JP7253206B2 - cosmetics - Google Patents

Description

The present invention relates to cosmetics.

A large number of cosmetic products claiming to have skin firmness and anti-wrinkle effects are on the market. Known methods for enhancing the firmness and elasticity of the skin include a method of blending plant extracts and a method of using vitamin A derivatives. Since these methods lack immediate effects, it is difficult to promote long-term continuous use until pharmacological effects are manifested. Therefore, by forming a cosmetic film on the skin, there are efforts to physically give it firmness and make the skin feel immediate effects, and efforts to make unevenness such as wrinkles less noticeable and give it a visual firmness and luster. It is done.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-269723) discloses that a water-soluble film-forming agent such as polyvinyl alcohol, a water-soluble moisturizing agent, and a specific ester oil are blended to give good spreadability and a glossy feel. Disclosed is a cosmetic that is high and excellent in imparting a feeling of firmness. Patent Document 2 (Japanese Patent Application Laid-Open No. 2010-235472) discloses that a combination of stearyl stearate, which is a solid oil, and a hydrocarbon provides an emulsified cosmetic excellent in providing a soft film and an appropriate feeling of firmness to the skin. is disclosed. Patent Document 3 (Japanese Patent Application Laid-Open No. 2013-136546) describes that the combined use of an oil-soluble film-forming agent and a highly volatile oil agent can provide an immediate feeling of firmness.

However, the water-soluble polymer, solid oil, and oil-soluble film-forming agent, which contribute to imparting firmness by forming a cosmetic film used in these, all feel sticky to the skin during and after application. . In addition, when the formed cosmetic film lacks flexibility, there is also a problem that the cosmetic film is torn due to the movement of the skin. Patent Document 4 (Japanese Patent Application Laid-Open No. 11-180817) obtains a firmness-imparting agent that can make the skin visually glossy and firm by using a powder that has strong specular reflection and diffuse reflection. However, this does not give a physical sense of firmness due to the cosmetic film.

On the other hand, cellulose nanofibers are being studied for their applications such as improving the strength of composite materials. Only the use as an agent (Patent Document 6 (Japanese Unexamined Patent Application Publication No. 2011-57567)) has been studied, and it has never been used to improve the physical properties of cosmetic films.

JP 2007-269723 A JP 2010-235472 A JP 2013-136546 A JP-A-11-180817 JP 2009-62332 A JP 2011-57567 A

The present invention was completed under such background art, and its object is to form a non-sticky, flexible, and tear-free cosmetic film on the skin, thereby giving the skin a feeling of physical firmness. To provide a cosmetic which imparts a smooth texture to the skin and visually makes the skin look fine.

As a result of intensive research, the inventors of the present invention found that a cosmetic containing a specific cellulose nanofiber can solve the above problems. The present invention that solves the problems is as follows.

(Means according to claim 1)
In addition to a thickening stabilizer, it contains cellulose nanofibers with an average fiber diameter of 10 to 1000 nm,
The cellulose nanofiber has a pulp viscosity of 1 to 10 cps and a coefficient of variation of fiber diameter distribution of 1.1 or less,
The raw material pulp of the cellulose nanofiber is a chemical pulp,
A cosmetic characterized by:

(Means according to claim 2)
Consists of an aqueous phase and an oil phase,
The oil phase contains an oil-soluble film-forming agent,
wherein the oil-soluble film-forming agent is a partially crosslinked organopolysiloxane;
Cosmetics according to claim 1.

(Means according to claim 3)
The chemical pulp is softwood bleached kraft pulp,
Cosmetics according to claim 1 .

(Means according to claim 4)
The cellulose nanofiber has a water retention rate of 300 to 480% ,
Cosmetics according to claim 1.

(Means according to claim 5)
The content of the thickening stabilizer is 0.01 to 5% by mass,
containing an ultraviolet scattering agent treated with a silicone compound;
Cosmetics according to claim 1.

According to the present invention, it becomes a cosmetic that imparts physical firmness to the skin and makes the skin look fine visually.

FIG. 4 is a diagram showing test results of film flexibility. FIG. 4 is a diagram showing test results of film flexibility. FIG. 4 is a diagram showing test results of film flexibility. FIG. 4 is a diagram showing test results of film flexibility. FIG. 4 is a diagram showing test results of film flexibility. FIG. 4 is a diagram showing test results of film flexibility.

Next, a mode for carrying out the invention will be described. Note that this embodiment is an example of the present invention. The scope of the present invention is not limited to the scope of this embodiment.

The cosmetic of this embodiment contains at least predetermined cellulose nanofibers in addition to the thickening stabilizer. Conventionally, cellulose nanofibers have been used as thickening and stabilizing agents. However, in this embodiment, cellulose nanofibers are used, for example, as a film-forming component. That is, in the present embodiment, a thickening stabilizer is also blended separately, and conventional cellulose nanofibers correspond to (associated with) one type of the thickening and stabilizing agent in the present embodiment.

As will be described in detail below, when cellulose nanofibers are used as a film-forming component, not all cellulose nanofibers that can be used as thickening stabilizers can be used. exists. Moreover, in the present embodiment, cellulose nanofibers are not used as a thickening and stabilizing agent, but the use of cellulose nanofibers as a thickening and stabilizing agent is not denied.

(cellulose nanofiber)
In this embodiment, a given cellulose nanofiber (CNF) functions as a film-forming component. Moreover, since the predetermined cellulose nanofiber is also a type of cellulose nanofiber, it has a function of suppressing stickiness. Furthermore, after being applied to the skin, cellulose nanofibers form a cosmetic film on the skin together with other non-volatile ingredients in the cosmetic, thereby giving the skin a physical sense of firmness and visually smooth skin. It has a function to show

The prescribed cellulose nanofibers in the present embodiment can be obtained by defibrating (refining) raw material pulp.

