JP2003252903A - Cellulose derivative particle, its manufacturing method and cosmetic using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose derivative particle having a spherical shape and hydrophilicity so that it can give a cosmetic a wet feeling and a smooth feeling and to provide its manufacturing method and a cosmetic using it. <P>SOLUTION: The cellulose derivative particle has such a structure that a part or all of the hydroxy groups is substituted with a carboxy group of a polyvalent carboxylic acid via an ester bond and its shape is spherical. When the cellulose derivative particle is mixed in the cosmetic, it gives a wet feeling due to hydrophilicity and a smooth feeling due to the spherical shape and further enhances dispersion of the composition and spread of the cosmetic. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cellulose derivative particle having a carboxyl group, a method for producing the same, and a cosmetic using the same. More specifically, the present invention provides
In order to improve the moist feeling, a cellulose derivative particle having a spherical shape and having hydrophilicity and a method for producing the same,
The present invention relates to a cosmetic using cellulose derivative particles.

[0002]

2. Description of the Related Art Cosmetics having a cream-like, gel-like or liquid-like (collectively referred to as liquid) dosage form are
A composition in which various compounds are mixed in a dispersion medium such as water or alcohol, and in the composition, a dispersion stabilizer that disperses each compound compounded, a shape-retaining agent that stably maintains the properties, Various polymer materials are used as moisturizers for adjusting moisturizing.

Currently, such polymer materials include water-soluble cellulose derivatives such as cellulose and carboxymethylcellulose salts, synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer and polyethylene glycol, xanthan gum, There are natural high molecular polysaccharides such as hyaluronate. Among them, natural high molecular polysaccharides are ideal because they are naturally derived, but most of them are water-soluble. Many give a unique sticky feeling when applied to. Also, some of them are very expensive because they are naturally extracted components, and moisturizing components derived from animals are becoming disliked due to the problem of mad cow disease. From such a background, it is required to use a relatively general-purpose plant-based raw material as a dispersion stabilizer, a shape-retaining agent, a moisturizing agent, etc. so as to provide a cosmetic having no sticky feeling peculiar to a water-soluble polymer. .

In connection with such a demand, Japanese Patent Laid-Open No. 11-
No. 116427 shows that spherical powdered cellulose fine particles are blended with a cosmetic to give a squeaky and silky feel when the cosmetic is used. Further, in JP-A-5-32519, cellulose particles obtained by hydrolysis and physical pulverization without regenerating natural cellulose are used as essential components, and the fat content is lower than that of conventional cosmetic compositions. It is shown that the composition can achieve creamy or milky properties. Furthermore, JP-A-5-
Japanese Patent No. 178723 discloses that a water-soluble pressure-sensitive adhesive containing an example in which cellulose is hydroxylated improves the feeling of use.

On the other hand, as conventionally known cosmetics, emulsions, creams and the like are blended with inorganic powders such as talc, titanium oxide and silicon dioxide, and organic powders such as nylon powder and polyethylene to make them sticky. There are things that produce a controlled, dry feel.

[0006]

However, the one disclosed in Japanese Patent Laid-Open No. 11-116427 is characterized in that it has a free-flowing feel, so that it has no moisturizing property and is neutral, so that it is stable. There is a problem that it can not be dispersed in. In addition, since those disclosed in JP-A-5-32519 have variations in particle size, the dispersibility of the cosmetic composition is insufficient and a rough feeling is produced depending on the composition, so that it should be applied in a wide composition range. However, the cellulose material has no moisturizing property. Further, the one disclosed in JP-A-5-178723 has a problem that it has no charge repulsion and cannot be stably dispersed because a neutral functional group is introduced into hydroxylated cellulose. . Furthermore, when various powders are blended in milky lotion, cream or the like so as to obtain a texture improving effect, the powders may directly rub against each other to cause a heavy tingling sensation. When blended, the feel-improving effect cannot be obtained, and depending on the hardness of the powder, there is a problem that the powder directly hits the skin and the irritation to the skin is too strong, causing pain and discomfort.

In view of such circumstances, the present invention provides a cellulose derivative particle having a spherical shape and hydrophilicity, a method for producing the same, and a cosmetic composition using the same so as to give the cosmetic composition a moist feeling and a dry feeling at the same time. The purpose is to do.

[0008]

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found cellulose derivative particles in which a polyvalent carboxylic acid is introduced into cellulose and the shape of which is spherical, and further, When the cellulose derivative particles were blended in a cosmetic, it was found that it imparts a moist feeling due to hydrophilicity and a smooth feeling due to a spherical shape at the same time, and further improves the dispersion stability of the composition and the effect of cosmetics, thus completing the present invention. Came to do.

That is, the cellulose derivative particles according to claim 1 of the present invention have a structure in which a part or all of the hydroxyl groups of cellulose are substituted with the carboxyl groups of the polycarboxylic acid by an ester bond, and the shape is The cellulose derivative particles according to claim 2 of the present invention have a spherical shape in which a part or all of the hydroxyl groups of cellulose are substituted with a carboxyl group of a polycarboxylic acid by an ester bond and the remaining carboxyl groups are It has a structure in which some or all are metal-chlorided with an alkali metal or an alkaline earth metal, and is spherical in shape and insoluble in water.

The cellulose derivative particles of the present invention have an average particle size in the wet state of 1 to 1 as described in claims 3 to 6.
1000 μm, cation exchange group capacity is 0.1
~ 3.0 meq / g,

[Equation 2] Circularity = Perimeter of circle calculated from equivalent radius of circle /
The circularity represented by the perimeter of the particle projection image is 0.9 to 1.0, and the substituted polycarboxylic acid is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid, Dodecyl succinic acid, glutaric acid, adipic acid and maleic acid are preferred.

Further, in the method for producing cellulose derivative particles according to claim 7 of the present invention, the cellulose is moistened with an acid anhydride so that the cellulose derivative particles according to any one of claims 1 to 6 can be produced. Is added to synthesize.

Furthermore, a cosmetic using the cellulose derivative particles according to claim 8 of the present invention contains the cellulose derivative particles according to any one of claims 1 to 6, and the cosmetic composition according to the present invention. A cosmetic using the cellulose derivative particles as set forth in Item 9, wherein the blending amount of the cellulose derivative particles as set forth in any one of Claims 1 to 6 is 0.01 to the total composition.
25% by weight, and the cosmetic using the cellulose derivative particles according to claim 10 of the present invention is defined by claim 1
The cellulose derivative particles according to any one of 6 above are blended in an amount of 0.01 to 10% by weight based on the total composition, and are prepared in a liquid state. Further, the cosmetic using the cellulose derivative particles may be prepared as a scrubbing agent as described in claim 11.

