Surface-treated polysaccharide particle, method for producing the same, and use thereof

Abstract

To provide a surface-treated polysaccharide particle that offers excellent hydrophobicity, allows superior feel to be exhibited when applied in cosmetics, exhibits excellent heat and water resistance, and allows easy production, also to provide a method for producing such a surface-treated polysaccharide particle, and further to provide an application of such a surface-treated polysaccharide particle.SOLUTION: A surface-treated polysaccharide particle according to an embodiment of the present invention comprises a surface-treated polysaccharide particle in which the surface of a polysaccharide is hydrophobically treated, the hydrophobic treatment being performed using a hydrophobizing agent and a polyvalent metal ion, the polysaccharide having a phosphate ester group, and the hydrophobizing agent being at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphate esters, sulfate esters, and salts thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to surface-treated polysaccharide particles, a method for producing the same, and uses thereof. [Background technology]

[0002] Conventionally, some cosmetics contain plastic particles for the purpose of imparting moisturizing properties, flexibility, slipperiness, etc. However, in recent years, due to concerns about environmental pollution and effects on the human body, regulations on the use of such petroleum-derived plastic particles, particularly microplastic particles, have become stricter.

[0003] As a result, attention has been focused on particles derived from natural products as alternatives to microplastic particles. Particles made from polysaccharides such as starch and cellulose are known as such naturally occurring particles.

[0004] However, such polysaccharide particles are hydrophilic, and therefore, for example, when a cosmetic containing such polysaccharide particles is applied to the skin, there arises a problem that the cosmetic does not last as long due to a decrease in water repellency.

[0005] In addition, such polysaccharide particles are poorly compatible with oily substances, which means that only small amounts of such polysaccharide particles can be incorporated into cosmetics such as oily creams, and even if they can be incorporated, problems such as separation and increased viscosity occur.

[0006] In order to solve the above problems, it is considered to make particles made of polysaccharides such as starch and cellulose hydrophobic.

[0007] For example, surface-treated starch or cellulose that has good properties suitable for cosmetics such as moist feeling and spreadability has been reported (Patent Document 1), which comprises a first step of primarily treating starch and / or cellulose powder with a dibasic acid anhydride derived from a dibasic acid having two carboxyl groups to convert the powder surface into a -COO alkali metal salt, and a second step of reacting the primarily treated powder with a water-soluble polyvalent metal salt having a metal ion with a valence of 2 to 4, and one or more alkali metal compounds selected from fatty acids having 6 to 22 carbon atoms, amino acids, amino acids bonded to fatty acids having 6 to 22 carbon atoms, water-soluble acidic polysaccharides, water-soluble acidic synthetic polymers, and water-soluble acidic ultraviolet absorbers via the polyvalent metal. Typically, in Example 1 of Patent Document 1, corn starch is primarily treated with octenylsuccinic anhydride, and the resulting primary treatment product is reacted with potassium myristate via aluminum metal to produce corn starch octenylsuccinate aluminum myristate.

[0008] However, when attempting to produce cosmetics and the like using the surface-treated starch or surface-treated cellulose reported in Patent Document 1, a phenomenon in which gelatinization occurs is observed depending on the production conditions. As a result of investigating this phenomenon, it was found that the gelatinization phenomenon occurs significantly when the production process includes a step of heating in hot water.

[0009] Furthermore, for example, a cosmetic composition has been reported as being made from naturally derived materials that can be efficiently produced, spreads well on the skin, and has excellent resistance to spoilage, the cosmetic composition comprising starch particles and a lubricant that contains a fatty acid and that covers at least a portion of the surface of the starch particles, wherein the mass of the lubricant relative to the total mass of the starch particles and the lubricant is 0.3% by mass to 20% by mass (Patent Document 2).

[0010] However, the cosmetic composition reported in Patent Document 2 has a problem in that, in order to produce it, child particles must be attached to the surface of mother particles using a special device called a high-shear mixer or a dry-type composite processing device. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2014-240479 A [Patent Document 2] International Publication No. 2019 / 131755 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above-mentioned problems in the prior art, and its main object is to provide surface-treated polysaccharide particles that have excellent hydrophobicity, can provide an excellent feeling when used in cosmetics, have excellent hot water resistance, and can be easily produced. It is also an object of the present invention to provide a method for producing such surface-treated polysaccharide particles. It is also an object of the present invention to provide uses of such surface-treated polysaccharide particles. [Means for solving the problem]

