JP2010222305A - Cosmetic and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsion cosmetic which is hard to ruin the makeup by the perspiration, has no feeling of stickiness, does not cause agglomeration precipitation even after a long time has elapsed, maintains a stable emulsion state, and can be easily washed off with soap after use, and a method for producing the same. <P>SOLUTION: The emulsion cosmetic contains a titanium oxide powder, a higher alcohol, an oily component other than the higher alcohol, and a polysaccharide including glucose, glucuronic acid, and rhamnose as monosaccharides constituting the main chain and fucose or mannose as a monosaccharide constituting a side chain and the content of the polysaccharide is set at 0.01-1 wt.% based on the entire amount of the cosmetic. The surface of the titanium oxide powder has been coated with anhydrous silicic acid and/or hydrous alumina and thereafter heat-treated at 200-900°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a UV-preventing cosmetic in which titanium oxide powder as an UV scattering agent is dispersed in oil, has excellent emulsification stability, has little whitening even when sweated, and is easily made with soap or the like. The present invention relates to a cosmetic that can be removed and a method for producing the same.

  In recent years, it has been clarified that ultraviolet rays are one of the factors that promote skin aging, and in order to protect the skin from ultraviolet rays, cosmetics and external preparations for skin containing ultraviolet absorbers and ultraviolet scattering agents are often used. ing. As an ultraviolet scattering agent, titanium oxide powder is frequently used, and is blended in various dosage forms such as solid powder, emulsion and oil depending on the purpose. Conventionally, most of these UV preventive cosmetics are W / O type emulsified cosmetics using a surfactant.

  The effect of preventing ultraviolet rays from the UV-preventing cosmetics can be obtained by reflecting the UV rays by the titanium oxide powder contained in the cosmetics. Therefore, in order to reflect ultraviolet rays more efficiently, the cosmetic containing titanium oxide needs to be uniform on the skin surface after application, and to maintain that state. In general, emulsified cosmetics have moisture that evaporates or penetrates into the skin after application, and the remaining oil component and dispersed titanium oxide remain uniformly on the skin and adhere to each other.

  However, since the W / O emulsified cosmetic contains a surfactant for emulsifying each component, sweat and the surfactant, as well as the oily component and titanium oxide become familiar when sweating. The titanium oxide attached to the skin flows away with sweat. For this reason, the titanium oxide powder adhering to the skin becomes mottled and looks bad, and the reflectance of ultraviolet rays is remarkably lowered, so that it does not function as a UV-preventing cosmetic.

  In order to prevent such problems, the W / O type emulsified cosmetics are blended with a high viscosity silicone that is not easily compatible with a surfactant. High-viscosity silicones form a film that encloses a mixture of titanium oxide powder, oily ingredients and surfactants attached to the skin. This high-viscosity silicone coating protects cosmetic ingredients and improves water resistance, and even when sweated, the uniformity of titanium oxide in the skin is maintained and the effect of preventing ultraviolet rays is sufficiently sustained.

  However, cosmetics with such a high-viscosity silicone compounded to improve water resistance make it difficult to remove makeup, and it is difficult to remove them with ordinary facial cleansing using soap or facial cleansing foam. For this reason, removing the makeup requires two steps of wiping off the high-viscosity silicone with a special oil and then performing a normal face wash using soap or a face-wash foam, which is troublesome. In addition, when applied to arms and legs or used by children, it is often cumbersome and only needs to be washed with soap, leaving a lot of UV protection cosmetics in pores, etc., causing rough skin and pimples. There was also a problem of becoming.

  In order to solve these problems, the inventors disperse and emulsify titanium oxide powder using a special polysaccharide as an emulsifier instead of a surfactant, and even when sweating, the titanium oxide attached to the skin is difficult to flow down, Moreover, UV-proof cosmetics that can be easily washed off with soap or facial cleansing foam have been developed (see Patent Document 1).

  That is, this cosmetic contains a special polysaccharide instead of a surfactant (that is, glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and fucose or mannose as the monosaccharide constituting the side chain. Polysaccharides) disperse titanium oxide fine particles and oil droplets. As shown in FIG. 1, this special polysaccharide is a fine particle 3 of about 50 nm with a hydroxyl group 1 which is a hydrophilic group in water and a hydrophobic group 2 inside, as shown in FIG. A structure in which the fine particles 3 are attached around the oil droplet 4 by van der Waals force is formed. Particularly in the dark state, the fine particles 3 are further stabilized by a three-dimensional network structure in which the fine particles 3 are connected to each other by hydrogen bonds (see FIGS. 3 and 4).

  By adding titanium oxide to this polysaccharide aqueous solution and stirring vigorously with a homogenizer, etc., and further adding oily components such as higher alcohol and squalane, olive oil and silicone oil, and further stirring vigorously, the three-dimensional polysaccharide The hydrogen bonds forming the network structure are cut off, and the polysaccharide fine particles come apart, come into contact with titanium oxide particles and oil droplets composed of oil components, and adhere by van der Waals force. The state of being surrounded and dispersed by the fine particles of polysaccharide by such van der Waals force is extremely stable, unlike the dispersion method in which the surface energy is lowered using a surfactant. Furthermore, when the cosmetics thus dispersed are applied to the skin, moisture evaporates and the fine particles of polysaccharides are linked by hydrogen bonding to form a three-dimensional network structure. Titanium oxide and oil droplets are tertiary It is taken into the original network structure and dispersed in an extremely stable state. For this reason, even if you sweat, this cosmetic hardly flows off with sweat, and you can easily wash it off with the polysaccharides that form a three-dimensional network structure by simply washing it off with soap or face-washing foam. it can. For this reason, makeup removal becomes extremely easy.

  In addition, higher alcohol is added to this cosmetic and plays the following role. That is, the higher alcohol takes a lamellar liquid crystal structure in the cosmetic, forms an aggregate, and can take in other oil components added to the cosmetic. Since the hydroxyl group of the higher alcohol is hydrophilic, composite particles are formed through hydrogen bonding on the surface of the polysaccharide fine particles having the same hydroxyl group. For this reason, when the oil agent is emulsified, the composite particles of higher alcohol liquid crystal and polysaccharide adhere to the surface of the oil agent and contribute to the stability of the emulsified state. In addition, the lamellar liquid crystal structure forms a colloidal gel crystal by cooling, and does not have a sticky feeling peculiar to an oily component even when a cosmetic is applied to the skin.

  In addition, there are the following non-patent documents 1 and 2 as documents related to the above-described prior art.

JP 2008-7491 A

The 43rd Annual Japan Oil Chemistry Conference, Osaka University Convention Center Abstract (11 / 1-11 / 2, 2004) The Chemical Society of Japan, 57th Annual Meeting on Colloid and Interface Chemistry (9 / 9-9 / 11, 2004),

  However, in the cosmetics containing titanium oxide using the above-mentioned conventional polysaccharide as an emulsifier, the polysaccharide aggregates and precipitates during long-term storage depending on the type of titanium oxide used as an ultraviolet scattering agent, and the three-dimensional network structure is There was a problem that it was destroyed and the dispersed state could not be maintained.

  The present invention has been made in view of the above-mentioned conventional situation, and is a cosmetic composition containing titanium oxide using a polysaccharide as an emulsifier, and it is difficult to remove makeup due to sweat and does not feel sticky. However, it is an object to be solved to provide a cosmetic in an emulsified state that does not aggregate and settle, maintains a stable emulsified state, and can be easily washed away with soap after use, and a method for producing the same.

  The inventors have intensively studied the cause of the aggregation and precipitation of polysaccharides depending on the type of titanium oxide in cosmetics containing titanium oxide using the above-mentioned conventional polysaccharides as emulsifiers. As a result, it was estimated that elution of polyvalent metal ions such as aluminum ions contained in titanium oxide or a coating agent coated with titanium oxide might be the cause. This is because the special polysaccharide contains glucuronic acid as a monosaccharide constituting the main chain, so that it is considered that glucuronate is formed and aggregated by polyvalent metal ions. And furthermore, in order to prevent elution of the polyvalent metal ions, it was found that the above-mentioned problems can be solved by heat treating titanium oxide previously coated with hydrous silicic acid and / or hydrous alumina, and the present invention was completed. It came to do.

That is, the emulsified cosmetic of the present invention contains titanium oxide powder, a higher alcohol, an oily component excluding the higher alcohol, and glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and has side chains. A polysaccharide containing fucose or mannose as a constituent monosaccharide, and
In the cosmetic in an emulsified state in which the content of the polysaccharide is 0.01% by weight to 1% by weight with respect to the total amount of the cosmetic,
The titanium oxide powder is heat-treated at 200 ° C. to 900 ° C. after the surface is coated with hydrous silicic acid and / or hydrous alumina.

  In the emulsified cosmetic of the present invention, the titanium oxide powder that scatters ultraviolet rays and the oil component are emulsified with polysaccharides. This polysaccharide contains glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and contains polysaccharide containing fucose or mannose as the monosaccharide constituting the side chain. The polysaccharide having this structure is a fine particle of about 50 nm with a hydroxyl group, which is a hydrophilic group in the surface, in the water, and a hydrophobic group portion on the inside, and adheres around titanium oxide and oily components. The ingredients are dispersed in the cosmetic in a very stable state. When this cosmetic is applied to the skin, moisture evaporates and the fine particles of polysaccharides are linked by hydrogen bonding, forming a three-dimensional network structure. Titanium oxide and oil components are contained in this three-dimensional network structure. It is taken in and adheres to the skin in a more stable state.

  The content of the polysaccharide is 0.01% by weight to 1% by weight with respect to the total amount of the cosmetic. If the content of the polysaccharide is less than 0.01% by weight relative to the total amount of the cosmetic, the amount of the fine particles composed of the polysaccharide is the amount necessary to surround the oil droplets and titanium oxide powder composed of the oil component. It is difficult to achieve a stable dispersion state. In addition, if the content of polysaccharide exceeds 1% by weight with respect to the total amount of the cosmetic, the viscosity becomes too high, and the workability in the emulsification process and the dispersion process is hindered. Will also rise. More preferably, the polysaccharide content is in the range of 0.1% to 0.5% by weight relative to the total amount of the cosmetic.

  The titanium oxide powder is heat-treated at 200 ° C. to 900 ° C. after the surface is coated with hydrous silicic acid and / or hydrous alumina in order to prevent the skin from being damaged by the photocatalytic action of titanium oxide. The heat treatment is performed for the following reason. That is, when the surface of titanium oxide powder is coated with hydrous silicic acid and / or hydrous alumina and used in cosmetics without heat treatment, aluminum ions are eluted from the hydrous alumina, and as impurities of titanium oxide powder. The elution of the polyvalent metal ion causes the glucuronic acid, which is a monosaccharide constituting the main chain of the polysaccharide, to form a salt and cause aggregation precipitation.

