JP4726682B2 - Eyelash cosmetic - Google Patents

Description

  The present invention relates to a cosmetic for eyelashes containing a film-forming polymer, which gives a good curl-up effect to eyelashes, has a high curl retention effect during use, and has a beautiful finish.

  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 enhance the curl-up effect, various film agents or powders have been used. For example, Patent Document 1 provides a mascara that produces a curl-up effect and a volume feeling by using a candelilla resin obtained by separating and extracting a highly flexible candelilla wax with an organic solvent. . Patent Document 2 discloses a mascara that exhibits a curl-up effect and an effect of deepening eyelashes by a combination of a film-forming polymer that can be bonded to keratin fibers and causes shrinkage exceeding 1% of the stratum corneum and a high hardness wax. providing. However, in addition to the problem that lumps are still likely to occur during use and the finish is not sufficient, the curled eyelashes turn downward over time, that is, the curl retention effect is low. Patent Document 3 discloses a method of enhancing the curl and its holding effect by combining a non-aqueous polymer dispersion and a hollow powder. However, when a large amount of powder is blended to maintain the curl, the uniformity of the film is disclosed. There is a problem that the finish is deteriorated due to lowering of the skin, and the makeup is easily broken.

JP 2003-95874 A JP-A-11-255619 JP 2004-315420 A

  An object of the present invention is to provide a cosmetic for eyelashes that gives a good curl-up effect to the eyelashes, has a high curl retention effect during use, and has a beautiful finish.

The present inventors have found that a cosmetic for eyelashes comprising a specific film-forming polymer having a high glass transition temperature (Tg), a solid oil component and a powder having a specific particle size has a good curl-up effect on eyelashes. It was found that the curl retention effect during use was high and the finish was beautiful. That is, the present invention
(1) Methacrylic acid and / or a salt thereof (monomer (a)) and at least one monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less are used as structural units, and the glass transition temperature (Tg) is 80. Polymer (A) having a temperature of ℃ or higher
(2) An oily component that is solid at 25 ° C. (3) An eyelash cosmetic containing a powder having an average particle diameter of 1 to 20 μm is provided.

  The cosmetics for eyelashes of the present invention can give a good curl-up effect to the eyelashes, have a high curl retention effect during use, and can give a beautiful finish.

The cosmetic for eyelashes of the present invention comprises a polymer comprising as a structural unit methacrylic acid and / or a salt thereof (monomer (a)) and at least one monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less. A cosmetic for eyelashes comprising A), an oily component that is solid at 25 ° C., and powder.
[Polymer (A)]
The polymer (A) according to the present invention comprises, as a structural unit, at least one monomer (b) having a solubility in methacrylic acid and / or a salt thereof (a) and 100 g of water at 20 ° C. of 2 g or less. The polymer (A) is a film-forming polymer, and has a property of forming a film when an aqueous solution or dispersion of the polymer is spread on a petri dish and dried.
The glass transition temperature (Tg) of the polymer (A) needs to be 80 ° C. or higher from the viewpoint of improving the curl-up effect, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 150 ° C. or higher. preferable. Further, the higher the glass transition temperature (Tg), the better from the viewpoint of improving the curl-up effect, but it is preferably 250 ° C. or lower and more preferably 230 ° C. or lower because of manufacturing limitations. By setting the glass transition temperature (Tg) of the polymer (A) high, it is considered that the shrinkage of the polymer is improved and the curl-up effect is enhanced.
The glass transition temperature is a value measured by a differential scanning calorimeter (DSC). Specifically, when measurement is performed under the conditions of the following continuous temperature programs 1 to 4, the value measured by the temperature program 3 is set as the glass transition temperature.
Temperature program:
1.30 to 250 ° C .: temperature rising rate 30 ° C./min, holding time 1 min
2.250 to -50 ° C: cooling rate 200 ° C / min, holding time 10 min
3. −50 to 250 ° C .: Temperature rising rate 10 ° C./min, holding time 1 min
4. 250-30 ° C .: cooling rate 30 ° C./min, holding time 2 min

The polymer (A) has a weight average molecular weight (measured by GPC, in terms of polystyrene) of preferably 5,000 to 1,000,000, and more preferably 8,000 to 500,000. If the weight average molecular weight is 5000 or more, a good curl-up effect can be obtained, and if it is 1000000 or less, coating is easy.
Moreover, even if the form of the polymer (A) is an aqueous solution, a water / alcohol mixed solution system, or an emulsion system, it can be used regardless of the form.

