JP2021075562A - Cosmetic - Google Patents

Abstract

To provide a cosmetic which gives a physical tight feeling to the skin and makes the skin look fine textured visually by forming a cosmetic film which has no stickiness, is flexible and causes no fracture on the skin.SOLUTION: There is provided a cosmetic which contains a cellulose nanofiber having an average fiber diameter of 10 to 1000 nm in addition to a thickening stabilizer.SELECTED DRAWING: Figure 1

Description

The present invention relates to cosmetics.

Many cosmetics that advocate the firmness and anti-wrinkle effect of the skin are on the market. Known methods for increasing the firmness and elasticity of the skin include a method of blending a plant extract and a method of using a vitamin A derivative. Since these methods lack immediate effect, it is difficult to promote long-term continuous use until the pharmacological effect appears. Therefore, by forming a cosmetic film on the skin, there are efforts to physically give firmness and realize the immediate effect, and efforts to make unevenness such as wrinkles less noticeable and visually give firmness and luster. It is done.

In Patent Document 1 (Japanese Unexamined Patent Publication No. 2007-269723), a water-soluble film-forming agent such as polyvinyl alcohol, a water-soluble moisturizer, and a specific ester oil are blended and spread well at the time of application, and a glossy feeling is obtained. Cosmetics that are expensive and have an excellent firmness are disclosed. According to Patent Document 2 (Japanese Unexamined Patent Publication No. 2010-235472), by combining stearyl stearate, which is a solid oil, and a hydrocarbon, an emulsified cosmetic having a soft film and excellent in imparting an appropriate firmness to the skin can be obtained. Is disclosed. Patent Document 3 (Japanese Unexamined Patent Publication No. 2013-136546) describes that an immediate-acting firmness can be imparted by using an oil-soluble film-forming agent and a highly volatile oil agent in combination.

However, the water-soluble polymers, solid oils, and oil-soluble film-forming agents, which contribute to giving a firm feeling by forming the cosmetic film used in these, all felt sticky during and after application to the skin. .. Further, 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. In Patent Document 4 (Japanese Unexamined Patent Publication No. 11-180817), by using a powder having strong specular reflection light and diffuse reflection light, a firmness imparting agent capable of visually glossing and firming the skin can be obtained. However, this does not give a physical firmness due to the cosmetic film.

On the other hand, the use of cellulose nanofibers for improving the strength of composite materials has been studied, but in the field of cosmetics, thickeners (Patent Document 5 (Japanese Patent Laid-Open No. 2009-62332)) and dispersion stabilization have been made. It has only been studied for use as an agent (Patent Document 6 (Japanese Unexamined Patent Publication No. 2011-57567)), and has never been used for improving the physical properties of a cosmetic film.

Japanese Unexamined Patent Publication No. 2007-269723 Japanese Unexamined Patent Publication No. 2010-235472 Japanese Unexamined Patent Publication No. 2013-136546 Japanese Unexamined Patent Publication No. 11-180817 JP-A-2009-62332 Japanese Unexamined Patent Publication No. 2011-57567

The present invention has been completed based on such a background technique, and an object of the present invention is to form a non-greasy, flexible and tear-free cosmetic film on the skin to give the skin a physical firmness. The purpose is to provide cosmetics that make the skin look finer visually.

Therefore, as a result of diligent research, the present inventors have found that a cosmetic containing a specific cellulose nanofiber solves the above-mentioned problems, and the present invention that solves the above-mentioned problems is as follows.

(Means according to claim 1)
In addition to the thickening stabilizer, it contains cellulose nanofibers with an average fiber diameter of 10 to 1000 nm.
The thickening stabilizers are (PEG-240 / decyltetradeceth-20 / HDI) copolymer, (Na acrylate / acryloyl dimethyl taurine) copolymer, (hydroxyethyl acrylate / acryloyl dimethyl taurine sodium) copolymer, (acryloyl). It is selected from one or a combination of two or more dimethyl taurine ammonium / VP) copolymers and (acryloyl dimethyl taurine ammonium methacrylate behenes-25) cross-polymers.
The cellulose nanofibers have a coefficient of variation of fiber diameter distribution of 1.1 or less.
A cosmetic that is characterized by that.

(Means according to claim 2)
The cellulose nanofibers have a peak value of a pseudo particle size distribution curve of 1 to 100 μm, and an integrated volume ratio of 100 μm or less is 90% or more.
The cosmetic according to claim 1.

(Means according to claim 3)
The cellulose nanofibers contain 0.01 to 3% by mass and an oil content of 1 to 50% by mass.
The cosmetic according to claim 1 or 2.

(Means according to claim 4)
Contains UV scatterers consisting of hydrophobized metal oxides,
The cosmetic according to any one of claims 1 to 3.