Raw material pulp for cellulose nanofibers includes, for example, wood pulp made from broad-leaved trees and coniferous trees, non-wood pulp made from straw, bagasse, cotton, hemp, pistil fibers, etc., recovered waste paper, waste paper, etc. It is possible to select and use one or more of waste paper pulp (DIP) and the like.

However, it is preferable to use wood pulp rather than non-wood pulp or waste paper pulp, because contamination of impurities is avoided as much as possible and α-cellulose, which is insoluble in alkali among cellulose components, can be obtained at a high content. By treating with alkali, alkali-soluble components can be removed, and the purity of cellulose can be increased.

As the wood pulp, for example, one or more of chemical pulps such as hardwood kraft pulp (LKP) and softwood kraft pulp (NKP), mechanical pulp (TMP), etc. can be selected and used.

The hardwood kraft pulp may be bleached hardwood kraft pulp, unbleached hardwood kraft pulp, or semi-bleached hardwood kraft pulp. Similarly, the softwood kraft pulp may be softwood bleached kraft pulp, softwood unbleached kraft pulp, or softwood semi-bleached kraft pulp.

Examples of mechanical pulp include stone ground pulp (SGP), pressure stone ground pulp (PGW), refiner ground pulp (RGP), chemi ground pulp (CGP), thermo ground pulp (TGP), ground pulp (GP), One or more of thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), refiner mechanical pulp (RMP), bleached thermomechanical pulp (BTMP) and the like can be selected and used. However, in order to avoid contamination with impurities other than the cellulose mentioned above, it is particularly preferable to use chemical pulp such as hardwood kraft pulp (LKP) and softwood kraft pulp (NKP).

Prior to defibration of cellulose nanofibers, pretreatment can also be performed by a chemical method. Examples of chemical pretreatments include hydrolysis of polysaccharides with acid (acid treatment), hydrolysis of polysaccharides with enzymes (enzyme treatment), swelling of polysaccharides with alkali (alkali treatment), and oxidation of polysaccharides with an oxidizing agent ( oxidation treatment), reduction of polysaccharides with a reducing agent (reduction treatment), and the like.

Alkali treatment prior to fibrillation dissociates some of the hydroxyl groups of hemicellulose and cellulose in the pulp, anionizing the molecules, weakening intramolecular and intermolecular hydrogen bonds, and promoting the dispersion of cellulose fibers during fibrillation. be.

Alkali used for alkali treatment include, for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia solution, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and the like. An organic alkali or the like can be used. However, from the viewpoint of production cost, it is preferable to use sodium hydroxide.

If enzymatic treatment, acid treatment, or oxidation treatment is performed prior to fibrillation, the water retention of cellulose nanofibers can be lowered, the degree of crystallinity can be increased, and homogeneity can be increased. In this regard, if the water retention of the cellulose nanofibers is low, dehydration is facilitated, and the dewaterability of the cellulose nanofiber dispersion (hereinafter also referred to as "slurry") is improved.

Enzyme treatment, acid treatment, and oxidation treatment of the raw material pulp decomposes the hemicellulose and amorphous regions of cellulose in the pulp. can be improved. The dispersibility of cellulose fibers contributes, for example, to improving the homogeneity of cellulose nanofibers. In this regard, in the field of cosmetics, since the amount of cellulose nanofibers is small relative to the total amount of cosmetics, improvement of homogeneity is an important factor. However, since pretreatment reduces the aspect ratio of cellulose nanofibers, it is preferable to avoid excessive pretreatment, particularly when used as a film-forming component.

For defibration of raw material pulp, for example, beaters, high-pressure homogenizers, homogenizers such as high-pressure homogenizers, grinders, stone mills such as grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, jet mills, etc. It can be carried out by beating the raw material pulp using However, it is preferable to use a refiner or a jet mill.

The fibrillation of raw material pulp depends on the average fiber diameter, average fiber length, water retention, crystallinity, variation coefficient of fiber diameter distribution, peak value in pseudo particle size distribution curve, pulp viscosity, dispersion liquid (slurry ) is preferably carried out so that the B-type viscosity of is the desired value or rating as shown below.

The average fiber diameter (average fiber width, average diameter of single fibers) of cellulose nanofibers is preferably 10 to 1000 nm, more preferably 10 to 100 nm, and particularly preferably 10 to 80 nm. If the average fiber diameter of the cellulose nanofibers is less than 10 nm, the function as a film-forming component may be impaired. In other words, the cosmetic film formed on the skin becomes less flexible, and there is a risk that the cosmetic film will break or crack due to movement of the skin after application. In addition, when the average fiber diameter of the cellulose nanofibers is less than 10 nm, the viscosity of the cosmetic increases, so that the spreadability of the cosmetic decreases. There is a risk that you will not be able to In addition, when the average fiber diameter of the cellulose nanofibers is less than 10 nm, the dewaterability of the slurry containing the cellulose nanofibers may deteriorate.

On the other hand, if the average fiber diameter of the cellulose nanofibers exceeds 1000 nm, the cosmetic material may become less rough, sticky, and less elastic. In terms of stickiness and firmness, the cellulose nanofibers preferably have an average fiber diameter of 100 nm or less.

The average fiber diameter of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, fibrillation, and the like.