  The carboxyl group contained in the polymer (A) may not be neutralized, but all or part of the carbonyl group is neutralized from the viewpoint of water solubility, curl-up effect and curl retention effect. It is preferable. The degree of neutralization is preferably 0.01 to 0.6, and more preferably 0.02 to 0.3. As the neutralizing agent, an inorganic base or an organic base can be used. Examples of the inorganic base include ammonia, potassium hydroxide, sodium hydroxide and the like, and examples of the organic base include L-arginine, 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1, Examples include 3-propanediol, triethanolamine, and tris (hydroxymethyl) aminomethane. As the neutralizing agent, one or more base compounds can be used. In order to obtain a high curl-up effect and a curl retention effect, it is preferable to use an inorganic base, and particularly preferably ammonia. In order to obtain makeup persistence, it is preferable to use an organic base, and it is particularly preferable to use 2-amino-2-methyl-1-propanol.

[Monomer (a)]
The content of the monomer (a) contained in the polymer (A) is preferably 11 to 98% by mass, preferably 20 to 98% by mass, and more preferably 20 to 90% by mass in order to obtain a sufficient curl-up effect. 40 to 80% by mass is more preferable. Moreover, in order to obtain a beautiful finish, 11-60 mass% is preferable as methacrylic acid, and 15-40 mass% is more preferable. As the salt to be constructed, the same base as that used as the neutralizing agent for the polymer (A) can be used. Examples of the inorganic base include ammonia, potassium hydroxide, and sodium hydroxide. Include L-arginine, 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, triethanolamine and tris (hydroxymethyl) aminomethane. As the neutralizing agent, one or more base compounds can be used. In order to obtain a high curl-up effect and a curl retention effect, it is preferable to use an inorganic base, and particularly preferably ammonia. In order to obtain makeup persistence, it is preferable to use an organic base, and it is particularly preferable to use 2-amino-2-methyl-1-propanol.

[Monomer (b)]
The content of the monomer (b) contained in the polymer (A) is 2 to 89% by mass, in order to obtain a sufficient curl retention effect, preferably 2 to 80% by mass, more preferably 10 to 80% by mass, -60 mass% is more preferable. Moreover, in order to obtain a beautiful finish, 40-89 mass% is preferable, and 60-85 mass% is more preferable.
The monomer (b) according to the present invention has a solubility in 100 g of water at 20 ° C. of 2 g or less and preferably does not dissolve in water. Moreover, the glass transition temperature as a homopolymer of the monomer (b) is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of the curl-up effect. Moreover, 250 degrees C or less is preferable from the restrictions on manufacture.
Preferred examples of the monomer (b) include alkyl acrylate monomers, alkyl methacrylate monomers, styrene monomers, alkyl acrylamide monomers, alkyl methacrylamide monomers, and the like. The alkyl group contained in these monomers includes not only a linear or branched hydrocarbon group, but also a hydrocarbon group having a monocyclic or polycyclic aliphatic ring or an aromatic ring, and is further linear in the ring. Or the thing containing the hydrocarbon group which has a branched alkyl group as a substituent is mentioned.
Among the above monomers (b), methyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, styrene, tert -Butylacrylamide and tert-butylmethacrylamide are preferable from the viewpoint of the curl-up effect, and methyl methacrylate and tert-butylacrylamide are more preferable.
In addition, a monomer (b) may be used individually by 1 type, and may use 2 or more types.

[Eyelash cosmetics]
The cosmetic for eyelashes of the present invention contains a polymer (A), an oily component that is solid at 25 ° C., and a powder having an average particle size of 1 to 20 μm.
In the cosmetic for eyelashes of the present invention, when the content of the polymer (A) is 1 to 30% by mass in the total cosmetic, a good curl-up effect and its retention effect can be expressed. From the viewpoint of the curl-up effect and the beautiful finish that does not generate lumps even if it is overcoated, it is particularly preferred to contain in the range of 1 to 10% by mass, and further 2 to 6% by mass.

