Title of the invention: Organic-inorganic composite particles, their production method, and cosmetics
Technical field
[0001]
　The present invention relates to spherical organic-inorganic composite particles having good biodegradability and cosmetics containing organic-inorganic composite particles.
Background technology
[0002]
　Currently, petroleum-derived synthetic polymers (plastics) are used in various industries and support modern life. Many synthetic polymers have been developed for long-term stability and are therefore difficult to decompose in the natural environment. Therefore, it causes various environmental problems. For example, there is a problem that plastic products spilled into the aquatic environment accumulate for a long period of time and cause great harm to marine and lake ecosystems. Further, in recent years, fine plastics having a length of 5 mm or less to the nano level, which are called microplastics, have become a big problem. Examples of microplastics include small personal consumption materials such as cosmetics, small lumps of unprocessed plastic resin, and large products that have become finer while floating in the sea.
[0003]
　In recent years, plastic particles of several hundred μm class (for example, polyethylene particles) are contained in the facial cleanser in order to give a rough texture and to enhance the cleaning effect. Since the true specific gravity of plastic particles is light, they are difficult to remove at sewage treatment plants and flow out into rivers, oceans, ponds and marshes. Furthermore, plastic particles easily adsorb chemical substances such as pesticides. These may accumulate in seafood, be concentrated, and affect the human body through them. This has been pointed out in the United Nations Environment Program, etc., and each country and various industry groups are considering regulations.
[0004]
　Against this background, the development of biodegradable plastics that are decomposed into water and carbon dioxide by microorganisms in the natural environment and incorporated into the carbon cycle in the natural world is being actively promoted all over the world. For example, a cleaning agent containing fibrous biodegradable plastic particles having a particle diameter of 425 μm or more as an abrasive is known (see Patent Document 1). Further, polylactic acid having a size of 1 to 44 μm suitable for use in a cosmetic composition is known (see Patent Document 2). Further, as fine biodegradable particles, polylactic acid-based resin fine particles having a number average particle diameter of less than 1 μm are known (see Patent Document 3).
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open No. 2013-136732
Patent Document 2: Japanese
Patent Application Laid-Open No. 2013-527204 Patent Document 3: Japanese Patent Application Laid-Open No. 2014-435666
Outline of the invention
Problems to be solved by the invention
[0006]
　Conventional biodegradable plastic particles require a long period of time for spontaneous decomposition when the particle size is large. The finer the particle size, the shorter the period of spontaneous decomposition, but the finer particles have the disadvantages of strong adhesion between particles and low fluidity. In addition, when it is added to cosmetics as a feel-improving material, its adhesion to the skin becomes stronger. Therefore, it is not suitable for a feel improving material that requires suitable stretchability. In addition, conventional biodegradable polymers float on water and easily adsorb and concentrate harmful chemical substances, which may cause environmental problems.
[0007]
　Therefore, an object of the present invention is to provide organic-inorganic composite particles having an average particle diameter of 0.5 to 25 μm, which are less likely to cause environmental problems, have good fluidity, and have high sphericity. is there. Such organic-inorganic composite particles are suitable for compounding in cosmetics, and can be safely used in the same applications as plastic beads.
Means to solve problems
[0008]
　The organic-inorganic composite particles of the present invention are spherical particles containing 1.0 to 83.0% by weight of a silica component and 17.0 to 99.0% by weight of a biodegradable plastic. The average particle diameter d 1 is 0.5 to 25 μm, the true density is 1.03 to 2.00 g / cm 3 , and the sphericity is 0.80 or more.
[0009]
　Further, the contact angle of the organic-inorganic composite particles with water was set to 90 ° or less. Further, the elastic modulus of the organic-inorganic composite particles was set to 2 to 30 GPa. Further, when the dispersion liquid of the organic-inorganic composite particles was dispersed for 60 minutes by an ultrasonic disperser , the ratio (d 3 / d 1 ) of the average particle diameter d 3 after dispersion and the average particle diameter d 1 before dispersion was obtained. , 0.95 to 1.05.
[0010]
　Further, the method for producing an organic-inorganic composite particle according to the present invention is an emulsification step of preparing an emulsified solution containing emulsified droplets by adding a surfactant and a non-aqueous solvent to a dispersion liquid containing a silica component and a biodegradable plastic. A step of dehydrating the emulsified droplets and a step of solid-liquid separating the non-aqueous solvent dispersion obtained in the dehydration step to obtain organic-inorganic composite particles as solids.
[0011]
　In addition, the cosmetic according to the present invention contains any of the above-mentioned organic-inorganic composite particles.
The invention's effect
[0012]
　The organic-inorganic composite particles according to the present invention do not float on water even if they flow out to the environment, do not easily adsorb harmful chemical substances that are water-insoluble, and have good biodegradability, which is an environmental problem. There is little concern that it will cause.
Mode for carrying out the invention
[0013]
　The organic-inorganic composite particles according to the present invention contain a silica component in the range of 1.0 to 83.0% by weight and a biodegradable plastic in the range of 17.0 to 99.0% by weight. The average particle diameter d 1 is 0.5 to 25 μm, the true density is 1.03 to 2.00 g / cm 3 , and the sphericity is 0.80 or more.
[0014]
　When the silica component is less than 1%, the effect of the silica component as a binder is low, and the number of contacts between fine biodegradable plastics is increased, which makes it difficult to re-separate. On the other hand, when the biodegradable plastic content is less than 17%, the soft and moist feeling peculiar to plastic beads cannot be obtained. Further, the silica component is preferably 1 to 79% by weight, and the biodegradable plastic is preferably 21 to 99% by weight. In particular, the silica component is preferably 5 to 70% by weight, and the biodegradable plastic is preferably 30 to 95% by weight.