(Means according to claim 5)

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

It is a figure which shows the test result of the flexibility of a film. It is a figure which shows the test result of the flexibility of a film. It is a figure which shows the test result of the flexibility of a film. It is a figure which shows the test result of the flexibility of a film. It is a figure which shows the test result of the flexibility of a film. It is a figure which shows the test result of the flexibility of a film.

Next, a mode for carrying out the invention will be described. The embodiment of the present invention is an example of the present invention. The scope of the present invention is not limited to the scope of the present 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 a thickening stabilizer. However, in this embodiment, cellulose nanofibers are used, for example, as a film-forming component. That is, in this embodiment, a thickening stabilizer is also separately blended, and the conventional cellulose nanofibers correspond to (associate with) one of the thickening stabilizers in this 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, and the conditions are predetermined. Exists. Further, in this embodiment, the cellulose nanofibers are not used as the thickening stabilizer, but it is not denied that the cellulose nanofibers are separately used as the thickening stabilizer.

(Cellulose nanofiber)
In this embodiment, predetermined cellulose nanofibers (CNFs) function as film-forming components. Further, since the predetermined cellulose nanofiber is also a kind of cellulose nanofiber, it has a function of suppressing a sticky feeling. Furthermore, after being applied to the skin, cellulose nanofibers form a cosmetic film on the skin together with other non-volatile components in the cosmetics, giving the skin a physical firmness and visually finer skin. It has a function to show to.

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

As raw material pulp for cellulose nanofibers, for example, wood pulp made from broadleaf tree, coniferous tree, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recovered waste paper, waste paper, etc. are used as raw materials. One type or two or more types can be selected and used from the waste paper pulp (DIP) and the like.

However, it is preferable to use wood pulp rather than non-wood pulp or used paper pulp because it is possible to obtain α-cellulose which is insoluble in alkali among the cellulose components as much as possible while avoiding the mixing of impurities. By treating with alkali, components soluble in alkali can be removed and the purity of cellulose can be increased.

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

The hardwood kraft pulp may be hardwood bleached kraft pulp, hardwood unbleached kraft pulp, or hardwood semi-bleached 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 the mechanical pulp include stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), chemi-grand pulp (CGP), thermo-grand pulp (TGP), ground pulp (GP), and the like. One or more of the 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 above-mentioned cellulose, 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, it can also be pretreated by chemical methods. Pretreatment by chemical method includes, for example, hydrolysis of polysaccharide with acid (acid treatment), hydrolysis of polysaccharide with enzyme (enzyme treatment), swelling of polysaccharide with alkali (alkali treatment), oxidation of polysaccharide with oxidizing agent (alkaline treatment). Oxidation treatment), reduction of polysaccharides with a reducing agent (reduction treatment), and the like can be exemplified.

When alkali treatment is performed prior to defibration, some of the hydroxyl groups of hemicellulose and cellulose contained in the pulp are dissociated, and the molecules are anionized, weakening the intramolecular and intermolecular hydrogen bonds and promoting the dispersion of cellulose fibers in defibration. To.

Examples of the alkali used for the alkali treatment include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and the like. Organic alkali or the like can be used. However, from the viewpoint of manufacturing cost, it is preferable to use sodium hydroxide.

When enzyme treatment, acid treatment, and oxidation treatment are performed prior to defibration, the water retention degree of the cellulose nanofibers can be lowered, the crystallization degree can be increased, and the homogeneity can be increased. In this respect, if the degree of water retention of the cellulose nanofibers is low, dehydration becomes easy, and the dehydration property of the dispersion liquid of the cellulose nanofibers (hereinafter, also referred to as “slurry”) is improved.

When the raw material pulp is subjected to enzyme treatment, acid treatment, or oxidation treatment, the hemicellulose and amorphous regions of cellulose contained in the pulp are decomposed, and as a result, the energy of the micronization treatment can be reduced, and the uniformity and dispersibility of the cellulose fibers can be improved. Can be improved. The dispersibility of cellulose fibers contributes to, for example, improving the homogeneity of cellulose nanofibers. In this respect, in the field of cosmetics, since the amount of cellulose nanofibers blended with respect to the total amount of cosmetics is small, improvement of homogeneity is an important factor. However, since the pretreatment reduces the aspect ratio of the cellulose nanofibers, it is preferable to avoid excessive pretreatment, especially when it is used as a film-forming component.

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

For defibration of raw material pulp, the average fiber diameter, average fiber length, water retention, crystallinity, coefficient of variation of fiber diameter distribution, peak value in pseudo particle size distribution curve, pulp viscosity, dispersion (slurry) of the obtained cellulose nanofibers are used. ) Is preferably set to a desired value or evaluation as shown below.