  The oily component (wax) solid at 25 ° C. used in the present invention can be appropriately selected from animal waxes, plant waxes, mineral waxes, synthetic waxes and the like. Specific examples include carnauba wax, beeswax, extremely hydrogenated jojoba oil, lanolin wax, microcrystalline wax, paraffin wax, glycerides solid at 25 ° C., and silicone wax. The above waxes may be used alone or in combination of two or more.

Of these waxes, it is more preferable to include 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 placed on a specified 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 needle penetration in 5 seconds, and the value obtained by multiplying the needle penetration distance (mm) by 10 was defined as the needle penetration. Specifically, among the above waxes, those having a penetration of 8 or more can be mentioned. In particular, beeswax and microcrystalline wax are preferably used. In addition, the above-mentioned wax having a penetration of 8 or more may be used alone or in combination of two or more.
The oily component that is solid at 25 ° C. is 0.1 to 40% by mass, preferably 5 to 30% by mass, and more preferably 10 to 25% by mass in the eyelash cosmetic. Moreover, it is preferable to contain in the cosmetics for eyelashes in the range of 0.1-20 mass%, and the wax whose penetration is 8 or more is 0.5-10 mass%, Furthermore, 1-6 mass%. preferable. By containing 0.1% by mass or more of the solid oil component at 25 ° C., a sufficient curling effect of the eyelashes can be obtained, and when it is 40% by mass or less, a good finish can be expected. it can.

The powder used in the present invention is not particularly limited as long as it is a powder having an average particle diameter of 1 to 20 μm, but from the viewpoint of the curl-up effect, 2 to 10 μm is particularly preferable. 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 measuring apparatus (for example, LA-920 manufactured by Horiba, Ltd.).
Further, the shape of the powder may be any of a spherical shape, a flat plate shape, a granular shape, a needle shape, a rod shape, an amorphous shape, and the like, and a spherical shape is particularly preferable.

The powder used in the present invention includes inorganic powder, organic powder, and the like. Inorganic powders include plate-like inorganic powders such as talc, mica, sericite, and kaolin, and spherical shapes such as silica, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium silicate, calcium carbonate, aluminum silicate, and magnesium carbonate. Or amorphous inorganic powder; organic powder such as polyamide resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, cellulose resin, polystyrene resin, copolymer of styrene and acrylic acid, silicone resin Etc.
Of these, inorganic powder is preferable, and spherical inorganic powder is more preferable. More specifically, it is preferable to use silica. In addition, in an organic powder, it will become a preferable form by carrying out a hydrophilic process.

  The above powder may be used singly or as a mixture of two or more. From the viewpoint of obtaining a beautiful finish and obtaining a high curl up effect, It is preferable to contain 0.1-20 mass% with respect to it, and also containing in 1-8 mass% is preferable.

  As the usage form of the powder, it may be used as an aqueous dispersion, and may be used in the state of dispersion dispersed in water using a water-soluble polymer or a surfactant. Specific examples include polyethylene dispersion, silicone resin dispersion, polystyrene resin dispersion, urethane dispersion, and nylon dispersion.

The eyelash cosmetic of the present invention can also contain a pigment. The pigment is not particularly limited as long as it is usually used in cosmetics, and examples thereof include inorganic pigments and organic pigments.
Specific examples include titanium oxide, black titanium oxide, zinc white, bengara, yellow iron oxide, black iron oxide and the like as inorganic pigments; tar dyes and the like as organic pigments.
It is preferable to contain 0.1-20 mass% of pigments with respect to the whole cosmetics for eyelashes, and also it is preferable to contain in 1-8 mass%.

The powder and pigment may be surface-treated, for example, silica treatment, alumina treatment, silica-alumina treatment, polyacrylic acid treatment, etc., hydrophilization surface treatment, silicone treatment, fluorine compound treatment, metal soap treatment, lecithin What gave hydrophobized surface treatments, such as a process and oil-fat process, can be used.
In particular, powders and pigments subjected to hydrophilic treatment have a high affinity with the polymer (A), and in particular, powders and pigments treated with polyacrylic acid are more preferable in terms of curl-up effect and finish.

