JP4755955B2 - Eyelash cosmetic - Google Patents

Description

  The present invention relates to a cosmetic for 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 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 tend 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 provides a mascara that gives a curl-up effect by a combination of a polymer that can adhere to a keratinous substance and other polymer particles, wax, or the like. Patent Document 4 discloses a method for enhancing curl and its holding effect by combining a non-aqueous polymer dispersion and a hollow powder. However, the curl holding force is not sufficient, and there is a problem that lumps are generated during use. was there. In addition, when a large amount of powder is blended to such an extent that curl is maintained, there is a problem that the uniformity of the film is lowered, the finish is deteriorated, and the makeup is easily broken.

JP 2003-95874 A JP-A-11-255619 JP 2003-55136 A JP 2004-315420 A

  The object of the present invention is to provide a cosmetic for eyelashes that easily gives a good curl-up effect to eyelashes, does not cause lumps during application, has a high curl retention effect during use and a long-lasting makeup effect, and has a beautiful finish. There is to do.

The inventor has found that the above object can be achieved by containing an emulsion of a specific film-forming polymer having a high glass transition temperature (Tg) and another film-forming polymer, and has completed the present invention.
That is, the present invention comprises (A) methacrylic acid and / or a salt thereof (hereinafter sometimes referred to as monomer (a)) and monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less. And a cosmetic for eyelashes containing a film-forming polymer having a glass transition temperature (Tg ₁ ) of 80 ° C. or higher and an emulsion of a film-forming polymer other than (B) component (A). .

  The cosmetics for eyelashes of the present invention can easily give a good curl-up effect to the eyelashes, do not cause lumps when applied, and can give a high curl retention effect and a long-lasting makeup effect during use, and a beautiful finish. .

  The cosmetic for eyelashes of the present invention comprises a polymer (A) having methacrylic acid and / or a salt thereof (monomer (a)) and a monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less as structural units. A cosmetic for eyelashes comprising an emulsion (B) of a film-forming polymer other than the component (A).

[Polymer (A)]
The polymer (A) according to the present invention is a film-forming polymer and comprises methacrylic acid and / or a salt thereof (monomer (a)) and a monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less. As a unit, the glass transition temperature (Tg ₁ ) is 80 ° C. or higher. Here, the film-forming property means that a polymer aqueous solution or aqueous dispersion is spread on a petri dish and dried at 25 ° C., and then has a property of forming a film. However, cracking may occur with drying, and it is not necessary to obtain a single film.

The glass transition temperature (Tg ₁ ) of the polymer (A) is required to be 80 ° C. or higher, from the viewpoint of improving the curl-up effect and moisture resistance, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly 150 degreeC or more is preferable. Further, the higher the glass transition temperature (Tg ₁ ), the better from the viewpoint of improving the curl-up effect. By setting the glass transition temperature (Tg ₁ ) of the polymer (A) higher, it is considered that the shrinkage of the polymer is improved and the curl-up effect is enhanced.
The glass transition temperature (Tg ₁ ) 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 a dispersion thereof (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, preferably 0.01 to 0.5, 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.
The neutralization may be performed after the film-forming polymer (A) is formed, or may be performed by using a salt from the monomer stage in the process of obtaining the film-forming polymer (A).

[Monomer (a)]
The monomer (a) in the present invention is methacrylic acid and / or a salt thereof. Examples of the salt of methacrylic acid include ammonium methacrylate and the like. The mass ratio of methacrylic acid and its salt is not particularly limited, and methacrylic acid alone or methacrylic acid salt alone may be used.

  As the base for forming the methacrylate, the same base as that used as the neutralizing agent for the polymer (A) can be used, and as the inorganic base, ammonia, potassium hydroxide, sodium hydroxide can be used. Examples of the organic base include L-arginine, 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, triethanolamine and tris (hydroxymethyl) amino. Examples include methane. 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.

The ratio (content) of the monomer (a) contained in the polymer (A) is preferably in the range of 11 to 98% by mass. Within this range, a sufficient curl-up effect and a beautiful finish can be obtained. In this respect, the proportion (content) of the monomer (a) included in the polymer (A) is more preferably 13 to 90% by mass, and particularly preferably 15 to 80% by mass.