  On the other hand, after the surface is coated with hydrous silicic acid and / or hydrous alumina, the titanium oxide heat treated at 200 ° C. to 900 ° C. is dehydrated and condensed with hydrous silicic acid and hydrous aluminum to become a dense inorganic polymer. The titanium oxide surface is covered. That is, hydrous silicic acid is gradually dehydrated and condensed at a temperature of 200 ° C. or higher, and a dense three-dimensional network structure is formed by siloxane bonds. Also, hydrous alumina is gradually dehydrated and condensed at a temperature of 200 ° C. or higher, causing rearrangement to boehmite (245 ° C.), dehydration of gibbsite (320 ° C.), and dehydration reaction of boehmite (550 ° C.) (see FIG. 5). It changes to a form in which aluminum ions are difficult to elute. Thus, elution of aluminum ions from titanium oxide coated with hydrous silicic acid and / or hydrous alumina and elution of polyvalent metal ions as impurities of titanium oxide powder can be prevented by heat treatment at 200 ° C. to 900 ° C. . As a result, the glucuronic acid of the monosaccharide constituting the main chain of the polysaccharide can be prevented from forming a salt with the eluted ion, and the polysaccharide is prevented from coagulating and precipitating. Can keep the emulsified state stable for a long time. Further, since the surface-treated titanium oxide is negatively charged in the cosmetic as the polysaccharide, it is possible to avoid the aggregation of the polysaccharide due to Coulomb force.

  Further, the emulsified cosmetic of the present invention contains a higher alcohol. The role of this higher alcohol is to eliminate the feeling of stickiness, improve skin familiarity, and further stabilize the emulsified state. That is, the higher alcohol has a lamellar liquid crystal structure in the cosmetic and takes in other oily components added to the cosmetic to form an aggregate. Since the hydroxyl group of the higher alcohol is hydrophilic, composite particles are formed through hydrogen bonding on the surface of the polysaccharide fine particles having the same hydroxyl group. For this reason, when the oil agent is emulsified, the composite particles of higher alcohol liquid crystal and polysaccharide adhere to the surface of the oil agent and contribute to the stability of the emulsified state. In addition, the lamellar liquid crystal structure forms a colloidal gel crystal by cooling, and does not have a sticky feeling peculiar to an oily component even when a cosmetic is applied to the skin.

  Therefore, according to the emulsified cosmetic of the present invention, it is difficult to remove makeup due to sweat, there is no feeling of stickiness, and there is no aggregation and precipitation even after a long period of time, and a stable emulsified state can be maintained.

  In the emulsified cosmetic of the present invention, the titanium oxide powder is preferably hydrophobized after the heat treatment. If it is like this, since titanium oxide powder is disperse | distributed in an oil-based component, when it sweats after apply | coating cosmetics to skin, it can prevent more effectively with sweat. Examples of the method of hydrophobizing treatment include polysiloxane treatment, fatty acid treatment with stearic acid, carboxylate treatment, wax treatment, and the like. Among these hydrophobizing treatments, a hydrophobizing treatment coated with a higher fatty acid or polysiloxane is particularly effective and preferable. Further, treatment with a silane coupling agent such as aminopropylsilane may be performed. Furthermore, it is possible to combine the various hydrophobizing treatments. The amount of these hydrophobizing agents can be appropriately set according to the type and purpose, but usually, the range of 0.1 to 20% by weight in terms of the total amount of organic matter relative to the amount of titanium oxide is appropriate. is there. Moreover, you may perform the classification by a particle size, washing | cleaning, drying, or a grinding | pulverization as needed.

The polysaccharide blended in the cosmetic of the present invention contains at least a polysaccharide represented by a repeating unit of the following general formula (Formula 1). This polysaccharide is the main component of the polysaccharide produced by the alkaline genus Lasus B-16 strain bacterium (FERM BP-2015), and the inventors have produced it using the polysaccharide extracted from the culture solution of this bacterial strain. It was confirmed that the cosmetic composition of the present invention is difficult to remove makeup due to sweat and does not feel sticky, does not aggregate and settle even after a long period of time, and achieves the problem of maintaining a stable emulsified state. Yes.

  The content of titanium oxide powder is preferably 1% to 20% by weight relative to the total amount of the cosmetic, and the content of higher alcohol is preferably 0.8% to 20% by weight relative to the total amount of the cosmetic. The content of the oil component excluding higher alcohols is preferably 0.5 to 30% by weight based on the total amount of the cosmetic. If the content of titanium oxide powder is less than 1% by weight, the effect of preventing ultraviolet rays may not be sufficiently obtained, and if it exceeds 30% by weight, the effect of preventing ultraviolet rays can be obtained, but whitening occurs after application and the appearance is poor. Become. Further, if the content of the higher alcohol is less than 0.8% with respect to the total amount of the cosmetic, emulsification may be insufficient. If it exceeds 20%, stable emulsification is possible. , The feel after applying the cosmetic becomes hard and the feeling of use becomes worse. In addition, when the content of the oily component excluding higher alcohol is less than 0.5% by weight based on the total amount of the cosmetic, the water resistance becomes poor and the cosmetic component easily flows off with sweat. The feeling of stickiness increases and the feeling of use as a cosmetic becomes worse.

  Further, the higher alcohol preferably contains two or more higher alcohols having a melting point of 45 ° C. or higher. This is because when two or more types of higher alcohols having a melting point of 45 ° C. or more are contained, the size of the aggregate of the higher alcohol and the polysaccharide becomes non-uniform and crystallization becomes difficult, thereby making the emulsification more stable. Higher alcohols can be emulsified by addition of only one kind, but water may be separated if left at a high temperature such as 40 ° C. The reason for this is that when only one kind of higher alcohol is added, the gel-liquid crystal transition temperature of the liquid crystal state in which the higher alcohol is aligned becomes a specific point. This is thought to be due to the accompanying water discharge phenomenon.

  The mixing ratio of the two or more higher alcohols is preferably in the range of 1: 1 to 5: 1 with the higher alcohol serving as the maximum blending amount and the higher alcohol serving as the minimum blending amount. In this case, a higher alcohol mixed with two or more types is equivalent to a higher alcohol and a polysaccharide having different molecular weights because one higher alcohol is mixed with 1/5 or more of at least one other higher alcohol. The aggregates having different sizes can be formed to prevent the formation of a uniform particle structure, and the emulsified state can be stabilized. A more preferable range is a mixing ratio of 2: 1 to 4: 1 between the higher alcohol having the maximum blending amount and the higher alcohol having the minimum blending amount.

The higher alcohol is two or more selected from hexadecanol, octadecanol, eicosanol and docosanol, and each of the two or more selected is contained in an amount of 0.4% by weight or more based on the total amount of the cosmetic. It is preferable that the sum total is 0.8 to 20% by weight based on the total amount of the cosmetic.
If 0.4% by weight or more of each higher alcohol is not used, the effect of using two or more higher alcohols cannot be obtained. If the content of the mixture of two or more higher alcohols is less than 0.8% by weight based on the total amount of the cosmetic, it is difficult to form an association of higher alcohols and polysaccharides, and more than 20% by weight. Even if contained, the effect of further stabilizing the dispersion cannot be obtained and is wasted, resulting in an increase in manufacturing cost. More preferably, the higher alcohol is two or more selected from hexadecanol, octadecanol, eicosanol and docosanol, and each of the two or more selected is 1% by weight or more based on the total amount of the cosmetic. It is included and the sum total is 2 to 10 weight% with respect to the whole quantity of cosmetics.

In addition, the oil component contained in the emulsified cosmetic of the present invention,
Examples of the oil component (A) include silicone oil, fluorinated hydrocarbons and derivatives thereof, hydrocarbons, fatty acids, fatty acid esters of monohydric alcohols, animal and vegetable oils and fats, oxycarboxylic acid esters, fatty acid esters of polyhydric alcohols and a melting point of 40. One or more selected from those having a temperature of less than ° C. and liquid wax;
As the oil component (B), one or more selected from solid wax, divalent higher alcohol, cyclic alcohol and fatty acid ester thereof, fatty acid ester of polyhydric alcohol having a melting point of 40 ° C. or higher, and phospholipid It is preferable that the said oil-based component (A) and the said oil-based component (B) are included in the range used as 2: 1-50: 1 by weight ratio (more preferably 4: 1-30: 1).

  By using a combination of the oil component (A) and the oil component (B), the balance with the higher alcohol of the present invention is improved, smoothness and penetration feeling when applying cosmetics, and improved film feeling after application. The effect of being done is acquired. The oily component is divided into two groups of an oily component (A) and an oily component (B), and a method of selecting and combining one or more of each oily component has been found empirically, The reason for the effect is not fully understood.

Furthermore, the oil component (A) is dimethylpolysiloxane, trimethylpolysiloxane, squalane, paraffin (n-hydrocarbon having 16 to 50 carbon atoms alone or a mixture thereof), liquid paraffin, isopropyl palmitate, myristyl myristate. , Isostearyl myristate, glyceryl triethylhexanoate, glyceryl tri (mixed acid of caprylic acid and capric acid), grape seed oil, rosehip oil, sunflower oil, olive oil, avocado oil, macadamia nut oil, medhome oil, shea oil, And at least one selected from jojoba oil,
Oil component (B) is beeswax, hydrogenated jojoba oil, hydrogenated palm oil, chimyl alcohol, batyl alcohol, cholesterol, cholesteryl stearate, phytosterol, cholesteryl hydroxystearate, N-lauroyl-L-glutamic acid di (Cholesteryl behenyl octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl octyldodecyl), N-lauroyl-L-glutamate di (2-octyldodecyl behenyl phytosteryl), glyceryl trimyristate, tristearin One or more selected from glyceryl acid, dipentaerythrityl hexahydroxystearate, (adipic acid, 2-ethylhexanoic acid, stearic acid) glyceroligoester, etc., and the oil component (A) It can be used in combination of the above oil component (B).

  In the emulsified cosmetic of the present invention, it is preferable that the surfactant is not substantially contained. This is because when the surfactant is contained, the titanium oxide adhering to the skin due to mixing of the sweat and the surfactant is likely to flow down. The term “substantially free of surfactant” means that the surfactant is at a concentration or less that has an effect on the dispersion of the oil component, specifically, it is at or below the limit micelle concentration. The term “surfactant” is intended to include all of cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants.