  The eyelash cosmetic of the present invention may further contain a water-soluble polymer as a powder and pigment dispersant or a system stabilizer. Specifically, polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, cationized hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, carboxy vinyl polymer, vinyl pyrrolidone / vinyl alcohol copolymer, polymethyl vinyl ether, gum arabic, guar gum, xanthan gum , Modified corn starch, starch, sodium alginate and the like. Among these, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, gum arabic, and xanthan gum are particularly preferable from the viewpoints of the dispersibility of the powder and pigment and the curl-up effect. These may be contained in the eyelash cosmetic of the present invention in an amount of 0.1 to 20% by mass, and further 1 to 5% by mass.

  Furthermore, in addition to the above polymer, other film forming properties or polymers that do not form a film can be added within a range not impairing the effects of the present invention. The polymer may be a solution or an emulsion.

  Moreover, in order to provide a long rush effect, a fiber can be further contained. 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 preferably has a cross-sectional thickness of 0.1 to 20 T and a length of 0.1 to 5 mm. 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, as other components, an oily component which is liquid at 25 ° C., a polyol and a surfactant can be contained.
Here, the oil component that is liquid at 25 ° C. includes hydrocarbon oils such as liquid isoparaffin, liquid paraffin, and heavy liquid isoparaffin; diisostearyl malate, isotridecyl isononanoate, glyceryl dimyristate, glyceryl diisostearate, myristin Examples thereof include esters and triglycerides such as acid / glyceryl isostearate, neopentyl glycol dicaprate, castor oil, macadamian nut oil, jojoba oil; silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane. From the viewpoint of obtaining a beautiful finish, these can be contained in the eyelash cosmetic of the present invention in an amount of 0.01 to 10% by mass.
Examples of the polyols include ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin and the like. Of these, propylene glycol, dipropylene glycol, and 1,3-butylene glycol are preferable from the viewpoint of ease of use, and 1,3-butylene glycol is particularly preferable from the viewpoint of obtaining a beautiful finish. These may be contained in the eyelash cosmetic of the present invention in an amount of 0.01 to 10% by mass.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphiphilic surfactant, and the like can be used alone or in combination.

  Further, the eyelash cosmetic of the present invention can contain a volatile oil. As a volatile oil agent, a volatile thing is mentioned among C8-C16 hydrocarbon oil and the linear or cyclic silicone of 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)

(Wherein u represents an integer of 3 to 5)
Examples of the hydrocarbon oil having 8 to 16 carbon atoms include petroleum-derived isoparaffin (light isoparaffin), isododecane (2,2,4,4,6-pentamethylheptane) and the like. Examples of the linear or cyclic silicone of the general formula (1) or (2) include octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.
These volatile oils can control the drying rate of the cosmetic for eyelashes of the present invention, and may be used alone or in combination of two or more. The blending amount is preferably 0.5 to 20% by mass.

  Furthermore, the eyelash cosmetic of the present invention can contain water and a lower alcohol having 1 to 4 carbon atoms. Examples of the lower alcohol include methanol, ethanol, isopropanol, butyl alcohol, and the like. From the viewpoint of ease of handling, it is particularly preferable to use ethanol. A C1-C4 lower alcohol may be used individually by 1 type, and 2 or more types can also be mixed and used for it. From the viewpoint of controlling the polymer solvent and the drying speed of the eyelash cosmetic, water and 1 to 4% by weight of the lower alcohol having 1 to 4 carbon atoms may be contained in the eyelash cosmetic in an amount of 1 to 80% by mass, and more preferably 10 to 50% by mass. preferable. Moreover, 0.5-20 mass% is preferable and, as for content of the lower alcohol in the eyelash cosmetics of this invention, 1-10 mass% is more preferable.