[0015]
　If the true density of the organic-inorganic composite particles is less than 1.03 g / cm 3 , the rate of biodegradation is delayed because they float on water when they flow out into an aqueous environment. On the other hand, particles having a true density of more than 2.00 g / cm 3 have a low content of biodegradable plastic, and it is difficult to obtain tactile characteristics like those of plastic particles. The true density is particularly preferably in the range of 1.10 to 1.90 g / cm 3 .
[0016]
　When the sphericity of the organic-inorganic composite particles is less than 0.80, the sustainability of the rolling feeling when applied on the skin is significantly reduced. The sphericity is particularly preferably 0.90 or more. The sphericity is obtained by an image analysis method from a photograph of a scanning electron microscope.
[0017]
　When the average particle diameter d 1 of the organic-inorganic composite particles is less than 0.5 μm, the feel characteristics of the cosmetic such as rolling feeling, sustainability of rolling feeling, and uniform spreading and spreading property are remarkably deteriorated. On the other hand, if it exceeds 25 μm, when the particle powder is touched, a grainy feeling is felt, and the soft feeling and the moist feeling are reduced. Further, the average particle size is more preferably 2 to 10 μm. The average particle size is obtained by the laser diffraction method.
[0018]
　Further, the organic-inorganic composite particles preferably have a contact angle with water of 90 ° or less. Organic-inorganic composite particles having a contact angle with water of more than 90 ° tend to float on water when they flow out into an aqueous environment, which may delay the rate of biodegradation. The contact angle depends on the properties of the biodegradable plastic that is a constituent. If the biodegradable plastic is hydrophobic, the contact angle often exceeds 90 °. In this case, the contact angle can be reduced to 90 ° or less by adding a surfactant or the like to the organic-inorganic composite particles. Hydrophilic organic-inorganic composite particles with a contact angle of 90 ° or less are not only less likely to cause delayed biodegradation, but are also less likely to adsorb water-insoluble harmful chemical substances such as polychlorinated biphenyl compounds and pesticides. Further, the contact angle is preferably 80 ° or less, and particularly preferably 70 ° or less.
[0019]
　Further, the elastic modulus of the organic-inorganic composite particles is preferably 2 to 30 GPa. If the elastic modulus is less than 2, the strength of the compression molded product such as a powder foundation is lowered, so that the amount of particles to be blended may be limited. When the elastic modulus exceeds 30 GPa, distortion due to stress is unlikely to occur, and a soft feeling and a moist feeling like plastic beads cannot be imparted. The elastic modulus is particularly preferably in the range of 3 to 20 GPa. Here, the elastic modulus is obtained by a microcompression test method.
[0020]
　When organic-inorganic composite particles are used in cosmetics, the particles may collapse in the manufacturing process of cosmetics, and the initially expected function may not be obtained. Therefore, it is preferable that ultrasonic waves are applied to the dispersion liquid of the particles and the rate of change in the average particle diameter before and after the application does not change. Therefore, the dispersion liquid in which the organic-inorganic composite particles were dispersed in distilled water was dispersed for 60 minutes using an ultrasonic disperser. The ratio (d 3 / d 1 ) of the average particle diameter d 3 after the dispersion test and the average particle diameter d 1 before the test is preferably within ± 0.05, that is, 0.95 to 1.05. When this ratio (d 3 / d 1 ) is less than 0.95, it means that the strength of the particles is low, and the particles are disintegrated by mechanical addition in the manufacturing process of cosmetics and the like, and a desired feel improving effect is obtained. May not be obtained. When this ratio is larger than 1.05, it means that the biodegradable plastic swells in water. Therefore, it is easy to thicken after manufacturing cosmetics and the like, and quality stability cannot be guaranteed. In addition, the tactile characteristics may change. The ratio (d 3 / d 1 ) is particularly preferably 0.97 to 1.03.
[0021]
　Further, as the organic-inorganic composite particles, particles having a hollow structure in which a cavity is formed inside the outer shell can be applied. Since the hollow particles are lighter than the solid particles having the same diameter, the number of the hollow particles is larger than the number of the solid particles when the component amounts (% by weight) are the same.
[0022]
　The ratio (T / OD) of the outer shell thickness T to the outer diameter OD of the organic-inorganic composite particles is preferably in the range of 0.02 to 0.45. When the thickness ratio (T / OD) of the outer shell exceeds 0.45, it becomes substantially equivalent to the particles having a non-hollow structure. On the other hand, if the thickness ratio of the outer shell is less than 0.02, the particles are likely to collapse. Further, the thickness ratio (T / OD) of the outer shell is particularly preferably in the range of 0.04 to 0.30. Here, the outer shell may be porous through which nitrogen gas passes or non-porous through which nitrogen gas does not pass.
[0023]
　Further, the specific surface area per unit volume determined by the BET method is preferably 5 to 60 m 2 / cm 3 or less. If the specific surface area of ​​the organic-inorganic composite particles is less than 5 m 2 / cm 3 , the biodegradability may be inferior. If the specific surface area is 60 m 2 / cm 3 or more, it conforms to the definition of nanomaterials and may not be used with confidence in the same applications as conventional plastic beads. The specific surface area is particularly preferably less than 10 to 60 m 2 / cm 3 .
[0024]
　The silica component and biodegradable plastic contained in the organic-inorganic composite particles of the present invention will be described in detail below.