The average fiber diameter (average fiber width; average diameter of single fibers) of the 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. That is, the flexibility of the cosmetic film formed on the skin becomes inferior, and the movement of the skin after application may cause tearing or cracking of the cosmetic film. Further, when the average fiber diameter of the cellulose nanofibers is less than 10 nm, the viscosity of the cosmetics increases, which causes a problem that the ease of spreading the cosmetics decreases, and a desired amount of cellulose nanofibers is added to the cosmetics. You may not be able to do it. In addition, if the average fiber diameter of the cellulose nanofibers is less than 10 nm, the dehydration property of the slurry containing the cellulose nanofibers may be deteriorated.

On the other hand, if the average fiber diameter of the cellulose nanofibers exceeds 1000 nm, the roughness, stickiness and firmness of the cosmetic material may be inferior. In terms of this sticky feeling and firmness, it is particularly preferable that the average fiber diameter of the cellulose nanofibers is 100 nm or less.

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

The 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 is filtered through a membrane filter made of Teflon (registered trademark), once with 100 ml of ethanol, and with 20 ml of t-butanol. Substitute the solvent 3 times. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed by an electron microscope SEM image at a magnification of 3000 times to 30,000 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. Further, 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 of the cellulose nanofibers (average length of single fibers) 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. Further, if the average fiber length of the cellulose nanofibers is less than 0.3 μm, the firmness may be inferior.

On the other hand, if the average fiber length of the cellulose nanofibers exceeds 200 μm, the fibers are likely to be entangled with each other, which may cause a problem of aggregation. The aggregation of the cellulose nanofibers may lead to a rough feeling of the cosmetic, and may cause an eraser-like lump (wrinkle).

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

The method for measuring the average fiber length of the cellulose nanofibers is the same as in the case of the average fiber diameter, and the length of each fiber is visually measured. The average fiber length is the medium length of the measured value.

The coefficient of variation of the fiber diameter distribution of the cellulose nanofibers is preferably 0.1 or more and 1.5 or less, and more preferably 0.3 to 1.1 or less. When the coefficient of variation of the fiber diameter distribution exceeds 1.1, the fiber diameter distribution becomes wide, and not only nano-sized cellulose fibers but also micro-sized fibers are included, and the fluidity 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 diameters tend to be uniform, but adjustment by pretreatment, defibration, or the like 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 by using the average value and the standard deviation value of the fiber diameters aggregated in the above-mentioned aggregation of the average fiber diameters.

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

On the other hand, when the water retention degree of the cellulose nanofibers exceeds 500%, the water retention capacity of the cellulose nanofibers themselves becomes high, and the dehydration property of the cellulose nanofibers may deteriorate.

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

The water retention of cellulose nanofibers is determined by Japan TAPPI No. It is a value measured according to 26 (2000).

The pulp viscosity of the cellulose nanofibers is preferably 1 to 10 cps, more preferably 2 to 9 cps, and particularly preferably 3 to 8 cps. The pulp viscosity is the viscosity of the solution after dissolving cellulose in the copper ethylenediamine solution, and the larger 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 firmness is poor and there is a high possibility that the affinity with the skin will be lost. If the degree of polymerization is low, the strength of the fiber itself will be lost and the film will easily crack. The degree of polymerization of the cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration and the like. When the pulp viscosity is within the above range, it can function as a film-forming component and prevent the occurrence of a rough feeling.

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

The peak value of the cellulose nanofibers is, for example, 1 to 100 μm, preferably 3 to 80 μm, and more preferably 5 to 60 μm. When the peak value of the cellulose nanofibers is less than 1 μm, the fineness of cellulose progresses, but on the other hand, when the peak value of the cellulose nanofibers exceeds 100 μm, the fibers may not be defibrated to the nano size.

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

The peak value of the cellulose nanofiber is a value measured according to ISO-13320 (2009). More specifically, first, a volume-based particle size distribution of an aqueous dispersion of cellulose nanofibers is investigated using a particle size distribution measuring device (a laser diffraction / scattering type particle size distribution measuring device manufactured by Seishin Enterprise Co., Ltd.). Next, the median diameter of the cellulose nanofibers is measured from this distribution. This median diameter is taken as the peak value.

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

The cellulose nanofibers obtained by defibration can be dispersed in an aqueous medium to prepare a dispersion liquid (slurry), if necessary. It is particularly preferable that the total amount of the aqueous medium is water (aqueous solution). However, the aqueous medium may be another liquid that is partially compatible with water. As the other liquid, for example, lower alcohols having 3 or less carbon atoms can be used.

The B-type viscosity of the dispersion of cellulose nanofibers (concentration 1.5%) is preferably 1,000 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 liquid is within the above range, mixing with other components constituting the cosmetic is facilitated, and the dehydration property of the slurry (dispersion liquid) is improved.