[0013] [1] The surface-treated polysaccharide particles according to an embodiment of the present invention are surface-treated polysaccharide particles in which the surface of the polysaccharide has been hydrophobized, the hydrophobization being carried out using a hydrophobizing agent and a polyvalent metal ion, the polysaccharide having a phosphate ester group, and the hydrophobizing agent being at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphate esters, sulfate esters, and salts thereof. [2] In the surface-treated polysaccharide particles described in [1] above, the polysaccharide may be a starch having a phosphate ester group. [3] In the surface-treated polysaccharide particles according to the above [1] or [2], the polyvalent metal ion may be at least one selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions. [4] A method for producing surface-treated polysaccharide particles according to an embodiment of the present invention is a method for producing surface-treated polysaccharide particles in which the surface of the polysaccharide has been hydrophobized, comprising using a polysaccharide having a phosphate ester group as the polysaccharide, reacting the polysaccharide with a hydrophobizing agent in the presence of a polyvalent metal ion, and the hydrophobizing agent being at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphate esters, sulfate esters, and salts thereof. [5] In the method for producing surface-treated polysaccharide particles described in [4] above, the polysaccharide having phosphate ester groups may be starch having phosphate ester groups. [6] In the method for producing surface-treated polysaccharide particles described in [4] or [5] above, the polyvalent metal ion may be at least one selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions. [7] A cosmetic preparation according to an embodiment of the present invention comprises the surface-treated polysaccharide particles described in any one of [1] to [3] above. Effect of the Invention

[0014] According to an embodiment of the present invention, it is possible to provide surface-treated polysaccharide particles that have excellent hydrophobicity, can provide an excellent feeling when used in a cosmetic, have excellent hot water resistance, and can be easily produced. It is also possible to provide a method for producing such surface-treated polysaccharide particles. Furthermore, it is also possible to provide uses of such surface-treated polysaccharide particles. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0016] ≪1. Surface-treated polysaccharide particles≫ The surface-treated polysaccharide particles according to an embodiment of the present invention are surface-treated polysaccharide particles in which the surface of the polysaccharide has been hydrophobized using a hydrophobizing agent and polyvalent metal ions.

[0017] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the polysaccharide has a phosphate ester group. By adopting a polysaccharide having a phosphate ester group as the polysaccharide, and combining it with a specific hydrophobizing agent (typically at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphate esters, sulfate esters, and salts thereof), the effects of the present invention can be realized, and in particular, surface-treated polysaccharide particles with excellent hot water resistance can be provided. If the polysaccharide does not have a phosphate ester group, it may gelatinize when exposed to an environment where it is heated in hot water.

[0018] The presence of phosphate ester groups in polysaccharides can be confirmed by any suitable method, such as NMR, IR, MS (mass spectrometry), elemental analysis, or other methods generally used to confirm the presence of specific functional groups.

[0019] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the fact that the polysaccharide has a phosphate ester group can also be supported by using a polysaccharide having a phosphate ester group as a raw material.

[0020] The polysaccharide having phosphate ester groups may be prepared by any suitable method as long as the effects of the present invention are not impaired, such as a method of preparing the polysaccharide by reacting it with a phosphoric acid compound, or a method of preparing a commercially available polysaccharide having phosphate ester groups.

[0021] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the polysaccharide having a phosphate ester group may be of only one type, or of two or more types.

[0022] As the polysaccharide, any appropriate polysaccharide may be used as long as it does not impair the effects of the present invention. Examples of such polysaccharides include starch and cellulose.

[0023] As the polysaccharide having a phosphate ester group, starch having a phosphate ester group is preferable in that it can further exert the effects of the present invention. The starch having a phosphate ester group can be prepared by any appropriate method as long as the effects of the present invention are not impaired. Examples of such methods include a method of preparing the starch by reacting it with a phosphoric acid compound, and a method of preparing a commercially available starch having a phosphate ester group.

[0024] As the starch to be reacted with the phosphoric acid compound, any suitable starch can be adopted within a range that does not impair the effects of the present invention. Examples of starches to be reacted with such phosphoric acid compounds include corn starch, rice starch, glutinous rice starch, wheat starch, potato starch, taro starch, sweet potato starch, tapioca starch, sago starch, amaranth starch, mung bean starch, adzuki bean starch, and acorn starch.

[0025] Modified starch may also be used as the starch to be reacted with the phosphoric acid compound. As the modified starch, any suitable starch generally known as modified starch may be used as long as it does not impair the effects of the present invention. Examples of such modified starches include acetylated adipic acid cross-linked starch and its metal salt, acetylated oxidized starch and its metal salt, acetylated phosphate cross-linked starch and its metal salt, oxidized starch and its metal salt, hydroxypropyl starch and its metal salt, hydroxypropylated phosphate cross-linked starch and its metal salt, carboxymethyl starch and its metal salt, starch acetate and its metal salt, alkenyl succinate starch and its metal salt, starch phosphate and its metal salt, phosphate cross-linked starch and its metal salt, and phosphate monoesterified phosphate cross-linked starch and its metal salt. Examples of the metal salt include divalent or trivalent metal salts such as sodium salt, magnesium salt, calcium salt, potassium salt, and aluminum salt.

[0026] Commercially available starches having phosphate ester groups include, for example, acetylated phosphate cross-linked starch and metal salts thereof, hydroxypropylated phosphate cross-linked starch and metal salts thereof, starch phosphate and metal salts thereof, phosphate cross-linked starch and metal salts thereof, and phosphate monoesterified phosphate cross-linked starch and metal salts thereof, among the above-mentioned modified starches.