A method for measuring the average fiber diameter of cellulose nanofibers is as follows.
First, 100 ml of an aqueous dispersion (slurry) of cellulose nanofibers having a solid content concentration of 0.01 to 0.1% by mass was filtered through a Teflon (registered trademark) membrane filter, filtered once with 100 ml of ethanol, and then filtered with 20 ml of t-butanol. Replace the solvent three times. It is then freeze-dried and coated with osmium to form a sample. This sample is observed with an electron microscope SEM image at a magnification of 3000 times to 30000 times depending on the width of the constituent fibers. Specifically, two diagonal lines are drawn on the observation image, and three straight lines passing through the intersections of the diagonal lines are arbitrarily drawn. Furthermore, the width of a total of 100 fibers intersecting with these three straight lines is visually measured. Then, the median diameter of the measured value is taken as the average fiber diameter.

The average fiber length (average length of single fibers) of cellulose nanofibers is preferably 0.3 to 200 μm, more preferably 0.4 to 200 μm, and particularly preferably 0.5 to 200 μm. If the average fiber length of the cellulose nanofibers is less than 0.3 μm, it may not function as a film-forming component. Moreover, when the average fiber length of the cellulose nanofibers is less than 0.3 μm, the feeling of firmness may be poor.

On the other hand, if the average fiber length of the cellulose nanofibers exceeds 200 μm, the fibers tend to become entangled with each other, which may cause the problem of aggregation. In addition, aggregation of cellulose nanofibers may lead to a rough feel of the cosmetic, and may cause an eraser-like clump (twist) to occur.

The average fiber length of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, fibrillation, and the like.

The average fiber length of cellulose nanofibers is measured by visually measuring the length of each fiber in the same manner as the average fiber diameter. Let the median length of the measured value be the average fiber length.

Cellulose nanofibers have a coefficient of variation in fiber diameter distribution of preferably 0.1 to 1.5, more preferably 0.3 to 1.1. When the coefficient of variation of the fiber diameter distribution exceeds 1.1, the fiber diameter distribution becomes wider, and not only nano-sized cellulose fibers but also micro-sized fibers are included, and the flowability of the cosmetic material itself decreases. In addition, it leads to discomfort such as roughness when applied to the skin. If the coefficient of variation is 0.3 or less, the nano-sized fiber diameter tends to be uniform, but adjustment by pretreatment, fibrillation, etc. tends to be difficult.

The coefficient of variation of the fiber diameter distribution is a value obtained by calculating the standard deviation value/average value using the average value and the standard deviation value of the fiber diameters aggregated in the aggregation of the average fiber diameters described above.

The water retention of cellulose nanofibers is preferably 500% or less, more preferably 300 to 480%. If the water retention of the cellulose nanofibers is less than 300%, the dispersibility of the cellulose nanofibers may deteriorate. Also, if the water retention of the cellulose nanofibers is less than 300%, it may cause the cosmetic material to become rough.

On the other hand, if the water retention rate of the cellulose nanofibers exceeds 500%, the water retention capacity of the cellulose nanofibers themselves increases, possibly deteriorating the dehydration properties of the cellulose nanofibers.

The water retention of cellulose nanofibers can be adjusted, for example, by selecting raw material pulp, pretreatment, fibrillation, and the like.

The water retention rate of cellulose nanofiber is determined by JAPAN TAPPI No. 26 (2000).

The pulp viscosity of the cellulose nanofibers is preferably 1-10 cps, more preferably 2-9 cps, and particularly preferably 3-8 cps. The pulp viscosity is the viscosity of the solution after dissolving cellulose in the copper ethylenediamine solution, and the higher the pulp viscosity, the higher the degree of polymerization of cellulose. It is related to the strength and rigidity of cellulose fibers. If the degree of polymerization is too high, the feeling of firmness will be poor and there is a high possibility that the affinity with the skin will be lost. The degree of polymerization of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, fibrillation, and the like. If the pulp viscosity is within the above range, it is possible to prevent the occurrence of rough feeling while functioning as a film-forming component.

The peak value (hereinafter also simply referred to as “peak value”) in the pseudo-particle size distribution curve of cellulose nanofibers is preferably one peak. When there is one peak, cellulose nanofibers have high uniformity in fiber length and fiber diameter, and are suitable for use as raw materials for cosmetics.

The peak value of cellulose nanofibers is, for example, 1-100 μm, preferably 3-80 μm, more preferably 5-60 μm. When the peak value of cellulose nanofibers is less than 1 μm, cellulose refinement progresses. On the other hand, when the peak value of cellulose nanofibers exceeds 100 μm, there is a possibility that the fibers may not be defibrated to nanosize.

The peak value of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, fibrillation, and the like.

The peak value of cellulose nanofiber is the value measured according to ISO-13320 (2009). More specifically, first, the volume-based particle size distribution of the aqueous dispersion of cellulose nanofibers is examined using a particle size distribution analyzer (laser diffraction/scattering particle size distribution analyzer manufactured by Seishin Enterprise Co., Ltd.). Next, the median diameter of cellulose nanofibers is measured from this distribution. Let this median diameter be a peak value.

In addition to the above peak values, the cellulose nanofibers preferably have a cumulative volume ratio of particles having a particle size of 100 µm or less of 70% or more, more preferably 90% or more. If the cumulative volume ratio of particles having a particle size of 100 µm or less is less than 70%, the stickiness and firmness are impaired, and the film-forming component's function is not sufficiently exhibited, as can be inferred from the test examples described later. There is a risk.

Cellulose nanofibers obtained by fibrillation can be dispersed in an aqueous medium as a dispersion (slurry), if necessary. It is particularly preferred that the aqueous medium is entirely water (aqueous solution). However, the aqueous medium may be another liquid partially compatible with water. As other liquids, for example, lower alcohols having 3 or less carbon atoms can be used.

