JP2005298497A - Cosmetic for eyelash - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic imparting good curl effect to eyelashes without forming lumps when used. <P>SOLUTION: The cosmetic for eyelashes comprises (A) ≥10 mass% nonvolatile component containing ≥70 mass% nonvolatile component being solid at normal temperature and containing a film-forming polymer (a) having characteristics of the following items (i) and (ii) and ≤30 mass% nonvolatile component being liquid at normal temperature and (B) ≥30 mass% volatile component and comprises the component (a) in an amount of 0.6-15 mass% based on total cosmetic. (i) The rate (ΔW) of change of polymer content from a time when film hardness became a pencil hardness of 2B to a time when the polymer was completely dried is ≥13 mass%. (ii) The weight-average molecular weight is 5,000 to 2,000,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cosmetic for eyelashes containing a film-forming polymer, which does not generate lumps during use and gives a good curling effect to the eyelashes.

In order to enhance the makeup effect of mascara that makes the eyes stand out, the ability to curl the eyelashes upward, that is, the curl-up effect, is very important. Conventionally, in order to increase the curl-up effect, a method of increasing the drying rate of the mascara bulk and drying the mascara during application to keep the eyelashes raised with the brush from falling down and maintaining the curled state is used. I came. In order to obtain a mascara bulk having a high drying rate, a method using a fast-drying film forming agent or a solvent having a high volatilization rate has been generally used.
However, in such a method utilizing quick drying, the mascara forms a film during coating, and thus the finish is often significantly impaired by overcoating. That is, there was a case in which a lump was generated due to drying during application.

Therefore, a mascara has been proposed for giving a good curl to the eyelashes by using a specific film-forming polymer and combining various solid particles. For example, Patent Document 1 provides a mascara that exhibits a curling effect and an effect of deepening eyelashes by a combination of a film-forming polymer that causes shrinkage exceeding 1% of the stratum corneum and a high-hardness wax. Patent Documents 2 to 5 provide a mascara that gives a curl effect by a combination of a polymer that can adhere to a keratinous substance and other polymer particles, wax, or the like.
However, there is still a problem that lumps are likely to occur during use.

Japanese Patent Laid-Open No. 11-255619 JP 2003-55136 A Japanese Patent Laid-Open No. 2003-55156 JP 2003-55157 A JP 2003-55158 A

  The subject of this invention is providing the cosmetics for eyelashes which give a favorable curl effect to eyelashes, without generating a lump at the time of use even if it coats repeatedly.

The present inventor has found that a film-forming polymer having a specific shrinkage and a cosmetic for eyelashes in combination with a volatile component are less likely to cause lumps during use and give a good curling effect to the eyelashes. That is, the present invention comprises a film having the following characteristics (i) and (ii) in the component (A) containing 10% by mass or more of the nonvolatile component (A) and 30% by mass or more of the volatile component (B). 70% by mass or more of the non-volatile component (a-1) that is solid at room temperature containing the formable polymer (a) and 30% by mass or less of the non-volatile component (a-2) that is liquid at normal temperature, and the film-forming property An eyelash cosmetic containing 0.5 to 15% by mass of the polymer (a) in the total cosmetic is provided.
(I) In the film formation test, the rate of change in polymer occupancy (ΔW) from when the film hardness becomes pencil hardness 2B to when the film is completely dried is 13% by mass or more.
(Ii) The weight average molecular weight is 5,000 to 2,000,000.

  The cosmetic for eyelashes of the present invention can give a good curl effect to the eyelashes without causing lumps during use even if it is overcoated.

The cosmetic for eyelashes of this invention is a cosmetic for eyelashes containing 10 mass% or more of non-volatile components (A) and 30 mass% or more of volatile components (B). Among these, the nonvolatile component (A) is composed of a nonvolatile component (a-1) that is solid at room temperature and a nonvolatile component (a-2) that is liquid at room temperature. Here, the non-volatile component refers to a compound having a vapor pressure of less than 10 Pa at normal temperature (25 ° C.) and normal pressure.
The non-volatile component (a-1) that is solid at room temperature is completely dried after the film hardness becomes pencil hardness 2B in the film formation test described in detail later (hereinafter, this time is referred to as “solidification”). Until then (hereinafter, this point is referred to as “at the time of drying”), it contains a film-forming polymer having a polymer occupancy change rate (ΔW) of 13% or more. When the rate of change in polymer occupancy (ΔW) of the film-forming polymer is 13% or more, the film-forming polymer (a) can contain a large amount of a volatile solvent at the start of solidification. Therefore, the cosmetics for eyelashes containing the polymer are easy to apply and do not generate lumps even if they are repeatedly applied. Then, it is considered that the eyelashes are effectively curled by the volumetric shrinkage of the film accompanying the drying from the time of solidification to the time of drying when the cosmetic for eyelashes is applied to the eyelashes to form a film.
The upper limit of the rate of change in polymer occupancy (ΔW) is preferably 35% or less from the viewpoint that the eyelash curl does not become too large. Furthermore, in order to have a moderate curl effect, it is preferable that it is 15 to 30%.
Here, the change rate of polymer occupancy (ΔW) and pencil hardness are specified or measured by the following methods.