  The cosmetic for eyelashes of the present invention is an oil-in-water emulsion composition (O / W), a water-in-oil emulsion composition (W / O), or any one using only liquid components other than water as volatile components. Is also included. Among these, from the viewpoint of improving the curl-up effect, a system containing water, particularly an oil-in-water emulsion composition (O / W) containing water and a lower alcohol having 1 to 4 carbon atoms is most preferable. .

  The cosmetics for eyelashes of the present invention include, in addition to the above-mentioned components, components that are usually contained in cosmetics in order to impart a cosmetic effect within a range that does not impair the effects of the present invention depending on the purpose, such as thickeners, ultraviolet rays. One type or two or more types of absorbers, ultraviolet scattering agents, humectants, antioxidants, fragrances, preservatives and the like can be included.

  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. More specifically, it can be prepared by heating and mixing an aqueous solution of polymer (A) or an aqueous phase containing a suspension and a pigment and a wax at a temperature equal to or higher than the melting point of the wax and then cooling.

  The cosmetic for eyelashes of the present invention is used for makeup of 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, the upper surface of the eyelashes by applying from the top of the eyelashes using a normal mascara applicator brush, comb applicator, coil applicator or brush, flocky, stick applicator, etc. Since the coating amount on the surface is larger than that on the lower surface, a good curl-up effect can be obtained.

Production Example 1 (Production of poly (methacrylic acid-methyl methacrylate) sodium salt aqueous solution (PMAA / MMA (Na)))
After putting ethanol 2000g in the glass reaction container and performing nitrogen bubbling for 30 minutes at room temperature, it heated to 63 degreeC by nitrogen atmosphere. After adding a solution of 5.3 g of azo polymerization initiator 2,2′-avizos (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 30 g of ethanol, A mixture of 230 g of acid and 270 g of methyl methacrylate (both manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added over 2 hours. After completion of the addition of the mixture, the mixture was stirred at 63 ° C. for 6 hours, then heated to 70 ° C. and stirred for 2 hours to perform polymerization.
The obtained polymer solution was dropped into a methanol / water = 1/2 mixed solution to perform reprecipitation. The precipitate was collected and dried at 70 ° C. for 12 hours or more under reduced pressure to obtain poly (methacrylic acid-methyl methacrylate). The polymer composition measured by NMR was methacrylic acid / methyl methacrylate = 44/56 (mass ratio). The weight average molecular weight measured by GPC was 72000 (polystyrene conversion).
86.7g of 1N sodium hydroxide aqueous solution was dripped at the liquid which melt | dissolved 80g of obtained poly (methacrylic acid-methyl methacrylate) in 270g of ethanol. Further, 360 g of water was added, and ethanol was distilled off with an evaporator to obtain a translucent aqueous solution of poly (methacrylic acid-methyl methacrylate) sodium salt (degree of neutralization 0.2). This aqueous polymer solution had a pH of 6 and a solid content of 20%.
Moreover, it was 193 degreeC as a result of measuring the glass transition temperature (Tg) of this polymer with the differential scanning calorimeter (Seiko Instruments Co., Ltd. product, DSC6200). The Tg of methyl methacrylate homopolymer is 105 ° C.

Production Example 2 (Production of poly (methacrylic acid-tert-butylacrylamide) sodium salt suspension (PMAA / tBuAAm (Na)))
1900 g of ethanol was put in a glass reaction vessel, nitrogen bubbling was performed at room temperature for 30 minutes, and then heated to 63 ° C. in a nitrogen atmosphere. After adding a solution prepared by dissolving 6.1 g of azo polymerization initiator 2,2′-avizos (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 30 g of ethanol, A mixture consisting of 300 g of acid, 300 g of tert-butylacrylamide and 490 g of ethanol was added over 2 hours. After completion of the addition of the mixture, the mixture was stirred at 63 ° C. for 6 hours, then heated to 71 ° C. and stirred for 2 hours to perform polymerization.
The obtained polymer solution was dropped into hexane to perform reprecipitation. The precipitate was collected and dried at 70 ° C. under reduced pressure for 12 hours or more to obtain poly (methacrylic acid-tert-butylacrylamide). The polymer composition measured by NMR was methacrylic acid / tert-butylacrylamide = 56/44 (mass ratio). The weight average molecular weight measured by GPC was 66000 (polystyrene conversion). To a solution obtained by dissolving 15 g of the obtained poly (methacrylic acid-tert-butylacrylamide) in 68 g of ethanol, 4.08 g of 1N sodium hydroxide aqueous solution was dropped. Further, 68 g of water was added, and ethanol was distilled off by an evaporator to obtain a white suspension of poly (methacrylic acid-tert-butylacrylamide) sodium salt (neutralization degree 0.04). This polymer water suspension had a pH of 5.0 and a solid content of 32%.
Moreover, it was 198 degreeC as a result of measuring the glass transition temperature (Tg) of this polymer with the differential scanning calorimeter (Seiko Instruments Co., Ltd. product, DSC6200).
The Tg of the tert-butylacrylamide homopolymer is 135 ° C.