[Monomer (b)]
It is essential that the monomer (b) according to the present invention has a solubility in 100 g of water at 20 ° C. of 2 g or less. The lower the solubility of the monomer (b) in water, the less likely it is to cause lumps during application, and the moisture resistance of the cosmetic for eyelashes is improved and a high curl retention effect can be obtained.
As the monomer (b), it is preferable to use a monomer having a glass transition temperature (Tg ₂ ) of a homopolymer obtained by homopolymerizing the monomer (b) of 80 ° C. or higher, more preferably 100 ° C. or higher. By using a monomer having such properties, a high curl-up effect can be obtained. Further, the glass transition temperature from manufacturing constraints (Tg ₂₎ is preferably used a monomer is 250 ° C. or less.

As the monomer (b), for example, alkyl acrylated Tomo Nomar, alkyl methacrylate click relays Tomo Nomar, styrene Nmo Nomar, alkyl acrylamide Domo Nomar, and alkyl methacrylate Ami Domo Nomar is preferably exemplified. 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.
More specifically, methyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobornyl acrylate, isobornyl methacrylate (the following general formula (1)), dicyclopentanyl acrylate, dicyclopentamethacrylate Nyl (the following general formula (2)), 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 together.

(When R ¹ is hydrogen, it is isobornyl acrylate, and when R ¹ is a methyl group, it is isobornyl methacrylate.)

(When R ¹ is hydrogen, it is dicyclopentanyl acrylate, and when R ¹ is a methyl group, it is dicyclopentanyl methacrylate.)

  In the cosmetic for eyelashes of the present invention, the content of the film-forming polymer (A) is preferably 0.5 to 30% by mass in the total cosmetic. By setting it as this range, a favorable curl-up effect and its holding effect can be expressed. Further, from the viewpoint of a curl-up effect and obtaining a beautiful finish that does not cause lumps even when overcoated, 1 to 10% by mass is further preferable, and a range of 2 to 6% by mass is more preferable.

  The cosmetic for eyelashes of the present invention is characterized by containing, as component (B), an emulsion of a film-forming polymer other than component (A). This polymer emulsion can obtain excellent water resistance and flexibility without impairing the shrinkability of the polymer by using in combination with the polymer (A). Therefore, the obtained cosmetic for eyelashes can obtain a high curl effect, a curl retention effect and a makeup persistence. Here, makeup persistence means makeup, and means that it takes a long time to prevent the mascara from flowing down due to sebum or sweat.

Examples of the polymer emulsion, acrylic walk Rimmer emulsion, acetate vinyl Lupo Rimmer emulsions include Binirupirorido emission port Rimmer emulsion or the like. Here, the acrylic walk Rimmer, poly (meth) acrylic acid or salts thereof, poly (meth) alkyl acrylate, acrylic acid / maleic acid copolymers, include acrylic acid alkyl / styrene copolymer, the acetate vinyl Lupo Rimmer, polyvinyl acetate, vinyl acetate / vinyl chloride copolymer, vinyl acetate / ethylene copolymer, vinyl acetate / acrylic acid copolymer, vinyl acetate / acrylic acid ester copolymer, vinyl acetate / It includes styrene copolymer, and the like polyvinylpyrrolidone / styrene copolymer as Binirupirorido emission port Rimmer.

Among the polymers which form the polymer emulsion, preferably acrylic walk Rimmer, in particular, (meth) acrylic acid or its salts / alkyl (meth) acrylate (alkyl group having a carbon number of 3 or 4) / (meth) acrylic acid A polymer emulsion composed of a methyl copolymer is preferable, and (meth) acrylic acid or a salt thereof / butyl (meth) acrylate / methyl (meth) acrylate is preferable, and acrylic acid or a salt thereof / acrylic acid More preferred is a butyl / methyl methacrylate copolymer.
The ratio of (meth) acrylic acid or a salt thereof to all monomer components constituting the copolymer is preferably 0.1 to 10% by mass from the viewpoint of the stability of the polymer emulsion, and more preferably 1 to 5% by mass. The ratio of alkyl (meth) acrylate (C3 or C4 alkyl group) is preferably 20 to 80% by mass from the viewpoint of flexibility and water resistance of the dried film, and more preferably 40 to 75% by mass. The proportion of methyl (meth) acrylate is preferably 10 to 70% by mass from the viewpoint of water resistance and hardness of the dried film, and more preferably 20 to 60% by mass.