(Definition of polymer occupancy change rate (ΔW) (film formation test))
The polymer to be measured is dissolved in heated water (80 ° C.) and then allowed to cool to room temperature (25 ° C.) to form a polymer solution, which is applied on a glass plate to a thickness of 250 μm with an applicator, Two polymer-developed glass plates are prepared. At this time, the polymer content W _pi (g) is calculated from the polymer concentration and the coating amount of the polymer solution.
Next, the two polymer spread glass plates are dried under the conditions of 23 ° C. and relative humidity of 65%. The solid content due to the mass change accompanying drying is calculated with one polymer-developed glass plate, and the film hardness is measured by the pencil hardness method with another polymer-developed glass plate. When the pencil hardness of the film reaches 2B (solidification), the coating film mass (W _t-2B ) and when the mass change is not seen for more than 50 minutes are completely dried (during drying) The mass (W _td ) of the coating film is measured. The polymer content (%) at each time point during solidification and drying is calculated by the following formula, and the difference is defined as the rate of change in polymer occupancy (ΔW).
_{X a = (W pi / W} t-2B) × 100
Y _a = (W _pi / W _td ) × 100
ΔW = Y _a -X _a
X _a; polymer content during solidification (%)
Y _a : Polymer content (%) when dried

(Measurement method of pencil hardness)
This was performed according to JIS K 5400. As a condition, the polymer solution was applied on a glass plate with an applicator to a thickness of 250 μm, dried under conditions of 23 ° C. and relative humidity 65%, and then a pencil (fixed angle 45 °) on the horizontal coating surface. The pencil hardness was measured by pressing a load of 750 g).

  In addition, the film-forming polymer according to the present invention preferably has an appropriate ease of application and a weight average molecular weight of 5,000 to 2,000,000 in order to obtain a sufficient curling effect. When the weight average molecular weight is less than 5,000, a sufficient curling effect cannot be obtained, and when it is 2 million or more, the feeling of use decreases. The balance between the feeling of use and the curl effect is more preferably 20,000 to 1,000,000, and particularly preferably 50,000 to 300,000.

As the film-forming polymer, for example, vinyl (co) polymers such as acrylic (co) polymers, urethanes such as polyurethane, acrylic-polyurethane, polyester-polyurethane, polyether-polyurethane, etc. are suitable. It is mentioned in.
Among these, as the vinyl-based (co) polymer, a copolymer obtained by polymerizing a vinyl monomer is preferable. Among them, a monomer containing an organic acid having a reactive vinyl group and / or a salt thereof is polymerized. The polymer obtained is preferable.

The organic acid having a reactive vinyl group is a water-soluble organic acid having one or more reactive vinyl groups and one or more acidic groups in the molecule. Specifically, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid; styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylic Unsaturated sulfonic acid monomers such as acid ester, bis (3-sulfopropyl) itaconate, vinyl sulfonic acid; vinyl phosphate, bis ((meth) acryloxyethyl) phosphate, diphenyl-2- (meth) acryloyloxyethyl Examples thereof include unsaturated phosphoric acid monomers such as phosphate, dibutyl-2- (meth) acryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, and the like. These may be used alone or in combination of two or more. Can be mixed and used.
Among the monomers containing the organic acid having a reactive vinyl group and / or a salt thereof, from the viewpoint of enhancing the curling effect on eyelashes, an unsaturated carboxylic acid monomer and / or a salt thereof, or an unsaturated sulfonic acid monomer and / or Of these, unsaturated carboxylic acid monomers having a relatively low acidity, methacrylic acid and / or a salt thereof, and styrenesulfonic acid and / or a salt thereof are preferable.
Examples of the organic acid salt having a reactive vinyl group include inorganic salts and organic salts of the above organic acids. Examples of inorganic salts include alkali metal (Na, K, etc.) salts, alkaline earth metal salts, ammonium salts, and the like. Examples of the organic salt include salts such as L-arginine and 2-aminomethyl-1-propanol. Of these, inorganic salts are preferable, and ammonium salts are particularly preferable.
In particular, sodium salts and ammonium salts of polymethacrylic acid and polystyrene sulfonic acid are preferable, and ammonium salts are particularly preferable. In the case of polymethacrylic acid and / or a salt thereof, the weight average molecular weight is 20,000 to 300,000, moreover, the weight average molecular weight is 50,000 to 200,000, and in the case of polystyrene sulfonic acid and / or its salt, the weight average molecular weight is 50,000 to 1,000,000. The thing of 10,000 to 500,000 is preferable.