The B-type viscosity (solid content concentration 1.5%) of the dispersion liquid of cellulose nanofibers is a value measured in accordance with "Method for measuring liquid viscosity" of JIS-Z8803 (2011). The B-type viscosity is the resistance torque when the dispersion liquid is agitated, and the higher the viscosity, the more energy required for agitation.

It is preferable to adjust the solid content concentration of the cellulose nanofibers in the dispersion liquid by adding a solvent such as water to the dispersion liquid of the cellulose nanofibers. The solid content concentration of the 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 be difficult to mix with other components. Further, even if the solid content concentration of the cellulose nanofibers exceeds 5.0% by mass, the fluidity is remarkably lowered, which may make it difficult to mix with other components.

Cellulose nanofibers may be dispersed in either the aqueous phase or the oil phase in the cosmetic. However, it is preferable that the cosmetics are dispersed in the aqueous phase in terms of storage stability of the cosmetics and ease of spreading on the skin.

The content of the cellulose nanofibers 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 the cellulose nanofibers is excessively small, the firmness is deteriorated, and the function as a film-forming component may not be exhibited. On the other hand, if the content of the cellulose nanofibers is excessively high, the spread of the cosmetic film is poor and the flexibility of the cosmetic film is reduced.

(Oil)
In the cosmetic of this form, oil is present as a dispersed phase. After being applied to the skin, the oil has the function of forming a cosmetic film together with cellulose nanofibers and the like to give the skin a firm feeling.

As the oil content, for example, any of them can be used regardless of the origin of animal oil, vegetable oil, synthetic oil or the like, or the properties of solid oil, semi-solid oil, liquid oil, volatile oil or the like.

The oil content is, for example, 1 from hydrocarbons, oils and fats, waxes, hydrogenated oils, ester oils, fatty acids, silicone oils, fluorooils, lanolin derivatives, oil-soluble ultraviolet absorbers and the like. Species or a combination of two or more can be used.

More specifically, for example, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, selecin wax, microcrystalline wax, mokurou, and montan wax;
Oils and fats such as olive oil, castor oil, jojoba oil, mink oil, 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 loginate, neopentyl glycol dioctanoate;
Silicones such as low degree of polymerization dimethylpolysiloxane, high degree of polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, fluorine-modified silicone;
Fluorine-based oils such as perfluoropolyether, perfluorodecane, and perfluorooctane;
Lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol;
It is possible to use one kind or a combination of two or more kinds from among the above.

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 flexibility of the cosmetic film may be inferior. On the other hand, if the oil content exceeds 50% by mass, the firmness may be reduced and the sticky feeling may not be removed.

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

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

Examples of the powder include titanium oxide, zinc oxide, zirconium oxide, cerium oxide, red iron oxide, yellow iron oxide, black iron oxide, konjo, ultramarine, silicic acid anhydride, magnesium carbonate, calcium carbonate, aluminum hydroxide, and water. Inorganic substances such as chromium oxide, carbon black, aluminum silicate, magnesium silicate, aluminum silicate magnesium 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, titanium mica, 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-acyllysine, polystyrene, nylon, polymethylmethacrylate, polymethylsilsesquioxane powder, organopolysiloxane elastomer powder, cellulose, crystalline cellulose, cellulose acetate;
It is possible to use one kind or a combination of two or more kinds from among the above.

If necessary, the above powders include inorganic compounds such as alumina, silica, and iron oxide, fluorine compounds, silicone compounds, phospholipids, phospholipid derivatives, metal soaps, waxes, surfactants, fats and oils, which are surface treatment agents. It can also be used by surface-treating it with a hydrocarbon or the like.

Among the above, when spherical organic powders such as polystyrene, nylon, polymethylmethacrylate, polymethylsilsesquioxane powder, organopolysiloxane elastomer powder, cellulose, crystalline cellulose, cellulose acetate, etc. are used, pores, fine wrinkles, etc. are used. Since the unevenness of the surface can be effectively concealed, a preferable finish is obtained.

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

As a commercially available product of silica-coated iron oxide, for example, SYMPHOLIGHT RW manufactured by JGC Catalysts and Chemicals Co., Ltd. can be used. Further, as a commercially available product of silica-coated iron oxide, for example, SYMPHOLIGHT Y10 can be used.

The content of the powder is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 25% by mass with respect to the total amount of the cosmetic. When the powder content is less than 1% by mass, the decorative film tends to be sticky. On the other hand, if the amount of powdered cosmetics exceeds 40% by mass, the flexibility of the cosmetic film may be inferior.

