WO2021145450A1

WO2021145450A1 - Uv ray-blocking particulate composition

Info

Publication number: WO2021145450A1
Application number: PCT/JP2021/001363
Authority: WO
Inventors: 睦洋勝家
Original assignee: 日産化学株式会社
Priority date: 2020-01-17
Filing date: 2021-01-15
Publication date: 2021-07-22
Also published as: TW202139964A

Abstract

The purpose of the present invention is to provide a cosmetic powder that has excellent UV-blocking capability and can also be used in combination with a conventional UV-blocking agent to improve the use sensation thereof and to enhance the UV-blocking capability thereof.　Provided is a particulate composition having a rugged structure on the surface thereof, and containing as main components: cellulose or a cellulose derivative; and a clay mineral. Also provided is a method for producing said particulate composition. Such particulate composition is soft, has a good use sensation and excellent UV-blocking capability, and in particular, exhibits the superior effect of enhancing the UV-blocking capability when mixed in a cosmetic containing a conventional UV-blocking agent. The particulate composition, therefore, is useful as a cosmetic.

Description

Particulate composition for UV protection

The present invention relates to a particulate composition for UV protection, which has an uneven structure on the surface and contains cellulose or a cellulose derivative and a clay mineral as main components, a method for producing the same, and a cosmetic product containing the composition.

In the sunlight reaching the ground, the amount of ultraviolet rays having a wavelength of 280 to 400 nm occupies about 6%, and in particular, 280 to 320 nm (hereinafter referred to as UVB) on the short wavelength side is about 0.5%, which is on the long wavelength side. 320 to 400 nm (hereinafter referred to as UVA) is about 5.5%. UVA reaches the dermis under the skin and causes photoaging such as wrinkles, slackness, and decreased elasticity, and is said to have an adverse effect on cell membranes and genes. UVB is scattered and absorbed by the epidermis and causes inflammation such as sunburn on the skin. Is known to cause.

In sunscreen cosmetics that protect the skin from such ultraviolet rays, inorganic powders such as titanium dioxide and zinc oxide have been used as ultraviolet scattering agents, and organic compounds such as para-aminobenzoic acid (PABA) derivatives have been used as ultraviolet absorbers.

However, although the organic ultraviolet absorber has an excellent effect of absorbing ultraviolet rays, it is not stable because it is an organic compound, and the effect cannot be expected to be sustained. In addition, the use of organic ultraviolet absorbers as cosmetic additives is restricted from the viewpoint of safety.
Inorganic UV scatterers have strong hiding power, whiten when applied to the skin, do not give a natural finish, and have high adhesion to the skin, so they squeak when blended in cosmetics. There was a problem that a favorable feeling could not be obtained.
From the above issues, various reports have been made with the aim of maintaining the UV protection effect while reducing the amount of UV absorbers and UV scatterers (hereinafter collectively referred to as "UV protection agents") in cosmetics as much as possible. Has been done.

Among them, there has been a report on an SPF booster agent capable of enhancing the ultraviolet shielding / absorbing effect of an ultraviolet protective agent by similarly scattering ultraviolet rays by using polyamide porous particles having an excellent visible light scattering effect (for example). , Patent Document 1). However, since the polyamide porous fine particles are plastic microbeads, there is a concern that they may pass through the sewage treatment and flow out into rivers and the ocean, be taken up by living organisms, and adversely affect the ecosystem. Since it is almost impossible to recover microbeads once they flow out into the environment, it has been particularly required in recent years to replace plastic microbeads with environmentally friendly materials such as natural materials (for example, cellulose). ..

Since the particles containing cellulose or a cellulose derivative and a clay mineral as main components have excellent usability and light scattering properties, the present inventors have been able to obtain a defocusing effect when blended in cosmetics. It has been found to be excellent (see, for example, Patent Document 2).

International Publication No. 2012/161084 Japanese Patent Application No. 2018-170746

Until now, it has not been clarified whether or not particles containing cellulose or a cellulose derivative and clay minerals as main components have an ultraviolet light scattering effect. In addition, there are organic and inorganic UV protection agents, but the organic has problems in safety and stability, and the inorganic has problems in usability and finish.

As a result of diligent studies by the present inventors, particles containing cellulose or a cellulose derivative and a clay mineral as main components show an effective UV protection ability, and when used in combination with an existing UV protection agent, the protection effect is exhibited. The present invention has been completed by finding that it is possible to improve the feeling of use and the finish. The present invention is as follows.