  In the make-up cosmetic of the present invention, the content of the film-forming polymer is 0.6 to 15% by mass in the total cosmetic, so that no lumps are generated even if it is overcoated, and the curl up An effect can be expressed. If it is less than 0.6% by mass, the curling effect is insufficient, and if it exceeds 15% by mass, the feeling of use is lowered. It is preferable to contain in the range of 1-10 mass% especially 2-6 mass% from the point which reduces generation | occurrence | production of a lump and can fully anticipate use feeling and a curl effect.

  In the present invention, it is preferable to contain a wax in addition to the above-mentioned film-forming polymer (a) as the non-volatile component (a-1) solid at room temperature. The wax used here can be appropriately selected from animal waxes, plant waxes, mineral waxes, synthetic waxes and the like. Specifically, carnauba wax, candelilla wax, rice wax, beeswax, extremely hydrogenated jojoba oil, lanolin wax, microcrystalline wax, ceresin, paraffin wax, polyethylene wax, solid glyceride at room temperature (25 ° C), silicone wax, etc. Can be illustrated.

Among these waxes, it is more preferable to contain a wax having a penetration of 8 or more from the viewpoint of obtaining a particularly high curl-up effect. Here, the penetration is a value measured according to JIS K-2235-5.4. That is, a wax sample kept at 25 ± 0.1 ° C. was subjected to a prescribed needle (needle mass 2.5 ± 0.02 g, needle holder mass 47.5 ± 0.02 g, weight mass 50 ± 0. .05 g) measured the length of penetration for 5 seconds, and the value obtained by multiplying the penetration distance (mm) by 10 was defined as the penetration. Specifically, beeswax and microcrystalline wax are preferable.
The wax having a penetration of 8 or more is preferably contained in the component (a-1) in the range of 0.1 to 20% by mass. By containing 0.1% by mass or more, a sufficient curl-up effect of the eyelashes is exhibited, and when it is 20% by mass or less, good spreading can be obtained at the time of application to the eyelashes. It is preferable to contain in the range of 1-15 mass% especially 3-10 mass% at the point which has the favorable spread at the time of application | coating, and has sufficient curl effect.
The film-forming polymer (a) / wax having a penetration of 8 or more (mass ratio) is preferably in the range of 1/30 to 3/1 from the viewpoint of the beauty of the finish and the high curl-up effect. A range of 1/5 to 1/1 is preferred.

In the present invention, it is preferable to further contain a powder having an average particle size of 0.1 to 20 μm or an aqueous dispersion thereof as the non-volatile component (a-1) that is solid at room temperature. When the thickness is 0.1 μm or more, the feel during application is good, and when the thickness is 20 μm or less, lumps hardly occur. In particular, the average particle size of the powder is more preferably 0.2 to 10 μm, and further preferably 1 to 10 μm. The average particle diameter of the powder is a value (median diameter) measured by a laser diffraction method using a laser diffraction / scattering particle size distribution analyzer (for example, LA-920 manufactured by Horiba, Ltd.).
The shape of the powder may be any of spherical, flat, granular, needle, rod, amorphous, and the like.
Examples of such powders include inorganic pigments, organic pigments, inorganic powders, organic powders, pearl pigments, and the like, and inorganic powders are preferable.

Specific examples include inorganic pigments such as titanium oxide, black titanium oxide, zinc white, bengara, yellow iron oxide, black iron oxide, etc .; organic pigments, tar dyes, etc .; inorganic powders such as talc, mica, sericite, Plate-like inorganic powder such as kaolin, spherical or amorphous inorganic powder such as silica, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium silicate, calcium carbonate, aluminum silicate, magnesium carbonate; polyamide as organic powder Resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, cellulosic resin, polystyrene resin, copolymer of styrene and acrylic acid, organic powder such as silicone resin; pearl pigment, mica titanium, bengara coated mica titanium, etc. Is mentioned. Of these, 1 to 10 μm spherical silica is particularly preferable.
Hydrophobic surface treatments such as silica treatment, alumina treatment, silica-alumina treatment, polyacrylic acid treatment, etc., silicone treatment, fluorine compound treatment, metal soap treatment, lecithin treatment, oil treatment, etc. Can also be applied. In particular, those subjected to hydrophilic treatment are preferable in terms of curling effect and finish, and among them, those subjected to polyacrylic acid treatment are most preferable.