[0027] The starch having a phosphate ester group is preferably cross-linked, and particularly preferably phosphate cross-linked starch and its metal salt. When cross-linked starch having a phosphate ester group is used as the polysaccharide having a phosphate ester group, the effect of the present invention can be more effectively exhibited, and in particular, surface-treated polysaccharide particles having excellent hot water resistance can be provided.

[0028] The hydrophobization treatment is carried out using a hydrophobizing agent and a polyvalent metal ion.

[0029] More preferably, such a hydrophobization treatment includes a treatment in which a polysaccharide having a phosphate group is reacted with a hydrophobizing agent in the presence of a polyvalent metal ion.

[0030] The hydrophobizing agent may be at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof. By adopting these specific hydrophobizing agents as the hydrophobizing agent and combining them with specific polysaccharides (typically, polysaccharides having a phosphate ester group), the effects of the present invention can be realized, and in particular, surface-treated polysaccharide particles with excellent hot water resistance can be provided. If the hydrophobizing agent is not at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof, there is a risk of gelatinization when exposed to an environment of heating in hot water.

[0031] Examples of the salt include salts having an organic ion as a cation and salts having a metal ion. Examples of the organic ion include an ammonium ion. Examples of the metal ion include a calcium ion, a sodium ion, a magnesium ion, a potassium ion, and an ammonium ion.

[0032] The hydrophobizing agent preferably has a molecular weight of 5000 or less, more preferably 50 to 1000, further preferably 100 to 600, and particularly preferably 200 to 500, in order to more effectively exert the effects of the present invention. The molecular weight means the number average molecular weight (Mn) for polymers, and the chemical formula weight for substances other than polymers. The number average molecular weight (Mn) is a value measured in terms of polystyrene by gel permeation chromatography.

[0033] In order to further exert the effects of the present invention, the carboxylic acid preferably has a carbon number of 6 to 30, more preferably 8 to 25, and further preferably 10 to 20. The carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid.

[0034] Examples of monovalent carboxylic acids include caproic acid, enanthic acid, caprylic acid, octylic acid, pelargonic acid, capric acid, undecylenic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, isostearic acid, oleic acid, vaccenic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, oxystearic acid, arachidic acid, mead acid, arachidonic acid, eicosapentaenoic acid, behenic acid, docosahexaenoic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, coconut oil fatty acid, and palm oil fatty acid.

[0035] Examples of polycarboxylic acids include octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, and eicosane dioic acid.

[0036] Examples of amino acids or derivatives thereof include sarcosine derivatives such as lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, and coconut oil fatty acid sarcosine; glutamic acid derivatives such as lauroyl glutamic acid, myristoyl glutamic acid, palmitoyl glutamic acid, stearoyl glutamic acid, coconut oil fatty acid acyl glutamic acid, cocoyl glutamic acid, acyl glutamic acid, and dilauroyl glutamic acid; glycine derivatives such as lauroyl glycine, myristoyl glycine, palmitoyl glycine, palmitoyl methyl glycine, coconut oil fatty acid acyl glycine, and cocoyl glycine; lauryl methyl alanine, myristoyl methyl alanine, cocoyl alanine, and coconut oil fatty acid. alanine derivatives such as fatty methylalanine; lysine derivatives such as lauroyl lysine, myristnoyl lysine, palmitoyl lysine, steanoyl lysine, oleyl lysine, and acylated lysine; aspartic acid derivatives such as lauroyl aspartic acid, myristyl aspartic acid, palmitoyl aspartic acid, and stearoyl aspartic acid; taurine derivatives such as lauroyl taurine, lauroyl methyl taurine, myristoyl taurine, myristoyl methyl taurine, palmitoyl taurine, palmitoyl methyl taurine, stearoyl taurine, and stearoyl methyl taurine; and proline derivatives such as lauroyl proline, myristoyl proline, and palmitoyl proline.

[0037] Examples of the phosphate ester include polyoxyalkylene alkyl ether phosphate ester and alkyl phosphate ester. Examples of the polyoxyalkylene alkyl ether phosphate ester include polyoxyethylene (2) stearyl ether phosphate ester. Examples of the alkyl phosphate ester include octyl phosphate, nonyl phosphate, decyl phosphate, undecyl phosphate, lauryl phosphate, myristyl phosphate, cetyl phosphate, and stearyl phosphate.

[0038] Examples of sulfates include alkyl sulfates, polyoxyethylene aryl ether sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and polyoxyethylene castor oil ether sulfates.

[0039] Examples of alkyl sulfates include lauryl sulfate, myristyl sulfate, cetyl sulfate, stearyl sulfate, and oleyl sulfate.

[0040] Examples of the polyoxyethylene aryl ether sulfate include polyoxyethylene polycyclic phenyl ether sulfate and polyoxyethylene aryl ether sulfate.

[0041] Examples of polyoxyalkylene alkyl ether sulfates include polyoxyethylene lauryl ether sulfate, polyoxyethylene myristyl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, polyoxyethylene oleyl ether sulfate, sulfate of a polyoxyethylene-polyoxypropylene block copolymer, sulfate of a polyoxyethylene-polyoxybutylene block copolymer, and sulfate of an alkyl ether of a polyoxyethylene-polyoxypropylene block copolymer.