(1) A particulate composition for UV protection, which has an uneven structure on the surface and contains cellulose or a cellulose derivative and a clay mineral as main components.
(2) The composition according to (1) above, which has a wrinkle-like or fold-like uneven structure on the surface.
(3) The composition according to (1) or (2) above, wherein the porosity is in the range of 5 to 60%.
(4) The composition according to any one of (1) to (3) above, which has a particle size in the range of 0.5 to 500 μm.
(5) The composition according to any one of (1) to (4) above, which has a hardness in the range of 0.1 to 50 MPa.
(6) The composition according to any one of (1) to (5) above, wherein the ultraviolet transmittance is in the range of 50% or less.
(7) The composition according to any one of (1) to (6) above, which contains 0.1 to 20 parts by mass of clay mineral with respect to 1 part by mass of cellulose or a cellulose derivative.
(8) The composition according to any one of (1) to (7) above, wherein the cellulose is crystalline cellulose.
(9) The composition according to any one of (1) to (8) above, wherein the clay mineral is at least one selected from the group consisting of talc, kaolin, and mica.
(10) It has an uneven structure on the surface and mainly contains cellulose or a cellulose derivative and a clay mineral, which includes a step of obtaining a dispersion liquid of cellulose or a cellulose derivative and a clay mineral and a step of spray-drying the obtained dispersion liquid. A method for producing a particulate composition for UV protection as an ingredient.
(11) The production method according to (10) above, wherein the dispersion is obtained by physically pulverizing cellulose or a cellulose derivative and a clay mineral.
(12) The production method according to (10) or (11) above, wherein the concentration of the solid content containing cellulose or a cellulose derivative and a clay mineral in the dispersion is 0.5 to 40% by mass.
(13) The production method according to any one of (10) to (12) above, wherein the dispersion contains 0.1 to 20 parts by mass of clay mineral with respect to 1 part by mass of cellulose or a cellulose derivative.
(14) A cosmetic product comprising the composition according to any one of (1) to (9) above, or the composition obtained by the production method according to any one of (10) to (13) above.

The particulate composition of the present invention is soft because it has an uneven structure on its surface (that is, because pores or voids are appropriately present), and is suitable for addition to cosmetics that come into direct contact with the skin. In addition to exhibiting an effective UV protection ability, the particulate composition of the present invention can enhance the protection effect when used in combination with an existing UV protection agent, so that the existing UV protection agent can be used. A reduction in quantity can also be expected.

(A) to (c) are scanning electron microscope (SEM) photographs of the particulate compositions of Examples 1 to 3 obtained in Evaluation Example 1, respectively. (A) to (c) are field emission scanning electron microscope (FE-SEM) photographs of the particulate compositions of Examples 1 to 3 obtained in Evaluation Example 1, respectively. Results of transmitted light evaluation of each film sample prepared in Evaluation Example 2 using the particulate composition of Example 1, microcrystalline cellulose (Comparative Example 1), and synthetic mica (Comparative Example 2) as evaluation particles. It is a graph showing. In addition to the existing ultraviolet scattering agent titanium oxide used in Evaluation Example 3, the particulate composition of Example 1, microcrystalline cellulose (Comparative Example 1), and synthetic mica (Comparative Example 2) were used as evaluation particles. It is a graph which showed the result of the transmitted light evaluation of each film sample prepared by using. In Evaluation Example 5, the results of transmitted light evaluation of a film sample obtained by forming an O / W foundation sample prepared by using the particulate composition of Example 1 and synthetic mica (Comparative Example 1) as evaluation particles are shown. It is a graph. A graph showing the results of transmitted light evaluation of a film sample obtained by forming an O / W foundation sample prepared by using the particulate composition of Example 2 and talc (Comparative Example 2) as evaluation particles in Evaluation Example 5. Is. In Evaluation Example 5, the results of transmitted light evaluation of a film sample obtained by forming an O / W foundation sample prepared by using the particulate composition of Example 3 and sericite (Comparative Example 3) as evaluation particles are shown. It is a graph. In Evaluation Example 6, in addition to the existing ultraviolet scattering agent, the particulate composition of Example 1, synthetic mica (Comparative Example 1), microcrystalline cellulose (Comparative Example 2), synthetic mica and microcrystalline cellulose were used as evaluation particles. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the film of the O / W foundation sample prepared using each of the mixed samples (Comparative Example 3). In Evaluation Example 6, O / W prepared by using the particulate composition of Example 2, microcrystalline cellulose (Comparative Example 2), and talc (Comparative Example 4) as evaluation particles in addition to the existing ultraviolet scattering agent. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the foundation sample. In Evaluation Example 6, in addition to the existing ultraviolet scattering agent, O / prepared using the particulate composition of Example 3, microcrystalline cellulose (Comparative Example 2), and sericite (Comparative Example 5) as evaluation particles, respectively. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the film | film of the W foundation sample. In Evaluation Example 7, in addition to the existing ultraviolet absorber, the particulate composition of Example 1, synthetic mica (Comparative Example 1), microcrystalline cellulose (Comparative Example 2), synthetic mica and microcrystalline cellulose were used as evaluation particles. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the film of the O / W foundation sample prepared using each of the mixed samples (Comparative Example 3) of. In Evaluation Example 7, O / W prepared by using the particulate composition of Example 2, microcrystalline cellulose (Comparative Example 2), and talc (Comparative Example 4) as evaluation particles in addition to the existing ultraviolet absorber. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the foundation sample. In Evaluation Example 7, in addition to the existing ultraviolet absorber, O / prepared using the particulate composition of Example 3, microcrystalline cellulose (Comparative Example 2), and sericite (Comparative Example 5) as evaluation particles, respectively. It is a graph which showed the result of the transmitted light evaluation of the film sample which formed the film | film of the W foundation sample.