In addition, the above powder may be used alone or in combination of two or more. From the viewpoint of obtaining a high curl effect without causing lumps, (A-1) It is preferable to contain 0.1-20 mass% in a component. If it is 0.1% by mass or more, a sufficient curl-up effect is exhibited, and if it is 20% by mass or less, lumps are hardly generated.
The film-forming polymer (a) / powder (mass ratio) is preferably in the range of 1/5 to 10/1, and more preferably 1/2 to 10 to suppress the occurrence of lumps and exhibit a high curl-up effect. A range of 2/1 is preferred.

Further, when the powder is used as an aqueous dispersion, the powder may be a hydrophilic powder that can be dispersed in water. It can be used in the state of dispersion dispersed in water using an activator.
Specific examples include polyethylene dispersion, silicone resin dispersion, polystyrene resin dispersion, urethane dispersion, and nylon dispersion.
There are no particular limitations on the dispersant used in the state of dispersion, and usually polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, cationized hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, carboxy vinyl polymer, vinyl pyrrolidone / vinyl. Water-soluble polymers such as alcohol copolymers, polymethyl vinyl ether, gum arabic, guar gum, xanthan gum, modified corn starch, starch, sodium alginate and the like can be mentioned. Among these, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, gum arabic, and xanthan gum are particularly preferable from the viewpoints of powder dispersibility and curling effect.

  Furthermore, as the component (a-1), in addition to the above-mentioned film-forming polymer, other film-forming or non-film-forming polymers can be added as long as the effects of the present invention are not impaired.

  Moreover, in order to provide a long rush effect, a fiber can be further contained as the component (a-1). As the fiber, any of natural fibers such as cotton, silk and hemp, recycled fibers such as rayon, and synthetic fibers such as polyamide, polyester, acrylic resin and polyolefin may be used, but polyamide fibers such as nylon are used from the viewpoint of strength. Is preferred. Furthermore, you may use the fiber which surface-treated as needed. For example, those subjected to surface treatment such as silica treatment, silicone treatment, fluorine compound treatment, metal soap treatment, oil treatment can be used. Further, from the viewpoint of adhesion to eyelashes, the fiber is preferably 0.1 to 20 T in thickness and 0.1 to 5 mm in length. The content of the fiber is preferably 0.1 to 6% by mass based on the total amount of the cosmetic because a sufficient long rush effect can be obtained.

In the present invention, the non-volatile component (a-2) that is liquid at room temperature includes liquid oils and / or polyols that are usually used in cosmetics.
Here, the non-volatile component that is liquid at normal temperature is a liquid oil component that does not volatilize at normal temperature (25 ° C.) and normal pressure, for example, hydrocarbon oils such as light isoparaffin, liquid isoparaffin, liquid paraffin, and heavy liquid isoparaffin; Esters and triglycerides such as diisostearyl malate, isotridecyl isononanoate, glyceryl dimyristate, glyceryl diisostearate, glyceryl myristate / isostearate, neopentyl glycol dicaprate, castor oil, macadamian nut oil, jojoba oil; dimethylpoly Examples thereof include silicone oils such as siloxane, methylphenylpolysiloxane, dimethylcyclopolysiloxane, and methylhydrogenpolysiloxane.
Examples of the polyols include ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, and glycerin. Among these, glycerin or 1,3-butylene glycol is preferable from the viewpoint of ease of use, and 1,3-butylene glycol is particularly preferable from the viewpoint of suppressing the occurrence of lumps.
Moreover, a surfactant can be mix | blended with (a-2) component. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphiphilic surfactant or the like can be used alone or in combination, and those having a melting point of 25 ° C. or less are preferably used. It is done.

  In the present invention, the above component (a-1) needs to be contained in the nonvolatile component (A) in an amount of 70% by mass or more, while the component (a-2) is 30% by mass or less. When the component (a-1) is 70% by mass or more, a sufficient curling effect of eyelashes can be obtained.

Moreover, the cosmetic of this invention needs to contain 30 mass% or more of volatile components (B) in all the cosmetics.
Here, the volatile component refers to a compound having a vapor pressure of 10 Pa or higher under normal temperature (25 ° C.) and normal pressure, and examples thereof include water, lower alcohol, volatile hydrocarbon oil, and volatile silicone.
Examples of the lower alcohol include alcohols having 1 to 4 carbon atoms, such as ethanol, propanol, isopropanol, butyl alcohol, and isobutyl alcohol. Examples of the volatile hydrocarbon oil include hydrocarbon oils having 8 to 16 carbon atoms, particularly petroleum-derived isoparaffin (light isoparaffin), isododecane (2,2,4,4,6-pentamethylheptane) and the like. Moreover, as a volatile silicone, the volatile thing is mentioned among the linear or cyclic silicone of the following general formula (1) or (2).