[0042] Examples of polyoxyalkylene alkenyl ether sulfates include sulfates of alkenyl ether of polyoxyethylene-polyoxyalkylene block copolymers.

[0043] An example of the polyoxyethylene castor oil ether sulfate is polyoxyethylene castor oil ether sulfate.

[0044] The polyvalent metal ions used in the hydrophobization treatment may be one type or two or more types. Examples of such polyvalent metal ions include aluminum ions, calcium ions, magnesium ions, zinc ions, strontium ions, barium ions, titanium ions, zirconium ions, iron ions, copper ions, and tin ions. Among these polyvalent metal ions, at least one selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions is preferred in terms of being able to more effectively exhibit the effects of the present invention, and aluminum ions are particularly preferred.

[0045] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the polyvalent metal ion used in the hydrophobization treatment is particularly preferably an aluminum ion. When an aluminum ion is used as the polyvalent metal ion used in the hydrophobization treatment, it is possible to exhibit very excellent hydrophobicity (for example, a water contact angle of 120 degrees or more), and the very excellent stability of the hydrophobicity over time can also be excellent.

[0046] The polyvalent metal ions used in the hydrophobization treatment can be used in the form of a water-soluble polyvalent metal salt. Any appropriate salt can be used as such a salt as long as it does not impair the effects of the present invention. In terms of being able to more effectively exhibit the effects of the present invention, such salts include halides and sulfates.

[0047] As a result of the hydrophobization treatment, the surface-treated polysaccharide particles according to the embodiment of the present invention preferably have a structure in which an organic group derived from a hydrophobizing agent, which is at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof, is attached to the surface of a polysaccharide having a phosphate group via a polyvalent metal derived from a polyvalent metal ion, more preferably, an organic group derived from a hydrophobizing agent, which is at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof, is attached to the surface of a starch having a phosphate group via a polyvalent metal derived from at least one polyvalent metal ion selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions, and even more preferably, an organic group derived from a hydrophobizing agent, which is at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof, is attached to the surface of a crosslinked starch having a phosphate group via aluminum. The surface-treated polysaccharide particles according to an embodiment of the present invention have such a structure, and therefore have excellent hydrophobicity, excellent usability when used in cosmetics, and excellent hot water resistance.

[0048] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the amount of the hydrophobizing agent relative to the polysaccharide having a phosphate ester group may be any appropriate amount within a range that does not impair the effects of the present invention. In order to further exert the effects of the present invention, the amount of the hydrophobizing agent relative to the polysaccharide having a phosphate ester group is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 7.5% by mass.

[0049] In the surface-treated polysaccharide particles according to the embodiment of the present invention, the amount of the water-soluble polyvalent metal salt in the hydrophobization treatment may be any appropriate amount within a range that does not impair the effects of the present invention. In order to further exhibit the effects of the present invention, the amount of the water-soluble polyvalent metal salt is preferably 0.4 mol to 20 mol, more preferably 0.5 mol to 15 mol, relative to 1 mol of the hydrophobizing agent.

[0050] 2. Manufacturing method of surface-treated polysaccharide particles The surface-treated polysaccharide particles according to the embodiment of the present invention described above can be produced by any appropriate method as long as the effects of the present invention are not impaired. A preferred embodiment of such a production method is the method for producing the surface-treated polysaccharide particles according to the embodiment of the present invention.

[0051] A method for producing surface-treated polysaccharide particles according to an embodiment of the present invention is a method for producing surface-treated polysaccharide particles in which the surface of the polysaccharide has been hydrophobized, in which a polysaccharide having a phosphate ester group is used as the polysaccharide, and the polysaccharide is reacted with a hydrophobizing agent in the presence of a polyvalent metal ion, the hydrophobizing agent being at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphate esters, sulfate esters, and salts thereof.

[0052] In the method for producing surface-treated polysaccharide particles according to an embodiment of the present invention, the hydrophobization treatment involves reacting a polysaccharide having a phosphate group with at least one hydrophobizing agent selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof in the presence of polyvalent metal ions. Specifically, the polysaccharide having a phosphate group is dispersed in water or an organic solvent containing water, and a hydrophobizing agent selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof or a hydrophobizing agent previously dissolved in water or the like is added, and then a polyvalent metal ion is added in the form of, for example, a water-soluble polyvalent metal salt. This results in a structure in which an organic group derived from at least one hydrophobizing agent selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof is attached to the surface of a polysaccharide having a phosphate group via a polyvalent metal derived from a polyvalent metal ion, more preferably, an organic group derived from at least one hydrophobizing agent selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof is attached to the surface of a starch having a phosphate group via a polyvalent metal derived from at least one polyvalent metal ion selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions, and even more preferably, an organic group derived from at least one hydrophobizing agent selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof is attached to the surface of a crosslinked starch having a phosphate group via aluminum. According to the method for producing surface-treated polysaccharide particles according to an embodiment of the present invention, surface-treated polysaccharide particles having such a structure can be easily produced, and the surface-treated polysaccharide particles produced have excellent hydrophobicity, can provide an excellent feel when used in cosmetics, and have excellent hot water resistance.