<Particulate composition>
The present invention relates to a particulate composition having a concavo-convex structure on the surface and containing cellulose or a cellulose derivative and a clay mineral as main components. Preferably, the present invention relates to a particulate composition having a wrinkled or fold-like uneven structure on the surface and containing cellulose or a cellulose derivative and a clay mineral as main components. "Having a wrinkled or pleated uneven structure" means that when a magnified image of a particle is observed, the surface thereof is not smooth and has groove-like streaks having a wrinkled or pleated appearance. do.

The particulate composition of the present invention contains cellulose or a cellulose derivative as a main component. The cellulose or cellulose derivative used in the present invention is a regenerated natural fiber such as wool, cotton, silk, hemp, pulp, rayon, polynosic, cupra (Bemberg (registered trademark)), lyocell (Tencel (registered trademark)), etc. Examples include those derived from fibers and cellulose produced by bacteria. Further, it may be derived from a cellulose composite fiber of a cellulosic fiber and a synthetic fiber (for example, a polyolefin fiber such as polyethylene or polypropylene).

Examples of the cellulose or cellulose derivative used in the present invention include those derived from natural fibers, for example, those derived from plants such as wood, bamboo, hemp, jute, kenaf, cotton, beet, and agricultural waste. , Hardwoods, softwoods or those derived from bamboo. Further, it is preferable to use a product obtained by partially depolymerizing α-cellulose obtained from such a fibrous plant with an acid and purifying it, for example, crystalline cellulose.

Further, in the present invention, it is preferable to use cellulose nanofibers as cellulose or a cellulose derivative. "Cellulose nanofiber (CNF)" is a fiber obtained by defibrating cellulose fibers to a nano-size level, and is generally a fiber having 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 can be obtained as a commercially available product. For example, it can be obtained from suppliers such as Daio Paper Corporation and Chuetsu Pulp & Paper Co., Ltd.

The particulate composition of the present invention also contains a clay mineral as a main component. The clay mineral used in the present invention means a natural or synthetic layered silicate mineral, and is not particularly limited as long as it swells in water and can exchange ions. Examples include talc, kaolin, montmorillonite, kaolinite, sericite, muscovite, gold mica, synthetic mica, red mica, black mica and other mica, vermiculite, zeolite, bentonite, smectite, black. Examples include light, erite, glow kaolin, and the like. Among them, at least one selected from the group consisting of talc, kaolin and mica is preferable from the viewpoint of combination with cellulose or a cellulose derivative and application of the particulate composition to cosmetics. These clay minerals are available from suppliers as pharmaceutical or cosmetic additives.

The layered silicate mineral is contained as a main component of a clay mineral, and its content is usually 60% or more, preferably 75% or more, and most preferably 80% or more.

In the present invention, "containing cellulose or cellulose derivative and clay mineral as main components" means that the ratio (mass basis) of cellulose or cellulose derivative and clay mineral in the particulate composition is more than 50% by mass. do. The ratio (mass basis) of cellulose or cellulose derivative to clay mineral 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. In the most preferred embodiment, the particulate composition of the present invention comprises only cellulose or a cellulose derivative and a clay mineral.

In the present invention, the blending ratio of the cellulose or the cellulose derivative and the clay mineral is not particularly limited as long as the effect of the present invention is obtained, but typically 0.1 to 20 to 1 part by mass of the cellulose or the cellulose derivative. It contains parts by mass, preferably 0.2 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass of clay mineral.

Examples of components other than cellulose or cellulose derivatives and clay minerals contained in the particulate composition include magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, and tungsten acid. Metal salts, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (eg zinc myristate, calcium palmitate, aluminum stearate), red iron oxide, iron yellow oxide, black iron oxide, ultramarine , Navy blue, carbon black, titanium oxide, fine particles and ultrafine particles of titanium oxide, zinc oxide, fine particles and ultrafine particles of zinc oxide, alumina, silica, fuming silica (ultrafine particles anhydrous silicic acid), mica titanium, fish scale foil, boron nitride, Photochromic pigments, synthetic fluorine gold mica, fine particle composite powder, inorganic powders of various sizes and shapes such as gold and aluminum, and silicones such as hydrogen silicone and cyclic hydrogen silicone or other silanes. Examples thereof include powders that have been treated with various surface treatment agents such as titanium coupling agents to make them hydrophobic or hydrophilic.