（式中、ｔは０〜３の整数を表す）

(Wherein t represents an integer of 0 to 3)

(In the formula, u represents an integer of 3 to 5).
Specific examples include octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.
One of these volatile components may be used alone, or two or more thereof may be mixed and used. Although content of a volatile component is 30 mass% or more, it is preferable to contain water especially in a volatile solvent. Furthermore, the blending amount of the volatile solvent other than water is preferably 0.5 to 20% by mass, and it is preferable to use lower alcohol having 1 to 4 carbon atoms, particularly ethanol from the viewpoint of ease of handling.
The film-forming polymer (a) / ethanol (mass ratio) is preferably in the range of 1/10 to 20/1, more preferably 1/4 to 5/1, from the viewpoints of polymer shrinkage and high curl-up effect. The range of is preferable.

  The cosmetic for eyelashes of the present invention is an oil-in-water emulsion system (O / W) using water as a volatile component (B), a water-in-oil emulsion system (W / O), and a volatile component other than water. Any of those using only the liquid component is included. Among these, from the viewpoint of improving the curl-up effect without generation of lumps, a system containing water as the volatile component (B), particularly a system containing water and a lower alcohol having 1 to 4 carbon atoms is included. An oil-in-water emulsion system (O / W) using these is most preferable.

  The cosmetic for eyelashes of the present invention is a part of a polyethylene terephthalate film having a width of 2 cm, a length of 5 cm, and a thickness of 75 μm, having a width of 4 mm at the center in the length direction and a length of 2 cm in the width direction. The polyethylene terephthalate film preferably has a bending angle of 5 degrees or more by applying 0.04 g and drying at 23 ° C. and a relative humidity of 60% for 12 hours. What shows 10 degree | times or more, especially 15 degree | times or more is preferable.

  In addition to the above-mentioned components, the cosmetics for eyelashes of the present invention are components that are usually blended in cosmetics in order to impart a cosmetic effect within a range that does not detract from the effects of the present invention depending on the purpose, such as thickeners. , UV absorbers, UV scattering agents, moisturizers, antioxidants, fragrances, preservatives, and the like may be included.

  Moreover, it is preferable that the viscosity in 25 degreeC of the cosmetics for eyelashes of this invention is 100-2000 Pa.s. When the viscosity is in the above range, the adhesion to the eyelashes is good, the finish is good, and the production is easy. A more preferable viscosity is 150 to 1000 Pa · s.

  The cosmetic for eyelashes of the present invention can be prepared by a generally used production method, for example, by uniformly mixing and stirring the aforementioned components.

  The cosmetic for eyelashes of the present invention is used for making up eyelashes, specifically as a mascara, but it is used not only as a pigment containing pigment but also as a so-called base material for eyelashes or a top coat. You can also.

  As a method of using the makeup cosmetics of the present invention, it may be applied to the eyelashes using a brush or the like usually used for mascara, but the curl can be further improved by increasing the amount of adhesion on the upper surface of the eyelashes. Can be obtained. For example, apply from the top of the eyelashes using a normal mascara applicator brush, comb applicator, coil applicator or brush, flocky, stick applicator, spatula applicator, etc. or repeatedly apply from below By doing so, since the amount of application to the upper surface of the eyelashes is larger than that of the lower surface, a good curling effect can be obtained.

Production Example 1 (Production of polymethacrylic acid)
A glass reaction vessel was charged with 300 g of methacrylic acid (Wako Pure Chemical), 1.5 L of ethanol and 1.73 g of V-65 (Wako Pure Chemical, initiator), and polymerized at 65 ° C. for 4 hours. The obtained polymer solution was dropped into 20 L of acetone to perform reprecipitation. The precipitate was collected and dried at 65 ° C. under reduced pressure for 12 hours or more to obtain polymethacrylic acid (PMAA). As a result of measuring the molecular weight by gel permeation chromatography (GPC) method, it was 180,000 in terms of polyethylene glycol. Moreover, the mass reduction rate (ΔW) from when the film hardness of polymethacrylic acid became pencil hardness 2B to when it was completely dried was 21% by mass. The polymethacrylic acid was adjusted to pH 6 using sodium hydroxide.

(1) Evaluation of curl Three hairs of 1 cm length are taken and fixed horizontally. The mascara composition shown in Table 1 was applied 10 times to the hair at 23 ° C. and a relative humidity of 60% so that the hair was lifted from the bottom to the top using a brush, and the warp angle of the hair from the horizontal plane was measured. The measurement was performed three times, and the average value was taken as the warp angle.