[0025]
　
　Examples of the silica component include a silicic acid binder and silica particles. As the silicate binder, a silicate aqueous solution such as an alkali metal silicate or an organic base silicate is treated with a cation exchange resin to dealkaliize (remove Na ions, etc.). Examples of the silicate include alkali metal silicates such as sodium silicate (water glass) and potassium silicate, and organic base silicates such as quaternary ammonium silicate.
[0026]
　Here, the silica particles represent inorganic oxide particles containing silica, and not only silica but also composite oxides such as silica-alumina, silica-zirconia, silica-titania, and silica-ceria can be exemplified. It is not necessary to change the production conditions of the organic-inorganic composite particles depending on the composition of the silica particles. Amorphous silica is suitable when blended in cosmetics.
[0027]
　The average particle diameter d 2 of the silica particles is preferably 5 nm to 1 μm. When the average particle size exceeds 1 μm, the effect as a binder for biodegradable particles is reduced. In addition, the dissolution rate of silica in the aquatic environment may decrease, resulting in impaired good biodegradability. If the average particle size is less than 5 nm, the stability as particles is low, which is not preferable in terms of industry. The range of 10 nm to 0.5 μm is particularly desirable.
[0028]
　Further, the organic-inorganic composite particles may contain 20% by weight or less of inorganic oxide particles containing at least one of titanium oxide, iron oxide, zinc oxide and cerium oxide. With this amount, the inorganic oxide particles can be uniformly contained inside the organic-inorganic composite particles. Here, as iron oxide, ferric oxide, α-oxyferroxide, and triiron tetroxide are preferable. Further, it is desirable that the average particle size of the inorganic oxide particles is at the same level as that of the silica particles. That is, the range of 5 nm to 1 μm is suitable.
[0029]
　It is preferable to use a silica component produced from a plant-derived raw material from the viewpoint of realizing a sustainable society. In addition, overseas such as Europe and the United States, there is an increasing need for natural and organic cosmetics from the viewpoint of harmony with the environment and safety. ISO 16128-1 (Guidelines on technical definitions and criteria for natural And organic cosmetic ingredients and products Part1: Definitions for ingredients) defines the raw materials. Silica sand is often used as a silica source. Silica derived from silica sand is a classification of mineral-derived raw materials, but if it is a plant-derived silica component, it is classified as a natural raw material and the natural index can be increased, so that the needs can be met.
[0030]
　Plant-derived silica components are abundant in grasses and can be extracted from rice husks and their rice ears. For example, it is known that high-purity silica can be obtained by a firing method disclosed in JP-A No. 7-196312 or a pressurized hydrothermal method disclosed in JP-A-2002-265257. The plant-derived silica component thus obtained is dissolved in sodium hydroxide to prepare sodium silicate, and then silica particles can be prepared according to a conventional method.
[0031]
　 As the
　biodegradable plastic, biodegradable plastic particles having an average particle diameter d 4 of 1 nm to 1 μm are preferable. Organic-inorganic composite particles obtained from such fine particles having an average particle size exhibit good biodegradability. The range of 0.1 to 0.5 μm is particularly preferable. In addition, cellulose nanofibers with a thickness of 1 to 500 nm and a length of 1 μm or more measured by electron micrographs and cellulose nanocrystals with a thickness of 10 to 50 nm and a length of 100 to 500 nm are also biodegradable plastics. Suitable.
[0032]
　In particular, crystalline cellulose having a glucose molecule as a constituent unit is preferable. Further, crystalline cellulose having an I-type crystalline form having a glucose molecule as a constituent unit is preferable. Cellulose that has undergone intentional chemical modification that is not in the I-type crystalline form may not be classified as a natural raw material based on the above definition of ISO16128-1. The crystal form of cellulose can be identified by infrared spectroscopy, and strong absorption is observed at 3365 to 3370 cm -1 . In addition, the solid 13C NMR method can also be used for identification from the difference in chemical shift and the diffraction angle by the X-ray diffraction method. Further, the crystal form may be either Iα or Iβ, or may be a mixture.
[0033]
　Petroleum-derived materials are widely used industrially for biodegradable plastics, but it does not matter what the raw material is as long as it is biodegradable. However, from the viewpoint of realizing a sustainable society, it is desirable that the biodegradable plastic is biomass plastic, which is a renewable organic resource, and polylactic acid, polycaprolactone, polybutylene succinate, and polyethylene succi made by chemical synthesis. Examples include nate, polyvinyl alcohol, polyaspartic acid, microbially produced purulan, polyglutamic acid, polyhydroxyalkanoic acid, plant and animal-derived starch, cellulose, amylose, amylopectin, chitin, chitosan and porphyran. In particular, plant-derived cellulose is suitable in terms of quality, price, distribution volume, and safety.
[0034]
　
　Next, a method for producing organic-inorganic composite particles will be described. First, a mixed solution in which a silica component and a biodegradable plastic are dispersed is prepared. A surfactant and a non-aqueous solvent are added to this mixed solution to form emulsified droplets (emulsification step). Then, the emulsified droplets are dehydrated (dehydration step). The obtained dispersion is solid-liquid separated and the organic-inorganic composite particles are taken out as a solid (solid-liquid separation step). This solid is dried and crushed (drying step).
[0035]
　Hereinafter, each step will be described in detail.