The particle size of the particulate composition of the present invention can be appropriately set according to the desired use of the particulate composition, and is, for example, in the range of 0.5 to 500 μm, preferably in the range of 1 to 200 μm, and more preferably in the range of 2 to 2. It is distributed in the range of 100 μm, particularly preferably 5 to 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 measuring device, and the average particle size means an arithmetic mean diameter calculated from the obtained particle size distribution.

The porosity of the particulate composition of the present invention can be appropriately set according to the desired use of the particulate composition, and is, for example, in the range of 5 to 60%, preferably in the range of 10 to 50%, and more preferably in the range of 15 to 15. It is in the range of 45%. In the present invention, the porosity refers to the porosity (particle cross-sectional image) when a particle cross-sectional image obtained by using a scanning electron microscope or the like is used and the cross-sectional area (the area of the entire cross section in the particle cross-sectional image) is 100. It means a value which shows the ratio of the total area of the porosity) as a percentage, and the average porosity means the arithmetic mean value of the obtained porosity. The porosity can be calculated in the same manner by using a method such as X-ray CT. When the porosity of the particulate composition of the present invention is in such a range, the softness of the particles can be maintained and excellent optical properties can be exhibited even during foundation formulation.

The hardness of the particulate composition of the present invention can be appropriately set according to the desired use of the particulate composition, and is, for example, in the range of 0.1 to 50 MPa, preferably in the range of 0.1 to 40 MPa, more preferably 0. It is in the range of .5 to 30 MPa. In the present invention, the hardness means a value measured by a microcompression tester, and is calculated from the following formula as the strength C (x) when the particle size is deformed by 10%.

(In the formula, P is the test force (N) when the particle size is deformed by 10%, π is the pi, d is the particle size (mm), and C (x) is the 10% intensity (MPa).)
When the hardness of the particulate composition of the present invention is in such a range, the softness of the particles can be maintained and excellent optical properties can be exhibited.

<Manufacturing method of particulate composition>
The particulate composition of the present invention can be produced by a method including a step of obtaining a dispersion liquid of cellulose or a cellulose derivative and a clay mineral, and a step of spray-drying the obtained dispersion liquid.

Examples and preferred embodiments of cellulose or cellulose derivatives and clay minerals in the dispersion according to the production method of the present invention are as described above. The dispersion can be prepared by any method, and is obtained, for example, by mixing cellulose or a cellulose derivative, a clay mineral and a dispersion medium, and pulverizing the mixture. Alternatively, first, a cellulose or cellulose derivative (or clay mineral) and a dispersion medium are mixed, and this is pulverized to obtain a cellulose or cellulose derivative (or clay mineral) dispersion liquid, and then the clay mineral (or cellulose or cellulose derivative). It can also be obtained by mixing the dispersion medium and further pulverizing the mixture. The dispersion medium is preferably an aqueous medium, more preferably water, a water-miscible organic solvent or a mixture thereof. 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, N, N-dimethylformamide and other amides, γ-butyrolactone and other lactones, tetrahydrofuran and other ethers. In the most preferred embodiment, the dispersion medium is water or a mixture of water and alcohols having 1 to 4 carbon atoms.

The dispersion liquid is 0.1 to 20 parts by mass, preferably 0.2 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass with respect to 1 part by mass of cellulose or a cellulose derivative. Contains some clay minerals. The concentration of the solid content containing cellulose or the cellulose derivative and the clay mineral in the dispersion is not particularly limited as long as it can be used in the subsequent spray drying step, but is, for example, 0.5 to 40% by mass, preferably 1 to 1 to 40% by mass. It is 35% by mass, more preferably 2 to 30% by mass.

The operation for obtaining the dispersion liquid is not particularly limited, and can be carried out by using the operation for obtaining the dispersion liquid known to those skilled in the art. Typically, the dispersion is obtained by milling a cellulose or cellulose derivative and a clay mineral, preferably by physical milling. Physical crushing refers to a mixture of cellulose or cellulose derivative and / or clay mineral and dispersion medium, a stirrer such as a magnetic stirrer or a stirring blade, a homogenizer such as a polytron, or an ultrasonic generator such as an ultrasonic crusher. It is carried out by applying a physical external force using a crusher such as a wet atomizing device (for example, Starburst; Sugino Machine Co., Ltd.). However, if a commercially available cellulose or cellulose derivative and / or clay mineral is sufficiently pulverized, a dispersion liquid may be obtained without performing the pulverization treatment. Further, in the production method of the present invention, a commercially available cellulose dispersion, for example, a commercially available cellulose nanofiber dispersion may be used instead of the step of obtaining the cellulose or cellulose derivative dispersion.

The particulate composition of the present invention is obtained by spray-drying the obtained dispersion. Spray drying is carried out using a known spray drying device such as an atomizer, a spray dryer, and a micro mist spray dryer. 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, and are carried out, for example, at an inlet temperature of 150 to 300 ° C. and an outlet temperature of 0 to 150 ° C. ..