(2) Evaluation of Dama The dama generation state when the prepared mascara composition was applied to the test eyelashes with a brush was visually evaluated, and the following determination was performed.
◎: Dama cannot be done ○: Dama can be made slightly, but there is no significant effect on the finish △: Dama can be made slightly and the finish is affected ×: Dama can be done

(3) Evaluation of shrinkage A 2 × 5 cm polyethylene terephthalate (PET) film (film thickness 75 μm) fixed on one side with a tape on a slide glass is 4 mm wide in the length direction at the center in the length direction. 0.04 g of cosmetic material was applied to a portion having a length of 2 cm in the direction, dried under conditions of 23 ° C. and a relative humidity of 60%, and the bending angle of the film after 12 hours was measured using a protractor. The larger the bending angle, the higher the shrinkage and the better. The PET film used was the trade name “Melinex S” (film thickness 75 μm) (Teijin DuPont Co., Ltd.), three points were measured per sample, and the average value was taken as the bending angle.

(4) Average particle diameter of powder The average particle diameter of the powder is a value obtained by measuring the median diameter by a laser diffraction method using a scattering type particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). .

Examples 1-5 and Comparative Examples 1-4
The mascara compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared by uniformly stirring and mixing the components having the compositions shown in Table 1. The viscosity of each composition was in the range of 100 to 2000 Pa · s at a temperature of 25 ° C.
About the mascara composition of each Example and the comparative example, evaluation of curl and evaluation of a dama were implemented according to the method shown below. The results are shown in Table 1.

  The mascaras of Examples 1 to 5 of the present invention exhibited a sufficient curling effect without generation of lumps. In contrast, Comparative Example 1 in which the film-forming polymer (a) is not used, and Comparative Examples 2 and 3 in which the film-forming polymer with low shrinkage are used have no curl effect and no effect of suppressing the occurrence of non-stickiness. In Comparative Example 4 in which the ratio of the shrinkable polymer in the component was small, only a slight curling effect was observed when mascara was not used.

[note]
(* 1) Polymethacrylic acid (* 2) sodium polystyrene sulfonate produced in Production Example 1; “PS-35” (Tosoh Corporation), weight average molecular weight 350,000, polymer occupancy change rate (ΔW) 17 mass %
(* 3) Wheat protein hydrolyzate; “TRITISOL (solid content 25%)” (Claude Japan Co., Ltd.), polymer occupancy change rate (ΔW) 1 mass%
(* 4) Sulfoisophthalate copolymer; “EASTMAN AQ-55S” (Eastman), polymer occupancy change rate (ΔW) 11 mass%
(* 5) Hydroxyethyl cellulose; “QP-100” (Union Carbide), Polymer occupancy change rate (ΔW) 1 mass%
(* 6) Carnauba wax; “Purified carnauba wax No. 1” (Cerarica Noda Co., Ltd.), penetration 1 or less (* 7) Beeswax; “BEES WAX-S” (Croda Japan Co., Ltd.), needle Degree 18
(* 8) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 1
(* 9) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34
(* 10) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 7
(* 11) Polyvinyl alcohol; “GOHSENOL EG-30” (Nippon Synthetic Chemical Co., Ltd.), polymer occupancy change rate (ΔW) 7% by mass
(* 12) Polyethylene powder aqueous dispersion; “Hydrocer100 (solid content 50%)” (Shamrock)
(* 13) Silica; “Sunsphere L31” (Asahi Glass Co., Ltd.)
(* 14) Talc; “Talc JA-46R” (Asada Flour Milling Co., Ltd.)
(* 15) Nylon fiber; Length: 2mm, Thickness: 6.7T (Unitika Ltd.)
* 16: Polyoxyethylene glyceryl monostearate; Nikkor TMGS-15 (Nikko Chemical Co., Ltd.)

(Curl evaluation using eyelashes)
The curled state after drying when the mascara prepared in Example 4 and Comparative Example 1 was applied to the eyelashes with a brush 10 times from the top and when applied 10 times from the bottom was evaluated. For the evaluation method of curl up, the same measurement as described above was performed three times, and the average value was evaluated based on the following criteria with the warp angle.
◎: 20 degrees or more ○: 15 degrees or more to less than 20 degrees △: 10 degrees or more to less than 15 degrees ×: less than 10 degrees

Production Example 2
20 g of polymethacrylic acid produced according to Production Example 1 was dissolved in 80 g of water. A 1N ammonia solution was added dropwise to this solution to adjust the pH to 4.1. An aqueous solution of translucent polymethacrylic acid (partially ammonium salt) having a solid content of 20% was obtained (degree of neutralization 0.08).
Using the polymethacrylic acid obtained in Production Example 1 and the polymethacrylic acid (partially ammonium salt) obtained in Production Example 2, a mascara composition is prepared according to the following formulation.