The B-type viscosity of the cellulose nanofiber dispersion (concentration 1.5%) is preferably 1,000 cps to 20,000 cps, more preferably 1,000 to 10,000 cps, and particularly preferably 1,000 to 5,000 cps. is. When the B-type viscosity of the dispersion is within the above range, mixing with other components constituting the cosmetic is facilitated, and dewatering properties of the slurry (dispersion) are improved.

The B-type viscosity (solid concentration: 1.5%) of the cellulose nanofiber dispersion is a value measured in accordance with JIS-Z8803 (2011) "Method for measuring liquid viscosity". The B-type viscosity is the resistance torque when the dispersion is stirred, and means that the higher the viscosity, the greater the energy required for stirring.

It is preferable to add a solvent such as water to the cellulose nanofiber dispersion to adjust the solid content concentration of the cellulose nanofiber in the dispersion. The solid content concentration of cellulose nanofibers is preferably 0.1% to 5.0%, more preferably 0.3 to 4.0%, and particularly preferably 0.5 to 3.0%. If the solid content concentration of the cellulose nanofibers is less than 0.1%, the fluidity becomes too high and it may become difficult to mix with other components. Moreover, even if the solid content concentration of the cellulose nanofibers exceeds 5.0% by mass, the fluidity is significantly reduced, which may make it difficult to mix with other components.

Cellulose nanofibers may be dispersed in either the water phase or the oil phase in the cosmetic. However, dispersing it in the aqueous phase is preferable from the viewpoint of the storage stability of the cosmetic and the ease of spreadability on the skin.

The cellulose nanofiber content in the cosmetic is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and particularly preferably 0.1 to 1% by mass. If the content of cellulose nanofibers is excessively low, the feeling of firmness will be poor, and there is a possibility that the function as a film-forming component will not be exhibited. On the other hand, if the content of cellulose nanofibers is excessively high, the spreadability of the cosmetic is poor and the flexibility of the cosmetic film is lowered.

(oil content)
The cosmetic of this embodiment contains oil as a dispersed phase. After being applied to the skin, the oil forms a cosmetic film together with cellulose nanofibers and the like, and has a function of giving the skin a feeling of firmness.

Any oil can be used regardless of its origin, such as animal oil, vegetable oil, or synthetic oil, or its properties, such as solid oil, semi-solid oil, liquid oil, or volatile oil.

Examples of oils include hydrocarbons, oils, waxes, hardened oils, ester oils, fatty acids, silicone oils, fluorine oils, lanolin derivatives, oil-soluble ultraviolet absorbers, and the like. species or combinations of two or more species can be used.

More specifically, for example, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, Japanese wax, montan wax;
Fats and oils such as olive oil, castor oil, jojoba oil, mink oil, and macadamia nut oil;
Waxes such as beeswax, lanolin, carnauba wax, candelilla wax, gay wax;
Esters such as cetyl isooctanate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, glyceryl tribehenate, pentaerythrite rosinate, neopentylglycol dioctoate;
Silicones such as low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and fluorine-modified silicone;
Fluorinated oils such as perfluoropolyether, perfluorodecane, and perfluorooctane;
Lanolin derivatives such as lanolin, lanolin acetate, isopropyl lanolin fatty acid, and lanolin alcohol;
It is possible to use one or a combination of two or more of these.

The oil content in the cosmetic is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 25% by mass. If the oil content is less than 1% by mass, the cosmetic film may be inferior in flexibility. On the other hand, if the oil content exceeds 50% by mass, the feeling of firmness is reduced, and there is a possibility that the sticky feeling cannot be removed.

(powder)
Powder can be blended in the cosmetic of this embodiment. When the cosmetic contains powder, the stickiness of the cosmetic film can be further suppressed. In addition, when the cosmetic of this embodiment is used as a base makeup cosmetic, desired covering power and finish can be obtained.

The powder is not limited by, for example, spherical, plate-like, spindle-like, or needle-like shape, particle size, or porous or non-porous particle structure. Moreover, any of inorganic powders, glittering powders, organic powders, pigments, and composite powders may be used.

Examples of powders include titanium oxide, zinc oxide, zirconium oxide, cerium oxide, red iron oxide, yellow iron oxide, black iron oxide, konjo, ultramarine blue, silicic anhydride, magnesium carbonate, calcium carbonate, aluminum hydroxide, and water. Inorganics such as chromium oxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, smectite, bentonite, kaolin, synthetic mica, synthetic sericite, sericite, talc, silicon carbide, barium sulfate, boron nitride, etc. powders;
Bright powders such as bismuth oxychloride, mica titanium, iron oxide-coated mica, iron oxide-coated mica titanium, organic pigment-coated mica titanium, and aluminum powder;
Organic powders such as magnesium stearate, zinc stearate, N-acyl lysine, polystyrene, nylon, polymethylmethacrylate, polymethylsilsesquioxane powder, organopolysiloxane elastomer powder, cellulose, crystalline cellulose, and cellulose acetate;
It is possible to use one or a combination of two or more of these.

The above powders may optionally contain surface treatment agents such as alumina, silica, inorganic compounds such as iron oxide, fluorine compounds, silicone compounds, phospholipids, phospholipid derivatives, metallic soaps, waxes, surfactants, oils and fats, It can also be used after being surface-treated with a hydrocarbon or the like.

Among the above, spherical organic powders such as polystyrene, nylon, polymethyl methacrylate, polymethylsilsesquioxane powder, organopolysiloxane elastomer powder, cellulose, crystalline cellulose, cellulose acetate, etc. are used to reduce pores and fine wrinkles. Since the unevenness of the coating can be effectively hidden, a favorable finish can be obtained.