  In the emulsified cosmetic of the present invention, it is also preferable that citric acid and / or citrate is contained in an amount of 0.01% by weight to 1% by weight with respect to the total amount of the cosmetic. This is due to the following reason. That is, the polysaccharide contained in the cosmetic of the present invention has a negative surface charge, and when a substance having a positive surface charge is mixed into the cosmetic for some reason, it is attracted by the Coulomb force between the polysaccharide and the polysaccharide. May work and agglomerate. On the other hand, if citric acid or citrate is added, the citrate ions can neutralize the positive charge and make the apparent charge negative, thereby preventing the aggregating action. If the amount of citric acid and / or citrate added is less than 0.01% by weight, the effect of changing the surface charge from positive to negative may be insufficient. Even if the amount of citric acid and / or citrate added exceeds 1% by weight, the effect of changing the surface charge from positive to negative does not change much. More preferably, citric acid and / or citrate is contained in an amount of 0.1% to 0.5% by weight based on the total amount of the cosmetic.

  In the emulsified cosmetic of the present invention, polysaccharides are subdivided into fine particles having random particle sizes. More specifically, polysaccharides are fine particles of about 50 nm with a hydroxyl group, which is a hydrophilic group in the surface, and a hydrophobic group portion inside, in water, and in a particularly dense state, these fine particles are linked together by hydrogen bonds. It is stabilized by a three-dimensional network structure connected to

The emulsified cosmetic of the present invention can be produced as follows.
That is, the method for producing an emulsified cosmetic according to the present invention comprises:
In the method for producing an emulsified cosmetic containing titanium oxide powder, a higher alcohol, an oil component excluding the higher alcohol, and a polysaccharide,
Titanium oxide coating step for coating the surface of titanium oxide powder with hydrous silicate and / or alumina, heat treatment step for heat-treating the surface-coated titanium oxide powder at 200 ° C. to 900 ° C., and monosaccharides constituting the main chain As a polysaccharide containing glucose, glucuronic acid and rhamnose and containing fucose or mannose as a monosaccharide constituting the side chain, water and an amount corresponding to 0.01% by weight to 1% by weight with respect to the total amount of the cosmetic / Or a polysaccharide solution preparation step in which a polysaccharide solution is dissolved in a hydrophilic solvent, and the polysaccharide solution and the higher alcohol correspond to 0.8 wt% to 20 wt% with respect to the total amount of the cosmetic. An amount corresponding to 0.5% to 30% by weight of the oily component with respect to the total amount of the cosmetic, and the heat-treated titanium oxide powder corresponding to 1% to 20% by weight of the cosmetic. Amount to do Emulsifying step stirred solution while heating to 60 ° C. or more is mixed and emulsified liquid, and having a cooling step of cooling to remain 40 ° C. or less was stirred emulsified liquid.

  In the titanium oxide coating step, the surface of the titanium oxide powder is coated with hydrous silicic acid and / or hydrous alumina, and in the heat treatment step, the surface-coated titanium oxide powder is heat treated at 200 ° C to 900 ° C. By this heat treatment step, the hydrous silicic acid and the hydrous aluminum coated on the surface of the titanium oxide powder are dehydrated and condensed to form a dense inorganic polymer and cover the titanium oxide. That is, hydrous silicic acid is gradually dehydrated and condensed at a temperature of 200 ° C. or higher, and a dense three-dimensional network structure is formed by siloxane bonds. Also, hydrous alumina is gradually dehydrated and condensed at a temperature of 200 ° C. or higher, causing rearrangement to boehmite (245 ° C.), dehydration of gibbsite (320 ° C.), and dehydration reaction of boehmite (550 ° C.) (see FIG. 5). It changes to a form in which aluminum ions are difficult to elute. Thus, titanium oxide coated with hydrous silicic acid and / or hydrous alumina is prevented from elution of aluminum ions and polyvalent metal ions as impurities of titanium oxide powder by heat treatment at 200 ° C. to 900 ° C.

  Furthermore, as a polysaccharide solution preparation step, for polysaccharides containing glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and fucose or mannose as monosaccharides constituting the side chain, the total amount of cosmetics An amount corresponding to 0.01% by weight to 1% by weight is dissolved in water and / or a hydrophilic solvent to obtain a polysaccharide solution.

  And, the polysaccharide solution, the amount corresponding to 0.8 to 20% by weight of the higher alcohol with respect to the total amount of the cosmetic, and the oily component with 0.5% by weight based on the total amount of the cosmetic. The amount corresponding to ˜30% by weight and the heat-treated titanium oxide powder mixed with the amount corresponding to 1% by weight to 20% by weight of the cosmetic, and stirred while heating to 60 ° C. or more to emulsify A liquid (emulsification step). In this emulsification step, the higher alcohol contained in the cosmetic becomes a lamellar liquid crystal, takes in other oily components, and the hydroxyl group of the higher alcohol is oriented toward the aqueous phase, so that it becomes hydrophilic. Further, polysaccharide fine particles whose outer side is made hydrophilic are adhered to form a stable emulsified state.

  Finally, the emulsion is cooled to 40 ° C. or lower with stirring (cooling step). In this cooling step, the aggregate of the higher alcohol and the oily component, which are in a stable emulsified state due to the adhesion of the polysaccharide fine particles, forms a colloidal gel crystal by cooling while maintaining the emulsified state. For this reason, even if cosmetics are applied to the skin while maintaining a stable emulsified state, there is no sticky feeling peculiar to oil components, and the skin feels smooth.

  When blending cosmetics with titanium oxide powder that has not been hydrophobized, the emulsification step includes the first emulsification step of dispersing titanium oxide powder that has not been hydrophobized in polyhydric alcohol; A second emulsification step in which the polysaccharide solution is added to and mixed with the dispersion obtained in the first emulsification step, and a higher alcohol and an oily component excluding the higher alcohol are added to the dispersion obtained in the second emulsification step. And a third emulsification step of mixing.

  When a titanium oxide powder that has not been subjected to a hydrophobization treatment is blended in the cosmetic, emulsification can be performed quickly and reliably by performing such an emulsification step. In addition, the polyhydric alcohol used in this step can also serve as a moisturizing component for the skin.

  On the other hand, when the titanium oxide powder that has been hydrophobized is added to the cosmetic, the emulsification step includes a dissolution step in which a polysaccharide solution is added to a polyhydric alcohol and the dissolution step, and the dissolution step It is preferable to comprise a dispersion step in which the hydrophobized titanium oxide powder, the higher alcohol, and the oil component other than the higher alcohol are added to and mixed with the solution obtained in (1).

  In the case where titanium oxide powder that has been subjected to a hydrophobization treatment is blended in the cosmetic, emulsification can be performed quickly and reliably by performing such an emulsification step.

By implementing the present invention, it is excellent in stability over time of emulsification and dispersion, there is little run-off of titanium oxide due to sweat, makeup is not lost, there is no stickiness during use, UV protection that can be easily washed away with soap after use Cosmetics for use are obtained.

It is a schematic cross section of microparticles | fine-particles which consist of polysaccharides. It is a schematic cross section which shows the state which the microparticles | fine-particles of the polysaccharide adhered to the circumference | surroundings of an oil droplet. It is a schematic diagram which shows the three-dimensional network structure where the microparticles | fine-particles of the polysaccharide adhering around the oil droplet were connected by the hydrogen bond. 2 is a scanning electron micrograph showing a three-dimensional network structure in which polysaccharide fine particles are connected by hydrogen bonds. It is a graph which shows the thermal-analysis result of a hydrous alumina.

  Hereinafter, embodiments of the present invention will be described.

In the emulsified cosmetic of the present invention, the polysaccharide added as an emulsifying dispersant contains glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and fucose or mannose as monosaccharides constituting the side chain. . Examples of such polysaccharides include polysaccharides represented by the following formula (Formula 2).

The polysaccharide represented by the above formula (Chemical Formula 2) can be obtained as a product of Bacteria alkaline genus B-16 strain (FERM BP-2015). Bacterium alkaline genus B-16 strain is cultivated by an ordinary microorganism culture method, and after the cultivation, when an organic solvent such as acetone, ethanol or isopropyl alcohol is added to the culture solution, the produced polysaccharide precipitates as an insoluble matter. In general, microorganisms often produce two or more types of polysaccharides, but unless they interfere with the effects of the present invention, the polysaccharides used in the present invention are polysaccharides other than the polysaccharides represented by the above formula (Chemical Formula 2). May be included. For example, it has been confirmed that at least two kinds of polysaccharides are contained in the polysaccharide produced by Alkaline nestus B-16 strain bacteria, and the constituent monosaccharide ratio of the polysaccharide separated from the culture solution is fucose in molar ratio. : Glucose: glucuronic acid: rhamnose = 1: (0.5-4) :( 0.5-2) :( 0.5-2), but this crude polysaccharide is composed of two types of polysaccharides One is a polysaccharide having a structure in which one fucose is branched to one glucose in the main chain of a repeating structure composed of glucose, glucuronic acid, and rhamnose represented by the above general formula (Formula 2), and the other Is a polysaccharide having repeating units of fucose and mannose. The former is a polysaccharide of the present invention, and is a high-molecular component having a monosaccharide composition ratio of fucose: glucose: glucuronic acid: rhamnose of 1: 2: 1: 1 and a molecular weight of about 10 ⁶ to 10 ⁹ [ See page 371 of the 1998 Annual Meeting of the Japanese Society for Agricultural Chemistry. The latter is a polysaccharide having a repeating structure of fucose and mannose of 1: 1, and is a low molecular component having a molecular weight of 10 ³ to 10 ⁷ [Y. Nohata, J .; Azuma, R.A. Kurane, Carbohydrate Research 293, (1996) 213-222]. Even if the low molecular component coexists with the high molecular component, the effect of the present invention is not hindered. Polysaccharides obtained from Alkaligenes latus B-16 strain bacteria are commercially available as “Alkathylan” (trade name); manufactured by Hakuto Co., Ltd. [INCName: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.].

Further, instead of Alkaligenes latus B-16 strain bacteria (FERM BP-2015), Sphingomonas true peri SPH-011 strain bacteria (FERM BP-08582) or Sphingomonas true peri strain SPH-012 strain bacteria (FERM BP- Even using 08579), the polysaccharide represented by the above chemical formula (Chemical Formula 2) can be obtained.
Furthermore, welan gum (manufactured by CP Kelco) or diyutan gum (manufactured by CP Kelco) can be used as the polysaccharide. These polysaccharides have glucuronic acid, glucose and rhamnose as the main chain and rhamnose as the side chain.

  Moreover, in the manufacturing method of the cosmetics of the emulsified state of this invention, a hydrous silicic acid and / or a hydrous alumina are coat | covered on the surface of a titanium oxide microparticle in a titanium oxide coating process. The amount of hydrous silicic acid and / or hydrous alumina is in the range of 0.1% to 100% by weight, preferably 5% to 20% by weight, expressed as the total amount in terms of oxide with respect to titanium oxide. Range.