Example 6
(1) 5% by mass of polymethacrylic acid produced in Production Example 1
(2) Beeswax; “BEES WAX-S” (Croda Japan Co., Ltd.), penetration 187% by mass
(3) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 16 mass%
(4) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34 3 mass%
(5) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 74 mass%
(6) Behenyl alcohol 1% by mass
(7) Stearic alcohol 2% by mass
(8) Polyvinyl alcohol; “GOHSENOL EG-30” (Nippon Synthetic Chemical Co., Ltd.), polymer occupancy change rate (ΔW 7%) 5% by mass
(9) Daitosol 5000AD (Daito Kasei Kogyo Co., Ltd. ethyl acrylate / ethyl methacrylate copolymer emulsion, 50% aqueous dispersion) 5% by mass
(10) Black iron oxide 8% by mass
(11) Silica (Sunsphere L31, Asahi Glass Co., Ltd. average particle size 3 μm) 5 mass%
(12) Talc (Talc JA-46R, Asada Flour Milling Co., Ltd. average particle size 8 μm) 1% by mass
(13) Nylon fiber (length: 2mm, thickness: 6.7T, Unitika Ltd.) 1% by mass
(14) 1,3-butylene glycol 5% by mass
(15) 2-Amino-2-methyl-1-propanol (AMP) 1% by mass
(16) Polyoxyethylene glycerol monostearate (Nikkor TMGS-15, Nikko Chemical Co., Ltd.) 0.5% by mass
(17) Methylparaben 0.2% by mass
(18) Ethanol 5% by mass
(19) Purified water balance (adjusted so that the total is 100% by mass)

Example 7
(1) 5% by mass of polymethacrylic acid produced in Production Example 1
(2) Beeswax; “BEES WAX-S” (Croda Japan Co., Ltd.), penetration 187% by mass
(3) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 16 mass%
(4) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34 3 mass%
(5) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 74 mass%
(6) Behenyl alcohol 1% by mass
(7) Stearic alcohol 2% by mass
(8) Polyvinyl alcohol; “GOHSENOL EG-30” (Nippon Synthetic Chemical Co., Ltd.), polymer occupancy change rate (ΔW 7%) 5% by mass
(9) Daitosol 5000AD (Daito Kasei Kogyo Co., Ltd. ethyl acrylate / ethyl methacrylate copolymer emulsion, 50% aqueous dispersion) 5% by mass
(10) 3% polyacrylic acid-treated black iron oxide (Miyoshi Kasei Co., Ltd.) 8% by mass
(11) Silica (Sunsphere L31, Asahi Glass Co., Ltd. average particle size 3 μm) 5 mass%
(12) Talc (Talc JA-46R, Asada Flour Milling Co., Ltd. average particle size 8 μm) 1% by mass
(13) Nylon fiber (length: 2mm, thickness: 6.7T, Unitika Ltd.) 1% by mass
(14) 1,3-butylene glycol 5% by mass
(15) 2-Amino-2-methyl-1-propanol (AMP) 1% by mass
(16) Polyoxyethylene glycerol monostearate (Nikkor TMGS-15, Nikko Chemical Co., Ltd.) 0.5% by mass
(17) Methylparaben 0.2% by mass
(18) Ethanol 5% by mass
(19) Purified water balance (adjusted so that the total is 100% by mass)

Example 8
(1) 5% by mass of polymethacrylic acid produced in Production Example 2
(2) Beeswax; “BEES WAX-S” (Croda Japan Co., Ltd.), penetration 185% by mass
(3) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 16 mass%
(4) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 74% by mass
(5) Behenyl alcohol 1% by mass
(6) Stearic alcohol 2% by mass
(7) Polyvinyl alcohol; “GOHSENOL EG-30” (Nippon Synthetic Chemical Co., Ltd.), polymer occupancy change rate (ΔW 7%) 5% by mass
(8) Daitosol 5000AD (Daito Kasei Kogyo Co., Ltd. polymer emulsion) 5% by mass
(9) Black iron oxide 8% by mass
(10) 2% by mass of silica (Sunsphere L31, Asahi Glass Co., Ltd. average particle size 3 μm)
(11) Talc (Talc JA-46R, Asada Flour Milling Co., Ltd. average particle size 8 μm) 0.5 mass%
(12) Nylon fiber (length: 2mm, thickness: 6.7T, Unitika Ltd.) 1% by mass
(13) 1,3-butylene glycol 5% by mass
(14) 2-Amino-2-methyl-1-propanol (AMP) 1% by mass
(15) Polyoxyethylene glyceryl monostearate (Nikkor TMGS-15, Nikko Chemical Co., Ltd.) 0.5% by mass
(16) Methylparaben 0.2% by mass
(17) Ethanol 1% by mass
(18) Balance of purified water (adjusted so that the total is 100% by mass)
The ratio (mass ratio) between the film-forming polymer (polymethacrylic acid) and the wax having a penetration of 8 or more is 5/4, and the ratio (mass ratio) between the film-forming polymer and the powder having a particle diameter of 1 μm or more is 5/4. 2/1, and the ratio (mass ratio) between the film-forming polymer and ethanol is 5/1.