<Cosmetics>
The particulate composition of the present invention has an uneven structure on its surface, is soft because it has an appropriate hardness and porosity, and has an effective UV protection ability, so that it comes into direct contact with the skin and protects against UV rays. Suitable for addition to cosmetics that require an effect. Examples of such cosmetics include hair care products such as shampoos and conditioners, makeup bases, powder foundations, liquid foundations, BB creams, concealers, lipsticks, makeup cosmetics such as sunscreens, etc. It can be used as a scrubbing agent for enhancing the cleaning effect or as a light scattering agent for exhibiting the defocus effect.

The particulate composition of the present invention can enhance its protective effect when used in combination with an existing ultraviolet protective agent. Therefore, it can be expected that the amount of existing UV protection agent used will be reduced. Generally, UV protective agents are roughly classified into UV absorbers and UV scatterers, but the particulate composition of the present invention can be used in combination with any type. In Japan, for example, such an ultraviolet protective agent is not particularly limited as long as it conforms to cosmetic standards, but examples of an ultraviolet absorber include paraaminobenzoic acid and its ester, and amyl paradimethylaminobenzoate. Paraaminobenzoic acid derivatives such as, dihydroxydimethoxybenzophenone, benzophenone derivatives such as dihydroxybenzophenone, silicate hexyl paramethoxysilicate, mono-2-ethylhexanoate glyceryl salicylic acid, octyl salicylate, etc. , Salicylic acid derivatives such as homomentyl salicylate, dibenzoylmethane derivatives such as 4-tert-butyl-4'-methoxydibenzoylmethane, and hydantin derivatives such as dimethoxybenzilidendioxoimidazolidine propionate 2-ethylhexyl. Examples of the ultraviolet scattering agent include titanium dioxide (TiO ₂ ), zinc oxide (ZnO) and aluminum oxide (Al ₂ O ₃ ).

[Reference Synthesis Example 1: 20% by Mass Microcrystalline Cellulose and Synthetic Mica Dispersion]
After dispersing 7.2 kg of microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and 28.8 kg of synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) in 144 kg of ion-exchanged water. The wet atomizer Starburst Co., Ltd. (manufactured by Sugino Machine Co., Ltd.) was used to grind the mixture twice at 150 MPa to obtain the title 20% by mass microcrystalline cellulose and synthetic mica dispersion.

[Reference Synthesis Example 2: 20% by Mass Microcrystalline Cellulose and Talc Dispersion]
After 4.0 kg of talc (MMR, manufactured by Asada Flour Milling Co., Ltd.) was dispersed in 20 kg of ion-exchanged water, it was pulverized twice at 150 MPa with a wet atomizer Starburst (manufactured by Sugino Machine Limited). .. 1.0 kg of microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) was added thereto, and the mixture was further pulverized twice to obtain the title 20% by mass microcrystalline cellulose and talc dispersion. ..

[Reference Synthesis Example 3: 20% by Mass Microcrystalline Cellulose and Mica Dispersion]
After dispersing 4.0 kg of mica (Serisite FSE, manufactured by Sanshin Mining Co., Ltd.) in 20 kg of ion-exchanged water, it is pulverized four times at 150 MPa with a wet atomizer Starburst (manufactured by Sugino Machine Co., Ltd.). Was done. 1.0 kg of microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) was added thereto, and the mixture was further pulverized twice to obtain the title 20% by mass microcrystalline cellulose and mica dispersion. ..

[Example 1: Cellulose: Synthetic mica = 1: 4 w / w particulate composition]
Reference: 5.14 kg of the dispersion obtained in Synthesis Example 1 is used as a stock solution with an RL-5 type (Okawara Kakohki Co., Ltd.) spray dryer equipped with an RJ-10 nozzle (Okawara Kakohki Co., Ltd.). The treatment amount was 9.6 kg / h, the spray pressure was 0.4 MPa, the inlet temperature was 250 ° C., the outlet temperature was 98 ° C., and the cyclone differential pressure was 1.7 kPa. The mixture was spray-dried to obtain 358 g of powder as the title particulate composition.

[Example 2: Cellulose: Talc = 1: 4 w / w particulate composition]
Reference: 7.95 kg of the dispersion obtained in Synthesis Example 2 is used as a stock solution with an RL-5 type (Okawara Kakohki Co., Ltd.) spray dryer equipped with an RJ-10 nozzle (Okawara Kakohki Co., Ltd.). The powder was spray-dried at a treatment amount of 8.5 kg / h, a spray pressure of 0.3 MPa, an inlet temperature of 250 ° C., an outlet temperature of 97 ° C., and a cyclone differential pressure of 1.7 kPa to obtain 1.32 kg of powder as the title particulate composition.