When the cosmetic of this embodiment is used as a base makeup cosmetic, one or more inorganic powders such as titanium oxide, red iron oxide, yellow iron oxide, and black iron oxide are used as the powder. It is preferable to use them in combination. In particular, inorganic powders coated with a metal oxide such as silica are excellent in emulsification stability and prevention of color change because they are well dispersed in a continuous aqueous phase.

As a commercial product of silica-coated red iron oxide, for example, SYMPHOLIGHT RW manufactured by Nikki Shokubai Kasei Co., Ltd. can be used. As a commercial product of silica-coated yellow iron oxide, for example, SYMPHOLIGHT Y10 can be used.

The powder content is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, particularly preferably 5 to 25% by mass, based on the total amount of the cosmetic. If the powder content is less than 1% by mass, the cosmetic film tends to be sticky. On the other hand, if the powder cosmetic content exceeds 40% by mass, the cosmetic film may be inferior in flexibility.

(UV protection agent)
As used herein, the term "ultraviolet protective agent" means a component that absorbs (ultraviolet absorber) or scatters (ultraviolet scattering agent) ultraviolet rays to protect the skin or cosmetic itself from ultraviolet rays. In this regard, it is said that general ultraviolet scattering agents used in cosmetics also have the ability to absorb ultraviolet rays. However, in the present embodiment, there is no need to clearly distinguish between the ultraviolet absorber and the ultraviolet scattering agent, and both are used to protect the skin and cosmetics themselves from ultraviolet rays. Therefore, in the present specification, both of them are defined as UV protective agents.

UV absorbers include water-soluble UV absorbers and oil-soluble UV absorbers classified as oil. Examples of water-soluble ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4 , 4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone , 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, and other benzophenone-based UV absorbers;
benzimidazole-based UV absorbers such as phenylbenzimidazole-5-sulfonic acid and its salts, phenylene-bis-benzimidazole-tetrasulfonic acid and its salts;
3-(4′-Methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl ester, etc. may be used alone or in combination of two or more. can.

Examples of oil-soluble ultraviolet absorbers include cinnamic acid-based ultraviolet absorbers such as benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, and glyceryl mono-2-ethylhexanoate di-paramethoxycinnamate;
Benzophenone UV absorbers such as hydroxymethoxybenzophenone, dihydroxymethoxybenzophenone, dihydroxybenzophenone, and tetrahydroxybenzophenone;
para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, amyl para-dimethylaminobenzoate, octyl para-dimethylaminobenzoate, ethyl 4-[N,N-di(2-hydroxypropyl)amino]benzoate, diethylaminohydroxy Benzoic acid ester-based ultraviolet absorbers such as hexyl benzoylbenzoate;
salicylic acid UV absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, para-tert-butylphenyl salicylate, and homomenthyl salicylate;
triazine-based UV absorbers such as ethylhexyltriazone (2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]1,3,5-triazine) and bisethylhexyloxyphenolmethoxyphenyltriazine;
4-tert-butyl-4'-methoxydibenzoylmethane, menthyl anthranilate, 2-(2-hydroxy-5-methylphenyl)benzotriazole, dimethoxybenzylidene dioxoimidazolidine 2-ethylhexylpropionate, octocrylene, dimethicodiethyl One or a combination of two or more of benzalmalonate and the like can be used.

The ultraviolet scattering agent is a fine particle powder, and is classified into the powders described above. This ultraviolet scattering agent is preferably a metal oxide having an average particle size of 100 nm or less. Specifically, for example, one or a combination of two or more of titanium oxide, zinc oxide, cerium oxide, and the like having an average particle size of 100 nm or less can be used.

As the ultraviolet scattering agent, one subjected to hydrophobic treatment is preferable in terms of water resistance. A normal surface treatment method can be employed as the hydrophobic treatment method. Specifically, for example, fats and oils are adsorbed on the powder surface, or functional groups such as hydroxyl groups are used to cause esterification or etherification to make the powder lipophilic. A metal soap treatment method using salt, magnesium salt, or aluminum salt, a silicone treatment method using silicone compounds such as dimethylsiloxane or hydrogen dimethicone, a method of treatment with a fluorine compound having a perfluoroalkyl group, and a treatment with an alkylalkoxysilane. method, etc. can be adopted. Among the above treatment methods, it is preferable to employ a silicone treatment using a silicone compound from the viewpoint of water resistance and emulsion stability.

The content of the UV protection agent is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, particularly preferably 5 to 25% by mass, based on the total cosmetic composition. If the content of the UV protection agent is less than 1% by mass, the UV protection effect is insufficient. On the other hand, if the content of the UV protection agent exceeds 40% by mass, the spreadability of the cosmetic on the skin may decrease.

(film component)
The cosmetic of the present embodiment includes an oil-in-water emulsified cosmetic and contains at least one film component selected from a water-soluble film-forming agent, an oil-soluble film-forming agent, and a film-forming polymer emulsion. preferred. By containing these film components, the firmness of the skin can be further enhanced.

A water-soluble film-forming agent dissolves in an aqueous component to form a cosmetic film. As the water-soluble film-forming agent, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, vinyl acetate/vinylpyrrolidone copolymer, modified corn starch, hydrolyzed hydrogenated starch, etc., may be used alone or in combination of two or more. can do.