[0036]
　
　A mixed solution in which a silica component and a biodegradable plastic are dispersed is prepared. A dispersion liquid of a silica component and a dispersion liquid of a biodegradable plastic may be mixed and prepared. The solid content concentration of this mixed solution is adjusted to be in the range of 0.01 to 50%. The solvent is preferably water. When the solid content concentration exceeds 50%, the viscosity of the aqueous dispersion is usually increased, and the uniformity of the emulsified droplet may be impaired. If the solid content concentration is less than 0.01%, there is no particular advantage and the economy is poor.
[0037]
　A non-aqueous solvent and a surfactant are added to this mixed solution. The non-aqueous solvent required for emulsification may be any one that is incompatible with water, and a general hydrocarbon solvent can be used. The surfactant may be any one capable of forming water droplet type emulsified droplets in oil, but a surfactant having an HLB value in the range of 1 to 10 is suitable depending on the polarity of the non-aqueous solvent. .. The HLB value of the surfactant is particularly preferably in the range of 1 to 5. Surfactants with different HLB values ​​may be used in combination.
[0038]
　Next, this solution is emulsified by an emulsifying device. In this way, an emulsified solution containing 0.5 to 500 μm emulsified droplets is prepared. The emulsifying device includes a general high-speed shearing device, a high-pressure emulsifying device that can obtain finer emulsified droplets, a membrane emulsifying device that can obtain more uniform emulsified droplets, and a conventionally known device such as a microchannel emulsifying device. It can be used according to the purpose.
[0039]
　
　Next, the emulsion obtained in the emulsification step is dehydrated. For example, water is evaporated by heating under normal pressure or reduced pressure. As a result, the emulsified droplets are dehydrated to obtain a non-aqueous solvent dispersion containing organic-inorganic composite particles having a particle diameter of 0.5 to 25 μm.
[0040]
　Specifically, in the heat dehydration method under normal pressure, a separable flask provided with a cooling tube is heated, and dehydration is performed while recovering a non-aqueous solvent. Further, in the heating dehydration method under reduced pressure, dehydration is performed while recovering the non-aqueous solvent by heating under reduced pressure using a rotary evaporator or an evaporative can. It is preferable to dehydrate the non-aqueous solvent dispersion to the extent that it can be taken out as a solid substance in the solid-liquid separation step described later. Note that if dehydration is insufficient, the morphology as spherical particles cannot be maintained in the solid-liquid separation step.
[0041]
　 In the
　solid-liquid separation step, the solid content is separated from the non-aqueous solvent dispersion obtained in the dehydration step by a conventionally known method such as filtration or centrifugation. As a result, a cake-like substance of organic-inorganic composite particles can be obtained.
[0042]
　 In the
　drying step, the non-aqueous solvent is evaporated from the cake-like substance obtained in the solid-liquid separation step by heating under normal pressure or reduced pressure. As a result, a dry powder of organic-inorganic composite particles having an average particle diameter of 0.5 to 25 μm can be obtained.
[0043]
　A freezing step may be provided between the emulsification step and the dehydration step. By cooling the emulsified droplets obtained in the emulsification step in the range of −50 to 0 ° C., a frozen emulsion obtained by freezing the water in the droplets can be obtained. Then, the frozen emulsion is dehydrated in the dehydration step. When the freezing temperature is −50 ° C. to −10 ° C., porous organic-inorganic composite particles can be prepared. At −10 to 0 ° C., the silica component and the biodegradable plastic component in the liquid drop are excluded to the outer periphery of the liquid drop as the ice crystals grow. Therefore, organic-inorganic composite particles having a hollow structure having cavities inside the outer shell can be prepared. In the freezing step, for example, a specific temperature in the range of −10 to 0 ° C. may be maintained, or may be varied within this range.
[0044]
　Further, the cake-like substance of the organic-inorganic composite particles obtained in the solid-liquid separation step may be washed to reduce the surfactant. When the organic-inorganic composite particles according to the present invention are used in a solid preparation such as a foundation, there is no particular problem, but when they are blended in a liquid preparation such as an emulsion, long-term stability may be impaired. Therefore, it is preferable that the residual amount of the surfactant is 500 ppm or less with respect to the organic-inorganic composite particles. In order to reduce the amount of surfactant, it is advisable to wash with an organic solvent.
[0045]
　
　The cosmetics obtained by blending organic-inorganic composite particles and various cosmetic ingredients will be specifically described below.
[0046]
　When the organic-inorganic composite particles of the present invention are used in cosmetics, unlike conventional particles composed of an inorganic single component such as silica particles, not only a rolling feeling, a long-lasting rolling feeling, and a uniform spreadability It is possible to obtain the typical feel characteristics required for a cosmetic feel improving material, such as a soft feeling and a moist feeling peculiar to plastic beads.