The titanium oxide powder used in the present invention can be produced as follows. First, a 150 to 220 g / l titanium sulfate aqueous solution or titanium tetrachloride aqueous solution is neutralized with an alkali solution such as sodium hydroxide while keeping it at 5 to 30 ° C. to precipitate colloidal amorphous titanium hydroxide. If necessary, this colloidal titanium hydroxide may be aged at 60 to 80 ° C. for 1 to 10 hours. The hydrous titanium oxide thus obtained is suspended in a solvent such as water to form a slurry, and further dispersed in a solvent such as water to obtain a sol.
In the titanium oxide coating step, a water-soluble aluminum salt such as sodium aluminate, aluminum sulfate, aluminum nitrate, or aluminum chloride is added to the sol after dissolving in water, or a water-soluble silicon salt such as sodium silicate. Is dissolved in water and added, or both of them may be added. Then, the pH is adjusted to precipitate hydrous silicic acid and / or hydrous alumina, and the surface of hydrous titanium oxide is coated with hydrous silicic acid and / or hydrous alumina. Further, this step will be described in detail. For example, a dispersion containing hydrous titanium oxide having a titanium oxide (TiO 2) concentration adjusted to 50 to 300 g / l as necessary is 40 to 90 ° C., preferably 60 to 80 ° C. While heating to a temperature range, a water-soluble salt of aluminum or silicon is added thereto, and then an alkaline aqueous solution such as sodium hydroxide or ammonia water is added to adjust the pH to preferably 6 to 8. To sum up.

  The amount of aluminum or silicon water-soluble salt added to the hydrous titanium oxide in the above step may be adjusted as appropriate, but in general, the total amount of titanium oxide converted to aluminum or silicon oxide is 0. It can be adjusted in the range of 1% by weight to 100% by weight, preferably in the range of 5% by weight to 20% by weight.

  Thus, after finishing the titanium oxide coating step, the surface-coated titanium oxide powder is heat-treated at 200 ° C. to 900 ° C. as a heat treatment step. There is no limitation in particular about the method of heat processing, It can carry out by various methods. For example, an electric furnace, a tunnel kiln, a rotary kiln, etc. can be used. Through this heat treatment step, hydrous silicic acid and hydrous alumina are dehydrated to form a dense network structure. If necessary, the product obtained by firing may be pulverized. The pulverization may be performed by wet pulverization using a sand mill, pebble mill, disk mill or the like, or by dry pulverization using a fluid energy mill, hammer mill, edge runner mill, or the like. It can be carried out.

  It is also preferable to hydrophobize the surface of the surface-coated titanium oxide powder after the firing step in this way. By performing the hydrophobic treatment, the dispersibility of the titanium oxide powder in the cosmetic and the durability of the coating film can be further improved. The hydrophobization method may be a wet method in which the titanium oxide powder is adsorbed and bonded, or a dry method in which a lipophilic organic substance is added when the titanium oxide powder is crushed and adhered to the surface of the titanium oxide powder. it can. As an organic substance for performing the hydrophobizing treatment, polysiloxane, fatty acid, or the like can be used. The amount of the organic substance added may be appropriately adjusted according to the purpose of the hydrophobization treatment, but is usually in the range of 0.1 to 20% by weight in terms of the total amount of organic substance relative to titanium oxide. The product obtained by the wet method may be subjected to fractionation, washing, drying, or pulverization as necessary.

  In the emulsification step in the method for producing an emulsified cosmetic of the present invention, the polysaccharide solution, the amount of higher alcohol corresponding to 0.8% to 20% by weight relative to the total amount of the cosmetic, and the oily component are made up. 60% by mixing the amount corresponding to 0.5% to 30% by weight with respect to the total amount of the preparation and the corresponding amount of 1% to 20% by weight of the cosmetic with the heat-treated titanium oxide powder. It is preferable to stir while heating to more than ° C. to make an emulsion. In emulsification, it is preferable to apply a strong share. A homogenizer (for example, TK Robot Mixer TK Homomixer MARK II2.5 type, manufactured by Tokushu Kika Kogyo Co., Ltd.) or a disperser (for example, the stirring section is TK). It is preferable to use TK Robotics, which is a homodisperser 2.5 type, manufactured by Tokushu Kika Kogyo Co., Ltd. The stirring time in the emulsification step varies depending on the stirring device and the amount of liquid and may be appropriately adjusted, but is usually about 10 minutes to 60 minutes. Cooling is started while stirring is continued. The cooling time varies depending on the apparatus and the amount of liquid, but it is brought to room temperature over 10 to 60 minutes. Thus, the emulsified cosmetic of the present invention can be obtained.

  The blending amount of the titanium oxide powder is preferably 1 to 20% by weight, desirably 3 to 15% by weight, more desirably 5 to 12% by weight, based on the total amount of the cosmetic. If it is less than 1% by weight, a sufficient ultraviolet ray preventing effect cannot be obtained. On the other hand, if it exceeds 20% by weight, the effect of preventing ultraviolet rays can be obtained, but whitening occurs after application, which impairs the cosmetic beauty. The blending amount of the oil component is 0.5% to 30% by weight, desirably 3% to 25% by weight, and more desirably 5% to 20% by weight. If it is 0.5% by weight or less, sufficient water resistance cannot be obtained. On the other hand, if it is 30% by weight or more, although water resistance is obtained, stickiness after application occurs, and the feeling of use as a cosmetic is deteriorated.

  Moreover, in the cosmetics of this invention, various components, such as a moisturizing agent, antiseptic | preservative, antioxidant, and a pigment | dye, can be mix | blended. Depending on the types and amounts of these various components, the stability may be insufficient only when two or more of the polysaccharides of the present invention and higher alcohols are blended. In particular, when ceramide powder, zinc oxide powder, mica powder or the like, which is a powder having surface activity, is added, or when ascorbic acid magnesium phosphate salt or ascorbic acid glucoside which is easily precipitated is blended, the influence is great. In that case, two or more of the polysaccharide of the present invention and a higher alcohol are blended, and in order to obtain a stable emulsified state, one or more of citric acid and / or citrate is added to the total amount of the cosmetic. It is preferable to add 0.01% by weight to 1% by weight. As a method of blending citric acid and citrate, it is preferable to dissolve citric acid and citrate in advance in an aqueous polysaccharide solution. In this case, even if there is a positively charged component in the component added later, the previously added citric acid and / or citrate changes the positive charge to a negative charge. The dispersion state is stabilized by repelling the charged polysaccharide.

In order to further stabilize the emulsified state, a hydrophilic component may be added. Examples of such hydrophilic components include amino acids, sugars and derivatives thereof, hydrophilic polymers, low molecular monohydric alcohols, low molecular polyhydric alcohols, and the like.
Examples of amino acids include asparagine, aspartic acid, alanine, arginine, isoleucine, ortinin, glutamine, glycine, glutamic acid and derivatives thereof, and salts thereof, cysteine, cystine, citrulline, threonine, serine, tyrosine, tryptophan, theanine, valine, histidine. , Hydroxylysine, hydroxyproline, pyrrolidone carboxylic acid and salts thereof.
Examples of sugars and derivatives thereof include honey, erythritol, maltose, maltitol, xylitol, xylose, pentaerythritol, fructose, dextrin and derivatives thereof, mannitol, sorbitol, inositol, trehalose, glucose, POE methyl glucoside, hydrolyzed hydrogenated starch, Examples include glucoside trehalose.
Examples of the hydrophilic polymer include xanthan gum, gum arabic, guar gum, caraya gum, carrageenan, pectin, fucoidan, quinseed gum, tranto gum, locust bean gum, galactomannan, curdlan, gellan gum, fucogel, casein, gelatin, starch, Natural polymers such as collagen, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, propylene glycol alginate, cellulose crystals, starch / sodium acrylate graft polymer, hydrophobized Semi-synthetic polymers such as hydroxypropylmethylcellulose, polyvinyl alcohol Lumpur, polyvinyl pyrrolidone, carboxyvinyl polymer, polyacrylates, and synthetic polymers such as polyethylene oxide.
In addition, inorganic minerals such as bentonite, laponite, and hectorite can be used in combination.
In addition, the low molecular weight monohydric alcohol is ethanol, and the low molecular weight polyhydric alcohol is 1,3-butylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, butanol. , Propanol, pentanediol, octanediol, 1- (2-ethylhexyl) glycol ether and the like.

  The cosmetics of the present invention have various types depending on the purpose of use. Therefore, if necessary, the cosmetics, quasi-drugs, cosmetics and the like are further mixed with purified water, hot spring water, deep water, increased water. Sticky agent, pigment, moisturizer, astringent, whitening agent, UV protection agent, anti-inflammatory (anti-inflammatory) agent, skin (cell) activator, antibacterial agent, transdermal absorption enhancer, refreshing agent, antioxidant, antiseptic Agents, chelating agents, anti-fading agents, buffering agents and the like are optionally added. This invention does not restrict | limit mix | blending these various additives in the range which does not prevent the target effect.

  In addition, the cosmetic of the present invention can be made into various forms of preparations such as internal preparations and injections in addition to external preparations within the range not impairing the effects of the present invention. It is preferably used as an external preparation for quasi-drugs and cosmetics. In addition, the form (dosage form) of the preparation when used as a cosmetic is not particularly limited, and any form such as a solution, paste, gel, solid, or powder can be used.

  Moreover, when using the cosmetics of this invention as sunscreen cosmetics, you may add oil, lotion, cream, milky lotion, gel, shampoo, hair rinse, etc. Furthermore, it can be used for hair conditioners, enamels, foundations, lipsticks, funny, packs, ointments, tablets, injection solutions, granules, capsules, powders, toothpastes, soaps, aerosols, cleansing foams and the like.

  Hereinafter, examples embodying the present invention will be described in detail in comparison with comparative examples.

Example 1
The cosmetic of Example 1 is a cosmetic having the composition shown in Table 1. In this table, category a is polyhydric alcohol and hydrous silicic acid / hydrated alumina-coated heat-treated titanium oxide, category b is higher alcohol and oily components other than higher alcohol, and category c is an aqueous polysaccharide solution.