[0053] For the polysaccharide having a phosphate group, the polyvalent metal ion, the water-soluble polyvalent metal salt, and the hydrophobizing agent, the explanations in <<1. Surface-treated polysaccharide particles>> can be used.

[0054] Examples of the water or water-containing organic solvent in which the polysaccharide having a phosphate group is dispersed include water and a mixed solvent of water and alcohol.

[0055] In the method for producing surface-treated polysaccharide particles according to the embodiment of the present invention, the amount of the hydrophobizing agent used relative to the polysaccharide having a phosphate ester group may be any appropriate amount within a range that does not impair the effects of the present invention. In order to further exert the effects of the present invention, the amount of the hydrophobizing agent used relative to the polysaccharide having a phosphate ester group is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5.0% by mass.

[0056] In the method for producing surface-treated polysaccharide particles according to the embodiment of the present invention, the amount of the water-soluble polyvalent metal salt used may be any appropriate amount within the range that does not impair the effects of the present invention. In order to further exert the effects of the present invention, the amount of the water-soluble polyvalent metal salt used is preferably 0.4 mol to 20 mol, more preferably 0.5 mol to 15 mol, relative to 1 mol of the hydrophobizing agent.

[0057] In the hydrophobization treatment, any appropriate treatment time can be adopted as long as the effects of the present invention are not impaired. In terms of being able to further exert the effects of the present invention, the treatment time of the hydrophobization treatment is preferably 1 minute to 24 hours.

[0058] In the hydrophobization treatment, any appropriate treatment temperature can be adopted as the treatment temperature within a range that does not impair the effects of the present invention.

[0059] After the hydrophobization treatment, the surface-treated polysaccharide particles obtained may be dried. As the drying method, any appropriate drying method may be adopted as long as it does not impair the effects of the present invention. As such a drying method, for example, a hot air circulation type dryer, spray drying, fluidized bed drying, tray drying, or freeze drying may be used.

[0060] 3. Uses of surface-treated polysaccharide particles The surface-treated polysaccharide particles according to the embodiment of the present invention may be used in any suitable application in which the effects of the present invention can be utilized. Among such applications, the surface-treated polysaccharide particles according to the embodiment of the present invention may be preferably used as an additive for cosmetics. That is, the cosmetics according to the embodiment of the present invention contain the surface-treated polysaccharide particles according to the embodiment of the present invention.

[0061] The content of the surface-treated polysaccharide particles according to the embodiment of the present invention in the cosmetic according to the embodiment of the present invention can be appropriately set depending on the type of the particles. Such a content is preferably 0.01% by mass to 99.99% by mass, more preferably 0.1% by mass to 99.9% by mass, even more preferably 1% by mass to 99% by mass, and particularly preferably 5% by mass to 95% by mass.

[0062] As the formulation of the cosmetic according to the embodiment of the present invention, any appropriate formulation may be adopted as long as it does not impair the effects of the present invention. Examples of such formulations include water-based, solubilized, oil-in-water, water-in-oil, and oil-based.

[0063] Examples of cosmetics according to the present invention include cleansing cosmetics such as soap, body shampoo, facial cleansing cream, scrub cleanser, and toothpaste; makeup cosmetics such as face powders (loose powder, pressed powder, etc.), foundations (powder foundation, liquid foundation, emulsion foundation, etc.), lipstick, lip balm, blusher, eye and brow cosmetics (eye shadow, eyeliner, mascara, etc.), and nail polish; lotions such as pre-shave lotion and body lotion; topical body preparations such as body powder and baby powder; skin care agents such as lotions, creams, and emulsions (cosmetic emulsions); antiperspirants (liquid antiperspirants, solid antiperspirants, cream antiperspirants, etc.); packs; hair washing cosmetics; hair dyes; hair styling products; aromatic cosmetics; bath products; sunscreen products; tanning products; and shaving cream.

[0064] Cosmetics according to the embodiments of the present invention can contain commonly used base ingredients or additives according to the purpose, as long as the effects of the present invention are not impaired. Examples of such base ingredients or additives include water, lower alcohols (alcohols having 5 or less carbon atoms), fats and oils or waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymeric compounds, coloring materials, fragrances, clay minerals, preservatives / bactericides, antioxidants, UV absorbers, and specially formulated additives.

[0065] Examples of oils, fats, and waxes include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame fat, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, macadamia nut oil, mink oil, egg yolk oil, Japan wax, coconut oil, rosehip oil, hardened oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, and lanolin.

[0066] Examples of the hydrocarbon include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, and squalane.

[0067] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids.

[0068] Examples of higher alcohols include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, and decyltetradecanol.

[0069] Examples of sterols include cholesterol, dihydrocholesterol, and phytocholesterol.