As described above, according to the cellulose derivative particles of claims 1 to 6, since the cellulose derivative has a structure in which a part or all of the hydroxyl groups of cellulose are substituted with the carboxyl group of the polyvalent carboxylic acid by an ester bond, Can have sex. Here, when a monobasic carboxylic acid having only one carboxyl group with respect to the hydroxyl group of cellulose is used, it cannot have hydrophilicity. Further, since it has a spherical shape, it can have a silky feel when used in a product used on the skin. Furthermore, since it has a structure in which it is metal-chlorided by an alkali metal or an alkaline earth metal and has a spherical shape and is insoluble in water, it can be easily commercialized by appropriately adjusting the pH.

The average particle size in the wet state is 1 to 1000 μm.
m, the cation exchange group capacity is 0.1 to 3.0
meq / g, the circularity is 0.9 to 1.0, or the substituted polycarboxylic acid is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid, Dodecyl succinic acid, glutaric acid, adipic acid, and maleic acid can be suitably used for products used on the skin.

According to the method for producing the cellulose derivative particles of claim 7, since the cellulose is wetted and the acid anhydride is added, the hydroxyl group of the cellulose and the acid anhydride are appropriately reacted to introduce the polycarboxylic acid. The cellulose derivative particles can be reliably manufactured.

According to the cosmetic using the cellulose derivative particles of claims 8 to 11, since the cellulose derivative is appropriately blended, a moist feeling due to hydrophilicity and a smooth feeling due to a spherical shape are provided at the same time, and moreover, polycarboxylic acid is used. It is possible to stably disperse the composition with charge repulsion due to an acid and a spherical shape, and improve the novi of makeup.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cellulose derivative particles of the present invention, the method for producing the cellulose derivative particles, and the cosmetics using the cellulose derivative particles will be described in order.

The cellulose derivative particles of the present invention have an average particle diameter of 1-1000 μm,
It has a structure in which a part or all of the hydroxyl groups of cellulose are replaced with the carboxyl groups of polyvalent carboxylic acid by an ester bond, and has a spherical shape. Further, a part or all of the remaining carboxyl group may have a structure in which metal chloride is formed by an alkali metal or an alkaline earth metal, and the shape may be spherical and insoluble in water. Here, the polycarboxylic acid having a carboxyl group is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid, dodecylsuccinic acid, glutaric acid, adipic acid, maleic acid, etc. A tribasic or higher polycarboxylic acid having 3 or more may be used. on the other hand,
As the alkali metal or alkaline earth metal, it is preferable to use an alkali metal or an alkaline earth metal of hydroxide, and particularly sodium with sodium hydroxide, potassium with potassium hydroxide, calcium with calcium hydroxide and the like are preferable.

The cellulose derivative particles are spherical with an average particle diameter in the wet state of 1 to 1000 μm, preferably 3 to 100 μm. Here, if the average particle size is larger than 1000 μm, it tends to cause a squeaky feeling when used in a product used on the skin, and 1 μm.
The smaller ones are spherical and cannot be manufactured. It should be noted that those having a thickness of 3 to 100 μm exhibit a suitable spherical shape and can be easily manufactured.

Further, the cellulose derivative particles have a cation exchange group capacity of 0.1 to 3.0 meq / g, preferably 0.5 to 2.5 meq / g. Here, if the cation exchange group capacity is larger than 3.0 meq / g, the spherical shape cannot be maintained, and if it is smaller than 0.1 meq / g, the polyvalent carboxylic acid cannot be introduced into the cellulose. In addition, the thing of 0.5-2.5 meq / g shows suitable spherical shape similarly to an appropriate average particle diameter,
It can be easily manufactured.

Furthermore, the cellulose derivative particles are

[Equation 3] Circularity = Perimeter of circle calculated from equivalent radius of circle /
The circularity represented by the perimeter of the particle projection image is 0.9 to 1.0. Here, the circularity is calculated by [Formula 3] by a flow type particle image analyzer FPIA-2100 of Sysmex Co., Ltd., and the circularity is equivalent to a circle equivalent diameter (the same as the actually captured perimeter). It is defined as a value obtained by dividing the perimeter calculated from the diameter of a perfect circle having a projected area) by the perimeter of an actually imaged particle. The value becomes 1 for a perfect circle, and the smaller the shape becomes, the smaller the value becomes. For this reason, it is preferable to use particles having an extremely high degree of sphericity with a circularity of 0.9 or more, and a dispersion in which fine particles are dispersed in water or the like is extremely stably dispersed due to charge repulsion,
When used in products, it has dispersion stability, thickening effect and moisturizing ability. When the circularity is less than 0.9, the spherical shape is not spherical, stable dispersibility is lost, and a rough feeling and a squeaky feeling are generated.

In addition, when importance is attached to transparency in the cellulose derivative particles, it is important that the crystallinity of the type II crystal structure peculiar to regenerated cellulose, which is related to transparency, be 0.3 or less. . Here, the evaluation of the crystallinity is calculated as cellulose II type crystalline fraction (X _I) by wide angle X-ray diffraction method (Rigaku Corporation using Corp.)
The cellulose II type crystallinity fraction (X _I ) was obtained by molding a cellulose sample into tablets and using a reflection method with a radiation source CuKα.
0) The absolute peak intensity h0 at 2θ = 12.6 ° attributed to the plane peak and the peak intensity h1 from the baseline at this plane interval are obtained by the following [Equation 4].

[0023]

## EQU4 ## X _I = h0 / h1

As described above, since the cellulose has a structure in which a part or all of the hydroxyl groups of the cellulose are substituted with the carboxyl groups of the polyvalent carboxylic acid by an ester bond, it can have hydrophilicity. Here, when a monobasic carboxylic acid having only one carboxyl group with respect to the hydroxyl group of cellulose is used, it cannot have hydrophilicity. Also, since the shape is spherical,
It can have a dry feel when used in products for use on the skin. Furthermore, since it has a structure in which it is metal-chlorided by an alkali metal or an alkaline earth metal and has a spherical shape and is insoluble in water, it can be easily commercialized by appropriately adjusting the pH.

The average particle size in the wet state is 1-100.
0 μm, and the cation exchange group capacity is 0.1 to 3.
0 meq / g, the circularity is 0.9 to 1.0, or the substituted polycarboxylic acid is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid. , Dodecyl succinic acid, glutaric acid, adipic acid, and maleic acid can be preferably used for products used on the skin.

Next, a method for producing the cellulose derivative particles will be described.