Among the above-mentioned components, polysaccharide (A-1) is a crude product of polysaccharide produced by Alkaline Generus B-16 strain bacteria (FERM BP-2015), and was prepared as follows.
That is, glucose [made by Wako Pure Chemical Industries, Ltd., reagent] 40.0 g, dipotassium hydrogen phosphate [made by Wako Pure Chemical Industries, Ltd., reagent] 4.0 g, potassium dihydrogen phosphate [Wako Pure Chemical Industries, Ltd. 2.0 g of sodium chloride [manufactured by Wako Pure Chemical Industries, reagent] 0.1 g, magnesium sulfate [manufactured by Wako Pure Chemical Industries, reagent] 0.2 g, potassium nitrate [Japanese Mitsui Chemicals Co., Ltd., Reagent] 1.0 g, Yeast Extract [Oxoid (OXOID) 1.5 g] was dissolved in ion-exchanged water, adjusted to pH 6.5 using sodium hydroxide or sulfuric acid, The total volume was 1000 mL. 150 mL of this aqueous solution is placed in a 500 mL Erlenmeyer flask, sterilized by heating (121 ° C., 15 minutes) using an autoclave, returned to room temperature, and inoculated with 1 platinum loop of Alkagen Genus Lasus B-16 strain (FERM BP-2015). The culture was shaken at 180 ° C. for 6 days (180 rpm). After completion of the culture, about 3 times the volume of isopropyl alcohol was added to the culture, and the mixture was stirred and mixed. The precipitated aggregate was filtered, collected, and dried under reduced pressure to produce a polysaccharide (A -1) was obtained. From the analysis by ¹ HNMR and ¹³ CNMR, this polysaccharide is known to contain two kinds of polysaccharides represented by the following chemical formula (Chemical Formula 3), and fucose, glucose, glucuronic acid, and rhamnose are in a molar ratio of 1: A polysaccharide composed of 2: 1: 1 as a main component and a polysaccharide composed of fucose and mannose in a molar ratio of 1: 1 are included, and the abundance ratio is 7: 1 (weight ratio). The constituent monosaccharides were analyzed by high performance liquid chromatography (HPLC) after hydrolyzing the polysaccharide with sulfuric acid.

The hydrous silicic acid / hydrous alumina-coated heat-treated titanium oxide (B-1) in the above table was prepared through a titanium oxide coating step and a heat treatment step as follows.
<Titanium oxide coating process>
By dissolving 300 g of titanium tetrachloride in 1 L of pure water at room temperature and neutralizing with an aqueous sodium hydroxide solution, a colloidal amorphous titanium hydroxide is precipitated, and further left to stand at room temperature for 1 hour. A type of fine titanium oxide sol was obtained. While stirring this fine titanium oxide sol, the temperature was raised to 80 ° C., and 8 g of a 50 wt% aqueous solution of sodium silicate was added while maintaining this temperature. Next, 0.5 g of a 30 wt% aqueous solution of sodium aluminate was added, and then slowly added with sulfuric acid (1 N) until the pH reached around 7.5 over 60 minutes. Then, by stirring for 1 hour at room temperature, fine particles of titanium oxide in which a fine titanium oxide sol was surface-coated with hydrous silica and hydrous alumina were obtained.
<Heat treatment process>
As the heat treatment step, the washing cake made of titanium oxide fine particles surface-coated with the hydrous silica and hydrous alumina obtained in the titanium oxide coating step is baked at 450 ° C. for 3 hours, and then pulverized with a hammer type mill to be hydrophilic. A heat-treated titanium oxide powder coated with hydrous silicic acid and hydrous alumina was obtained. The particle size was distributed between 0.05 and 1 μm, and the average particle size was 0.2 μm.

<Polysaccharide solution preparation process>
The polysaccharide (A-1) is added to purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-1) solution of section c.

<First emulsification step>
And as a 1st emulsification process, the component (namely, polyhydric alcohol and hydrous silicic acid / hydrous alumina covering heat treatment titanium oxide (B-1)) of the above-mentioned a section is measured, heated to 80 ° C., stirred and oxidized. A titanium dispersion was obtained.

<Second emulsification step>
Next, as a second emulsification step, the polysaccharide (A-1) solution obtained in the polysaccharide solution preparation step and the titanium oxide dispersion obtained in the first emulsification step are mixed at 8000 rpm using a homogenizer or a homomixer. Mixing and stirring were performed to obtain an emulsion in the second emulsification step.

<Third emulsification step>
Further, in the third emulsification step, the above-mentioned component b (that is, a mixture of hexadecanol and octadecanol as the higher alcohol and other oily components) is gradually added to the emulsion in the second emulsification step and stirred for 10 minutes. To obtain an emulsified liquid in the third emulsification step.

<Cooling process>
Finally, as a cooling step, the emulsion obtained in the third emulsification step was cooled to room temperature to obtain the cosmetic of Example 1.

(Example 2)
In Example 2, the polysaccharide (A-2) was used in place of the polysaccharide (A-1) used in Example 1. This polysaccharide (A-2) is obtained by purifying the polysaccharide (A-1) by the method shown below.
That is, a 0.5 wt% aqueous solution of polysaccharide (A-1) is prepared, and an aqueous sodium hydroxide solution is added to adjust the pH to 12. Then, this solution was treated with a column of ion exchange resin “Diaion HPA-75 (OH—)” (trade name) (manufactured by Nippon Nensui Co., Ltd.) at 8 Ru or less, and further a filter aid “Radiolite”. Filtration was performed with “RL700” and a 5 μm membrane filter to remove proteins, nucleic acids, microorganisms and the like. Dilute hydrochloric acid is added to the filtrate thus obtained to adjust the pH to 7, and the filtrate is concentrated under reduced pressure. Acetone is added to the concentrate to precipitate the polysaccharide, which is filtered off. The polysaccharide thus obtained was washed with 10 times the amount of acetone to obtain a purified polysaccharide (A-2). This polysaccharide (A-2) was found to be composed of fucose: glucose: glucuronic acid: rhamnose = 1: 2: 1: 1 from analysis by ¹ HNMR and ¹³ CNMR. As a result of molecular weight measurement by GPC, the molecular weight was about 50 million.

  Except having used polysaccharide (A-2), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

Example 3
In Example 3, the polysaccharide (A-3) was used in place of the polysaccharide (A-1) used in Example 1. As this polysaccharide (A-3), a commercially available polysaccharide (“Alcacylan” (trade name); manufactured by Hakuto Co., Ltd.) [INCName: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.] was used as it was.
The polysaccharide (A-3) has a monosaccharide composition ratio of fucose: glucose: glucuronic acid: rhamnose of 1: 2: 1: 1, a molecular weight of about 10 ⁶ to 10 ⁹ , fucose and mannose. Is a mixture with a polysaccharide having a repeating structure of 1: 1 and a molecular weight of 10 ³ to 10 ⁷ .

  Except having used polysaccharide (A-3), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

Example 4
In Example 4, the polysaccharide (A-4) was used in place of the polysaccharide (A-1) used in Example 1. This polysaccharide (A-4) is a crude product of a polysaccharide produced by Sphingomonas true peri SPH-011 strain bacteria (FERM BP-08582), and was prepared as follows.
Specifically, 50 L of a medium having the following composition was placed in a 90 L fermentor manufactured by Marubishi Engineering Co., and after sterilization, Sphingomonas true peri SPH-011 strain bacteria (FERM BP-08582) were inoculated and cultured.
<Composition of medium> (per liter)
Glucose [manufactured by Wako Pure Chemical Industries, Ltd.] 4.00 g
Dipotassium hydrogen phosphate [Wako Pure Chemical Industries, Ltd.] 0.40 g
Potassium dihydrogen phosphate [manufactured by Wako Pure Chemical Industries, Ltd.] 0.20g
Sodium chloride [Wako Pure Chemical Industries, Ltd.] 0.01g
Magnesium sulfate [Wako Pure Chemical Industries, Ltd.] 0.02g
Potassium nitrate [Wako Pure Chemical Industries, Ltd.] 0.10g
Yeast extract ["Hy-Yeast 142" (trade name); manufactured by Sigma]
0.15g

The agitation blade of the fermenter was agitated in the range of 700 rpm to 800 rpm using a turbine agitation blade, and the aeration amount was in the range of 1 vvm to 2 vvm. The pH was controlled using a 1N aqueous solution of NaOH so as to be in the range of 6.5 ± 0.4. The culture temperature was controlled at 30 ± 0.2 ° C. The culture was performed for 6 days. After completion of the culture, about 3 times the volume of isopropyl alcohol is added to the culture and stirred and mixed. The precipitated aggregate is filtered, recovered, and dried under reduced pressure to produce a sphingomonas true peri strain SPH-011. A saccharide (A-4) was obtained. The polysaccharide (A-4) obtained in this way was measured from ¹ HNMR and ¹³ CNMR, and analyzed by high performance liquid chromatography (HPLC) after hydrolysis of the polysaccharide with sulfuric acid. It was found that the main component is a polysaccharide composed of glucuronic acid and rhamnose in a molar ratio of 1: 2: 1: 1, and other polysaccharides composed of rhamnose and mannose in a molar ratio of 2: 1.

  Except having used polysaccharide (A-4), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Example 5)
In Example 5, the polysaccharide (A-5) was used in place of the polysaccharide (A-1) used in Example 1. This polysaccharide (A-5) was used in place of the Sphingomonas true peri SPH-011 bacterium, except that the Sphingomonas true peri SPH-012 bacterium (FERM BP-08579) was used. A-4) is prepared by the same method, and detailed description is omitted. The polysaccharide (A-5) was measured by ¹ HNMR and ¹³ CNMR, and the polysaccharide was hydrolyzed with sulfuric acid and analyzed by high performance liquid chromatography (HPLC). As a result, fucose, glucose, glucuronic acid, rhamnose were analyzed. It was found that the main component is a polysaccharide composed of a molar ratio of 1: 2: 1: 1, and other polysaccharides composed of fucose and mannose in a molar ratio of 1: 1.

  Except having used polysaccharide (A-5), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Example 6)
In Example 6, the polysaccharide (A-6) was used in place of the polysaccharide (A-1) used in Example 1. This polysaccharide (A-6) is obtained by purifying the polysaccharide (A-4) used in Example 4 as follows.
That is, sodium hydroxide was added to a 0.5 wt% aqueous solution of polysaccharide (A-4) to a concentration of 0.02 wt%, and the mixture was stirred overnight to disperse the polysaccharide. And it heated and dissolved on 121 degreeC and the conditions for 10 minutes. Next, the cells were removed by centrifugation (40,000 G, 40 minutes). Confirmation of bacterial cell removal was judged by the transparency of the supernatant. And it filtered with the filter aid "Radiolite RL700" and a 5 micrometer membrane filter, and obtained the filtration residue. The filtration residue thus obtained is again added with about 100 times the amount of pure water as a volume, stirred, and then refiltered. This operation was repeated 5 times to demineralize water-insoluble components. The gel-like water-insoluble component dehydrated to some extent by the membrane filter system was dried as it was at room temperature under reduced pressure to obtain a polysaccharide (A-6) (purified product).