Example 9
(1) 2% by mass of polymethacrylic acid produced in Production Example 1
(2) Beeswax; “BEES WAX-S” (Croda Japan Co., Ltd.), penetration 187% by mass
(3) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 16 mass%
(4) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34 3 mass%
(5) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 74 mass%
(6) Behenyl alcohol 1% by mass
(7) Stearic alcohol 2% by mass
(8) Polyvinyl alcohol; “GOHSENOL EG-30” (Nippon Synthetic Chemical Co., Ltd.), polymer occupancy change rate (ΔW 7%) 5% by mass
(9) Daitosol 5000AD (Daito Kasei Kogyo Co., Ltd. ethyl acrylate / ethyl methacrylate copolymer emulsion, 50% aqueous dispersion) 5% by mass
(10) 3% polyacrylic acid-treated black iron oxide (Miyoshi Kasei Co., Ltd.) 8% by mass
(11) 3% by mass of silica (Sunsphere L31, Asahi Glass Co., Ltd. average particle size 3 μm)
(12) Talc (Talc JA-46R, Asada Flour Milling Co., Ltd. average particle size 8 μm) 1% by mass
(13) Nylon fiber (length: 2mm, thickness: 6.7T, Unitika Ltd.) 1% by mass
(14) 1,3-butylene glycol 5% by mass
(15) 2-Amino-2-methyl-1-propanol (AMP) 1% by mass
(16) Methylparaben 0.2% by mass
(17) Ethanol 8% by mass
(18) Balance of purified water (adjusted so that the total is 100% by mass)
The ratio (mass ratio) between the film-forming polymer (polymethacrylic acid) and the wax having a penetration of 8 or more is 2/7, and the ratio (mass ratio) between the film-forming polymer and the powder having a particle diameter of 1 μm or more is 2/1, and the ratio (mass ratio) between the film-forming polymer and ethanol is 1/4.

The cosmetics of the present invention are preferably used as makeup for eyelashes, specifically as mascara. A good curling effect can be given to eyelashes without causing lumps during use.

Claims (10)

A film-forming polymer (a) containing 10% by mass or more of the non-volatile component (A) and 30% by mass or more of the volatile component (B) and having the following characteristics (i) and (ii) in the component (A) 70% by mass or more of the non-volatile component (a-1) that is solid at normal temperature and 30% by mass or less of the non-volatile component (a-2) that is liquid at normal temperature, and the film-forming polymer (a) Cosmetics for eyelashes containing 0.6 to 15% by mass in cosmetics.
(I) In the film formation test, the rate of change in polymer occupancy (ΔW) from when the film hardness becomes pencil hardness 2B to when the film is completely dried is 13% by mass or more.
(Ii) The weight average molecular weight is 5,000 to 2,000,000.   The cosmetic for eyelashes according to claim 1, wherein the film-forming polymer has a weight average molecular weight of 20,000 to 1,000,000.   The cosmetic for eyelashes according to claim 1 or 2, wherein the film-forming polymer is a polymer obtained by polymerizing a vinyl monomer.   The cosmetic for eyelashes according to any one of claims 1 to 3, wherein the film-forming polymer is a polymer obtained by polymerizing a monomer containing an organic acid having a reactive vinyl group and / or a salt thereof.   The cosmetic for eyelashes according to claim 4, wherein the organic acid having a reactive vinyl group is at least one selected from methacrylic acid and styrenesulfonic acid.   The cosmetic for eyelashes according to any one of claims 1 to 5, further comprising a wax having a penetration of 8 or more as the component (A).   The cosmetic for eyelashes according to any one of claims 1 to 6, further comprising a powder having an average particle diameter of 0.1 to 20 µm as the component (A).   The cosmetics for eyelashes in any one of Claims 1-7 which contain water and a C1-C4 lower alcohol in a volatile component (B), and form an oil-in-water emulsion composition.   0.04 g of a polyethylene terephthalate film having a width of 2 cm, a length of 5 cm, and a thickness of 75 μm is applied to a central portion in the length direction of 4 mm in the length direction and 2 cm in the width direction at 23 ° C. and relative humidity. The cosmetic for eyelashes according to any one of claims 1 to 8, wherein the polyethylene terephthalate film exhibits a bending angle of 5 degrees or more by drying for 12 hours under a condition of 60%. Use of the cosmetics which attaches much cosmetics for eyelashes in any one of Claims 1-9 to the upper surface of eyelashes.