The oil-soluble film-forming agent dissolves or disperses in the oily component to form a cosmetic film. Examples of oil-soluble film-forming agents include trimethylsiloxysilicic acid, partially crosslinked organopolysiloxane, trimethylsiloxysilylpropylcarbamic acid, fluorine-modified silicone, acrylic-modified silicone, silicone-based resins such as silicone dendrimer-modified resin compounds, and penta rosin acid. One or a combination of two or more of rosin acid resins such as erythritol and glyceryl rosinate, candelilla resin, polyvinyl acetate resin, polyvinyl isobutyl ether, polyisobutylene, and the like can be used.

However, among the above, the partially crosslinked organopolysiloxane is particularly preferable because it can form a less sticky, water-resistant cosmetic film. Partially crosslinked organopolysiloxanes are available in the form of gels dispersed in liquid oils. Commercially available partially crosslinked organopolysiloxanes include, for example, KSG-15 (dimethicone/vinyl dimethicone) crosspolymer and cyclopentasiloxane manufactured by Shin-Etsu Chemical Co., Ltd., (dimethicone/vinyl dimethicone) crosspolymer and methyl trimethicone. KSG-1510 consisting of (dimethicone/vinyl dimethicone) crosspolymer and KSG-16 consisting of dimethicone, KSG-18A consisting of (dimethicone/phenyl vinyl dimethicone) crosspolymer and diphenylsiloxyphenyl trimethicone, (vinyl dimethicone/lauryl dimethicone) cross KSG-41A consisting of polymer and liquid paraffin, KSG-43 consisting of (vinyl dimethicone/lauryl dimethicone) crosspolymer and triethylhexanoin, KSG- consisting of (lauryl polydimethylsiloxyethyl dimethicone/bis-vinyl dimethicone) crosspolymer and isododecane 042Z, Dow Corning Toray 9040 and 9045 Silicone Elastomer Blends consisting of dimethicone crosspolymer and cyclopentasiloxane, 9041 Silicone Elastomer Blend consisting of dimethicone crosspolymer and dimethicone, 3901 Liquid consisting of (dimethicone/vinyl dimethicone) crosspolymer and dimethicone. EL-8051 IN Silicone Organic Elastomer Blend consisting of Satin Blend, (dimethicone/bis-isobutyl PPG-20) crosspolymer and isodecyl neopentanoate, alkyl (C30-45) cetearyl dimethicone crosspolymer from Momentive Performance Materials and Velvesil 125, which consists of cyclopentasiloxane; Velvesil 034, which consists of alkyl (C30-45) cetearyl dimethicone crosspolymer and caprylyl methicone; Velvesil DM, which consists of cetearyl dimethicone crosspolymer and dimethicone;

A film-forming polymer emulsion is an aqueous dispersion of water-insoluble polymers. Film-forming polymer emulsions include, for example, alkyl acrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, styrene/alkyl acrylate copolymer emulsions, styrene/alkyl methacrylate copolymer emulsions, and vinyl acetate polymers. Emulsion, vinylpyrrolidone/styrene copolymer emulsion, alkyl acrylate/vinyl acetate copolymer emulsion, alkyl methacrylate/vinyl acetate copolymer emulsion, acrylic acid/alkyl acrylate copolymer emulsion, alkyl acrylate/methacrylate Copolymer emulsions, methacrylic acid/alkyl acrylate copolymer emulsions, methacrylic acid/alkyl methacrylate copolymer emulsions, alkyl dimethicone acrylate copolymer emulsions, etc., may be used alone or in combination of two or more. be able to.

The content of the coating component is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total amount of the cosmetic. If the amount of the film component is too small, the effect of enhancing the firmness may not be obtained. On the other hand, if the film component is too much, there is a possibility that stickiness cannot be suppressed.

(thickening stabilizer)
The cosmetic composition of the present embodiment contains a thickening and stabilizing agent that functions as at least one of a thickening agent and a stabilizing agent. As a result, it is possible to improve the feeling of use such as ease of spreading of the cosmetic, and to keep the emulsified state and the dispersed state stably for a long period of time. As the thickening stabilizer, for example, water-soluble polymers other than water-soluble film-forming agents, clay minerals, and the like can be used.

More specifically, thickening stabilizers include, for example, carboxyvinyl polymer, sodium polyacrylate, alkyl acrylate/methacrylate copolymer, (PEG-240/decyltetradeceth-20/HDI) copolymer. , (Na acrylate/acryloyldimethyltaurine) copolymer, (hydroxyethyl acrylate/sodium acryloyldimethyltaurate) copolymer, (acryloyldimethyltaurate ammonium/VP) copolymer, (acryloyldimethyltaurate ammonium methacrylate beheneth-25) crosspolymer, ( Alkyl Acrylate/Steareth-20 Methacrylate) Copolymer, (Dimethylacrylamide/Na Acryloyldimethyltaurate) Crosspolymer, Polyacrylamide, Polyoxyethylene Polyoxypropylene Block Copolymer, Polyvinyl Methyl Ether, Methylcellulose, Ethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose , hydroxypropyl methylcellulose, sodium carboxymethylcellulose, cationic cellulose, sodium alginate, propylene glycol alginate, guar gum, locust bean gum, gum arabic, tragacanth, galactan, carob gum, karaya gum, pectin, agar, quince seed (quince), algecolloid. (brown algae extract), carrageenan, xanthan gum, dextran, pullulan, bentonite, montmorillonite, hectorite, magnesium aluminum silicate, laponite, etc., may be used singly or in combination of two or more.

However, it is preferable to use one or a combination of two or more of carboxyvinyl polymer, alkyl acrylate/methacrylate copolymer, xanthan gum, (Na acrylate/acryloyldimethyltaurine) copolymer, and hydroxypropylmethyl cellulose.

