose: yellow iron oxide: glycyrrhizic acid 2K = 1:4:0.1 (w/w/w)]
The liquid composition, which is a microcrystalline cellulose/yellow iron oxide/glycyrrhizic acid 2K dispersion prepared in Example 17, was subjected to a CL-8 model (Okawara Kakoki Co., Ltd.) equipped with an RJ-5 nozzle (manufactured by Okawara Kakoki Co., Ltd.). (manufactured by Co., Ltd.) spray drying for 5 minutes at a stock solution throughput of 2.0 kg/h, a spray pressure of 0.2 MPa, an inlet temperature of 170°C, an outlet temperature of 118°C, and a cyclone differential pressure of 0.5 kPa. 10 g of powder were obtained as particles.

[Example 28: Composite pigment fine particles of cellulose: yellow iron oxide: Na polyacrylate = 1:4:0.125 (w/w/w)]
The liquid composition of microcrystalline cellulose/yellow iron oxide/Na polyacrylate dispersion prepared in Example 21 was subjected to a CL-8 model (Okawara Kako Co., Ltd.) equipped with an RJ-5 nozzle (manufactured by Okawara Kako Spray drying is performed for 5 minutes using a spray drier manufactured by Ki Co., Ltd., at an undiluted solution throughput of 2.0 kg/h, a spray pressure of 0.2 MPa, an inlet temperature of 170°C, an outlet temperature of 97°C, and a cyclone differential pressure of 0.5 kPa. 10 g of powder were obtained as title particles.

[Example 29: Particles of cellulose: yellow iron oxide: Na tripolyphosphate = 1: 4: 0.125 (w/w/w)]
The liquid composition of microcrystalline cellulose / yellow iron oxide / sodium tripolyphosphate dispersion prepared in Example 23 was subjected to a CL-8 model (Okawara Kakoki Co., Ltd.) equipped with an RJ-5 nozzle (manufactured by Okawara Kakoki Co., Ltd.) (manufactured by Co., Ltd.) spray drying for 7 minutes at a stock solution throughput of 2.0 kg/h, a spray pressure of 0.2 MPa, an inlet temperature of 170°C, an outlet temperature of 90°C, and a cyclone differential pressure of 0.5 kPa. 11 g of powder were obtained as particles.

[Evaluation Example 1: Morphological Observation of Particles]
Each of the particles obtained in Examples 27 to 29 was attached to a carbon tape and subjected to morphological observation using a scanning electron microscope Miniscope (registered trademark) TM3000 (manufactured by Hitachi High-Technologies Corporation). The results of particle morphology observation are shown in FIGS. 1 to 3, respectively. The particles obtained in Example 27 were each attached to a carbon tape, and a field emission scanning electron microscope JSM-7400F (manufactured by JEOL Ltd.) was used to measure the acceleration voltage at 0.7 kV or 1.0 kV and the amount of current. Morphological observation was performed at 10 μV. The morphological observation results of the particles are shown in FIGS. 4 and 5. FIG.

[Evaluation Example 2: Particle size evaluation]
Using a scattering-type particle size distribution measuring device LA-960 (manufactured by Horiba, Ltd.), the circulation speed was set to "3" and the stirring speed was set to "2", and the semiconductor laser was The concentration of the sample solution of each particle obtained in Example 27 was adjusted so that the transmittance of (650 nm) and light emitting diode (405 nm) was 90.0% or less. The obtained sample solution was irradiated with ultrasonic waves at an ultrasonic intensity of "3" for 1 to 5 minutes, and then the particle size was measured. The results are shown in order in FIG.

[Examples 30 to 33, Comparative Example 3: Preparation of liquid composition]
According to Table 6, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 8% by mass microcrystalline cellulose dispersion obtained in Reference Synthesis Example 2 (described as 8% cellulose dispersion in the table), a dispersant, and purified water. The mixture was stirred at room temperature for 20 minutes at 300 rpm. After that, red iron oxide was slowly added so as to form lumps, and the mixture was stirred at room temperature for 3 hours at 600 rpm to obtain liquid compositions of Examples 30 to 33 or Comparative Example 3.
The viscosities of the obtained various liquid compositions were measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. Examples 30, 31, 32 and 33 were confirmed to have viscosities of 400 mPa s or less, and liquid compositions that are stable cellulose/pigment/dispersant slurries were obtained by controlling the structure, molecular weight, and addition amount of the dispersant. things have been prepared.