The glass transition temperature (Tg ₃ ) of the film-forming polymer constituting the polymer emulsion is preferably from −25 to 15 ° C., more preferably from 0 to 10 ° C., from the viewpoint of the curl-up effect and retention.
The glass transition temperature (Tg ₃ ) is a value measured by a differential scanning calorimeter (DSC) for the glass transition temperature of the film after the polymer emulsion is dried under reduced pressure under the following measurement conditions. 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 defined as the glass transition temperature (Tg ₃ ).
Temperature program:
1.30 to 150 ° C .: Temperature rising rate 30 ° C./min, holding time 1 min
2.150 to -50 ° C .: cooling rate 200 ° C./min, holding time 10 min
3. −50 to 150 ° C .: Temperature rising rate 10 ° C./min, holding time 1 min
4. 150-25 ° C .: cooling rate 30 ° C./min, holding time 2 min

The polymer emulsion is preferably obtained by polymerization using an emulsifier such as a surfactant. As the emulsifier, an emulsifier used for general polymerization can be used. From the viewpoint of obtaining excellent water resistance and flexibility without impairing the shrinkability of the polymer (A), an anionic surfactant is used. N-stearoyl-N-methyltaurine sodium is particularly preferable.
0.1-3 mass parts is preferable with respect to 100 mass parts of polymers in a polymer emulsion, and, as for the usage-amount of such an emulsifier, 0.2-1.5 mass parts is more preferable.

The content of the polymer emulsion (B) in the eyelash cosmetic of the present invention is:
0.1-40 mass% is preferable from the point of makeup persistence and the beauty of a finish, 1-30 mass% is more preferable, and 3-20 mass% is further more preferable. Further, the content of the film-forming polymer in the polymer emulsion is preferably 20 to 60% by mass, and more preferably 30 to 55% by mass from the viewpoint of the stability of the polymer emulsion itself and the compoundability in cosmetics.
Furthermore, the mass ratio (in terms of solid content) of the polymer (A) and the film-forming polymer constituting the polymer emulsion (B) is 1/9 to 7/3 from the viewpoint of achieving both shrinkage and flexibility of the polymer. Is preferable, and 2/8 to 6/4 is more preferable.

  In the cosmetic for eyelashes of the present invention, (C) a solid oily component (wax) that is solid at 25 ° C. can be used. (C) The oily component (wax) solid at 25 ° C. 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 room temperature (25 ° C.), and silicone wax. The above waxes may be used alone or in combination of two or more.

  Among these waxes, a wax having a penetration of 8 or more is more preferable 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, 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 content of the oily component (wax) that is solid at 25C in the cosmetic for eyelashes of the present invention is preferably 0.1 to 40% by mass, more preferably 5 to 30% by mass, and 10 to 25% by mass. % Is more preferable. By containing 0.1% by mass or more, a sufficient curl-up effect of eyelashes can be obtained, and when it is 40% by mass or less, a good finish can be expected. Moreover, when it contains the wax whose penetration is 8 or more as (C) component, it is preferable to contain in the range of 0.1-20 mass% in cosmetics for eyelashes, 0.5-10 mass % Is more preferable, and 1 to 6% by mass is more preferable.

The present invention may further include (D) a powder having an average particle diameter of 1 to 20 μm. The powder is not particularly limited as long as the average particle diameter is in the range of 1 to 20 μm, and both inorganic powder and organic powder can be used.
When the average particle diameter of the powder is within the above range, a more sufficient curl-up effect can be obtained. From the above viewpoint, the average particle size of the powder is more preferably 2 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 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.

Examples of inorganic powders that can be suitably used in the present invention include plate-like inorganic powders such as talc, mica, sericite, and kaolin, silica, barium sulfate, aluminum hydroxide, calcium carbonate, magnesium silicate, calcium carbonate, and silica. Examples include spherical or amorphous inorganic powders such as aluminum oxide and magnesium carbonate, and organic powders include polyamide resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, cellulose resin, polystyrene resin, styrene. And a copolymer of acrylic acid and organic powders such as silicone resin.
Of these, inorganic powder is preferable, and spherical inorganic powder is particularly preferable. More specifically, it is preferable to use silica, particularly spherical 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.

  The powder may be used as an aqueous dispersion, or may be used in a state of being 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 cosmetic for eyelashes of the present invention can also contain a pigment. If a pigment is normally used for cosmetics, it will not restrict | limit, For example, an inorganic pigment, an organic pigment, etc. are mentioned.
Specific examples include titanium oxide, black titanium oxide, zinc white, red iron oxide, yellow iron oxide, black iron oxide and the like as inorganic pigments, and 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 powders and pigments may be surface-treated, such as silica treatment, alumina treatment, silica-alumina treatment, polyacrylic acid treatment, etc., hydrophilic treatment, silicone treatment, fluorine compound treatment, metal soap treatment, lecithin, etc. What gave hydrophobized surface treatments, such as a process and oil-fat treatment, 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 can 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.