The method for producing cellulose derivative particles is shown in FIG.
In the pretreatment step, the dry cellulose spherical particles having an average particle diameter of 1 to 1000 μm or the wet cellulose spherical particles (cellulosic raw material) are alkali-substituted as a pretreatment step. The concentration of spherical particles or wet cellulose spherical particles is 1 to 50% by weight, preferably 10 to 25% by weight.
Fully immersed in a mixed solvent of the alkaline aqueous solution and an organic solvent such as acetone at room temperature to 100 ° C, preferably 30 to
0.5 to 24 hours at a treatment temperature of 50 ° C., preferably 1
Process for ~ 3 hours. After being replaced with alkali, the cellulose particles are filtered and subjected to the next reaction in a wet state. Examples of the alkali used for the alkali substitution include alkali metal or alkaline earth metal hydroxides, ammonia and the like, among which sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia are preferable. Note that organic bases such as pyridine, trialkylamine, and morpholines are not preferable because the reaction does not proceed properly.
The alkali is used in an amount of 0.1-100 equivalents, preferably 0.5-6.0 equivalents, relative to the glucose ring unit of cellulose. When the amount of the alkali is less than this, the rate of substitution of the hydroxyl group with the polycarboxylic acid becomes small, which is not preferable. Furthermore, it may be partially crosslinked, or the cellulose particles may not be crosslinked at all because they retain their shape due to a secondary structure such as a hydrogen bond.

After treating the dry cellulose particles or the wet cellulose spherical particles in the pretreatment stage, the alkali-substituted cellulose (alkali-impregnated cellulose) is immersed in an organic solvent, and a polyvalent carboxylic anhydride is added dropwise. The reaction is performed at room temperature to 100 ° C., preferably 30 to 50 ° C. for about 1 minute to 1 day, preferably 30 minutes to 3 hours. Here, polyhydric carboxylic anhydride is tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, malonic acid, succinic anhydride, dodecyl succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, etc. That is, 0.1 to 10 times equivalents, preferably 0.3 to 3 times equivalents, of the hydroxyl groups present in the glucose ring are added. The organic solvent is an aprotic solvent such as acetone, tetrahydrofuran or dioxane, or a protic solvent such as tert-butyl alcohol. Further, the introduction of polyvalent carboxylic acid anhydride into cellulose can be controlled so as to have a cation exchange capacity of 0.1 to 3.0 meq / g, and it can be introduced at a high rate. Further, a mixed solvent of the above-mentioned alkaline aqueous solution can be used, and in that case, the mixing ratio of the organic solvent and the aqueous solution is 0.2 to 50: 1, preferably 15 to 15.
25: 1 is preferred. Further, in order to improve the swelling property, a substance such as lithium chloride or urea that breaks the intermolecular hydrogen bond of cellulose may be added. Moreover, it is desirable that the polycarboxylic acid anhydride is dissolved in an aprotic organic solvent and added dropwise.

After the reaction, the product is treated with an organic solvent, hydrochloric acid,
The cellulose derivative particles (carboxylated cellulose) having an average particle diameter in the wet state of 1 to 1000 μm are isolated by washing with an acid such as a mineral acid such as sulfuric acid or the like, water, and filtering. At this time, if the purpose is to obtain the metal chlorinated cellulose derivative particles, it is not necessary to wash with acid such as mineral acid such as hydrochloric acid or sulfuric acid.

After washing the product, the cellulose derivative particles (carboxylated cellulose) are added at a concentration of 0.00
By substituting with 5 to 2 mol, preferably 0.01 to 0.2 mol of a dilute alkaline solution, the metal chlorinated cellulose derivative particles (carboxyl Na chlorocellulose in FIG. 1) can be obtained. Here, partial metal chlorination can also be selected depending on the application by changing the concentration of the dilute alkaline aqueous solution. It is also possible to change the pH of the particles from acidic to neutral or alkaline by partially or entirely metallizing the carboxyl groups. Further, particles having different ion exchange capacities may be mixed for the purpose of adjusting pH. Further, the alkali is preferably a hydroxide of an alkali metal or an alkaline earth metal, especially sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

After obtaining the cellulose derivative particles or the metal chloride-containing cellulose derivative particles, the circularity calculated by the flow-type particle image analyzer and the crystallinity using the wide-angle X-ray diffraction method described above are obtained. The state of the cellulose derivative particles may be confirmed by the evaluation.

As described above, according to the method for producing the cerose derivative particles, since the cellulose is wetted and the acid anhydride is added, the hydroxyl group of the cellulose is appropriately reacted with the acid anhydride to introduce the polyvalent carboxylic acid. The produced cellulose derivative can be reliably produced.

Next, a cosmetic using cellulose derivative particles will be described.

Cosmetics using cellulose derivative particles are
The average particles obtained by the above production method have a diameter of 15
Cellulose derivative particles having a particle size of less than or equal to .mu.m were added to the composition of 0.
It is blended in an amount of 01 to 25% by weight, preferably 0.05 to 20% by weight, and an emulsion, cream,
It is prepared in the form of solid, paste, gel, powder, multilayer or mousse. Here, the cosmetics are basic cosmetics, makeup cosmetics, antiperspirants, ultraviolet protective materials, nail polishes, pharmaceuticals, quasi-drugs, etc., and the amount of cellulose derivative particles to the total composition is If it is less than 0.01% by weight, the moisturizing property will be reduced.
The viscosity becomes high and it becomes difficult to apply to the skin. In addition, 0.
When blended in an amount of from 05 to 20% by weight, a moisturizing and moisturizing feel as well as a silky feel are suitably provided, and further application to the skin (novi when used) can be made extremely good.

Further, the cosmetic using the cellulose derivative particles contains 0.01 to 10% by weight, preferably 0.01 to 10% by weight, of the cellulose derivative particles having an average particle diameter of 15 μm or less, which is obtained by the above-mentioned production method. 0.05-5% by weight
And are prepared in a liquid form by a usual manufacturing method. Here, the cosmetics are lotions, beauty essences, milky lotions, pharmaceuticals, quasi-drugs, etc. When the amount of the cellulose derivative particles is less than 0.01% by weight of the total composition, the moisturizing effect decreases. If it is more than 10% by weight, the dispersibility of the composition in the liquid becomes poor. When blended in an amount of 0.05 to 5% by weight, a moisturizing and moisturizing feel as well as a silky feel can be suitably provided, and further extremely stable dispersibility can be provided.

Further, the cosmetic using the cellulose derivative particles has 0.1% of the cellulose derivative particles obtained by the above-mentioned production method and having an average particle diameter larger than 15 μm.
-25% by weight, preferably 0.5-20% by weight, and prepared in the form of emulsion, cream, solid, paste, gel, powder, multilayer, mousse by a conventional production method. Formulated into a scrubbing agent. Here, the cosmetics of the scrubbing agent are cosmetics for peeling, cleaning cosmetics such as facial cleansing foam, cleansing, soap, hair cosmetics (shampoo, conditioner), pharmaceuticals, quasi drugs, etc. When the compounding amount of the derivative particles is less than 0.1% by weight based on the total composition, the function as a scrubbing agent is weak, and when the compounding amount is more than 25% by weight, the viscosity becomes high and it becomes difficult to apply to the skin. When blended in an amount of 0.5 to 20% by weight, a moisturizing and moisturizing feel as well as a silky feel are suitably provided, and furthermore, application to the skin (novi when used) can be made extremely good.