[Examples 34 and 35, Comparative Examples 4 to 6: Preparation of liquid compositions]
According to Table 7, to a 200 mL beaker (manufactured by HARIO Co., Ltd.), the 5 mass% microcrystalline cellulose dispersion obtained in Reference Synthesis Example 1 (described as 5% cellulose dispersion in the table) or various thickeners Agent slurry, dispersant, and purified water were added. The mixture was heated and stirred at 300 rpm for 20 minutes in a water bath set at a temperature of about 50°C. After that, yellow iron oxide was slowly added so as to follow the lumps, and heated and stirred at 600 rpm for 3 hours in a water bath at 50 ° C. A liquid composition was obtained.
The viscosity of the resulting liquid composition was measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd.). A slurry with a viscosity of 5,000 mPa·s or less is defined as a slurry with good dispersibility, and x in the table indicates a viscosity of more than 5,000 mPa·s. In Examples 34 and 35, it was confirmed that the viscosity was 250 mPa·s or less, and a liquid composition of cellulose or cellulose derivative/pigment/dispersant slurry could be prepared.

In the production method of the present invention, a dispersant is added to a dispersion containing an inorganic pigment and cellulose or a cellulose derivative, and a liquid composition having a predetermined viscosity or less is used for spray drying. As a result, the energy cost can be suppressed without taking excessive time for the pulverization and fibrillation process for the inorganic pigment and cellulose or cellulose derivative. Moreover, since the solid content concentration in the dispersion liquid is not lowered, the waste liquid treatment cost can be suppressed. Furthermore, it is also excellent in that clogging of the spray nozzle during spray drying can be prevented and uniform particles can be stably produced. As a result, the composite pigment fine particles have excellent dispersibility in cosmetic base materials, improve dullness of colors, suppress pigment aggregation, and are soft and comfortable to use due to the cellulose on the particle surface. It is possible to provide a cheap and efficient manufacturing method that can stably manufacture with quality.

Claims (15)

A cellulose or cellulose comprising the steps of obtaining a liquid composition containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa·s or less, and spray-drying the obtained liquid composition. A method for producing composite pigment fine particles containing a derivative and an inorganic pigment. The production method according to claim 1, wherein the concentration of solids containing cellulose or a cellulose derivative and an inorganic pigment in the liquid composition is 1 to 50% by mass. The production method according to claim 1 or 2, wherein the cellulose is crystalline cellulose. The production method according to any one of claims 1 to 3, wherein the inorganic pigment is at least one selected from the group consisting of white pigments, colored pigments, pearlescent pigments and functional pigments. Claims wherein the inorganic pigment is selected from the group consisting of red iron oxide, yellow iron oxide, black iron oxide, chromium oxide, ultramarine blue, Prussian blue, manganese purple, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, barium sulfate and boron nitride. Item 5. The production method according to any one of items 1 to 4. The production method according to any one of claims 1 to 5, wherein the ratio (weight) of cellulose or cellulose derivative to inorganic pigment is in the range of 1:1 to 1:20. The production method according to any one of claims 1 to 6, wherein the dispersant has an acid functional group, its salt or ester. The dispersant is selected from the group consisting of glycerin fatty acid ester, polyglycerin fatty acid ester, alkyl ether carboxylate, glycyrrhizinate, higher fatty acid salt, polyacrylate, polyphosphate, phosphonate, and acid mucopolysaccharide salt Selected, the manufacturing method according to any one of claims 1 to 7. Dispersants include polyglyceryl laurate, polyglyceryl isostearate, polyglyceryl monostearate, sodium polyoxyethylene lauryl ether acetate, dipotassium glycyrrhizinate, sodium oleate, sodium polyacrylate, sodium tripolyphosphate, 1-hydroxyethylidene-1,1 - disodium diphosphonate, tetrasodium 1-hydroxyethylidene-1,1-diphosphonate, and sodium hyaluronate. The production method according to any one of claims 1 to 9, wherein the dispersant is dipotassium glycyrrhizinate. A liquid composition containing cellulose or a cellulose derivative, an inorganic pigment, a dispersant and water and having a viscosity of 5,000 mPa·s or less. Composite pigment fine particles comprising cellulose or a cellulose derivative, an inorganic pigment and a dispersant, obtained by the production method according to any one of claims 1 to 10. 13. The composite pigment fine particles according to claim 12, having a particle size in the range of 0.1 to 500 μm. 14. The fine composite pigment particles according to claim 12 or 13, which are used for cosmetics. A cosmetic comprising the composite pigment particles according to any one of claims 12-14.

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