(UV protection agent)
In the present specification, the ultraviolet protective agent means a component that protects the skin and the cosmetic itself from ultraviolet rays by absorbing or scattering ultraviolet rays (ultraviolet absorber) (ultraviolet absorber). In this respect, it is said that general ultraviolet scattering agents used in cosmetics also have the ability to absorb ultraviolet rays. However, in this embodiment, it is not necessary to clearly distinguish between the ultraviolet absorber and the ultraviolet scattering agent, and both are used to protect the skin and the cosmetic itself from ultraviolet rays. Therefore, in the present specification, both are defined as an ultraviolet protective agent.

Examples of the ultraviolet absorber include a water-soluble ultraviolet absorber and an oil-soluble ultraviolet absorber classified as an oil component. Examples of the water-soluble ultraviolet absorber 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 ultraviolet absorbers such as phenylbenzimidazole-5-sulfonic acid and its salt, phenylene-bis-benzimidazole-tetrasulfonic acid and its salt;
One or a combination of two or more of 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, etc. can be used. it can.

Examples of the oil-soluble UV absorber include benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, and mono-2-ethylhexanoate diparamethoxycinnamate glyceryl silicate.
Benzophenone-based UV absorbers such as hydroxymethoxybenzophenone, dihydroxymethoxybenzophenone, dihydroxybenzophenone, and tetrahydroxybenzophenone;
Paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2-hydroxypropyl) amino] ethyl benzoate, diethylaminohydroxy Benzoic acid ester-based UV absorbers such as hexyl benzoyl benzoate;
Salicylic acid-based UV absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, parallel butyl phenyl salicylate, homomentyl salicylate;
Triazine-based UV absorbers such as ethylhexyltriazone (2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine), bisethylhexyloxyphenol methoxyphenyl triazine;
4-Tershary Butyl-4'-methoxydibenzoylmethane, Menthyl anthranylate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate, octocrylene, dimethicodiethyl One or a combination of two or more of benzylmalonate and the like can be used.

The ultraviolet scattering agent is a fine particle powder and is classified into the above-mentioned powder. The 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 diameter of 100 nm or less can be used.

The ultraviolet scattering agent is preferably hydrophobically treated in terms of water resistance. As the hydrophobic treatment method, a usual surface treatment method can be adopted. Specifically, for example, an oil / fat treatment method in which an oil / fat is adsorbed on the surface of a powder or a functional group such as a hydroxyl group is used to cause esterification or etherification to make the powder a lipophilic substance, zinc fatty acid. Metal soap treatment method using salt, magnesium salt or aluminum salt, silicone treatment method using silicone compound such as dimethylsiloxane or hydrogendimethicone, treatment method with fluorine compound having perfluoroalkyl group, treatment with alkylalkoxysilane It is possible to adopt a method or the like. Among the above treatment methods, it is preferable to adopt a silicone treatment using a silicone compound from the viewpoint of water resistance and emulsion stability.

The content of the UV protective agent is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 25% by mass with respect to the total cosmetics. 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 ultraviolet protective agent exceeds 40% by mass, the ease of spreading the cosmetic on the skin may decrease.

(Film component)
The cosmetic of this embodiment includes an oil-in-water emulsified cosmetic, and contains one or more film components selected from a water-soluble film-forming agent, an oil-soluble film-forming agent, and a film-forming polymer emulsion. Suitable. By including these film components, the firmness of the skin can be further enhanced.

The water-soluble film-forming agent dissolves in an aqueous component to form a cosmetic film. As the water-soluble film-forming agent, for example, one or a combination of two or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, vinyl acetate / vinylpyrrolidone copolymer, modified cornstarch, hydrolyzed hydrogenated starch and the like is used. can do.

The oil-soluble film-forming agent dissolves or disperses in the oil-based component to form a cosmetic film. Examples of the oil-soluble film-forming agent include silicone-based resins such as trimethylsiloxysilicic acid, partially crosslinked organopolysiloxane, trimethylsiloxysilylpropylcarbamic acid, fluorine-modified silicone, acrylic-modified silicone, and silicone dendrimer-modified resin compounds, and pentaloginate. One or a combination of two or more can be used from among logonic acid-based resins such as erythlit and glyceryl loginate, candelilla resin, polyvinyl acetate-based resin, polyvinylisobutyl ether, and polyisobutylene.