The content of the thickening stabilizer is preferably 0.01 to 5% by mass, more preferably 0.02 to 4% by mass, and particularly preferably 0.05 to 3% by mass, based on the total amount of the cosmetic. . If the content of the thickening and stabilizing agent is less than 0.01% by mass, it is impossible to improve the feel during use and stabilize the emulsified/dispersed state. Cellulose nanofibers have conventionally been used as thickening and stabilizing agents, but in the present embodiment, they are used as film-forming components. In the present embodiment, the cellulose nanofibers are blended in the cosmetic under predetermined conditions in order to function as a film-forming component, and the thickening and stabilizing agent is separately blended to function for thickening and stabilizing.

(Surfactant)
Nonionic surfactants, polymer emulsifiers, anionic (anionic) surfactants, cationic (cationic) surfactants, amphoteric surfactants, semipolar surfactants, etc. of surfactants can be blended. Surfactants can function as emulsifiers as well as, for example, solubilizers, wetting agents, detergents, and the like.

Examples of anionic surfactants include fatty acid soaps, ether carboxylic acids and salts thereof, carboxylic acid salts such as condensation of amino acids and fatty acids, alkylsulfonic acids, alkene sulfonates, sulfonates of fatty acid esters, and fatty acid amides. Sulfonates, alkylsulfonates and their formalin condensate sulfonates, alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates, fatty acid ester sulfates, fatty acid alkylols Examples include amide sulfates, sulfates such as funnel oil, alkyl phosphates, alkyl ether phosphates, alkyl allyl ether phosphates, and amide phosphates.

Examples of cationic surfactants include alkylamine salts, amine salts such as polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts, and the like. can.

Examples of amphoteric surfactants include betaine, aminocarboxylates, imidazoline derivatives and the like.

Examples of nonionic surfactants include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, oxidized ethylene derivatives of glycerin fatty acid esters, propylene glycol fatty acid esters, and oxidized propylene glycol fatty acid esters. Ethylene derivatives, polyethylene glycol fatty acid esters, sucrose esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene castor oil derivatives, polyoxyethylene hydrogenated castor oil derivatives, polyoxyethylene phyto Examples include stanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, and the like.

(moisturizer)
A moisturizing agent can be blended in the cosmetic of this embodiment. As the moisturizing agent, for example, polyhydric alcohols, saccharides, sugar alcohols, amino acids, peptides, water-soluble polymers and the like can be used singly or in combination of two or more. In addition, as moisturizing agents, for example, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, collagen, sodium lactate, dl-pyrrolidone carboxylate, rose rose extract, yarrow extract, melilot extract, etc. are blended. be able to.

(other ingredients)
Cosmetics of this form include, for example, antibacterial agents, preservatives, fragrances, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients, vitamins, amino acids, nucleic acids, inclusion Various ingredients, such as chemical compounds, which are usually blended in cosmetics can be blended.

(Production method)
In producing the cosmetic of the present embodiment, a normal production method, for example, a method in which an aqueous phase and an oil phase are separately prepared, and then the oil phase is gradually added to the aqueous phase while stirring to form an oil-in-water emulsifier. , a soap emulsification method, a reaction emulsification method, a D-phase emulsification method, or the like can be employed.

(Usage, etc.)
The cosmetic of this form may be in any form of cream, gel, milky lotion, or liquid (thin milky lotion). The cosmetic of this embodiment is particularly excellent as a make-up cosmetic such as a foundation and a base. However, the cosmetic of this embodiment is also excellent as a make-up cosmetic such as an emulsion-like or cream-like eye shadow, blush, concealer, and the like.

Next, various test results are shown to further clarify the effects of the present invention.
An oil-in-water emulsified cosmetic (sample) having the composition shown in Table 1 was prepared according to the following production procedure. Next, each of the prepared samples was applied to the skin (face) of the evaluation panel and the urethane artificial skin for evaluation (manufactured by Beaulux) and dried at room temperature for 30 minutes or more. Various samples were evaluated according to the following criteria.

Softwood bleached kraft pulp was used as the raw material for the cellulose fibers (CNF-A, CNF-B, MFC) blended in each sample. As CNF-C, Rheocrysta (TEMPO oxidized CNF), a product of Daiichi Kogyo Seiyaku Co., Ltd., was used. Table 2 shows the physical properties of each cellulose fiber. The average fiber width of CNF-A and CNF-B was determined by the method described above (observation using SEM images). CNF-C was determined using a transmission electron microscope (TEM). Furthermore, MFC was measured using a fiber analyzer "FS5" manufactured by Valmet. Moreover, the drying shrinkage rate was obtained by the following method.

(Drying shrinkage rate)
First, a cellulose fiber such as CNF was used as an aqueous dispersion, and the concentration was adjusted to 0.5% by mass. Next, 30 g of the water dispersion adjusted to the concentration was placed in a petri dish with a diameter of 7.5 cm and dried at 105°C. Then, the shrinkage rate of the diameter of the cellulose fiber membrane obtained by this drying was measured. The shrinkage ratio was calculated by calculating the diameter of the cellulose fiber membrane (calculating the average of four lines) and using the following formula.
Shrinkage ratio = diameter of cellulose fiber membrane / inner diameter of container (7.5 cm) x 100 (%)

(manufacturing procedure)
The oil-in-water emulsified foundation with the formulation shown in Table 1 was prepared according to the manufacturing procedure shown below, and "non-stickiness", "tension", "no tightness", "fineness of finish", "film We evaluated each item of "flexibility" and "texture score by image analysis". Regarding Table 1,
(1) Components Nos. 1 to 4 were mixed at the mixing ratio shown in Table 1 and heated to 80° C. to dissolve to prepare an aqueous phase (a).
(2) Components Nos. 5 to 11 were mixed at the mixing ratio shown in Table 1 and heated to 80° C. to dissolve to prepare an oil phase (b).
(3) While stirring the water phase (a), the oil phase (b) was mixed little by little with the water phase (a) to prepare the emulsified phase (c).
(4) The emulsified phase (c) was cooled, and components Nos. 12 to 18 were mixed at a mixing ratio shown in Table 1 at 35°C to prepare cosmetics.