[Example 3: Cellulose: mica = 1: 4 w / w particulate composition]
Reference: 15.80 kg of the dispersion obtained in Synthesis Example 3 is used as a stock solution with an RL-5 type (Okawara Kakohki Co., Ltd.) spray dryer equipped with an RJ-10 nozzle (Okawara Kakohki Co., Ltd.). The powder was spray-dried at a treatment amount of 9.2 kg / h, a spray pressure of 0.3 MPa, an inlet temperature of 250 ° C., an outlet temperature of 94 ° C., and a cyclone differential pressure of 1.7 kPa to obtain 2.71 kg of powder as the title particulate composition.

[Evaluation example 1: Observation of particle morphology]
The particulate composition obtained in Examples 1 to 3 was attached to a carbon tape, and morphological observation was carried out using a scanning electron microscope Miniscope (registered trademark) TM3000 (manufactured by Hitachi High-Technologies Corporation). The morphological observation results of the particulate composition are shown in FIGS. 1 (a) to 1 (c). Further, the particulate compositions obtained in Examples 1 to 3 were attached to carbon tapes, respectively, and an acceleration voltage of 0.7 kV or 1 was used using a field emission scanning electron microscope JSM-7400F (manufactured by JEOL Ltd.). Morphological observation was carried out at 0.0 kV and a current amount of 10 μV. The morphological observation results of the particles are shown in FIGS. 2 (a) to 2 (c), respectively.

[Evaluation example 2: Evaluation of UV protection ability]
8.55 g of silicone rubber KE-1300T (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.95 g of curing agent CAT-1300 (manufactured by Shin-Etsu Chemical Co., Ltd.) were weighed into a 20 mL vial, and 0.5 g of evaluation particles were added. .. Then, the rotation / revolution mixer Awatori Rentaro ARE-310 (manufactured by Shinky Co., Ltd.) was used to stir and mix at 2000 rpm for 10 minutes, and defoamed at 2200 rpm for 2 minutes. The prepared sample was formed into a film using an applicator to a thickness of 50 μm on a vertical black-and-white B type concealment test paper (manufactured by TP Giken Co., Ltd.) and dried overnight to prepare a film sample. These film samples were evaluated for transmitted light with an ultraviolet-visible near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation). As the evaluation particles, the particulate composition obtained in Example 1 was used. Further, as Comparative Example 1, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) was used, and as Comparative Example 2, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) was used with Example 1. A film sample was prepared in the same manner. The ultraviolet transmittance of the film sample using the particulate composition of the present invention was 50% or less, specifically about 35%. On the other hand, the ultraviolet transmittance of the film sample using microcrystalline cellulose and synthetic mica was about 70%. The results are shown in FIG.

[Evaluation example 3: Evaluation of UV protection ability enhancing effect]
Weigh silicone rubber KE-1300T (manufactured by Shin-Etsu Chemical Co., Ltd.) 8.55 g and curing agent CAT-1300 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.95 g (w / w) into a 20 mL vial, and superimpose it there. Fine particle titanium oxide ST-455WS (manufactured by Titanium Industry Co., Ltd.) 0.05 g and evaluation particles 0.5 g were added. Then, the rotation / revolution mixer Awatori Rentaro ARE-310 (manufactured by Shinky Co., Ltd.) was used to stir and mix at 2000 rpm for 10 minutes, and defoamed at 2200 rpm for 2 minutes. The prepared sample was formed into a film using an applicator to a thickness of 50 μm on a vertical black-and-white B type concealment test paper (manufactured by TP Giken Co., Ltd.) and dried overnight to prepare a film sample. These film samples were evaluated for transmitted light with an ultraviolet-visible near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation). As the evaluation particles, the particulate composition obtained in Example 1 was used. Further, as Comparative Example 1, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) was used, and as Comparative Example 2, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) was used as Example 1 and A film sample was prepared in the same manner. The results are shown in FIG. The particulate composition of the present invention enhanced the UV protection of titanium oxide.