However, among the above, the partially crosslinked organopolysiloxane is particularly preferable because it can form a water-resistant decorative film with less stickiness. The partially crosslinked organopolysiloxane is available in the form of a gel dispersed in a liquid oil. Commercially available products of partially crosslinked organopolysiloxane include, for example, KSG-15 composed of (dimethicone / vinyldimethicone) crosspolymer and cyclopentasiloxane manufactured by Shin-Etsu Chemical Industry Co., Ltd., (dimethicone / vinyldimethicone) crosspolymer and methyltrimethicone. KSG-1510, KSG-16 consisting of (dimethicone / vinyldimethicone) crosspolymer and dimethicone, KSG-18A consisting of (dimethicone / phenylvinyldimethicone) crosspolymer and diphenylsiloxyphenyltrimethicone, (vinyldimethicone / lauryldimethicone) cloth KSG-41A consisting of polymer and liquid paraffin, KSG-43 consisting of (vinyldimethicone / lauryldimethicone) crosspolymer and triethylhexanoin, KSG-43 consisting of (laurylpolydimethylsiloxyethyldimethicone / bis-vinyldimethicone) crosspolymer and isododecane 042Z, 9040 and 9045 Silicone Elastomer Blend composed of dimethicone crosspolymer and cyclopentasiloxane manufactured by Toray Dowcorning, 9041 Silicone Elastomer Blend composed of dimethicone crosspolymer and dimethicone, (dimethicone / vinyl dimethicone 39 dimethicone id Satin Blend, EL-8051 IN Silicone Organic Elastomer Blend consisting of (dimethicone / bis-isobutyl PPG-20) crosspolymer and isodecyl neopentate, alkyl (C30-45) cetearyl dimethicone crosspolymer from Momentive Performance Materials. And Velvesil 125 made of cyclopentasiloxane, Velvesil 034 made of alkyl (C30-45) cetearyl dimethicone crosspolymer and caprylylmethicone, Velvesil DM made of cetearyl dimethicone crosspolymer and dimethicone and the like.

A film-forming polymer emulsion is an aqueous dispersion of a water-insoluble polymer. Examples of the film-forming polymer emulsion include an alkyl acrylate copolymer emulsion, an alkyl methacrylate copolymer emulsion, a styrene / alkyl acrylate copolymer emulsion, a styrene / alkyl methacrylate copolymer emulsion, and a vinyl acetate polymer. Emulsion, vinylpyrrolidone / styrene copolymer emulsion, alkyl acrylate / vinyl acetate copolymer emulsion, alkyl methacrylate / vinyl acetate copolymer emulsion, acrylate / alkyl acrylate copolymer emulsion, alkyl acrylate / alkyl methacrylate Use one or a combination of two or more from copolymer emulsions, alkyl methacrylate / alkyl acrylate copolymer emulsions, alkyl methacrylate / alkyl methacrylate copolymer emulsions, alkyl dimethicone acrylate copolymer emulsions, and the like. be able to.

The content of the film component is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 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 amount of the film component is too large, the sticky feeling may not be suppressed.

(Thickening stabilizer)
The cosmetic of this embodiment contains a thickening stabilizer that functions as at least one of a thickener and a stabilizer. As a result, the feeling of use such as the ease of spreading the cosmetic can be improved, and the emulsified state and the dispersed state can be kept stable for a long period of time. As the thickening stabilizer, for example, a water-soluble polymer other than the water-soluble film-forming agent, a clay mineral, or the like can be used.

More specifically, examples of the thickening stabilizer include carboxyvinyl polymers, sodium polyacrylates, acrylate / alkyl methacrylate copolymers, and (PEG-240 / decyltetradeceth-20 / HDI) copolymers. , (Na acrylate / acryloyldimethyltaurine) copolymer, (hydroxyethyl acrylate / sodium acryloyldimethyltaurine) copolymer, (acryloyldimethyltaurinammonium / VP) copolymer, (acryloyldimethyltaurinammonium methacrylate behenes-25) crosspolymer, ( Alkyl acrylate / steareth methacrylate-20) copolymer, (dimethylacrylamide / acryloyldimethyltaurine Na) crosspolymer, polyacrylamide, polyoxyethylene polyoxypropylene block copolymer, polyvinylmethyl ether, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose , Hydroxypropyl methylcellulose, sodium carboxymethylcellulose, cationized cellulose, sodium alginate, propylene glycol alginate, guar gum, locust bean gum, arabic gum, tragacanth, galactan, carob gum, karaya gum, pectin, agar, quince seed (malmero), algae colloid (Brown algae extract), carrageenan, xanthan gum, dextran, purulan, bentonite, montmorillonite, hectrite, magnesium aluminum silicate, laponite and the like can be used alone or in combination of two or more.

However, it is preferable to use one or a combination of carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer, xanthan gum, (Na acrylate / acryloyldimethyltaurine) copolymer, and hydroxypropylmethylcellulose.

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 stabilizer is less than 0.01% by mass, it is not possible to improve the usability and stabilize the emulsified / dispersed state. Cellulose nanofibers have conventionally been used as a thickening stabilizer, but in this embodiment, they are used as a film-forming component. In this embodiment, in order to make the cellulose nanofibers function as a film-forming component, the cellulose nanofibers are blended in the cosmetic under predetermined conditions, and the thickening stabilizer described above is separately blended to function the thickening stabilization.