[0070] Examples of fatty acid esters include linoleic acid esters such as ethyl linoleate; lanolin fatty acid esters such as isopropyl lanolinate; lauric acid esters such as hexyl laurate; myristate esters such as isopropyl myristate, myristyl myristate, cetyl myristate, and octyldodecyl myristate; oleic acid esters such as decyl oleate and octyldodecyl oleate; dimethyloctanoic acid esters such as hexyldecyl dimethyloctanoate; and isooctanoic acid esters such as cetyl dimethyloctanoate. isooctanoic acid esters such as cetyl (2-ethylhexanoate); palmitic acid esters such as decyl palmitate; cyclic alcohol fatty acid esters such as glyceryl trimyristate, tri(caprylic / capric)glycerin, propylene glycol dioleate, glyceryl triisostearate, glyceryl triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate, cholesteryl isostearate, and cholesteryl 12-hydroxystearate.

[0071] Examples of metal soaps include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.

[0072] Examples of moisturizing agents include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidone carboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylitol, and maltitol.

[0073] Examples of surfactants include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acylglutamates, and phosphate salts; cationic surfactants such as amine salts and quaternary ammonium salts; amphoteric surfactants such as betaine types, amino acid types, imidazoline types, and lecithin; and nonionic surfactants such as fatty acid monoglycerides, polyethylene glycols, propylene glycol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, and ethylene oxide condensates.

[0074] Examples of the polymer compound include natural polymer compounds such as gum arabic, gum tragacanth, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, and casein; semi-synthetic polymer compounds such as sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropylcellulose, and crystalline cellulose; and synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles, poly(meth)acrylic acid ester particles (e.g., polymethyl methacrylate particles), polystyrene particles, silicone particles, urethane particles, polyethylene particles, and silica particles.

[0075] Examples of raw color materials include inorganic pigments such as iron oxide (red iron oxide, yellow iron oxide, black iron oxide, etc.), ultramarine, konjou, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, and ceramic powder; and tar dyes such as azo dyes, nitro dyes, nitroso dyes, xanthene dyes, quinoline dyes, anthraquinoline dyes, indigo dyes, triphenylmethane dyes, phthalocyanine dyes, and pyrene dyes.

[0076] Examples of the fragrance include anisaldehyde, benzyl acetate, and geraniol.

[0077] Examples of clay minerals include components that combine several functions such as an extender pigment and an adsorbent, such as talc, mica, sericite, titanium sericite (sericite coated with titanium oxide), muscovite, and VEEGUM (registered trademark) manufactured by Vanderbilt.

[0078] Examples of preservatives and disinfectants include methylparaben, ethylparaben, propylparaben, benzalkonium, and benzethonium.

[0079] Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and tocopherol.

[0080] Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle iron oxide, and fine particle zirconium oxide; and organic ultraviolet absorbers such as benzoic acid, para-aminobenzoic acid, anthranilic acid, salicylic acid, cinnamic acid, benzophenone, and dibenzoylmethane.

[0081] Examples of specially formulated additives include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, and prednisone; vitamins such as vitamin A, vitamin B, vitamin C, and vitamin E; skin astringents such as citric acid, tartaric acid, lactic acid, aluminum chloride, aluminum potassium sulfate, chlorohydroxyaluminum allantoin, zinc paraphenolsulfonate, and zinc sulfate; hair growth promoters such as cantharides tincture, capsicum tincture, ginger tincture, Swertia japonica extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid glyceride, vitamin E, estrogen, and photosensitizers; and skin whitening agents such as magnesium-L-ascorbyl phosphate and kojic acid. EXAMPLES

[0082] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0083] <Evaluation of hydrophobicity> The evaluation of hydrophobicity was carried out in an environment of temperature: 23±1° C. and humidity: 50±5%, and distilled water was used as the water. (Hydrophobic) The hydrophobicity of the particles to be measured was evaluated based on the contact angle (degrees) with water. Specifically, a double-sided tape (trade name "Nistack (registered trademark) NW-10S" manufactured by Nichiban Co., Ltd.) was attached to a slide glass, and 0.5 g of the particles to be measured was placed on the double-sided tape and lightly rubbed against the adhesive surface. After that, excess particles were removed with a blower to prepare a test sample for measuring the contact angle with water. The contact angle of the test sample with water was measured under the following measurement conditions using a contact angle measuring device (product name "Drop Master face", manufactured by Kyowa Interface Science Co., Ltd.) based on the sessile drop method (static contact angle) and JIS-R3257-1999. In detail, the contact angle with water immediately after one drop (1 μL to 5 μL) of distilled water was dropped with a syringe onto the surface of the particle to be measured (contact angle A), and the contact angle with water 180 seconds after one drop (1 μL to 5 μL) of distilled water was dropped with a syringe (contact angle B) were measured. The measurement was performed three times for each test sample, and the average value was taken as the contact angle of the particle to be measured with water. When the contact angle with respect to water 180 seconds after dropping (contact angle B) was 80 degrees or more, it was evaluated as ◯, and when it was less than 80 degrees, it was evaluated as ×. (Stability over time) The stability over time of the particles to be measured was evaluated based on the contact angle with water measured during the hydrophobicity evaluation. Specifically, the contact angle with water 180 seconds after dropping (contact angle B) divided by the contact angle with water immediately after dropping (contact angle A) (contact angle B / contact angle A) was evaluated as 0.75 or more, and was evaluated as x when it was less than 0.75.