[Evaluation example 4: Evaluation of average friction coefficient and fluctuation of average friction coefficient]
0.05 g of ultrafine titanium oxide (ST-455WS, manufactured by Titan Kogyo Co., Ltd.) and 0.2 g of evaluation particles were weighed into a 10 mL vial, and the mixture was stirred and mixed with VORTEX3 (manufactured by IKA) for 1 minute. As the evaluation particles, the particulate compositions obtained in Examples 1 to 3 were used. In addition, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) as Comparative Example 1, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) as Comparative Example 2, and mica (Mica (manufactured by Nippon Koken Kogyo Co., Ltd.)) as Comparative Example 3. Serisite FSE, manufactured by Sanshin Mining Ind. Co., Ltd., as Comparative Example 4, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) Was mixed at a mass ratio of 1: 4, and as Comparative Example 5, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and talc (MMR, manufactured by Asada Flour Milling Co., Ltd.) were mixed at a mass ratio of 1: 4. A mixed sample, as Comparative Example 6, a sample in which microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and mica (Serisite FSE, manufactured by Sanshin Mining Co., Ltd.) were mixed at a mass ratio of 1: 4. Using. Weigh 15 mg of each prepared sample, apply the sample powder evenly on the artificial leather supplement (registered trademark) (manufactured by Idemitsu Technofine Co., Ltd.), and then use the friction tester KES-SE (manufactured by Katou Tech Co., Ltd.). The average friction coefficient (MIU) and the fluctuation of the average friction coefficient (MMD) were evaluated. A 10 mm square silicon wire was used as the sensor, the measurement distance was set to 20 mm, the static load was set to 25 gf, the measurement speed was set to 1.0 mm / sec, and the contact surface width was set to 10 mm. The results of each sample are shown in Table 1. MIU is an index showing the slipperiness felt when touching the surface of an object with a human finger, and the smaller the value, the slippery. MMD is an index expressing the feeling of roughness felt when the surface of an object is touched by a human finger. The larger the MMD value, the more grainy it feels.

[Evaluation example 5: Evaluation of UV protection ability]
The O / W foundation sample formulation composition used for the evaluation is shown in Table 2 below. The raw materials in columns A and B were heated to about 80 ° C., respectively, and stirred with a homomixer at 7000 rpm for 3 minutes. Then, it was stirred and cooled with a propeller stirrer at 300 rpm until it reached room temperature. When the temperature returned to room temperature, the raw material in column C was added, and stirring was continued for another 10 minutes. To 9.5 g of this formulation, 0.5 g of evaluation particles are added, and the mixture is stirred and mixed at 2000 rpm for 2 minutes with a rotation / revolution mixer Awatori Rentaro ARE-310 (manufactured by Shinky Co., Ltd.) for 2 minutes at 2200 rpm. By defoaming, an O / W foundation sample was obtained. The prepared sample was formed into a film on a polyester film mirror (registered trademark) T-60 (thickness 100 μm) (manufactured by Toray Industries, Inc.) with a thickness of 100 μm using an applicator, and dried at room temperature to prepare a film sample. The produced film sample was evaluated for transmitted light using an ultraviolet-visible near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation) (blank: polyester film mirror (registered trademark) T-60). The results are shown in FIGS. 5a-5c. In addition, a quantitative comparison of the ultraviolet light transmittance was also performed by calculating the integrated value of the transmittance from the graph of the obtained spectrum data at 305 to 400 nm. The results of each sample are shown in Table 3.
As the evaluation particles, the particulate compositions obtained in Examples 1 to 3 were used. In addition, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) as Comparative Example 1, talc (MMR, Asada Flour Milling Co., Ltd.) as Comparative Example 2, and mica (Serisite FSE, Sanshin Mining Co., Ltd.) as Comparative Example 3. (Manufactured by Co., Ltd.) was used.

[Evaluation example 6: Evaluation of UV protection ability enhancing effect]
The O / W foundation sample formulation composition used for the evaluation is as shown in Table 2 above. The raw materials in columns A and B were heated to about 80 ° C., respectively, and stirred with a homomixer at 7000 rpm for 3 minutes. Then, it was stirred and cooled with a propeller stirrer at 300 rpm until it reached room temperature. When the temperature returned to room temperature, the raw material in column C was added, and stirring was continued for another 10 minutes. To 9.45 g of this formulation, 0.5 g of evaluation particles and 0.05 g of ultrafine titanium oxide MT-500SA (manufactured by TAYCA CORPORATION) were added, and a rotation / revolution mixer Awatori Rentaro ARE-310 type (Co., Ltd.) An O / W foundation sample was obtained by stirring and mixing at 2000 rpm for 2 minutes and defoaming at 2200 rpm for 2 minutes. The prepared sample was formed into a film on a polyester film mirror (registered trademark) T-60 (thickness 100 μm) (manufactured by Toray Industries, Inc.) with a thickness of 100 μm using an applicator, and dried at room temperature to prepare a film sample. The produced film sample was evaluated for transmitted light using an ultraviolet-visible near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation) (blank: polyester film mirror (registered trademark) T-60). The results are shown in FIGS. 6a to 6c. In addition, a quantitative comparison of the ultraviolet light transmittance was also performed by calculating the integrated value of the transmittance from the graph of the obtained spectrum data at 305 to 400 nm. The results of each sample are shown in Table 4. The particulate composition of the present invention enhances the ultraviolet protection ability of titanium oxide, which is an inorganic ultraviolet scattering agent.
As the evaluation particles, the particulate compositions obtained in Examples 1 to 3 were used. In addition, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) as Comparative Example 1, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) as Comparative Example 2, and microcrystalline cellulose as Comparative Example 3. A sample in which (compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) are mixed at a mass ratio of 1: 4, and talc (MMR, Asada) as Comparative Example 4 Mica (Serisite FSE, Sanshin Mining Co., Ltd.) was used as Comparative Example 5 (manufactured by Flour Milling Co., Ltd.).