[0047]
　化粧料成分としては、以下のものが挙げられる。オリーブ油、ナタネ油、ホホバ油、牛脂等の油脂類。カルナバロウ、キャンデリラロウ、ミツロウ等のロウ類。パラフィン、スクワラン、合成及び植物性スクワラン、α－オレフィンオリゴマー、マイクロクリスタリンワックス、ペンタン、ヘキサン等の炭化水素類。ステアリン酸、ミリスチン酸、オレイン酸等の脂肪酸類。イソステアリルアルコール、オクチルドデカノール、ラウリルアルコール、エタノール、イソプロパノール、ブチルアルコール、ミリスチルアルコール、セタノール、ステアリルアルコール、ベヘニルアルコール等のアルコール類。アルキルグリセリルエーテル類、ミリスチン酸イソプロピル、パルチミン酸イソプロピル、ステアリン酸エチル、オレイン酸エチル、ラウリル酸セチル、オレイン酸デシル等のエステル類。エチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジグリセリン等の多価アルコール類。ソルビトール、ブドウ糖、ショ糖等の糖類。メチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルシリコーン油、各種変性シリコーン油、環状ジメチルシリコン油等のシリコーン油。シリコーン系等の有機化合物にて架橋させたシリコーンゲル。ノニオン系、カチオン系、アニオン系、または両性の界面活性剤。パーフルオロポリエーテル等のフッ素油。アラビアガム、カラギーナン、寒天、キサンタンガム、ゼラチン、アルギン酸、グアーガム、アルブミン、プルラン、カルボキシビニルポリマー、セルロース及びその誘導体、ポリアクリル酸アミド、ポリアクリル酸ナトリウム、ポリビニルアルコール等の高分子。パラメトキシケイ皮酸オクチル等のケイ皮酸系、サリチル酸系、安息香酸エステル系、ウロカニン酸系、ベンゾフェノン系をはじめとした紫外線防御剤。各種粒子径、粒子径分布および形状を有する酸化チタン、酸化亜鉛、酸化アルミニウム、水酸化アルミニウム、ベンガラ、黄色酸化鉄、黒色酸化鉄、酸化セリウム、酸化ジルコニウム、シリカ、マイカ、タルク、セリサイト、窒化ホウ素、硫酸バリウム、パール光沢を有する雲母チタン、およびそれらの複合物。酢酸ブチル、アセトン、トルエン等の溶剤。動植物抽出物、アミノ酸及びペプチド類、ビタミン類、殺菌・防腐剤、酸化防止剤、変性又は未変性の粘土鉱物、各種有機顔染料、水、香料。ここで、前述の酸化チタンや酸化亜鉛等の無機化合物では、その表面に予めシリコーン処理、フッ素処理、金属石鹸処理などを施してもよい。
[0048]
　Further, resin particles such as methyl polyacrylate, nylon, silicone resin, silicone rubber, polyethylene, polyester and polyurethane may be contained.
[0049]
　Furthermore, as active ingredients having a whitening effect, arbutine, kodiic acid, vitamin C, sodium ascorbate, magnesium ascorbic acid phosphate, ascorbyl di-paltimate, ascorbic acid glucoside, other ascorbic acid derivatives, placenta extract, sulfur, Plant extracts such as oil-soluble licorice extract and quail extract, linoleic acid, linoleic acid, lactic acid, tranexamic acid and the like may be contained.
[0050]
　In addition, as an active ingredient having a rough skin improving effect, anti-aging effects such as vitamin C, carotenoid, flavonoid, tannin, caffeine derivative, lignan, saponin, retinoic acid and retinoic acid structural analog, N-acetylglucosamine, α-hydroxyic acid and the like. Active ingredients with, polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol, mixed isomerized sugars, trehalose, saccharides such as purulan, sodium hyaluronate, collagen, elastin, chitin / chitosan, sodium chondroitin sulfate. Biopolymers such as, amino acids, betaines, ceramides, sphingolipids, cholesterol and its derivatives, ε-aminoated proic acid, glycyrrhizinic acid, various vitamins and the like may be included.
[0051]
　In addition, quasi-drug raw material standards 2006 (published by Yakuji Nippo Co., Ltd., June 16, 2006), International Cosmetic Ingredient Dictionary and Handbook (published by The Cosmetic, Toiletry, and Fragrance Association, Eleventh Edition 2006), etc. You can use the cosmetic ingredients listed in.
[0052]
　Such cosmetics can be produced by a conventionally known general method. Cosmetics are used in various forms such as powder, cake, pencil, stick, cream, gel, mousse, and liquid. Specific examples include the following products. Cleaning cosmetics such as soap, cleansing foam, and makeup remover cream. Skin care cosmetics for moisturizing / rough skin prevention, acne, keratin care, massage, wrinkle / sagging, dullness / dark circles, UV care, whitening, antioxidant care, etc. Base makeup cosmetics such as powder foundation, liquid foundation, cream foundation, mousse foundation, pressed powder, and makeup base. Point makeup cosmetics such as eye shadow, eyebrow, eyeliner, mascara, and lipstick. Hair care cosmetics for hair growth, dandruff prevention, itch prevention, cleaning, conditioning / hair styling, permanent waving, hair coloring / hair bleaching, etc. Body care cosmetics such as cleansing, sun protection, rough hands, slimming, blood circulation improvement, itch control, body odor prevention, antiperspirant, hair care, liperant, body powder, etc. Fragrance cosmetics such as perfume, eau de parfum, eau de toilette, cologne, shower colon, perfume, body lotion, bath oil, etc. Oral care products such as toothpaste and mouthwash.
Example
[0053]
　Hereinafter, examples of the present invention will be specifically described.
[0054]
　[Example 1]
　50 g of a commercially available silica sol (manufactured by Nikki Catalyst Kasei Co., Ltd .: SS-300, average particle diameter 300 nm, silica concentration 20% by mass) is concentrated with a rotary evaporator to obtain 25 g of silica sol having a silica concentration of 40% by mass. A cation resin (SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) is added to this silica sol at once to adjust the pH to 2.5, and then the cation exchange resin is separated. As a result, dealkali treatment (removal of Na ions, etc.) is performed, and a slurry a having a silica particle concentration of 39.3% by mass is obtained. A polymer dispersion in which 10 g of type I cellulose particles (Theoras (registered trademark) RC-N30 manufactured by Asahi Kasei Corporation) and 30 g of pure water are uniformly dispersed is added to the slurry a to prepare the slurry b.