[0084] <Evaluation of Usability> Two expert panelists rubbed the particles to be measured between their thumb and index finger and judged their smoothness as follows: <Evaluation criteria> Good: Feels smooth and does not feel squeaky. ×: The feel of the surface is poor, such as smoothness, and a squeaky feeling is felt.

[0085] <Evaluation of hot water resistance> The hot water resistance of the particles to be measured was evaluated based on the presence or absence of gelatinization of the dispersion when dispersed in hot water. Specifically, a 10% by mass aqueous dispersion of the particles to be measured was prepared, heated at 80°C for 30 minutes, and then it was confirmed whether gelatinization had occurred. If gelatinization did not occur, it was marked with an ◯, and if gelatinization occurred, it was marked with an ×.

[0086] [Production Example 1] A container was charged with 121 parts by mass of ion-exchanged water, 35 parts by mass of sodium chloride (manufactured by Ako Kasei Co., Ltd., product name "Mishio"), and 1.2 parts by mass of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature to dissolve the ingredients, producing an aqueous solution. 100 parts by mass of rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow") was added to the aqueous solution, and the mixture was stirred and dispersed at room temperature using a stirring blade at a rotation speed of 425 rpm, producing a rice starch dispersion. 5 parts by mass of sodium trimetaphosphate (manufactured by Yoneyama Chemical Industry Co., Ltd.) and 0.54 parts by mass of Orientase 22BF (manufactured by HBI Corporation) as an alkaline protease were added to the prepared rice starch dispersion liquid, and dissolved by stirring at room temperature. Next, the mixture was stirred for 18 hours using a stirrer while maintaining the temperature at 40°C, and reacted. After 18 hours, the obtained dispersion liquid was neutralized by adding hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 20% hydrochloric acid), and the neutralized dispersion liquid was put into a pressure filtration device (manufactured by Advantec Co., Ltd., product name "KST-293-16-UH") and pressure filtered. After pressure filtration, the mixture was washed with ion-exchanged water and further dehydrated to obtain a powder. The obtained powder was dried at 80°C for 24 hours using a vacuum constant temperature dryer (manufactured by Yamato Scientific Co., Ltd., product name "DP43") to obtain phosphate cross-linked starch (1). The resulting phosphate cross-linked starch (1) was analyzed, and it was confirmed that it had phosphate ester groups.

[0087] [Example 1] 1.0 g of the phosphate cross-linked starch (1) prepared in Production Example 1, 0.035 g of sodium laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydrophobizing agent, and 3.3 g of ion-exchanged water were weighed out and placed in a container. The phosphate cross-linked starch (1) was dispersed in water using an ultrasonic cleaner to dissolve the hydrophobizing agent, thereby obtaining a slurry. Next, 1 g of a 20% by mass aqueous solution of aluminum sulfate 14-18 hydrate was added to the resulting slurry while stirring it, followed by filtration, washing with water, and drying at 80°C for 6 hours or more using a hot air circulation dryer, followed by pulverization and mesh classification to obtain surface-treated polysaccharide particles (1). The results are shown in Table 1.

[0088] [Example 2] Surface-treated polysaccharide particles (2) were obtained in the same manner as in Example 1, except that sodium laurate was replaced with potassium myristate (manufactured by Nikko Chemicals Co., Ltd., trade name "potassium myristate MK-140") as the hydrophobizing agent. The results are shown in Table 1.

[0089] [Example 3] Surface-treated polysaccharide particles (3) were obtained in the same manner as in Example 1, except that sodium lauroyl glutamate (manufactured by Asahi Kasei Finechem Corporation, product name "AminoSurfact (registered trademark) ALMS-P1") was used as the hydrophobizing agent instead of sodium laurate. The results are shown in Table 1.

[0090] [Example 4] Surface-treated polysaccharide particles (4) were obtained in the same manner as in Example 1, except that sodium laurate was replaced with sodium dilauroyl glutamate lysine (manufactured by Asahi Kasei Finechem Corporation, product name "Pellicer L-30", an aqueous solution with a purity of approximately 29%) as the hydrophobizing agent. The results are shown in Table 1.

[0091] [Example 5] Surface-treated polysaccharide particles (5) were obtained in the same manner as in Example 1, except that sodium lauryl phosphate (manufactured by Nikko Chemicals Co., Ltd., product name "SLP-N") was used instead of sodium laurate as the hydrophobizing agent. The results are shown in Table 1.

[0092] [Example 6] Surface-treated polysaccharide particles (6) were obtained in the same manner as in Example 1, except that sodium lauryl sulfate (manufactured by Kao Corporation, product name "EMAL 2F Needle") was used instead of sodium laurate as the hydrophobizing agent. The results are shown in Table 1.