  Except having used polysaccharide (A-6), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Example 7)
In Example 7, the polysaccharide (A-7) was used in place of the polysaccharide (A-1) used in Example 1. This polysaccharide (A-7) is obtained by purifying the polysaccharide (A-5) used in Example 5 in the same manner as in Example 6.

  Except having used polysaccharide (A-7), it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Comparative Example 1)
In Comparative Example 1, in place of the hydrous silicic acid / hydrated alumina-coated heat-treated titanium oxide (B-1) used in Example 1, hydrous silicic acid / hydrated alumina-coated non-heat treated titanium oxide before heat treatment was used. The manufacturing method of this hydrous silicic acid / hydrous alumina-coated non-heat-treated titanium oxide is as follows. That is, 300 g of titanium tetrachloride was dissolved in 1 L of pure water at room temperature, and neutralized with an aqueous sodium hydroxide solution to precipitate a colloidal amorphous titanium hydroxide. A rutile type fine titanium oxide sol was obtained by allowing it to stand at room temperature for 1 hour. The fine titanium oxide sol was heated to 80 ° C. while stirring, and 8 g of a 50 wt% sodium silicate aqueous solution was added while maintaining this temperature. Next, 0.5 g of a 30% by weight aqueous solution of sodium aluminate was added, and the mixture was slowly neutralized with sulfuric acid (1 N) until the pH reached around 7.5 over 60 minutes. The mixture was stirred at room temperature for 1 hour to obtain hydrophilic titanium oxide whose surface was coated with hydrous silica and hydrous alumina. This was filtered with 200 mesh nylon, washed with pure water three times, dried, and then pulverized with a hammer type mill to obtain hydrous silicic acid / hydrous alumina coated non-heat treated titanium oxide fine particles. The particle size of this product was distributed between 0.05 and 1 μm, and the average particle size was 0.2 μm.

  About others, it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Comparative Example 2)
In Comparative Example 2, in place of the hydrous silicic acid / hydrated alumina-coated heat-treated titanium oxide used in Example 1, hydrous silicic acid / hydrated alumina-coated non-heat treated titanium oxide (“MT-100SA” (trade name) ); Teica Co., Ltd.) was used.

  About others, it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Comparative Example 3)
In Comparative Example 3, sucrose myristate sodium ("M-160" (trade name); which is a surfactant as the component a, except for the c-class polysaccharide (A-1) used in Example 1; 1% by weight of Daiichi Kogyo Seiyaku Co., Ltd. was added.
In this case, the <polysaccharide solution preparation step> of Example 1 is eliminated, and the <second emulsification step> is as follows.
<Second emulsification step>
Next, as the second emulsification step, the titanium oxide dispersion obtained in the first emulsification step and the purified water of section c are mixed and stirred at 8000 rpm using a homogenizer or homomixer to obtain an emulsion in the second emulsification step. It was.

  About others, it is the same as that of the cosmetics of Example 1, and description is abbreviate | omitted.

(Example 8)
The cosmetic of Example 8 is a cosmetic having the composition shown in Table 2. In this table, the a section is a polyhydric alcohol, the b section is a stearic acid-coated heat treated titanium oxide (B-2) hydrophobized with stearic acid, a higher alcohol, and an oil component other than the higher alcohol, c The classification is a polysaccharide (A-3) (“Alcacylan” (trade name); manufactured by Hakuto Co., Ltd.) [INCName: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.] aqueous solution.

In Table 2 above, stearic acid-coated heat-treated titanium oxide B-2 is prepared through a titanium oxide coating step, a heat treatment step, and a hydrophobization treatment step as follows.
<Titanium oxide coating process>
By dissolving 300 g of titanium tetrachloride in 1 L of pure water at room temperature and neutralizing with an aqueous sodium hydroxide solution, a colloidal amorphous titanium hydroxide is precipitated, and further left to stand at room temperature for 1 hour. A type of fine titanium oxide sol was obtained.
Next, the slurry of the fine titanium oxide sol was heated to 70 ° C., and 26 g of a 40 wt% aqueous solution of aluminum sulfate was added little by little over 30 minutes while stirring. Further, a 20 wt% sodium hydroxide solution was added until pH 7 was reached, so that the surface of fine titanium oxide was coated with hydrous alumina. After leaving at room temperature for 1 hour, it was filtered through 200 mesh nylon and washed three times with pure water.
<Heat treatment process>
The washed cake thus obtained was baked at 450 ° C. for 3 hours. Further, the calcined titanium oxide was dispersed in 500 ml of pure water, and then wet pulverized with a sand mill to obtain a slurry of fine titanium oxide particles.
<Hydrophobicization treatment process>
This slurry was heated and stirred to 70 ° C., and 3 g of sodium stearate heated to 70 ° C. was added and dissolved therein. After stirring for 30 minutes, the mixture was cooled to 30 ° C. to coat stearic acid on the titanium oxide particles. This was filtered through 200 mesh nylon, washed three times with pure water, dried, and then pulverized with a hammer type mill to obtain lipophilic (hydrophobic) stearic acid-coated heat-treated titanium oxide fine particles. . The coated powder particle size after pulverization was distributed between 0.05 to 1 μm, and the average particle size was 0.2 μm.

<Polysaccharide solution preparation process>
The polysaccharide (A-3) is dissolved in purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-3) solution of section c.

<Dissolution process>
And as a dissolution process, the component (namely, polyhydric alcohol) of the said division | segmentation a is measured and it heats at 80 degreeC, Furthermore, the polysaccharide (A-3) solution heated at 80 degreeC is added, and a homogenizer or Mix and stir at 8000 rpm using a homomixer.

<Dispersing process>
Next, as a dispersion step, the above-mentioned component b (ie, stearic acid-coated heat-treated titanium oxide, a mixture of eicosanol and docosanol as higher alcohol, and other oily components) is heated to 80 ° C. and dispersed to dissolve the above-mentioned solution Gradually add to the liquid obtained in the process and continue stirring for 10 minutes to obtain an emulsion.

<Cooling process>
Finally, as the cooling step, the emulsion obtained in the dispersing step was cooled to room temperature, and the cosmetic of Example 8 was obtained.

(Comparative Example 4)
In Comparative Example 4, in place of the stearic acid-coated heat-treated titanium oxide used in Example 8, no heat treatment was performed, and only stearic acid-coated non-heat-treated titanium oxide (B-5) subjected to hydrophobic treatment with stearic acid. Was used. A method for producing stearic acid-coated non-heat treated titanium oxide (B-5) is shown below.
That is, 300 g of titanium tetrachloride is dissolved in 1 L of pure water at room temperature, and further neutralized with an aqueous sodium hydroxide solution to precipitate a colloidal amorphous titanium hydroxide. Further, by allowing it to stand at room temperature for 1 hour, a rutile-type fine titanium oxide sol was obtained. This fine titanium oxide sol slurry was heated to 70 ° C., and 26 g of a 40 wt% aqueous solution of aluminum sulfate was added over 30 minutes while stirring well. Further, a 20 wt% sodium hydroxide solution was added until the pH reached 7, thereby coating the surface of fine titanium oxide with hydrous alumina. Next, this slurry was heated to 70 ° C., and 3 g of sodium stearate was added and dissolved with good stirring while maintaining the temperature at 70 ° C. And after stirring for 30 minutes, it cooled to 30 degreeC and the stearic acid was coat | covered on this titanium oxide particle. The dispersion was filtered, washed, dried, and then pulverized with a hammer type mill to obtain lipophilic (hydrophobic) stearic acid-coated non-heat treated titanium oxide fine particles. The coated powder particle size after pulverization was distributed between 0.05 to 1 μm, and the average particle size was 0.2 μm.

  About the other cosmetics manufacturing method, it is the same as that of the cosmetics of Example 8, and description is abbreviate | omitted.

(Comparative Example 5)
In Comparative Example 5, in place of the stearic acid-coated heat-treated titanium oxide used in Example 8, after coating with hydrous alumina, stearic acid coating was performed without heat treatment, and the non-heat-treated titanium oxide (B-6) ("MT-01" (trade name); manufactured by Teika Co., Ltd.) was used.

  About the other cosmetics manufacturing method, about others, it is the same as that of the cosmetics of Example 8, and description is abbreviate | omitted.

Example 9
The cosmetic of Example 9 is a cosmetic having the composition shown in Table 3. In this table, a section is a polyhydric alcohol, b section consists of polysiloxane-coated heat-treated titanium oxide (B-3) hydrophobized with polysiloxane, a higher alcohol, and an oil component other than the higher alcohol, Category c is a polysaccharide (A-3) ("Alcacylan" (trade name); manufactured by Hakuto Co., Ltd.) [INCName: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.] aqueous solution.

In Table 3 above, the polysiloxane-coated heat-treated titanium oxide (B-3) was subjected to a titanium oxide coating step and a heat treatment step in the same manner as the stearic acid-coated heat treated titanium oxide (B-2) in Example 8, and the hydrous alumina. After obtaining the coated heat treated titanium oxide, the hydrous alumina coated heat treated titanium oxide was prepared by performing the following hydrophobizing treatment step.
<Hydrophobicization treatment process>
The above-mentioned hydrous alumina-coated heat-treated titanium oxide was dispersed in 500 ml of pure water, and then wet pulverized with a sand mill to obtain titanium oxide fine particle slurry. 6 g of methyl hydrogen polysiloxane was added to the titanium oxide fine particle slurry while stirring with a Henschel mixer, and then heat treatment was performed at 150 ° C. to coat the polysiloxane on the titanium oxide particles. The titanium oxide particles after the heat treatment were pulverized with a hammer type mill to obtain a lipophilic (hydrophobic) polysiloxane-coated heat-treated titanium oxide (B-3). The coated powder particle size after pulverization was distributed between 0.05 to 1 μm, and the average particle size was 0.2 μm.

<Polysaccharide solution preparation process>
The polysaccharide (A-3) is dissolved in purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-3) solution of section c.

<Dissolution process>
And as a dissolution process, the component (namely, polyhydric alcohol) of the said division | segmentation a is measured and it heats at 80 degreeC, Furthermore, the polysaccharide (A-3) solution heated at 80 degreeC is added, and a homogenizer or Mix and stir at 8000 rpm using a homomixer.

<Dispersing process>
Next, as a dispersion step, the above-mentioned component b (that is, polysiloxane-coated heat-treated titanium oxide (B-3), a mixture of octadecanol and docosanol as a higher alcohol, and other oily components) is heated to 80 ° C. The dispersed liquid is gradually added to the liquid obtained in the dissolution step, and stirring is continued for 10 minutes to obtain an emulsion.