Further, the cellulose derivative particles can be used alone or in combination of two or more kinds. In addition to the cellulose derivative particles, components used in ordinary cosmetics, for example, powders other than the cellulose derivative particles, water-soluble alcohols, surfactants, viscosity modifiers, oils, silicones, pH modifiers, amino acids , Anti-inflammatory agents, singlet oxygen scavengers or antioxidants, ultraviolet absorbers, whitening agents, blood circulation promoters, vitamins, sebum suppressants, antiperspirants, astringents, preservatives,
A metal chelating agent, a fragrance, a dye and the like can be appropriately selected and blended within a range not impairing the effects of the present invention.

Hereinafter, other specific components of the cellulosic derivative particles used in cosmetics will be shown. The powder is not limited as long as it is used in ordinary cosmetics, and examples thereof include silicic acid and anhydrous. Silicic acid, magnesium silicate,
Talc, kaolin, mica, bentonite, titanium coated mica, red iron oxide, bismuth oxychloride, zirconium oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, iron oxide, ultramarine blue, navy blue, chromium oxide, chromium hydroxide, calamine, zeolite , Inorganic powder such as carbon black; polyamide, polyester, polyethylene, polypropylene, polyurethane, vinyl resin, urea resin,
Various resin powders such as phenol resin, fluororesin, silicon resin, acrylic acid resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene / styrene copolymer and the like, or copolymer resin powder composed of two or more of these. Organic powders of polysaccharides, wool, silk, etc .; red 20
No. 1, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405
No. 203, Orange No. 203, Orange No. 204, Yellow No. 204, Yellow No. 401, Blue No. 404, etc., organic pigment powders; Red No. 3,
Red No. 104, Red No. 106, Red No. 227, Red No. 23
No. 0, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3, Blue 1, etc. Pigments consisting of zirconium, barium or aluminum lake, etc. Powder; metal soaps such as magnesium stearate, calcium stearate, zinc laurate, zinc palmitate and the like can be mentioned.
These powders are treated with silicone such as methylhydrogenmethylpolysiloxane, trimethylsiloxysilicic acid and methylpolysiloxane; treated with fluorine such as perfluoroalkyl phosphate ester and perfluoroalcohol; treated with amino acid such as N-acylglutamic acid;
It is also possible to use those subjected to surface treatment such as lecithin treatment, metal soap treatment, fatty acid treatment, alkyl phosphate ester treatment and the like. It is also possible to use a composite of two or more of these powders.

Examples of the water-soluble alcohols include polyglycerin such as glycerin, diglycerin, triglycerin and tetraglycerin, ethylene glycol, 1, 3
-Butylene glycol, 1,4-butylene glycol,
Propylene glycol, dipropylene glycol, polyethylene glycol, 1,3-propanediol, glucose, maltose, maltitol, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol, erythritol, starch-resolving sugar reducing alcohol, sorbit, poly An oxyalkylene alkyl glucoside etc. are mentioned. Of these, glycerin, 1,3-butylene glycol and 1,3-propanediol are particularly preferable. Also, these alcohols
It is also possible to use a composite of two or more species.

As the surface active agent, any of nonionic surface active agents, anionic surface active agents, amphoteric surface active agents and the like can be preferably used. Among these, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester. , Fatty acid monoglyceride, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil alkyl sulfate ester, polyoxyethylene castor oil, polyoxyethylene alkyl sulfate ester, polyglycerin fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, alkyl phosphorus Examples thereof include acid esters, polyoxyethylene alkyl phosphates, fatty acid alkali metal salts and alkyl glyceryl ethers.

Examples of the anionic surfactant include linear or branched alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates having an alkyl group or an alkenyl group, olefin sulfonates, alkane sulfonates, and unsaturated. Fatty acid salt, alkyl or alkenyl ether carboxylic acid salt, α-sulfo fatty acid salt or ester having alkyl group or alkenyl group, N-acyl amino acid type surfactant having acyl group and free carboxylic acid residue, alkyl group or alkenyl group And phosphoric acid mono- or diester-type surfactants having

Examples of the amphoteric surfactant include imidazoline-based amphoteric surfactants having an alkyl group, an alkenyl group or an acyl group, carbobetaine-based, amidobetaine-based, sulfobetaine-based, hydroxysulfobetaine-based or amidosulfobetaine-based amphoteric surfactant. Examples thereof include surfactants. Here, when blending these surfactants,
One kind or a combination of two or more kinds can be used.

Examples of the viscosity modifier include xanthan gum, cationized cellulose, sodium hyaluronate,
Alginic acid, chitin, chitosan, carboxymethyl cellulose, methyl hydroxypropyl cellulose, iota carrageenan, lambda carrageenan, pullulan, jellyfish, gati gum, trehalose, agar, JP-A-64
Polysaccharides such as acidic heteropolysaccharides described in JP-A-10997; polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymers, vinyl polymers such as sodium polyacrylate; chitosample run emulsion,
Emulsion system such as alkyl acrylate copolymer emulsion; Polypeptide system such as soluble collagen, hydrolyzed elastin, silk extract; molecular weight 20000-40
00000 polyethylene glycol; other gelatin, tragacanth gum, pectin, mannan, locust bingham, galactan, gum arabic, dextran,
Succinoglucan, curdlan, quince seed, soagina, casein, albumin, polyvinyl methyl ether, hydroxyethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, starch, carboxymethyl starch, methyl starch, agarose, propylene glycol alginate, sodium alginate, guar gum, etc. Can be mentioned.