[0055]
　The obtained slurry b is added to a solution in which 1300 g of heptane (manufactured by Kanto Chemical Co., Inc.) and 9.75 g of a surfactant AO-10V (manufactured by Kao Corporation) are mixed, and an emulsification disperser (TK Robo manufactured by Primix Corporation) is added. Emulsify at 10000 rpm for 10 minutes using the mix). The obtained emulsion is heated at 60 ° C. for 16 hours to dehydrate it from the emulsified droplets, and then a quantitative filter paper (No. 2 manufactured by Advantech Toyo Co., Ltd.) is used using a Buchner funnel (3.2 L manufactured by Sekiya Rika Glass Instruments Co., Ltd.). Filter with. Then, it is repeatedly washed with heptane to remove the surfactant to obtain a cake-like substance. The cake-like substance is dried at 120 ° C. for 12 hours. This dry powder was pulverized with a juicer mixer (manufactured by Hitachi, Ltd.) for 10 seconds and sieved with a 250 mesh sieve (JIS test standard sieve) to obtain a powder of organic-inorganic composite particles. Table 1 shows the preparation conditions for the organic-inorganic composite particles for each example. In addition, the physical properties of the powder of the organic-inorganic composite particles were measured by the following method. The results are shown in Table 2.
[0056]
　(1) Average particle size of each particle (d 1 , d 2 , d 4 ) Using the
　laser diffraction method, the particle size distribution of organic-inorganic composite particles, silica particles, and biodegradable plastic particles was measured, and from this particle size distribution. The median diameter was calculated and used as the average particle size. In this way, the average particle diameter d of the organic-inorganic composite particles 1 , the average particle diameter d of the silica particles 2 average particle diameter d of and biodegradable plastic particles 4 were obtained. For the measurement of the particle size distribution by the laser diffraction method, a laser diffraction / scattering type particle size distribution measuring device LA-950v2 (manufactured by HORIBA, Ltd.) was used. However, the average particle diameter d of the fibrous biodegradable plastic particles typified by cellulose nanofibers and cellulose nanocrystals, etc. 4 For an average from the specific surface area and specific gravity of the particle, the equivalent spherical translated using the following formula The particle size was calculated.
[0057]
　　　　　　"Average particle size" = 6000 ÷ ("true density" x "specific surface area")
[0058]
　(2) Average particle size ratio (d 3 / d 1 )
　When measuring the average particle size of organic-inorganic composite particles with the laser diffraction / scattering type particle size distribution measuring device LA-950v2, the dispersion condition of the device is set to "super". After setting the sound wave to "60 minutes" and dispersing, the particle size distribution is measured. From the particle size distribution after dispersion, the average particle diameter d 3 represented by the median diameter is obtained . From this, the average particle size ratio (d 3 / d 1 ) before and after ultrasonic dispersion is obtained.
[0059]
　(3) Method for Measuring True Density of
　Organic-Inorganic Composite Particles Approximately 30 mL of organic-inorganic composite particles are collected in a magnetic crucible (B-2 type), dried at 105 ° C. for 2 hours, and then placed in a desiccator to cool to room temperature. Next, 15 mL of a sample was taken, and the true density was measured using a fully automatic pycnometer (manufactured by QUANTACHROME: Ultrapyc1200e).
[0060]
　(4) Coefficient of variation of silica particles A
　photograph (SEM photograph) is taken with a scanning electron microscope (JSM-7600F manufactured by JEOL Ltd.) at a magnification of 20,000 to 250,000 times. For 250 particles of this image, the average particle size was measured using an image analyzer (manufactured by Asahi Kasei Co., Ltd., IP-1000), and the coefficient of variation (CV value) related to the particle size distribution was calculated.
[0061]
　(5) From
　a photographic projection obtained by taking a picture of silica particles and organic-inorganic composite particles with a sphericity transmission electron microscope (H-8000, manufactured by Hitachi, Ltd.) at a magnification of 2000 to 250,000 times. Arbitrary 50 particles were selected, the ratio (DS / DL) of the maximum diameter DL to the minor diameter DS orthogonal to each was measured, and the average value thereof was taken as the sphericity.
[0062]
　(6) Specific Surface Area of
　Organic-Inorganic Composite Particles Approximately 30 mL of powder of organic-inorganic composite particles was collected in a magnetic crucible (B-2 type), dried at a temperature of 105 ° C. for 2 hours, and then placed in a desiccator and cooled to room temperature. To do. Next, 1 g of this sample was taken, and the specific surface area (m 2 / g) was measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics, Multisorb 12 type) . Specific gravity (for example, 2.2 g / cm 3 when silica is 100%, 1 when cellulose is 100% ) obtained from the composition ratio (blending weight ratio) of silica mixed in organic-inorganic composite particles and biodegradable plastic. This was converted at .5 g / cm 3 ) to determine the specific surface area per unit volume.
[0063]
　(7) The pore volume of the organic-inorganic composite particles, the pore diameter
　take powder 10g organic-inorganic composite particles in a crucible and dried 1 hour at 105 ° C., then cooled to room temperature in a desiccator, automatic porosimeter (Counter Chrome The pore size distribution was measured by a mercury intrusion method using a PoreMaster PM33GT manufactured by Instruments. Specifically, mercury is press-fitted at 1.5 kPa to 231 MPa, and the pore size distribution can be obtained from the relationship between the pressure and the pore size. According to this method, mercury is press-fitted into pores of about 7 nm to about 1000 μm, so that both the small-diameter pores existing inside the organic-inorganic composite particles and the gaps between the particles of the organic-inorganic composite particles are small. It appears in the pore size distribution. The gap between the particles is approximately 1/5 to 1/2 of the average particle size of the particles. The pore volume and the average pore diameter were calculated based on the pore diameter distribution depending on the pores, excluding the portion depending on the gap between the particles. At this time, peak separation software (attached to the automatic porosimeter) is used as needed.