(Evaluation: feeling of use)
Each sample (Examples 1, 2 and Comparative Examples 3 to 6) was applied to the face of a female evaluation panel (5 people), and the feeling of use (non-stickiness, firmness, lack of tightness, fineness of finish). , sensory evaluation according to the following criteria. Table 3 shows the results of non-stickiness, firmness and fineness of finish, and Table 4 shows the results of non-tight feeling. Each item is evaluated on a three-level scale: "Good (Rating: 2)", "Neither (Rating: 1)", or "Bad (Rating: 0)". bottom.
[Judgment]: [Average score]
5: 1.5 or more 4: 1.2 or more and less than 1.5 3: 0.8 or more and less than 1.2 2: 0.3 or more and less than 0.8 1: less than 0.3

(Flexibility of film)
First, the artificial skin made of urethane with a thickness of 2 mm (manufactured by Beaulux Co., Ltd., skin model No. 77 2T# black) was cut into a rectangle of 30 mm × 70 mm, and each sample (Examples 1 and 2) was cut into a 30 mm × 50 mm surface. and Comparative Examples 3 to 6) 0.05 g was uniformly applied and dried at room temperature for 30 minutes or more to prepare test pieces. Using a rheometer CR-100 manufactured by Sun Science Co., Ltd., fix 10 mm of the uncoated part on the top and bottom of the long side of the test piece with a jig for tensile test, lower the sample stage at a speed of 20 mm / min, and elongate it by 20 mm (140%). Observed the time. Judgment was made according to the following criteria. The coating flexibility results are shown in Table 4 and Figures 1-6. 1 to 6, (A) is the test piece before stretching, and (B) is the test piece after stretching. FIG. 1 shows the sample 11 of Example 1 applied. FIG. 2 shows the sample 12 of Example 2 coated. FIG. 3 shows the sample 13 of Comparative Example 3 coated. FIG. 4 shows the sample 14 of Comparative Example 4 coated. FIG. 5 shows the sample 15 of Comparative Example 5 applied. FIG. 6 shows the sample 16 of Comparative Example 6 coated.
[judgement]
5: No cracks or the like were observed in the cosmetic film, and the black artificial skin was concealed.
3: A crack with a width of less than 1 mm is observed and a black background is visible.
1: A crack with a width of 1 mm or more is observed.
(Texture score by image analysis)
Appropriate amounts of each sample (Examples 1 and 2 and Comparative Examples 3 to 6) were applied to the faces (left and right cheeks) of two women in their twenties, and photographed using a skin image analyzer VISIA EVOLUTION (manufactured by Canfield). , a texture score, which is an index of skin smoothness, was calculated using the attached analysis software. The imaging was performed by applying the same sample to each of the left and right cheeks at four locations (eight locations in total). Then, each sample (Examples 1 and 2 and Comparative Examples 3 to 6) was photographed. The T value was obtained by dividing the texture score calculated for the same sample by the texture score calculated for the sample containing no cellulose nanofibers (Comparative Example 1) at the same site of the same subject.

(T value) = (texture score calculated for each sample (Examples 1, 2 and Comparative Examples 3 to 6)) / (texture score calculated for Comparative Example 1)
The obtained T values per eight points were simply averaged to obtain the average value of (T), which was judged according to the following criteria. The results of the texture score are shown in Table 4.
[Judgment]: [Average value of (T)]
5: Less than 0.9 3: 0.9 or more and less than 1.0 1: 1.0 or more

(Discussion)
From Table 3, it can be seen that the addition of cellulose nanofibers suppresses stickiness and imparts firmness. However, as is clear from Table 4, when the average fiber diameter of the cellulose nanofibers is too small, a taut feeling occurs and the cosmetic film lacks flexibility.

INDUSTRIAL APPLICABILITY The present invention can be used as cosmetics such as foundations and base makeup cosmetics.

11 Sample 12 of Example 1 Sample 13 of Example 2 Sample 14 of Comparative Example 3 Sample 15 of Comparative Example 4 Sample 16 of Comparative Example 5 Sample of Comparative Example 6

Claims (5)

In addition to a thickening stabilizer, it contains cellulose nanofibers with an average fiber diameter of 10 to 1000 nm,
The cellulose nanofiber has a pulp viscosity of 1 to 10 cps and a coefficient of variation of fiber diameter distribution of 1.1 or less,
The raw material pulp of the cellulose nanofiber is a chemical pulp,
A cosmetic characterized by: Consists of an aqueous phase and an oil phase,
The oil phase contains an oil-soluble film-forming agent,
wherein the oil-soluble film-forming agent is a partially crosslinked organopolysiloxane;
Cosmetics according to claim 1. The chemical pulp is softwood bleached kraft pulp,
Cosmetics according to claim 1 . The cellulose nanofiber has a water retention rate of 300 to 480% ,
Cosmetics according to claim 1. The content of the thickening stabilizer is 0.01 to 5% by mass,
containing an ultraviolet scattering agent treated with a silicone compound;
Cosmetics according to claim 1.

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