[0093] [Example 7] Surface-treated polysaccharide particles (7) were obtained in the same manner as in Example 1, except that the 20% by mass aqueous solution of aluminum sulfate 14-18 hydrate was changed to a 20% by mass aqueous solution of calcium chloride. The results are shown in Table 1.

[0094] [Example 8] Surface-treated polysaccharide particles (8) were obtained in the same manner as in Example 1, except that the 20% by mass aqueous solution of aluminum sulfate 14-18 hydrate was changed to a 20% by mass aqueous solution of magnesium chloride. The results are shown in Table 1.

[0095] [Example 9] Surface-treated polysaccharide particles (9) were obtained in the same manner as in Example 1, except that the 20% by mass aqueous solution of aluminum sulfate 14-18 hydrate was changed to a 20% by mass aqueous solution of zinc chloride. The results are shown in Table 1.

[0096] [Comparative Example 1] Surface-treated polysaccharide particles (C1) were obtained in the same manner as in Example 1, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0097] [Comparative Example 2] Surface-treated polysaccharide particles (C2) were obtained in the same manner as in Example 2, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0098] [Comparative Example 3] Surface-treated polysaccharide particles (C3) were obtained in the same manner as in Example 3, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0099] [Comparative Example 4] Surface-treated polysaccharide particles (C4) were obtained in the same manner as in Example 4, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0100] [Comparative Example 5] Surface-treated polysaccharide particles (C5) were obtained in the same manner as in Example 5, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0101] [Comparative Example 6] Surface-treated polysaccharide particles (C6) were obtained in the same manner as in Example 6, except that the phosphate cross-linked starch (1) was changed to rice starch (manufactured by Joetsu Starch Co., Ltd., product name "Fine Snow"). The results are shown in Table 1.

[0102] [Comparative Example 7] Surface-treated polysaccharide particles (C7) were obtained in the same manner as in Example 1, except that sodium laurate was replaced with sodium tetradecene sulfone (manufactured by Kao Corporation, product name "K Lipolan PJ-400CJ"). The results are shown in Table 1. When an attempt was made to measure the contact angle, the sample immediately absorbed water, and was therefore rated as "measurable."

[0103] [Comparative Example 8] 1.0 g of sodium starch octenylsuccinate (manufactured by Nippon Starch Chemical Co., Ltd., product name "Nyuka W"), 0.023 g of sodium lauroyl glutamate as a hydrophobizing agent (manufactured by Asahi Kasei Finechem Corporation, product name "AminoSurfact (registered trademark) ALMS-P1"), and 2.027 g of ion-exchanged water were weighed out, and the sodium starch octenylsuccinate was dispersed in the water using an ultrasonic cleaner to dissolve the hydrophobizing agent, thereby obtaining a slurry. Next, 0.1 g of 27.2% aqueous aluminum chloride solution was added to the resulting slurry while stirring it, and the slurry was then filtered, washed with water, and dried at 80°C for 6 hours or more using a hot air circulation dryer, followed by pulverization and mesh classification to obtain surface-treated polysaccharide particles (C8). The results are shown in Table 1.

[0104] [Table 1] [Industrial Applicability]

[0105] The surface-treated polysaccharide particles according to an embodiment of the present invention and the surface-treated polysaccharide particles obtained by the production method according to an embodiment of the present invention have excellent hydrophobicity, can provide an excellent feeling when used in cosmetics, and have excellent hot water resistance, so that they can be suitably used in cosmetics.

Claims

1. A surface-treated polysaccharide particle in which the surface of the polysaccharide is hydrophobized, the hydrophobization treatment is carried out using a hydrophobizing agent and a polyvalent metal ion; The polysaccharide has a phosphate ester group, the hydrophobizing agent is at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof; Surface-treated polysaccharide particles.

2. 2. The surface-treated polysaccharide particles of claim 1, wherein the polysaccharide is a starch having phosphate ester groups.

3. 2. The surface-treated polysaccharide particles according to claim 1, wherein the polyvalent metal ion is at least one selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions.

4. A method for producing surface-treated polysaccharide particles in which the surface of a polysaccharide is hydrophobized, comprising the steps of: A polysaccharide having a phosphate ester group is used as the polysaccharide, reacting the polysaccharide with a hydrophobizing agent in the presence of a polyvalent metal ion; the hydrophobizing agent is at least one selected from the group consisting of carboxylic acids, amino acids or derivatives thereof, phosphates, sulfates, and salts thereof; Method for producing surface-treated polysaccharide particles.

5. The method for producing surface-treated polysaccharide particles according to claim 4 , wherein the polysaccharide having a phosphate ester group is a starch having a phosphate ester group.

6. 5. The method for producing surface-treated polysaccharide particles according to claim 4, wherein the polyvalent metal ion is at least one selected from the group consisting of aluminum ions, calcium ions, magnesium ions, and zinc ions.

7. A cosmetic preparation comprising the surface-treated polysaccharide particles according to any one of claims 1 to 3.

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