Production Example 3 (Production of poly (methacrylic acid-methyl methacrylate) ammonium salt aqueous solution (PMAA / MMA ammonium salt))
42 ml of 1N ammonia solution was dropped into a solution obtained by dissolving 60 g of poly (methacrylic acid-methyl methacrylate) obtained in Production Example 1 in 180 g of ethanol. Further, 360 g of water was added, and ethanol was distilled off with an evaporator to obtain a translucent aqueous solution of poly (methacrylic acid-methyl methacrylate) ammonium salt (degree of neutralization 0.12). This aqueous polymer solution had a pH of 6.1 and a solid content of 20%.
Moreover, it was 174 degreeC as a result of measuring the glass transition point (Tg) of this polymer with the differential scanning calorimeter (Seiko Instruments Co., Ltd. product, DSC6200).

Production Example 4 (Production of poly (methacrylic acid-tert-butylacrylamide) ammonium salt aqueous suspension (PMAA / tBuAAm ammonium salt))
To a solution obtained by dissolving 15 g of poly (methacrylic acid-tert-butylacrylamide) obtained in Production Example 2 in 68 g of ethanol, 8.3 ml of 1N ammonia solution was dropped. Further, 270 g of water was added, ethanol was distilled off by an evaporator, and a white suspension of poly (methacrylic acid-tert-butylacrylamide) ammonium salt aqueous suspension was obtained (degree of neutralization 0.08). This polymer aqueous suspension had a pH of 6.0 and a solid content of 20%.
Moreover, it was 197 degreeC as a result of measuring the glass transition point (Tg) of this polymer with the differential scanning calorimeter (The Seiko Instruments make, DSC6200).

Production Example 5 (Production of poly (methacrylic acid-methyl methacrylate) 2-amino-2-methyl-1-propanol salt aqueous solution (PMAA / MMA (AMP)))
793 g of ethanol was placed in a glass reaction vessel, nitrogen bubbling was performed at room temperature for 30 minutes, and then heated to 63 ° C. in a nitrogen atmosphere. After adding a solution prepared by dissolving 2.07 g of azo polymerization initiator 2,2′-avizos (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 20 g of ethanol, A mixture of 54 g of acid and 146 g of methyl methacrylate (both manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added over 2 hours. After completion of the addition of the mixture, the mixture was stirred at 65 ° C. for 4 hours, then heated to 70 ° C. and stirred for 2 hours to perform polymerization.
The obtained polymer solution was added dropwise to a methanol / water = 3/7 mixed solution for reprecipitation. The precipitate was collected and dried at 70 ° C. for 12 hours or more under reduced pressure to obtain poly (methacrylic acid-methyl methacrylate). The polymer composition measured by NMR was methacrylic acid / methyl methacrylate = 20/80 (mass ratio). The weight average molecular weight measured by GPC was 59700 (polystyrene conversion). Moreover, it was 156 degreeC as a result of measuring the glass transition point (Tg) of this polymer with the differential scanning calorimeter (Seiko Instruments Co., Ltd. product, DSC6200).
34.7 g of the obtained poly (methacrylic acid-methyl methacrylate) was dissolved by heating at 60 ° C. in a mixed solution of 105 g of ethanol, 30.8 g of 2-amino-2-methyl-1-propanol 10% aqueous solution and 177 g of water. I let you. Then, ethanol was distilled off by an evaporator to obtain a poly (methacrylic acid-methyl methacrylate) 2-amino-2-methyl-1-propanol salt aqueous solution (degree of neutralization 0.42). This aqueous polymer solution had a pH of 6.0 and a solid content of 20%. Moreover, it was 172 degreeC as a result of measuring the glass transition temperature (Tg) of this polymer with the differential scanning calorimeter (Seiko Instruments Co., Ltd. product, DSC6200).