The oil content is not particularly limited, and examples thereof include hydrocarbons such as solid or liquid paraffin, vaseline, crystal oil, ceresin, ozokerite, montan wax, squalane, squalene; eucalyptus oil, hardened palm oil, coconut oil, Mint oil, evening primrose oil, beeswax, camellia oil, almond oil, cacao oil, castor oil, sesame oil, macadamia nut oil, sunflower oil, peanut oil, avocado oil, beef tallow, lard, horse fat, egg yolk fat, olive oil, carnauba wax, lanolin. , Hydrogenated lanolin, jojoba oil; glycerin monostearate, glycerin distearate, glycerin monooleate, myristyl palmitate, cetyl palmitate, cetyl 16-hydroxypalmitate, cetyl isooctanoate, palmitin Isopropyl, isobutyl palmitate, isopropyl stearate, butyl stearate, isocetyl stearate, isopropyl myristate, 2-octyldodecyl myristate, hexyl laurate, isopropyl laurate, decyl oleate, neopentyl glycol dicaprate, diethyl phthalate. , Myristyl lactate, diisopropyl adipate,
Hexadecyl adipate, cetyl myristate, myristyl lactate, diisostearyl malate, diisopropyl adipate, cetyl myristate, cetyl lactate, 1-isostearyl-3-myristoylglycerol, cetyl 2-ethylhexanoate, palmitate-2- Ethylhexyl, 2-octyldodecyl myristate, Di-2-
Neopentyl glycol ethylhexanoate, 2-octyldodecyl oleate, glycerol triisostearate, di-paramethoxycinnamic acid-glyceryl mono-2-ethylhexanoate, pentaerythritol tetraester, glycerin triester, glycerol tri-2
-Ester oil such as ethylhexanoic acid ester; stearic acid, oleic acid, linoleic acid, isostearic acid, myristic acid, palmitoleic acid, ricinoleic acid, lauric acid, behenic acid and hydroxy fatty acids having a hydroxy group in the alkyl group of these fatty acids, Higher fatty acids such as palmitic acid; benzyl alcohol, isocetyl alcohol, isostearyl alcohol, behenyl alcohol,
Hexadecyl alcohol, phenylethyl alcohol,
Cetanol, stearyl alcohol, oleyl alcohol, 2-octyldodecanol, batyl alcohol, 2
-Higher alcohols such as hexyldecanol; phospholipids,
Examples thereof include naturally-extracted sphingosine derivatives and their synthetic products (eg, glucosylceramide, galactosylceramide, ceramide, etc.), and one or more of these can be used. Here, when these oils are blended, it is preferable to use them in a range where they can be emulsified, microemulsified, gelled, and solubilized, and 0.001 in the total composition is used.
It is preferably blended in an amount of up to 60% by weight, particularly 30% by weight or less.

The silicones are not particularly limited as long as they are usually blended in cosmetics, and for example, octamethylpolysiloxane, tetradecamethylpolysiloxane,
Methyl polysiloxane, highly polymerized methyl polysiloxane,
In addition to methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and other methylpolycyclosiloxanes, trimethylsiloxysilicic acid, and further polyether-modified silicone, polyether-alkyl-modified silicone, oxazolyl-modified silicone, alkyl Examples thereof include glyceryl ether-modified silicone and modified silicone such as specific modified organopolysiloxane described in JP-A-6-72851.

Examples of the pH adjusting agent include metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, triethanolamine, isopropanolamine,
Organic acids such as diisopropanolamine, urea, ε-aminocaproic acid, sodium pyrrolidonecarboxylate, sodium hydrogenphosphate, sodium citrate, citric acid, lactic acid, succinic acid, tartaric acid, betaines such as glycine betaine, lysine betaine, etc. Can be mentioned. The cosmetic of the present invention preferably has a pH range of 2 to 11, particularly a pH range of 4 to 8.

Examples of amino acids include glycine, serine, cystine, alanine, threonine, cysteine,
Neutral amino acids such as valine, phenylalanine, methionine, leucine, tyrosine, proline, isoleucine, tryptophan, hydroxyproline; aspartic acid,
Acidic amino acids such as asparagine, glutamine and glutamic acid; basic amino acids such as arginine, histidine and lysine; and betaine and amino acid derivatives such as acyl sarcosine and its salts, acyl glutamic acid and its salts, acyl-β-alanine and its salts. , Glutathione, pyrrolidonecarboxylic acid and salts thereof; oligopeptides such as glutatin, carnosine, gramcygin S, tyrosidine A, and tyrosidine B, and guanidine derivatives and salts thereof described in JP-A-6-228023. Here, when these amino acids are blended, one kind or two or more kinds may be used in combination, and 0.001 to 30% by weight, particularly 0.01 to 5% by weight in the entire composition. Preferably.

Examples of the anti-inflammatory agent include glycyrrhizic acid and its salts, glycyrrhetinic acid and its salts, epsilon aminocaproic acid and its salts, allantoin, lysozyme chloride, guaiazulene, methyl salicylate, γ-oryzanol, bisabolol and the like. Of these, glycyrrhetinic acid, stearyl glycyrrhetinate,
Epsilon aminocaproic acid is preferred. Here, when these anti-inflammatory agents are blended, one kind or a combination of two or more kinds can be used, and 0.001 to
It is preferable to add 5% by weight, particularly 0.01 to 2% by weight.

As the singlet oxygen scavenger or antioxidant,
For example, carotenoids such as α-carotene, β-carotene, γ-carotene, lycopene, clibutoxanthin, lutein, zeaxanthin, isozeaxanthin, rhodoxanthin, capsanthin, and crocetin; 1,4-diazacyclooctane, 2,5-dimethyl. Furan, 2-methylfuran, 2,5-diphenylfuran, 1,3-diphenylisobenzofuran, α-tocopherol, β-tocopherol, γ-tocopherol, d-tocopherol, histidine, tryptophan, methionine, L-cystine,
L-cysteine, alanine or an alkyl ester thereof;
Dibutylhydroxytoluene, butylhydroxyanisole, ascorbic acid, tannic acid, epicatechin, epicarocatechin, epicatechin gallate, tancaine such as epicalocatechin gallate, flavonoids such as rutin; superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase Enzymes such as Enju, Peralmin, Platonin, Capsaicin, Yellow Gon Extract and the like. Of these, carotene, tocopherol, ascorbic acid, tannic acid, epicatechin gallate, and epicarocatechin gallate are preferable. Here, when these singlet oxygen scavengers or antioxidants are blended, one kind or a combination of two or more kinds can be used, and 0.001 to 5 in the entire composition can be used.
It is preferable to add the composition in an amount of 0.01% by weight, especially 0.01 to 2% by weight.

As described above, according to the cosmetic using the cellulose derivative particles, since the cellulose derivative particles are appropriately blended, a moist feeling due to the hydrophilicity and a smooth feeling due to the spherical shape are simultaneously provided, and the polycarboxylic acid It is possible to stably disperse the composition with charge repulsion due to an acid and a spherical shape, and improve the novi of makeup.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Although spherical cellulose particles are used as a raw material, the method for producing the raw material cellulose spherical particles is not limited to a particular method. In the present invention, a production example of cellulose derivative particles used as a moisturizer is shown below. [Production Example] As a production method of the raw material cellulose spherical particles, as shown in the production method described in JP-A-62-246935, a viscose fine particle dispersion is generated in the first step, and cellulose fine particles are added in the second step. In the third step, the fine cellulose particles are separated from the mother liquor to obtain sieved spherical spherical spherical particles (average particle size 5 μm or 100 μm).