[0064]
　(8) Composition analysis of
　organic-inorganic composite particles 0.2 g of powder of organic-inorganic composite particles is precisely weighed in a platinum dish, 10 mL of sulfuric acid and 10 mL of hydrofluoric acid are added, and white smoke of sulfuric acid is emitted on a sand bath. Heat up to. After cooling, about 50 mL of water is added to heat and dissolve. After cooling, dilute to 200 mL of water and use this as the test solution. The composition of organic-inorganic composite particles is determined for this test solution using an inductively coupled plasma emission spectrophotometer (ICPS-8100, manufactured by Shimadzu Corporation, analysis software ICPS-8000).
[0065]
　(9) Contact Angle After
　1 g of the organic-inorganic composite particles are dried at 105 ° C., they are placed in a cell having a diameter of 1 cm and a height of 5 cm and pressed with a load of 50 kgf to obtain a molded product. A drop of water was dropped on the surface of the obtained molded product, and the contact angle with water was measured.
[0066]
　(10) Elastic modulus One
　particle having an average particle diameter in the range of ± 0.5 μm was selected from the powder of the organic-inorganic composite particles and used as a sample. Using a microcompression tester (MCTM-200, manufactured by Shimadzu Corporation), a load was applied to this sample at a constant load rate, and the compressive elastic modulus was measured.
[0067]
　[Example 2]
　BiNFi-s WMa-10002 manufactured by Sugino Machine Limited was used instead of the type I cellulose particles in the polymer dispersion used in Example 1. Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0068]
　[Example 3]
　Leocrysta C-2SP manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used instead of the type I cellulose particles in the polymer dispersion used in Example 1. Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0069]
　[Example 4]
　The mixing amount of type I cellulose particles (Theoras (registered trademark) RC-N30 manufactured by Asahi Kasei Corporation) in the polymer dispersion was changed to 4.3 g. Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0070]
　[Example 5]
　The mixing amount of type I cellulose particles (Theoras (registered trademark) RC-N30 manufactured by Asahi Kasei Corporation) in the polymer dispersion was changed to 23.3 g. Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0071]
　[Example 6] The
　emulsified solution is allowed to stand in a constant temperature bath at −5 ° C. for 16 hours to freeze the emulsified droplets, and the emulsion is left at room temperature. .2 L) was used to filter with a quantitative filter paper (No. 2 manufactured by Advantech Toyo Co., Ltd.). Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0072]
　[Example 7] The
　emulsified solution was allowed to stand in a constant temperature bath at −25 ° C. for 16 hours to freeze the emulsified droplets. Other than this, organic-inorganic composite particles were prepared in the same manner as in Example 6, and their physical properties were measured in the same manner as in Example 1.
[0073]
　[Example 8] A
　commercially available product (SS-160 manufactured by Nikki Catalyst Kasei Co., Ltd., average particle size 160 nm, solid content concentration 16% by mass) of 62.5 g was used as the silica sol, and the silica sol was concentrated with an evaporator to have a silica concentration of 40% by mass. Organic-inorganic composite particles were prepared in the same manner as in Example 1, and their physical properties were measured in the same manner as in Example 1.
[0074]
　[Example 9] The same
　as in Example 1 except that 50 g of a commercially available product (SI-550 manufactured by Nikki Catalyst Kasei Co., Ltd., average particle size 5 nm, solid content concentration 20% by mass) was used as the silica sol and concentration was not performed by an evaporator. Organic-inorganic composite particles were prepared and their physical properties were measured in the same manner as in Example 1.
[0075]
　[Example 10]
　200 g of a silicic acid solution (solid content concentration 5%) was used as the slurry a, and 10 g of type I cellulose particles (Theoras (registered trademark) RC-N30 manufactured by Asahi Kasei Corporation) and 30 g of pure water were mixed thereto. A polymer dispersion was added to prepare a slurry b. After that, organic-inorganic composite particles were prepared in the same manner as in Example 6, and their physical properties were measured in the same manner as in Example 1.
[0076]
　[Example 11]
　Organic-inorganic composite particles were prepared and carried out in the same manner as in Example 1 except that emulsification was carried out at 5000 rpm for 10 minutes using an emulsification disperser (TK Robomix manufactured by Primix Corporation). Physical properties were measured in the same manner as in Example 1.
[0077]
　[Comparative Example 1]
　Organic-inorganic composite particles were used in the same manner as in Example 1 except that the mixing amount of cellulose particles (Seoras (registered trademark) RC-N30 manufactured by Asahi Kasei Co., Ltd.) in the polymer dispersion was changed to 1.1 g. It was prepared and its physical properties were measured in the same manner as in Example 1.
[0078]
　[Comparative Example 2]
　Organic-inorganic composite particles were prepared in the same manner as in Example 1 except that the emulsion was heated at 95 ° C. for 4 hours, and the physical properties were measured in the same manner as in Example 1. By rapidly heating at a high temperature, the emulsified droplets collapsed before dehydration, so that particles with high sphericity could not be obtained.
[0079]
　[Comparative Example 3]
　Organic-inorganic composite particles were prepared and carried out in the same manner as in Example 1 except that emulsification was carried out at 500 rpm for 10 minutes using an emulsification disperser (TK Robomix manufactured by Primix Corporation). Physical properties were measured in the same manner as in Example 1.