(1) Evaluation of curling up Three hairs having a length of 1 to 1.5 cm are taken and fixed horizontally. After applying the mascara composition to the hair 10 times with a brush at 23 ° C. and a relative humidity of 60% so as to lift the hair from the bottom to the top, the warp angle of the hair was measured. The measurement was performed three times, and the average value was evaluated as the warp angle.

(2) Evaluation of curl retention effect The warp angle immediately after applying mascara to the hair by the above method and after 3 hours was measured, and [(warp angle after 3 hours) / (next warp angle)] × 100 = The curl retention rate was used as an index of the curl retention effect.

(3) Evaluation of the finish The state of occurrence of lumps when the prepared mascara composition was applied to the test eyelashes with a brush was visually evaluated, and the following determination was made.
◎: 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

(4) Evaluation of makeup persistence The prepared mascara composition was applied to the eyelashes with a brush, and the makeup persistence after 8 hours was evaluated. Evaluation was performed by 10 women.
◎: 9 or more out of 10 evaluated that makeup persistence was good ○: 6 to 8 out of 10 evaluated that makeup persistence was good △: 3 to 5 out of 10 had good makeup persistence ×: Less than 2 out of 10 evaluated that makeup persistence was good

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

Examples 1-8 and Comparative Examples 1-3
The mascara compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were prepared by uniformly stirring and mixing the components having the compositions shown in Table 1.
About the mascara composition of each Example and the comparative example, evaluation of the curl-up effect, the curl retention effect, the finish, and the makeup persistence was performed according to the above-described method. The results are shown in Table 1.

  The mascara compositions of Examples 1 to 8 of the present invention exhibited a sufficient curl-up effect, an excellent curl retention effect, and a beautiful finish. On the other hand, Comparative Example 1 in which no film-forming polymer is used and Comparative Example 2 in which no powder is added show the same effects as in Examples 1 to 7 in terms of finish, but no curl-up effect or curl retention effect is observed. It was. Further, in Comparative Example 3 in which no wax was added, sufficient effects were not recognized in terms of curl-up effect, curl retention effect, and finish.

[note]
(* 1) Poly (methacrylic acid-methyl methacrylate) sodium salt aqueous solution produced in Production Example 1 (* 2) Poly (methacrylic acid-tert-butylacrylamide) sodium salt suspension produced in Production Example 2 (* 3) ) Poly (methacrylic acid-methyl methacrylate) ammonium salt aqueous solution produced in Production Example 3 (* 4) Poly (methacrylic acid-tert-butylacrylamide) ammonium salt aqueous suspension produced in Production Example 4 (* 5) Carnauba wax; “Purified Carnauba Wax No. 1” (Ceralica Noda Co., Ltd.), penetration 1 or less (* 6) Beeswax; “BEES WAX-S” (Crowda Japan Co., Ltd.), penetration 18
(* 7) Extremely hydrogenated jojoba oil; (Koei Kogyo Co., Ltd.), penetration 1
(* 8) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34
(* 9) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 7
(* 10) Silica; “Sunsphere L31” (Asahi Glass Co., Ltd.), average particle size 3 μm, spherical powder (* 11) talc; “Talc JA-46R” (Asada Flour Milling Co., Ltd.), average particle size 8 μm , Plate-like powder (* 12) polyvinyl alcohol; “GOHSENOL EG-30” (Nippon GOHSEI)
(* 13) Polymer emulsion; “Yodosol GH34” (NSC Japan)
(* 14) Polyoxyethylene glycerol monostearate; Nikkor TMGS-15 (Nikko Chemical Co., Ltd.)
(* 15) Polyacrylic acid-treated black iron oxide; “PA-Black BL-100” (manufactured by Miyoshi Kasei Co., Ltd.), 3% polyacrylic acid-treated black iron oxide (* 16) nylon fiber; Length: 2 mm Thickness: 6.7T (Unitika Ltd.)
(* 17) Manufactured in Production Example 5 (Poly (methacrylic acid-methyl methacrylate) 2-amino-2-methyl-1-propanol salt aqueous solution