An example of the production of carboxylated cellulose spherical particles (cellulose derivative particles) using 5 μm cellulose spherical particles is shown. [Example 1] (1) Cellulose succinate spherical particles Acetone / KOH (double equivalent to glucose residue)
In a water / water (acetone: water = 20: 10) solution, spherical cellulose particles (average particle size 5 μm) were dispersed, and the mixture was stirred at 50 ° C. for 2 hours.
Stir for hours. Subsequently, a double equivalent of a succinic anhydride solution dissolved in acetone was added dropwise over 0.5 hour, and after completion of the addition, the mixture was stirred for 24 hours. After completion of the reaction, the particles were collected by filtration, washed with acetone, water and acetone, further washed with dilute hydrochloric acid, and replaced with water to obtain cellulose succinate spherical particles. When the FT-IR spectrum of the obtained dried cellulose succinate spherical particles is compared with that of untreated cellulose spherical particles, as shown in FIG. 2, the FT-IR spectrum shows that the carbonyl of the carboxyl group is around 1740 cm ^−1. Sharp absorption derived from the base stretching vibration is observed, and it is clear that the polyvalent carboxylic acid succinic acid has been introduced. Ion exchange capacity 2.15 meq / g

[Example 2] (2) Cellulose glutarate spherical particles Acetone / KOH (double equivalent to glucose residue)
In a water / water (acetone: water = 20: 10) solution, spherical cellulose particles (average particle size 5 μm) were dispersed, and the mixture was stirred at 50 ° C. for 2 hours.
Stir for hours. Subsequently, a twice-equivalent solution of anhydrous acid dissolved in acetone was added dropwise over 0.5 hour, and after the addition was completed, the mixture was stirred for 24 hours. After the reaction is completed, the particles are collected by filtration,
The particles were washed with acetone, water and acetone, further washed with dilute hydrochloric acid, and replaced with water to obtain cellulose glutarate spherical particles. F of the obtained cellulose succinate spherical particles after drying
When the T-IR spectrum is measured, as shown in FIG.
Sharp absorption derived from the carbonyl group stretching vibration of the carboxyl group is observed near 740 cm ⁻¹ . Ion exchange capacity 1.84 meq / g

An example of the production of carboxylated cellulose spherical particles (cellulose derivative particles) using 100 μm cellulose spherical particles is shown. Example 3 (1) Cellulose succinate spherical particles at a pretreatment temperature of 50 ° C. Acetone / KOH (double equivalent to glucose residue)
/ Cellulose spherical particles (average particle size 100 μm) were dispersed in a / water (acetone: water = 20: 10) solution and stirred at room temperature for 2 hours. 2 dissolved in acetone
A double equivalent of succinic anhydride solution was added dropwise over 0.5 hour,
After the completion of dropping, the mixture was stirred for 24 hours. After completion of the reaction, the particles were collected by filtration, washed with acetone, water and acetone, further washed with dilute hydrochloric acid, and replaced with water to obtain cellulose succinate spherical particles. When the FT-IR spectrum of the obtained dried cellulose succinate spherical particles was measured, as shown in FIG. 4, sharp absorption derived from the carbonyl group stretching vibration of the carboxyl group was observed at around 1740 cm ⁻¹ . Ion exchange capacity 1.45 meq / g (calculated by back titration method)

Example 4 (2) Cellulose succinate spherical particles acetone / KOH (double equivalent to glucose residue) at a pretreatment temperature of room temperature
Cellulose spherical particles (average particle size 100 μm) were dispersed in a / water (acetone: water = 20: 10) solution, and the mixture was stirred at 50 for 2 hours. 2 dissolved in acetone
A double equivalent of succinic anhydride solution was added dropwise over 0.5 hour,
After the completion of dropping, the mixture was stirred for 24 hours. After completion of the reaction, the particles were collected by filtration, washed with acetone, water and acetone, further washed with dilute hydrochloric acid and replaced with water to obtain cellulose glutarate spherical particles. When the FT-IR spectrum of the obtained dried cellulose succinate spherical particles was measured, as shown in FIG. 5, a sharp absorption derived from the carbonyl group stretching vibration of the carboxyl group was observed at around 1740 cm ⁻¹ . Ion exchange capacity 1.79 meq / g (calculated by back titration method)

Example 5 (3) Spherical particles of cellulose glutarate at a pretreatment temperature of 50 ° C. Acetone / KOH (double equivalent to glucose residue)
/ Cellulose spherical particles (average particle size 100 μm) were dispersed in a / water (acetone: water = 20: 10) solution and stirred at room temperature for 2 hours. 2 dissolved in acetone
A double-equivalent glutaric anhydride solution was added dropwise over 0.5 hour, and after completion of the addition, the mixture was stirred for 24 hours. After completion of the reaction, the particles were collected by filtration, washed with acetone, water and acetone, further washed with dilute hydrochloric acid and replaced with water to obtain cellulose glutarate spherical particles. When the FT-IR spectrum of the obtained dried cellulose glutarate spherical particles was measured, as shown in FIG. 6, a sharp absorption due to the carbonyl group stretching vibration of the carboxyl group was observed at around 1740 cm ⁻¹ . Ion exchange capacity 1.27 meq / g (calculated by back titration method)

Example 6 (4) Cellulose glutarate spherical particles acetone / KOH (double equivalent to glucose residue) at a pretreatment temperature of room temperature
Cellulose spherical particles (average particle size 100 μm) were dispersed in a / water (acetone: water = 20: 10) solution at 50 ° C.
Stir for 2 hours. Subsequently, a double equivalent of a glutaric anhydride solution dissolved in acetone was added dropwise over 0.5 hours, and after the addition was completed, the mixture was stirred for 24 hours. After completion of the reaction, the particles were collected by filtration, washed with acetone, water and acetone, further washed with dilute hydrochloric acid and replaced with water to obtain cellulose glutarate spherical particles. When the FT-IR spectrum of the obtained dried cellulose glutarate spherical particles was measured, as shown in FIG. 7, a sharp absorption due to the carbonyl group stretching vibration of the carboxyl group was observed near 1740 cm ⁻¹ . Ion exchange capacity 1.42 meq / g (calculated by back titration method)

Next, in order to perform metal chlorination and sodium chlorination of the carboxylated celluloses (cellulose derivative particles) of Examples 1 to 6, each particle and an equivalent amount of sodium hydroxide were added and stirred for 1 hour. It was collected by filtration and washed with distilled water. An example of producing spherical polyvalent carboxylic acid metal chlorinated cellulose particles is shown below.

Example 7 The particles described in Example 1 were mixed with 0.0
1 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the particles after drying was measured, as shown in FIG. 8, there was a sharp absorption near 1740 cm ⁻¹ with a sharp absorption derived from the carbonyl group stretching vibration of the ester moiety and 1570 cm ^−1.
Sharp absorption derived from carbanion was observed near cm ⁻¹ .

Example 8 The particles described in Example 2 were mixed with 0.0
1 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the dried particles is measured (not shown),
Around 1740 cm ^-1, with a sharp absorption derived from the carbonyl group stretching vibration of the ester moiety, at 1570 cm
A sharp absorption derived from a carbanion was observed near ^-1 .