[0080]
[table 1]

[0081]
[Table 2]

[0082]
　[Tactile characteristics of powder of organic-inorganic composite particles]
　Next, the tactile characteristics were evaluated using the powders obtained in each Example and Comparative Example. Each powder was subjected to a sensory test by 20 specialized panelists. Interview surveys were conducted on seven evaluation items: silky feeling, moist feeling, rolling feeling, uniform spreading and spreading, adhesion to the skin, sustainability of rolling feeling, and soft feeling, and the following evaluation point criteria (a) were met. Evaluate based on. The evaluation points of each person were totaled, and the feel of the organic-inorganic composite particles was evaluated based on the following evaluation criteria (b). The results are shown in Table 3. As a result, it was found that the powder of each example was extremely excellent as a feel improving material for cosmetics, but the powder of the comparative example was not suitable as a feel improving material.
Evaluation score criteria (a)
　　5 points: Very good.
　　4 points: Excellent.
　　3 points: Normal.
　　2 points: Inferior.
　　1 point: Very inferior.
Evaluation criteria (b)
　　◎: Total score is 80 points or more
　　○: Total score is 60 points or more and less than 80 points
　　△: Total score is 40 points or more and less than 60 points
　　▲: Total score is 20 points or more and less than 40 points
　　×: Total score Is less than 20 points
[0083]
[Table 3]

[0084]
　[Usage feeling of powder foundation]
　Next, a powder foundation was prepared using powders of organic-inorganic composite particles so as to have a blending ratio (% by weight) shown in Table 4. That is, the powder of Example 1 (component (1)) and components (2) to (9) were put into a mixer and stirred, and mixed uniformly. Next, the cosmetic ingredients (10) to (12) were put into this mixer and stirred, and further uniformly mixed. Next, after the obtained cake-like substance was crushed, about 12 g of the obtained cake-like substance was taken out, placed in a 46 mm × 54 mm × 4 mm square metal plate, and press-molded. The powder foundation thus obtained was subjected to a sensory test by 20 specialized panelists. Interviews were conducted on the six evaluation items of uniform elongation during application to the skin, moist feeling, smoothness, and uniformity, moist feeling, and softness of the cosmetic film after application to the skin, and the evaluation point criteria (a) ) Based on the evaluation. In addition, the evaluation points of each person were totaled, and the usability of the foundation was evaluated based on the evaluation standard (b). The results are shown in Table 5. Here, the cosmetics A to C according to Examples 1 to 3 were taken up as representative examples and evaluated. It was found that the cosmetics A to C based on the examples were very excellent in usability both during and after application. However, it was found that the cosmetics a to c of Comparative Examples 1 to 3 did not have a good usability.
[0085]
[Table 4]

[0086]
[Table 5]

The scope of the claims
[Claim 1]
　Spherical organic-inorganic composite particles containing 1.0 to 83.0% by weight of silica component and 17.0 to 99.0% by weight of biodegradable plastic, having an average particle diameter d 1 of 0.5 to 25 μm and true. Organic-inorganic composite particles having a density of 1.03 to 2.00 g / cm 3 and a sphericity of 0.80 or more.
[Claim 2]
　The organic-inorganic composite particle according to claim 1, wherein the contact angle with water is 90 ° or less.
[Claim 3]
　The organic-inorganic composite particle according to claim 1 or 2, wherein the elastic modulus is 2 to 30 GPa.
[Claim 4]
　When the dispersion liquid of the organic-inorganic composite particles was dispersed for 60 minutes using an ultrasonic disperser , the ratio of the average particle diameter d 3 after dispersion to the average particle diameter d 1 before dispersion (d 3 / d 1). ) Is in the range of 0.95 to 1.05, according to any one of claims 1 to 3.
[Claim 5]
The organic-inorganic composite particle according to any one of claims 1 to 4, 　wherein the silica component contains silica particles having an average particle diameter d 2 in the range of 5 nm to 1 μm.
[Claim 6]
The organic-inorganic composite particle according to any one of claims 1 to 5, 　wherein the biodegradable plastic is a particle having an average particle diameter d 4 of 1 nm to 1 μm.
[Claim 7]
　The organic-inorganic composite particle according to any one of claims 1 to 6, wherein the biodegradable plastic is crystalline cellulose having a glucose molecule as a constituent unit.
[Claim 8]
　The organic-inorganic composite particle according to any one of claims 1 to 7, wherein the organic-inorganic composite particle is a hollow particle having a cavity inside the outer shell.
[Claim 9]
　A cosmetic containing the organic-inorganic composite particles according to any one of claims 1 to 8.
[Claim 10]
　An emulsification step of preparing an emulsified solution containing emulsified droplets by adding a surfactant and a non-aqueous solvent to a dispersion liquid in which a silica component and a biodegradable plastic are dispersed, and a
　dehydration step of dehydrating the emulsified droplets. A
　method for producing an organic-inorganic composite particle, which comprises a step of solid-liquid separating the non-aqueous solvent dispersion obtained in the dehydration step to obtain an organic-inorganic composite particle as a solid substance.
[Claim 11]
　The method for producing an organic-inorganic composite particle according to claim 10, further comprising a freezing step of freezing the emulsified droplets between the emulsifying step and the dehydrating step.
[Claim 12]
　The method for producing an organic-inorganic composite particle according to claim 11, wherein the emulsified droplet is frozen at −10 to 0 ° C. in the emulsification step.