[Evaluation example 7: Evaluation of UV protection ability enhancing effect]
The O / W foundation sample formulation composition used for the evaluation is as shown in Table 2 above. The raw materials in columns A and B were heated to about 80 ° C., respectively, and stirred with a homomixer at 7000 rpm for 3 minutes. Then, it was stirred and cooled with a propeller stirrer at 300 rpm until it reached room temperature. When the temperature returned to room temperature, the raw material in column C was added, and stirring was continued for another 10 minutes. To 9.45 g of this formulation, 0.5 g of evaluation particles and 0.05 g of ethylhexyl methoxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the rotation / revolution mixer Awatori Rentaro ARE-310 type (Co., Ltd.) An O / W foundation sample was obtained by stirring and mixing at 2000 rpm for 2 minutes and defoaming at 2200 rpm for 2 minutes. The prepared sample was formed into a film on a polyester film mirror (registered trademark) T-60 (thickness 100 μm) (manufactured by Toray Industries, Inc.) with a thickness of 100 μm using an applicator, and dried at room temperature to prepare a film sample. The produced film sample was evaluated for transmitted light using an ultraviolet-visible near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation) (blank: polyester film mirror (registered trademark) T-60). The results are shown in FIGS. 7a-7c. In addition, a quantitative comparison of the ultraviolet light transmittance was also performed by calculating the integrated value of the transmittance from the graph of the obtained spectrum data at 305 to 400 nm. The results of each sample are shown in Table 5. The particulate composition of the present invention enhanced the UV protection ability of ethylhexyl methoxycinnamate, which is an organic UV absorber.
As the evaluation particles, the particulate compositions obtained in Examples 1 to 3 were used. In addition, synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) as Comparative Example 1, microcrystalline cellulose (Compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) as Comparative Example 2, and microcrystals as Comparative Example 3. A sample in which cellulose (compressel M101, manufactured by Fushimi Pharmaceutical Co., Ltd.) and synthetic mica (NK-8G, manufactured by Nippon Koken Kogyo Co., Ltd.) are mixed at a mass ratio of 1: 4, and talc (MMR, MMR, manufactured as Comparative Example 4) Mica (Serisite FSE, manufactured by Sanshin Mining Co., Ltd.) was used as Comparative Example 5 (manufactured by Asada Flour Milling Co., Ltd.).

The particulate composition of the present invention is mainly composed of a natural material and has an uneven structure on its surface (that is, because pores or voids are appropriately present), so that it is soft and can be added to cosmetics that come into direct contact with the skin. Suitable for. In addition to exhibiting an effective UV protection ability, the particulate composition of the present invention can enhance the protection effect when used in combination with an existing UV protection agent, so that the existing UV protection agent can be used. A reduction in quantity can also be expected.

Claims

A particulate composition for UV protection that has an uneven structure on the surface and contains cellulose or a cellulose derivative and clay minerals as main components.
The composition according to claim 1, which has a wrinkle-like or fold-like uneven structure on the surface.
The composition according to claim 1 or 2, wherein the porosity is in the range of 5 to 60%.
The composition according to any one of claims 1 to 3, wherein the particle size is in the range of 0.5 to 500 μm.
The composition according to any one of claims 1 to 4, which has a hardness in the range of 0.1 to 50 MPa.
The composition according to any one of claims 1 to 5, which has an ultraviolet transmittance in the range of 50% or less.
The composition according to any one of claims 1 to 6, which contains 0.1 to 20 parts by mass of clay mineral with respect to 1 part by mass of cellulose or a cellulose derivative.
The composition according to any one of claims 1 to 7, wherein the cellulose is crystalline cellulose.
The composition according to any one of claims 1 to 8, wherein the clay mineral is at least one selected from the group consisting of talc, kaolin, and mica.
It has an uneven structure on the surface and contains cellulose or a cellulose derivative and a clay mineral as main components, including a step of obtaining a dispersion liquid of cellulose or a cellulose derivative and a clay mineral, and a step of spray-drying the obtained dispersion liquid. A method for producing a particulate composition for UV protection.
The production method according to claim 10, wherein the dispersion is obtained by physically pulverizing cellulose or a cellulose derivative and a clay mineral.
The production method according to claim 10 or 11, wherein the concentration of the solid content containing cellulose or a cellulose derivative and a clay mineral in the dispersion is 0.5 to 40% by mass.
The production method according to any one of claims 10 to 12, wherein the dispersion liquid contains 0.1 to 20 parts by mass of clay mineral with respect to 1 part by mass of cellulose or a cellulose derivative.
A cosmetic product containing the composition according to any one of claims 1 to 9 or the composition obtained by the production method according to any one of claims 10 to 13.