Example 9 The particles described in Example 3 were mixed with 0.0
1 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the dried particles is measured (not shown),
Around 1740 cm ^-1, with a sharp absorption derived from the carbonyl group stretching vibration of the ester moiety, at 1570 cm
A sharp absorption derived from a carbanion was observed near ^-1 .

Example 10 The particles described in Example 4 were mixed with 0.
01 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the particles after drying was measured (not shown), it was found to be 157 with sharp absorption derived from carbonyl group stretching vibration of the ester moiety near 1740 cm ^−1.
A sharp absorption derived from a carbanion was observed near 0 cm ⁻¹ .

Example 11 The particles described in Example 5 were mixed with 0.
01 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the particles after drying was measured (not shown), it was found to be 157 with sharp absorption derived from carbonyl group stretching vibration of the ester moiety near 1740 cm ^−1.
A sharp absorption derived from a carbanion was observed near 0 cm ⁻¹ .

Example 12 The particles described in Example 6 were mixed with 0.
01 M sodium hydroxide was added in an amount equivalent to the ion exchange capacity of the particles described in Example 1, filtered, and washed with water. When the FT-IR spectrum of the particles after drying was measured (not shown), it was found to be 157 with sharp absorption derived from carbonyl group stretching vibration of the ester moiety near 1740 cm ^−1.
A sharp absorption derived from a carbanion was observed near 0 cm ⁻¹ .

Example 13 Using a differential scanning calorimeter, a small amount of water was added to each particle, and the ability to bind water, which is directly related to the moisturizing property of each particle by the thermal behavior of water, was investigated.
In addition, untreated cellulose is listed as a comparative example. Figure 9
As shown in, the polyvalent carboxylic acid anhydride had a melting point of water shifted to the negative side and broadened as compared with the untreated cellulose particles. Furthermore, sodium chloride was further shifted to the negative side. This also indicates that the amount of bound water is increasing, as is also seen with water absorbent resins such as hyaluronic acid. By the way, the untreated cellulose particles are -1.0 ° C, the cellulose succinate particles are -1.9 ° C, the sodium succinate chloride particles are -5.3 ° C, and the glutarate cellulose particles are-.
1.3 [deg.] C., the sodium glutarate cellulose particles were -4.
It was 8 ° C.

Example 14 FIG. 10 (a) shows untreated cellulose particles, FIG. 10 (b) shows cellulose succinate particles, and FIG. 10 (c) shows glutarate cellulose particles by optical microscope photographs. It was It is clear that spheres are more ordered and swelling is also seen compared to untreated cellulose particles.

Example 15 Cellulose succinate particles,
The circularity of the cellulose glutarate particles, the sodium succinate chloride particles, and the sodium glutarate cellulose chloride particles was measured. Cellulose succinate particles 0.935, sodium succinate chloride particles 0.940, glutarate cellulose particles 0.96.
6, sodium glutarate cellulose chloride particles 0.9
66, and all showed high circularity of 0.9 or more.

Example 16 As an evaluation of crystallinity, FIG.
1 (a) shows untreated cellulose particles, FIG. 11 (b) shows cellulose succinate particles, FIG. 11 (c) shows cellulose glutarate particles, and FIG. 11 (d) shows sodium succinate chloride particles. 11 (e) shows the sodium glutarate chlorinated cellulose particles as the X-ray diffraction results, respectively. As a result, the structure of untreated cellulose was confirmed to be a cellulose II type higher-order structure (II type crystallinity X
_II = 0.34). On the other hand, the structure of polycarboxylic acid cellulose has a broad peak, which maintains the high-order structure of cellulose II type but has a crystallinity of X.
_II is as low as less than 0.30, which suggests that it is involved in the flexibility of the polycarboxylic acid cellulose. Further, the peak of the crystallinity of the sodium chlorinated cellulose spherical particles becomes broader, and the type II crystallinity is also X _II =
It was as low as less than 0.25. By the way, cellulose succinate particles have X _II = 0.27, sodium succinate cellulose particles have X _II = 0.21, cellulose glutarate particles have X _II = 0.25, and sodium glutarate cellulose particles have X _II =. It was 0.14.

Example 17 The evaporation rate of water was examined by a differential thermal balance. 12 (a) shows only glutarate and water, FIG. 12 (b) shows glutarate and untreated cellulose, and FIG. 12 (c) shows Na glutarate.
Fig. 13 shows cellulose and cellulose glutarate.
Only cellulose succinate and water are shown in (a), and FIG.
(B) Cellulose succinate and untreated cellulose,
FIG. 13C shows Na cellulose succinate and cellulose succinate. From this, it is clear that the carboxylated cellulose particles and the sodium carboxylated cellulose have a slower evaporation rate and are less likely to dry than the untreated cellulose, and thus have excellent moisturizing properties.

[Example 18] A lotion containing cellulose derivative particles (cellulose succinate beads or cellulose glutarate beads) was compared with lotion containing untreated cellulose spherical particles (untreated cellulose beads). With this, each of the cosmetics was used to evaluate the non-stickiness, the sticky feeling, the moisturizing feeling, the dry feeling, and the refreshing feeling. Toner lotion was produced by a conventional method, and the composition and results are shown in [Table 1].

[0071]

[Table 1]

(Evaluation Method) By 25 female monitors,
A sensory evaluation was conducted on the moisturization, sticky feeling, moisturizing feeling, dry feeling, and refreshing feeling when the lotion was applied to the face, and the results were judged according to the following criteria. ◯: More than half confirmed the effect. Δ: 1/4 or more and less than half were effective. X: 1/4 or less confirmed the effect. From the results in [Table 1], it can be seen that the lotion containing the cellulose derivative particles gave a moist feeling while maintaining good moistness and dryness as compared with the lotion containing the untreated cellulose spherical particles. Further, if importance is attached to the dry feeling, succinic acid derivatized cellulose is more preferable than lotion containing glutaric acid derivatized cellulose.

[0073]

The cellulose derivative particles of the present invention, the method for producing the same, and the cosmetics using the same can exhibit various excellent effects as described below.

I) The cellulose derivative particles according to claims 1 to 6 have a structure in which a part or all of the hydroxyl groups of cellulose are substituted with the carboxyl groups of the polyvalent carboxylic acid by an ester bond. Can have. Further, since it has a spherical shape, it can have a silky feel when used in a product used on the skin. Furthermore, since it has a structure in which it is metal-chlorided by an alkali metal or an alkaline earth metal and has a spherical shape and is insoluble in water, it can be easily commercialized by appropriately adjusting the pH.

II) The average particle size in the wet state is from 1 to 10
Cation exchange group capacity of 0.1 to 100 μm
It is 3.0 meq / g, and the circularity is 0.9 to 1.
0 or the substituted polycarboxylic acid is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid, dodecylsuccinic acid, glutaric acid, adipic acid, maleic acid, It can be suitably used for products used on the skin.