(Surfactant)
The cosmetics of this embodiment include nonionic surfactants, polymer emulsifiers, anionic (anionic) surfactants, cationic (cationic) surfactants, amphoteric surfactants, semipolar surfactants and the like. Surfactant can be blended. The surfactant can function not only as an emulsifier but also as, for example, a solubilizer, a wetting agent, a cleaning agent and the like.

Examples of the anionic surfactant include fatty acid slakes, ether carboxylic acids and salts thereof, carboxylic acid salts such as condensation of amino acids and fatty acids, alkyl sulfonic acids, alken sulfonates, sulfonates of fatty acid esters, and fatty acid amides. Sulfate, alkyl sulfonate and its formalin condensate sulfonate, alkyl sulfate ester salt, secondary higher alcohol sulfate ester salt, alkyl and allyl ether sulfate ester salt, fatty acid ester sulfate ester salt, fatty acid alkylol Examples thereof include sulfate esters of amide, sulfate esters such as funnel oil, alkyl phosphates, alkyl ether phosphates, alkyl allyl ether phosphates, and amid phosphates.

Examples of the cationic surfactant include amine salts such as alkylamine salts, polyamines and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts and imidazolium salts. it can.

Examples of amphoteric surfactants include betaine, aminocarboxylic acid salt, and imidazoline derivatives.

Examples of the nonionic surfactant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, propylene glycol fatty acid ester, and oxidation of propylene glycol fatty acid ester. Ethylene derivative, polyethylene glycol fatty acid ester, sucrose ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil derivative, polyoxyethylene hydrogenated castor oil derivative, polyoxyethylene phyto Examples thereof include stanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, and polyoxyalkylene-modified organopolysiloxane.

(Moisturizer)
A moisturizer can be added to the cosmetic of this form. As the moisturizer, for example, one or a combination of two or more of polyhydric alcohols, sugars, sugar alcohols, amino acids, peptides, water-soluble polymers and the like can be used. As the moisturizer, for example, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, collagen, sodium lactate, dl-pyrrolidone carboxylate, isaiyobara extract, sardine extract, melilot extract and the like are blended. be able to.

(Other ingredients)
The cosmetics of this form include, for example, antibacterial agents, preservatives, fragrances, antioxidants, pH adjusters, chelating agents, refreshing agents, anti-inflammatory agents, skin-beautifying ingredients, vitamins, amino acids, nucleic acids, clathrates. Various ingredients to be blended in ordinary cosmetics such as compounds can be blended.

(Production method)
In producing the cosmetic of this embodiment, a usual production method, for example, a method of preparing an aqueous phase and an oil phase, respectively, and then gradually adding the oil phase to the aqueous phase while stirring to obtain an oil-in-water emulsifying agent. , The number emulsification method, the reaction emulsification method, the D phase emulsification method and the like can be adopted.

(Use, etc.)
The cosmetic in this form may be in any form of cream, gel, milky liquid, and liquid (dilute milky lotion). This form of cosmetic is particularly excellent as a make-up cosmetic for foundations, foundations, etc., for example. However, this form of cosmetic is also excellent as a make-up cosmetic such as milky or creamy eye shadow, blusher, and concealer.

Next, various test results will be shown to clarify the effect 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 Bulux Co., Ltd.), and dried at room temperature for 30 minutes or more. Various samples were evaluated according to the following criteria.

Coniferous bleached kraft pulp was used as a raw material for the cellulose fibers (CNF-A, CNF-B, MFC) blended in each sample. As CNF-C, Leocrysta (TEMPO oxidized CNF), which is a product of Dai-ichi Kogyo Seiyaku Co., Ltd., was used. The physical characteristics of each cellulose fiber are shown in Table 2. The average fiber width was determined for CNF-A and CNF-B by the above-mentioned method (observation by SEM image). Further, CNF-C was determined using a transmission electron microscope (TEM). Further, MFC was measured using a fiber analyzer "FS5" manufactured by Valmet. The drying shrinkage was determined by the following method.

(Dry 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-WET of the aqueous dispersion adjusted to the concentration was put into a petri dish having 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 rate was calculated by calculating the diameter of the cellulose fiber membrane (calculating the average of the four lines) and using the following formula.
Shrinkage rate = diameter of cellulose fiber membrane ÷ inner diameter of container (7.5 cm) x 100 (%)

(Manufacturing procedure)
The oil-in-water emulsification foundation of the formulation shown in Table 1 was prepared by the manufacturing procedure shown below, and was "non-sticky", "tight", "non-tacky", "fine finish", and "film". Each item of "flexibility" and "texture score by image analysis" was evaluated. About Table 1
(1) Each component of Nos. 1 to 4 was mixed at the mixing ratio shown in Table 1 and dissolved by heating at 80 ° C. to prepare an aqueous phase (a).
(2) Each component of Nos. 5 to 11 was mixed at the mixing ratio shown in Table 1 and melted by heating at 80 ° C. to prepare an oil phase (b).
(3) While stirring the aqueous phase (a), the oil phase (b) was mixed little by little with the aqueous phase (a) to prepare an emulsified phase (c).
(4) The emulsified phase (c) was cooled, and each component of Nos. 12 to 18 was mixed at 35 ° C. at the mixing ratio shown in Table 1 to prepare a cosmetic.