The cosmetic for eyelashes of the present invention can contain fibers in order to enhance the long lash effect. 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. Fiber 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.
From the viewpoint of adhesion to the eyelashes, the fibers preferably have a thickness of 0.1 to 20 T and a length of 0.1 to 5 mm. The content of this fiber is preferably 0.1 to 6% by mass with respect to the total amount of the cosmetic because a sufficient long rush effect can be obtained.

In the present invention, as other components, a non-volatile oily component that is liquid at 25 ° C., polyols, and a surfactant can be contained.
Here, non-volatile oily components that are liquid at 25 ° C. include hydrocarbon oils such as liquid isoparaffin, liquid paraffin, and heavy liquid isoparaffin; diisostearyl malate, isotridecyl isononanoate, glyceryl dimyristate, glyceryl diisostearate And esters and triglycerides such as glyceryl myristic acid / glyceryl isostearate, neopentyl glycol dicaprate, castor oil, macadamian nut oil and jojoba oil; and silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane. 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.

  Next, examples of the polyols include ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, and glycerin. 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 can be contained in the cosmetic for eyelashes 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 cosmetic for eyelashes 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 (3) or (4).

(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 (3) or (4) 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 with respect to the entire eyelash cosmetic.

  Furthermore, the cosmetic for eyelashes 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, butanol, and the like. From the viewpoint of ease of handling, it is 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 solvent of the polymer 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 are contained in the eyelash cosmetic, and further 10 to 50% by weight. Is preferred. Moreover, 0.5-20 mass% is preferable and, as for content of the lower alcohol in the cosmetics for eyelashes of this invention, 1-10 mass% is more preferable.

  Further, the eyelash cosmetic of the present invention, in addition to the above-mentioned components, in a range that does not detract from the effects of the present invention depending on the purpose, components that are usually blended in cosmetics to give a cosmetic effect, for example, One or more thickeners, ultraviolet absorbers, ultraviolet scattering agents, humectants, antioxidants, fragrances, preservatives and the like can be blended.

  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 water-containing system, 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 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 cosmetics of the present invention, it may be applied to the eyelashes using a brush or the like usually used for mascara, but particularly good curl is obtained by increasing the amount of adhesion to the upper surface of the eyelashes. be able to. 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.

  Hereinafter, the present invention will be described specifically by way of examples.

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. A solution obtained by dissolving 5.3 g of azo-based polymerization initiator 2,2′-avizos (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 30 g of ethanol was added and stirred. Below, a mixture of 230 g of methacrylic 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 solubility of methyl methacrylate in 100 g of water at 20 ° C. is 1.5 g.
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 poly (methacrylic acid-methyl methacrylate) sodium salt aqueous solution (degree of neutralization 0.2). This aqueous polymer solution had a pH of 6 and a solid content of 20% by mass.
The glass transition temperature of the polymer (Tg ₁₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 193 ° C.. The glass transition temperature (Tg ₂ ) of the homopolymer of methyl methacrylate was 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. A solution obtained 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 was added and stirred. A mixture consisting of 300 g of methacrylic 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 solubility of tert-butylacrylamide in 100 g of water at 20 ° C. is 0.7 g.
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. Furthermore, 68 g of water was added, ethanol was distilled off by an evaporator, and a water suspension of poly (methacrylic acid-tert-butylacrylamide) sodium salt was obtained (neutralization degree 0.04). This polymer aqueous suspension had a pH of 5.0 and a solid content of 32% by mass.
The glass transition temperature of the polymer (Tg ₁₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 198 ° C..
The glass transition temperature (Tg ₂₎ of the homopolymer of tert- butylacrylamide was 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 an aqueous solution of translucent 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% by mass.
The glass transition temperature of the polymer (Tg ₁₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 174 ° C..

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% by mass.
The glass transition temperature of the polymer (Tg ₁₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 197 ° C..

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. A solution obtained by dissolving 2.07 g of azo-based polymerization initiator 2,2′-avizos (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 20 g of ethanol was added and stirred. Below, a mixture of 54 g of methacrylic 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% by mass.
The glass transition temperature of the polymer (Tg ₁₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 172 ° C..