<Cooling process>
Finally, as the cooling step, the emulsion obtained in the dispersing step was cooled to room temperature, and the cosmetic of Example 9 was obtained.

(Comparative Example 6)
The cosmetic of Comparative Example 6 is a cosmetic having the composition shown in Table 4. In this table, the a section consists of polyhydric alcohol, sucrose myristic acid ester as a surfactant, and purified water, and the b section is a dimethicone / methicone copolymer hydrophobized with a dimethylpolysiloxane-methylpolysiloxane copolymer. It consists of coated titanium oxide (B-8) and various polysiloxanes, and the c section consists of oily components.

The cosmetic material of Comparative Example 6 was produced as follows.
(1) Dimethicone / methicone copolymer-coated titanium oxide (B-8) hydrophobized with a dimethylpolysiloxane-methylpolysiloxane copolymer of category b and various polysiloxanes are mixed at 80 ° C.
(2) Weigh the oil component in section c and mix at 80 ° C. to make a uniform solution.
(3) Weigh the polyhydric alcohol in category a, sucrose myristic acid ester as a surfactant, and purified water and mix at 80 ° C. to make a uniform solution.
(4) A polyhydric alcohol and sucrose myristic acid aqueous solution of a section are added little by little to the dimethicone / methicone copolymer-coated titanium oxide (B-8) dispersion of the b section to obtain a dispersion.
(5) While stirring the dispersion obtained in the procedure (4), the oil component solution of section c was gradually added. After the addition was completed, stirring was continued for another 10 minutes, followed by cooling to room temperature. I got cosmetics.

(Example 10)
The cosmetic of Example 10 is a cosmetic having the composition shown in Table 5. In this table, a section is polyhydric alcohol and hydrophilic hydrous silicic acid / hydrous alumina coated heat-treated titanium oxide (B-1), b section is composed of higher alcohol and oil component, c section is polysaccharide (A- 3) ("Arcasilan" (trade name); manufactured by Hakuto Co., Ltd.) [INC Iname: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.)] Sodium citrate was added to the aqueous solution, and d-category was L-ascorbic acid glucoside And an aqueous solution of L-arginine.

The cosmetic of Example 10 was produced as follows.
<Polysaccharide solution preparation process>
The polysaccharide (A-3) and sodium citrate are added to purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-3) solution of section c.

<First emulsification step>
And as a 1st emulsification process, the component (namely, polyhydric alcohol and hydrous silicic acid / hydrous alumina coating heat treatment titanium oxide (B-1)) of the above-mentioned division a is measured, heated to 80 ° C., stirred, A titanium dispersion is used.

<Second emulsification step>
Next, as the second emulsification step, the polysaccharide (A-3) solution obtained in the polysaccharide solution preparation step and the titanium oxide dispersion obtained in the first emulsification step are mixed at 8000 rpm with a homogenizer or homomixer. Stir.

<Third emulsification step>
Further, as a third emulsification step, the above-mentioned component of b category (mixture of various higher alcohols and other oily components) is gradually added to the emulsified liquid of the second emulsification step, and stirring is continued for 10 minutes for the third emulsification. An emulsion of the process was obtained.

<Cooling process>
Finally, as the cooling step, the emulsion obtained in the third emulsification step was cooled to room temperature, and the d-segment solution was added and stirred and mixed to obtain the cosmetic of Example 10.

(Example 11)
In Example 11, the same amount of potassium citrate was used in place of sodium citrate in section c used in Example 10. Other than that is the same as that of the cosmetic of Example 10, and description is abbreviate | omitted.

Example 12
In Example 12, the same amount of citric acid was used in place of the sodium citrate of section c used in Example 10. Other than that is the same as that of the cosmetic of Example 10, and description is abbreviate | omitted.

(Example 13)
In Example 13, the sodium c citrate of section c used in Example 10 was not added. Other than that is the same as that of the cosmetic of Example 10, and description is abbreviate | omitted.

(Example 14)
The cosmetic of Example 14 is a cosmetic having the composition shown in Table 6. In this table, a section is polyhydric alcohol and methylparaben as preservative, b section is stearic acid-coated heat treated titanium oxide (B-2) hydrophobized with stearic acid, higher alcohol, and other than higher alcohol It is an oily component, and c classification contains polysaccharide (A-3) ("Arcasilan" (trade name); manufactured by Hakuto Co., Ltd.) [INCName: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.]) and sodium citrate D section is L-ascorbic acid glucoside and L-arginine aqueous solution.

  The cosmetic material of Example 14 was produced as follows.

<Polysaccharide solution preparation process>
The polysaccharide (A-3) and sodium citrate are added to purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-3) solution of section c.

<Dissolution process>
And as a dissolution process, the component (namely, polyhydric alcohol and methylparaben) of the above section a is weighed and heated to 80 ° C., and then the polysaccharide (A-3) solution heated to 80 ° C. is added, Mix and stir at 8000 rpm with a homogenizer or homomixer.

<Dispersing process>
Next, as a dispersion step, a liquid in which the above-mentioned component b (that is, stearic acid-coated heat-treated titanium oxide (B-2), higher alcohol and other oily components) is heated and dispersed at 80 ° C. in the dissolution step. Gradually add to the resulting liquid and continue stirring for 10 minutes to make an emulsion.

<Cooling process>
Finally, as the cooling step, the emulsion obtained in the dispersing step was cooled to room temperature, and the d-segment solution was added and stirred and mixed to obtain the cosmetic of Example 14.

(Example 15)
In Example 15, the sodium c citrate of section c used in Example 14 was not added. Other than that is the same as that of the cosmetic of Example 14, and description is abbreviate | omitted.

(Example 16)
The cosmetic of Example 16 is a cosmetic having the composition shown in Table 7. In this table, a section is polyhydric alcohol, b section is polysiloxane-coated heat-treated titanium oxide (B-3) hydrophobized with polysiloxane, higher alcohol, and oil component other than higher alcohol, c Classification is an aqueous solution containing polysaccharide (A-3) ("Arcasilan" (trade name); manufactured by Hakuto Co., Ltd.) [INCIname: Alcaligenes Polysacchaides, manufactured by Hakuto Co., Ltd.] and sodium citrate, d classification Are L-ascorbic acid glucoside and L-arginine aqueous solution.

  The cosmetic material of Example 16 was produced as follows.

<Polysaccharide solution preparation process>
The polysaccharide (A-3) and sodium citrate are added to purified water, heated to 80 ° C., and stirred and mixed with a disperser to obtain a polysaccharide (A-3) solution of section c.

<Dissolution process>
And as a dissolution process, the component (namely, polyhydric alcohol) of the said division | segmentation a is measured and it heats at 80 degreeC, Furthermore, the polysaccharide (A-3) solution heated at 80 degreeC is added, and a homogenizer or Mix and stir with a homomixer at 8000 rpm.

<Dispersing process>
Next, as a dispersion step, a liquid in which the above-mentioned component b (that is, polysiloxane-coated heat-treated titanium oxide (B-3), higher alcohol and other oily components) is heated to 80 ° C. and dispersed is used in the dissolution step. Gradually add to the resulting liquid and continue stirring for 10 minutes to make an emulsion.

<Cooling process>
Finally, as the cooling step, the emulsion obtained in the dispersion step was cooled to room temperature, and the d-segment solution was added and stirred and mixed to obtain the cosmetic of Example 16.

-Evaluation-
The stability test and the water resistance test were performed on the cosmetics of Examples 1 to 9 and Comparative Examples 1 to 5 manufactured as described above.
(Stability test)
The cosmetics immediately after preparation are taken into a 200 ml sample bottle, stoppered, and placed in a thermostatic chamber under the conditions of 5 ° C., 50 ° C., and a cycle test (a test repeated at −10 ° C. for 1 day and at 50 ° C. for 1 day). It was allowed to stand and visually observed after 1 week and 3 months. The stability evaluation by visual observation was performed as follows.
Stability: No separation / precipitation is observed visually.
Separation of water: Visual separation of water phase and / or formation of precipitate is observed.

(Water resistance test)
No. with a side of 30mm. 2 0.5 g of the cosmetic material immediately after preparation is evenly applied to the back surface of 2 filter paper (manufactured by Advantic), dried at 105 ° C. for 1 hour, and then weighed (weight before immersion). Then, the dried filter paper is immersed for 30 minutes in a 200 ml beaker containing 100 ml of purified water with the cosmetic-coated side down. Then, the filter paper is pulled up from the water, dried again at 105 ° C. for 1 hour, and the weight is measured again (weight after immersion). And according to the following formula | equation, the outflow ratio was calculated | required and water resistance was evaluated.
-Outflow ratio (%) = (weight before immersion-weight after immersion) / weight before immersion x 100
・ Water-soluble component ratio (%)
= Water-soluble component blending amount (%) / {100-purified water blending amount (%)} × 100
・ Outflow ratio = Outflow ratio (%) / Water-soluble component ratio (%)
In the above test, when only the water-soluble component blended in the test cosmetic flows out, the outflow ratio becomes 1.00. When a component other than the water-soluble component blended in the test cosmetic flows out into water, the outflow ratio becomes 1.00 or more. However, the smaller the outflow of components other than the water-soluble component, the lower the outflow ratio is 1. It is close to 00 and has high water resistance.
Here, the water-soluble component mix | blended with test cosmetics is the various polyhydric alcohol of the a division of Table 1-Table 3, and the polysaccharide of c division.

(result)
The results are shown in Table 8.

For the stability test, the cosmetics of Examples 1 to 9 and Comparative Example 3 maintained a stable dispersion state for 3 months in all storage conditions, whereas in Comparative Examples 1, 2, 4, and 5, The stability of the emulsified state was 1 week or less.
This is because the titanium oxide powder used in the cosmetics of Examples 1 to 9 and Comparative Example 3 is heat-treated, whereas the titanium oxide powder used in Comparative Examples 1, 2, 4, and 5 contains water. Although it is coated with silicic acid / hydrous alumina or stearic acid, it is not heat-treated, so it is easy for polyvalent metal ions such as aluminum ions to elute, causing polysaccharides to aggregate and water separation. Presumed to be.

Moreover, about the water resistance test, since the value of the outflow ratio of the cosmetic of Comparative Example 3 is larger than the outflow ratio of the cosmetic of Examples 1 to 9 and Comparative Examples 1, 2, 4, and 5, The cosmetic of Example 3 has a large outflow of titanium oxide and the like other than the water-soluble component, indicating that the water resistance is inferior.
This is because the cosmetics of Examples 1 to 9 and Comparative Examples 1, 2, 4, and 5 use specific polysaccharides, so they are included in the purified water used in the test and the cosmetics applied to the filter paper. Titanium oxide and oily components are not emulsified and do not easily flow out from the filter paper to the purified water side (high water resistance), but use a surfactant (sodium sucrose myristate) instead of a specific polysaccharide. In the cosmetic of Comparative Example 3, the purified water and the titanium oxide / oil component blended in the cosmetic are emulsified by the emulsifying power of the surfactant and flow out from the filter paper to the purified water (water resistance). Is low).