III) According to the method for producing the cerose derivative particles according to claim 7, since the cellulose is wetted and the acid anhydride is added, the hydroxyl group of the cellulose and the acid anhydride are appropriately reacted to form the polyvalent carboxylic acid. The introduced cellulose derivative can be reliably manufactured.

IV) According to the cosmetic using the cellulose derivative particles of claims 8 to 11, since the cellulose derivative particles are appropriately blended, a moist feeling due to hydrophilicity and a smooth feeling due to a spherical shape are simultaneously provided, and further, It is possible to stably disperse the composition by providing charge repulsion due to polyvalent carboxylic acid and spherical shape, and to improve the cosmetic effect.

[Brief description of drawings]

FIG. 1 is a flowchart showing a process for producing carboxylated cellulose or carboxyl Na chlorinated cellulose in a method for producing cellulose derivative particles according to an embodiment of the present invention.

FIG. 2 is an FT-IR spectrum showing cellulose succinate spherical particles (5 μm) and untreated cellulose spherical particles.

FIG. 3 is an FT-IR spectrum showing spherical particles of cellulose glutarate (5 μm).

FIG. 4 is an FT-IR spectrum showing spherical particles of cellulose succinate (100 μm, pretreatment temperature: 50 ° C.).

FIG. 5 is an FT-IR spectrum showing spherical particles of cellulose succinate (100 μm, pretreatment temperature: room temperature).

FIG. 6 Cellulose glutarate spherical particles (100 μm,
It is an FT-IR spectrum showing a pretreatment temperature: 50 ° C.

FIG. 7: Cellulose glutarate spherical particles (100 μm,
It is an FT-IR spectrum showing a pretreatment temperature: room temperature.

FIG. 8: Cellulose sodium chloride succinate spherical particles (5μ
It is an FT-IR spectrum showing m).

FIG. 9 is a plot showing quantification of bound water by differential scanning calorimetry of carboxylated cellulose, carboxyl chloride cellulose particles and untreated cellulose particles.

FIG. 10 is an optical micrograph showing untreated cellulose particles in (a), cellulose succinate particles in (b), and cellulose glutarate particles in (c).

11 (a) shows untreated cellulose particles, (b) shows cellulose succinate particles, (c) shows glutarate cellulose particles, (d) shows sodium succinate-chlorinated cellulose particles, and (e) shows them. FIG. 3 is a plot of X-ray diffraction showing sodium glutarate chlorinated cellulose particles, respectively.

FIG. 12 shows the difference in the evaporation rate of water between (a) cellulose glutarate and water alone, (b) cellulose glutarate and untreated cellulose, and (c) sodium glutarate and glutarate. It is a plot figure of a thermobalance.

FIG. 13 is a differential diagram showing the evaporation rate of water as (a) cellulose succinate and water only, (b) cellulose succinate and untreated cellulose, and (c) Na cellulose succinate and cellulose succinate. It is a plot figure of a thermobalance.

   ─────────────────────────────────────────────────── ─── Continued front page    (71) Applicant 591202155             Kumamoto Prefecture             6-18-1, Suizenji Temple, Kumamoto City, Kumamoto Prefecture (72) Inventor Hirotaka Ihara             Kumamoto City, Kumamoto City, Takahira 3-21-9 (72) Inventor Toshihiko Sakurai             Maison, 6-63, Toka, Kumamoto City, Kumamoto Prefecture             Gene 206 (72) Inventor Makoto Takafuji             Kumamoto City Kumamoto City Hakkei Mizutani 4-chome 3-73             Nomiya Flat 202 (72) Inventor Yasunori Takiguchi             45 Iwano, Ueki-cho, Kumamoto-gun, Kumamoto Prefecture             Pu Pharmaceutical Co., Ltd. (72) Inventor Atsuko Tobata             45 Iwano, Ueki-cho, Kumamoto-gun, Kumamoto Prefecture             Pu Pharmaceutical Co., Ltd. (72) Inventor Shinichiro Ishihara             Harayama 3-chome 14-13-403 Saitama City, Saitama Prefecture (72) Inventor Shoji Nagaoka             Kumamoto Prefecture Kumamoto City Higashimachi 3-11-38 Kumamoto Prefecture Industry             Inside the technical center (72) Inventor Masanori Nagata             Kumamoto Prefecture Kumamoto City Higashimachi 3-11-38 Kumamoto Prefecture Industry             Inside the technical center F-term (reference) 4C083 AC102 AC122 AC302 AC482                       AD261 AD262 CC04 EE06                       EE07                 4C090 AA05 BA29 BB03 BB12 BB36                       BB52 BB65 BD22 BD34

Claims (11)

[Claims] 1. Cellulose derivative particles having a structure in which a part or all of the hydroxyl groups of cellulose are substituted with a carboxyl group of a polyvalent carboxylic acid by an ester bond, and having a spherical shape. 2. A part or all of the hydroxyl groups of cellulose is replaced with a carboxyl group of a polyvalent carboxylic acid by an ester bond, and a part or all of the remaining carboxyl groups is metal chloride with an alkali metal or an alkaline earth metal. Cellulose derivative particles having a structured structure and having a spherical shape and being insoluble in water. 3. The average particle size in a wet state is 1 to 1000.
The cellulose derivative particle according to claim 1 or 2, which has a diameter of μm. 4. The cation exchange group capacity is 0.1 to 3.0.
The cellulose derivative particle according to any one of claims 1 to 3, which has a meq / g. 5. Mathematical Formula 1 Circularity = Circumferential length of circle calculated from equivalent radius of circle /
The circularity represented by the perimeter of the projected particle image is 0.9 to 1.0.
7. The cellulose derivative particle according to any one of 1. 6. The substituted polycarboxylic acid is tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, malonic acid, succinic acid, dodecylsuccinic acid, glutaric acid, adipic acid, maleic acid. 5. The cellulose derivative particle according to any one of 5 above. 7. A method for producing cellulose derivative particles, which comprises synthesizing cellulose by wetting cellulose and adding an acid anhydride so that the cellulose derivative particles according to any one of claims 1 to 6 can be produced. . 8. A cosmetic using cellulose derivative particles, comprising the cellulose derivative particles according to any one of claims 1 to 6. 9. The blending amount of the cellulose derivative particles according to claim 1 to 0.01 to the total composition.
25% by weight of a cosmetic material using cellulose derivative particles. 10. The blending amount of the cellulose derivative particles according to claim 1 is 0.01 based on the total composition.
A cosmetic using cellulose derivative particles, characterized in that the content is adjusted to be 10% by weight and liquid. 11. A cosmetic using the cellulose derivative particles according to any one of claims 8 to 10 formulated to be a scrubbing agent.