(Evaluation: Usability)
Apply each sample (Examples 1 and 2 and Comparative Examples 3 to 6) to the faces of the female evaluation panel (5 people), and about the feeling of use (non-stickiness, firmness, lack of tension, fineness of finish). , Sensory evaluation was performed according to the following criteria. Table 3 shows the results of non-stickiness, firmness, and fineness of the finish, and Table 4 shows the results of non-tightness. Each item is evaluated on a three-point scale of "good (score: 2)", "neither can be said (score: 1)", and "bad (score: 0)", and the quality of performance is judged based on the following criteria from the average score. did.
[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: 0.3 or less

(Film flexibility)
First, the above-mentioned artificial skin made of urethane having a thickness of 2 mm (skin model No. 77 2T # black manufactured by Bulux Co., Ltd.) is cut into a rectangle of 30 mm × 70 mm, and each sample (Examples 1 and 2) is formed on a surface of 30 mm × 50 mm. And Comparative Examples 3 to 6) 0.05 g was uniformly applied and dried at room temperature for 30 minutes or more as a test piece. Using a rheometer CR-100 manufactured by Sun Scientific Co., Ltd., fix the uncoated parts 10 mm above and below the test piece in the long side direction with a tensile test jig, lower the sample table at a speed of 20 mm / min, and extend it by 20 mm (140%). The state of time was observed. Judgment was made according to the following criteria. The results of film flexibility are shown in Table 4 and FIGS. 1 to 6. In each of FIGS. 1 to 6, (A) is a photographed test piece before stretching, and (B) is a photographed test piece after stretching. FIG. 1 is a coating of Sample 11 of Example 1. FIG. 2 is a coating of Sample 12 of Example 2. FIG. 3 shows a sample 13 of Comparative Example 3 coated. FIG. 4 shows a sample 14 of Comparative Example 4 coated. FIG. 5 shows a sample 15 of Comparative Example 5 coated. FIG. 6 shows a sample 16 of Comparative Example 6 coated.
[Judgment]
5: No cracks in the cosmetic film are seen, and the artificial skin on a black background is concealed.
3: Cracks with a width of less than 1 mm are observed, and a black background is visible.
1: Cracks with a width of 1 mm or more are 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). , The texture score, which is an index of skin smoothness, was calculated by the attached analysis software. The same sample was applied to each of the left and right cheeks at 4 locations (8 locations in total). Then, photography was performed on each sample (Examples 1 and 2 and Comparative Examples 3 to 6). The value obtained by dividing the texture score calculated for the same sample by the texture score calculated for the sample without cellulose nanofibers (Comparative Example 1) at the same site of the same subject was defined as the T value.

(T value) = (texture score calculated for each sample (Examples 1 and 2 and Comparative Examples 3 to 6)) / (texture score calculated for Comparative Example 1)
The T values for each of the obtained eight locations were simply averaged to obtain the average value of (T), and the determination was made 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 when the cellulose nanofibers are blended, the sticky feeling is suppressed and the firmness is imparted. However, as is clear from Table 4, if the average fiber diameter of the cellulose nanofibers is too small, a feeling of tension is generated and the decorative film lacks flexibility.

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

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

Claims (4)

In addition to the thickening stabilizer, it contains cellulose nanofibers with an average fiber diameter of 10 to 1000 nm.
The thickening stabilizers are (PEG-240 / decyltetradeceth-20 / HDI) copolymer, (Na acrylate / acryloyl dimethyl taurine) copolymer, (hydroxyethyl acrylate / acryloyl dimethyl taurine sodium) copolymer, (acryloyl). It is selected from one or a combination of two or more dimethyl taurine ammonium / VP) copolymers and (acryloyl dimethyl taurine ammonium methacrylate behenes-25) cross-polymers.
The cellulose nanofibers have a coefficient of variation of fiber diameter distribution of 1.1 or less.
A cosmetic that is characterized by that. The cellulose nanofibers have a peak value of a pseudo particle size distribution curve of 1 to 100 μm, and an integrated volume ratio of 100 μm or less is 90% or more.
The cosmetic according to claim 1. The cellulose nanofibers contain 0.01 to 3% by mass and an oil content of 1 to 50% by mass.
The cosmetic according to claim 1 or 2. Contains UV scatterers consisting of hydrophobized metal oxides,
The cosmetic according to any one of claims 1 to 3.

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