  From the above results, it was found that the emulsion dispersion stability of cosmetics is improved by heat-treating titanium oxide blended in the cosmetics. Moreover, it turned out that water resistance improves by mix | blending a specific polysaccharide instead of surfactant as an emulsifier. Water resistance is an index of cosmetic run-off due to sweat when used in cosmetics, and the higher the water resistance, the less the cosmetic run-off due to sweat, so a specific polysaccharide is added instead of a surfactant. As a result, it was found that the cosmetics can be prevented from flowing down due to sweat.

  Moreover, the same stability test was done about the cosmetics of Examples 10-16 which mix | blended L-ascorbic acid glucoside which made the emulsification stability of cosmetics unstable as mentioned above, and was easy to precipitate. The results are shown in Table 9.

The cosmetics of Examples 10-12, 14, and 16 kept stable dispersion for 3 months in all storage conditions, whereas in Examples 13 and 15, separation of water separation occurred within 3 months in the cycle test. Admitted.
This is because the cosmetics of Examples 10-12, 14, and 16 are further blended with citric acid and citrate which have the effect of making the surface potential negative even when L-ascorbic acid glucoside is blended. Therefore, while a stable emulsified dispersion state could be maintained, in Examples 13 and 15, since citric acid and citrate were not blended, the emulsification dispersion was unstable due to blending of L-ascorbic acid glucoside. This is because it could not be prevented. From the above results, it was found that the incorporation of citric acid or citrate into the cosmetic prevented the destabilization of the emulsification dispersion of the cosmetic due to L-ascorbic acid glucoside or the like.

(Soap washing test and wiping test)
In order to evaluate the ease of makeup removal, the soaps of Examples 1, 8, 9 and Comparative Example 6 were subjected to a soap washing test and a wiping test. That is, for each of 10 testers, 2 g of each of the cosmetics of Examples 1, 8, 9 and Comparative Example 6 immediately after the preparation were extended to the face until the whitening disappeared, and were acclimated. Then, after one hour had passed and the water had sufficiently evaporated, the face was washed with soap and the degree of removal of the test cosmetic was evaluated. The evaluation method was a sensory evaluation of the subject. After the face washes, there was no stickiness and an evaluation was made based on whether or not a refreshing and good touch was obtained. In addition, after washing the face, 1 g of cyclopentasiloxane (“KF-995” (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.) was moistened with cotton, and the cosmetic on the face was wiped off and oxidized to the wiped cotton. It was visually evaluated whether or not titanium adhered. When titanium oxide adheres to the cotton, the cotton turns white. The results are shown in Table 10.

  As a result, as shown in Table 10, the cosmetics of Examples 1, 8, and 9 of the present invention obtained many sensory evaluations of “good and refreshed” after washing with soap. It was found that it can be easily washed away. On the other hand, the cosmetic of emulsified cosmetics using a surfactant of the prior art, and the cosmetic of Comparative Example 6 blended with high-viscosity silicone to prevent the outflow of titanium oxide due to sweat, was “sticky” after washing with soap. It was found that it cannot be washed away with soap and remains on the skin even after face washing. This is also clear from the result of the wiping test with cotton, in Comparative Example 6, that the titanium oxide adhered to the cotton after wiping of all the subjects (10 persons).

  Based on the above results, the cosmetics of the present invention blended with a heat-treated titanium oxide using a specific polysaccharide as an emulsifier has excellent stability over time of emulsification and dispersion, and there is little run-off / make-up of titanium oxide due to sweat. It was shown that there was no stickiness during use, and it could be easily washed away with soap after use.

  The present invention is not limited to the description of the embodiment of the invention. Various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the description of the scope of claims.

  The cosmetic of the present invention can be used as a cosmetic for preventing ultraviolet rays.

Claims (16)

Titanium oxide powder, a higher alcohol, an oily component excluding the higher alcohol, a polysaccharide containing glucose, glucuronic acid and rhamnose as a monosaccharide constituting the main chain, and a polysaccharide containing fucose or mannose as a monosaccharide constituting a side chain Containing,
In the cosmetic in an emulsified state in which the content of the polysaccharide is 0.01% by weight to 1% by weight with respect to the total amount of the cosmetic,
The titanium oxide powder is a cosmetic in an emulsified state, wherein the surface is coated with hydrous silicic acid and / or hydrous alumina and then heat-treated at 200 ° C to 900 ° C.   2. The emulsified cosmetic according to claim 1, wherein the titanium oxide powder is subjected to a hydrophobizing treatment after heat treatment.   The emulsified cosmetic according to claim 1 or 2, wherein the hydrophobization treatment is performed by coating the particle surface of the titanium oxide powder with a higher fatty acid or polysiloxane. The emulsified state according to any one of claims 1 to 3, wherein the polysaccharide contains at least a polysaccharide represented by a repeating unit of the following general formula (Formula 1). Cosmetics.
  The titanium oxide powder is contained in an amount of 1 to 20% by weight based on the total amount of the cosmetic, and the higher alcohol is contained in an amount of 0.8 to 20% by weight based on the total amount of the cosmetic. The oily component excluding higher alcohol is contained in an amount of 0.5 to 30% by weight with respect to the total amount of the cosmetic, according to any one of claims 1 to 4. Cosmetics.   The emulsified cosmetic according to any one of claims 1 to 5, wherein the higher alcohol contains two or more higher alcohols having a melting point of 45 ° C or higher.   7. The mixing ratio of the two or more higher alcohols is such that the mixing ratio of the higher alcohol that is the maximum blending amount and the higher alcohol that is the minimum blending amount is 1: 1 to 5: 1. The emulsified cosmetic as described.   The higher alcohol is two or more selected from hexadecanol, octadecanol, eicosanol and docosanol, and each of the two or more selected is contained in an amount of 0.4% by weight or more based on the total amount of the cosmetic. The emulsified cosmetic according to any one of claims 1 to 7, wherein the total amount is 0.8 to 20% by weight based on the total amount of the cosmetic. The oil component is at least as an oil component (A), silicone oil, fluorinated hydrocarbon and its derivatives, hydrocarbon, fatty acid, fatty acid ester of monohydric alcohol, animal and vegetable oil, oxycarboxylic acid ester, fatty acid ester of polyhydric alcohol And having at least one selected from those having a melting point of less than 40 ° C. and liquid wax, and oily component (B) as solid wax, divalent higher alcohol, cyclic alcohol and fatty acid ester thereof, polyhydric alcohol A fatty acid ester having a melting point of 40 ° C. or higher, and one or more selected from phospholipids, the oil component (A) and the oil component (B) are 2: 1 to 50: 1 in a weight ratio. The emulsified cosmetic according to any one of claims 1 to 8, wherein the cosmetic is in an emulsified state.   The oil component (A) is dimethylpolysiloxane, trimethylpolysiloxane, squalane, paraffin (n-hydrocarbon having 16 to 50 carbon atoms alone or a mixture thereof), liquid paraffin, isopropyl palmitate, myristyl myristate. , Isostearyl myristate, glyceryl triethylhexanoate, glyceryl tri (mixed acid of caprylic acid and capric acid), grape seed oil, rosehip oil, sunflower oil, olive oil, avocado oil, macadamia nut oil, medhome oil, shea oil, And the oily component (B) is beeswax, hydrogenated jojoba oil, hydrogenated palm oil, chimyl alcohol, batyl alcohol, cholesterol, cholesteryl stearate, phytosterol. , N-lau One or more selected from yl-L-glutamate di (2-octyldodecyl behenyl phytosteryl), glyceryl trimyristate, glyceryl tristearate, and dipentaerythrityl hexahydroxystearate, the oil component (A) and The emulsified cosmetic according to claim 9, wherein the oily component (B) is used in combination.   The emulsified cosmetic according to any one of claims 1 to 10, wherein the cosmetic does not substantially contain a surfactant.   The citric acid and / or citrate is contained in an amount of 0.01 to 1% by weight based on the total amount of the cosmetic, and the emulsified state according to any one of claims 1 to 11, Cosmetics.   The emulsified cosmetic according to any one of claims 1 to 12, wherein the polysaccharide is subdivided into fine particles having a random particle size. In the method for producing an emulsified cosmetic containing titanium oxide powder, a higher alcohol, an oil component excluding the higher alcohol, and a polysaccharide,
A titanium oxide coating step for coating the surface of the titanium oxide powder with hydrous silicate and / or hydrous alumina, and a heat treatment step for heat-treating the titanium oxide powder coated with the hydrous silicate and / or hydrous alumina at 200 ° C. to 900 ° C. When,
About polysaccharides containing glucose, glucuronic acid and rhamnose as monosaccharides constituting the main chain, and fucose or mannose as monosaccharides constituting the side chain, 0.01% by weight to 1% by weight relative to the total amount of the cosmetic A polysaccharide solution preparation step in which an amount corresponding to is dissolved in water and / or a hydrophilic solvent to form a polysaccharide solution;
The polysaccharide solution, the amount of the higher alcohol corresponding to 0.8% to 20% by weight based on the total amount of the cosmetic, and the oily component of 0.5% to 30% based on the total amount of the cosmetic. Mixing the amount corresponding to wt% and the heat-treated titanium oxide powder corresponding to 1 wt% to 20 wt% of the cosmetic and stirring while heating to 60 ° C or higher, An emulsifying step,
And a cooling step of cooling the emulsified liquid to 40 ° C. or lower while stirring.   The emulsification step includes a first emulsification step of dispersing titanium oxide powder that has not been hydrophobized after the heat treatment in a polyhydric alcohol, and a polysaccharide solution is added to the dispersion obtained in the first emulsification step and mixed. 15. A second emulsification step, and a third emulsification step in which a higher alcohol and an oily component excluding the higher alcohol are added to and mixed with the dispersion obtained in the second emulsification step. The manufacturing method of the cosmetics of the emulsified state of description.   The emulsification step includes a dissolution step of adding a polysaccharide solution to polyhydric alcohol and dissolving the solution, a titanium oxide powder hydrophobized after the heat treatment, a higher alcohol, and a higher alcohol in the solution obtained in the dissolution step. The method for producing a cosmetic in an emulsified state according to claim 14, further comprising a dispersion step of adding and mixing an oily component excluding.