  The mascara of Examples 9 and 10 below was prepared in the same manner as Example 1. All showed sufficient curl-up effect, excellent curl retention effect, and beautiful finish.

Example 9 (mass%)
Polymer of Production Example 5 * 1 6
Candelilla wax 3
Beeswax 6
Extremely water-added jojoba oil 3
Paraffin wax 8
Silica 1
Polyvinyl alcohol 2
Polymer emulsion * 2 10
1,3-butylene glycol 5
Stearic acid 3
Methylparaben 0.2
Polyacrylic acid-treated black iron oxide 5
Nylon fiber 1
2-Amino-2-methyl-1-propanol 0.5
Ethanol 5
Purified water balance Total 100

Example 10 (mass%)
Polymer of Production Example 5 * 1 6
Candelilla wax 3
Beeswax 1
Extremely water-added jojoba oil 3
Paraffin wax 8
Silica 7
Talc 1
Polyvinyl alcohol 2
Polymer emulsion * 2 10
1,3-butylene glycol 5
Stearic acid 3
Methylparaben 0.2
Polyacrylic acid-treated black iron oxide 5
Nylon fiber 1
2-Amino-2-methyl-1-propanol 0.5
Ethanol 5
Purified water balance Total 100

[note]
(* 1) Manufactured in Production Example 5 (poly (methacrylic acid-methyl methacrylate) 2-amino-2-methyl-1-propanol salt aqueous solution (* 2) polymer emulsion; “Yodosol GH34” (manufactured by NSC Japan)

The cosmetics for eyelashes of the present invention are suitably used for makeup for eyelashes, specifically as mascara. A good curl-up effect is given to the eyelashes, and the curl retention effect during use is high, and the finish can be made beautiful.

Claims (7)

The following components (1) to (3)
(1) Containing methacrylic acid and / or a salt thereof (hereinafter referred to as monomer (a)) and at least one monomer (b) selected from alkyl methacrylate monomer and alkylacrylamide monomer, and containing monomer (a) The polymer (A) having a rate of 20 to 80% by mass, a content of the monomer (b) of 40 to 89% by mass, and a glass transition temperature (Tg) of 150 ° C. or higher.
(2) An oily component that is solid at 25 ° C. containing a wax having a penetration of 8 or more. (3) A cosmetic for eyelashes containing a powder having an average particle diameter of 1 to 20 μm.   The cosmetic for eyelashes according to claim 1, wherein the monomer (b) is at least one selected from methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, and tert-butyl acrylamide.   The cosmetic for eyelashes according to claim 1 or 2, wherein the carboxyl group contained in the polymer (A) is neutralized with a degree of neutralization of 0.01 to 0.6.   The cosmetic for eyelashes according to claim 3, wherein the carboxyl group contained in the polymer (A) is neutralized with ammonia and / or 2-amino-2-methyl-1-propanol.   Polymer (A) is poly (methacrylic acid-methyl methacrylate) sodium salt, poly (methacrylic acid-tert-butylacrylamide) sodium salt, poly (methacrylic acid-methyl methacrylate) ammonium salt, poly (methacrylic acid-tert- The cosmetic for eyelashes according to claim 1 or 2, which is a butyl acrylamide) ammonium salt or a poly (methacrylic acid-methyl methacrylate) 2-amino-2-methyl-1-propanol salt. The eyelash cosmetic according to any one of claims 1 to 5 , wherein the powder having an average particle diameter of 1 to 20 µm is an inorganic powder. The cosmetic for eyelashes according to any one of claims 1 to 6 , which is an oil-in-water emulsion composition further containing water and a lower alcohol having 1 to 4 carbon atoms.