Production Example 6 (Production of polymer emulsion)
A glass reaction vessel was charged with 0.6 g of sodium N-stearoyl-N-methyltaurine (Nikko Chemical Co., Nikkor SMT) and 875 g of ion-exchanged water. After performing nitrogen substitution while stirring, the internal temperature reached 70 ° C. Heated. After adding a solution prepared by dissolving 2.5 g of ammonium persulfate in 25 g of ion-exchanged water, a mixture of 200 g of methyl methacrylate, 285 g of butyl acrylate, and 15 g of acrylic acid was added dropwise over 3 hours with stirring. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 1 hour, then heated to 75 ° C., further reacted for 3 hours, cooled, and 73 g of 1N sodium hydroxide aqueous solution was added. Concentration was performed using an evaporator to obtain a polymer latex. When measured with a particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.), the particle size of the polymer latex was 0.1 μm. Moreover, pH of this polymer latex was 6.5 and solid content was 50 mass%.
Further, the glass transition temperature of the polymer emulsion constituting the polymer (Tg ₃₎ a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200) results measured at, was 5 ° C..

Evaluation method (1) Curling up evaluation method (hair test)
Take three pieces of hair with a length of 1 to 1.5 cm and fix them horizontally. The mascara composition of Table 1 was applied 10 times to this hair at 23 ° C. and a relative humidity of 60%, and after drying, the warp angle of the hair from the horizontal plane was measured. The measurement was performed 3 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 method described in (1) above and after 3 hours was measured, and [(the warp angle after 3 hours) / (the warp angle immediately after )] × 100 = curl retention ratio, which is an index of the curl retention effect.

(3) Finishing evaluation method About the hair which applied the mascara by the method as described in said (1), the dama generation | occurrence | production state was visually observed with the specialized panelist, 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

(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 to 5 , Reference Examples 1 to 5, Comparative Examples 1 and 2
The mascara compositions of Examples 1 to 5 , Reference Examples 1 to 5 , and Comparative Examples 1 and 2 were prepared by uniformly stirring and mixing the components having the compositions shown in Table 1. The results evaluated by the above method are shown in Table 1.

[note]
(* 1) PMAA / MMA (Na) salt; poly (methacrylic acid-methyl methacrylate) sodium salt aqueous solution produced in Production Example 1 (* 2) PMAA / tBuAAm (Na) salt; poly (produced in Production Example 2) Methacrylic acid-tert-butylacrylamide) sodium salt aqueous suspension (* 3) PMAA / MMA (ammonium) salt; poly (methacrylic acid-methyl methacrylate) ammonium salt aqueous solution prepared in Production Example 3 (* 4) PMAA / tBuAAm (Ammonium) salt; poly (methacrylic acid-tert-butylacrylamide) ammonium salt aqueous suspension produced in Production Example 4 (* 5) PMAA / MMA (AMP) salt; produced in Production Example 5 (poly (methacrylic acid- Methyl methacrylate) 2-amino-2-methyl-1-propanol salt aqueous solution (* 6) Poly Chromatography emulsion; polymer emulsion prepared in Preparation Example 6 (* 7) polymer emulsion; "Yodosol GH34" (manufactured by Nippon NSC Ltd.), Tg ₃ = -16 ℃
(* 8) Carnauba wax; “refined carnauba wax No. 1” (Cerarica Noda Co., Ltd.), penetration 1 or less (* 9) candelilla wax: “refined candelilla wax SR-2” (Mitsuba Trading Co., Ltd.) ))
(* 10) Beeswax; “BEES WAX-S” (Crowda Japan Co., Ltd.), penetration 18
(* 11) Extremely hydrogenated jojoba oil (Koei Kogyo Co., Ltd.), penetration 1
(* 12) Microcrystalline wax; “Multiwax W-445” (Witco), penetration 34
(* 13) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 7
(* 14) Silica; “Sunsphere L31” (Asahi Glass Co., Ltd.), average particle size 3 μm, spherical powder (* 15) talc; “Talc JA-46R” (Asada Flour Milling Co., Ltd.), average particle size 8 μm , Plate-like powder (* 16) polyvinyl alcohol; “Gohsenol EG-30” (Nippon Synthetic Chemical Co., Ltd.)
(* 17) Polystearic acid polyoxyethylene glycerol; Nikkor TMGS-15 (Nikko Chemical Co., Ltd.)
(* 18) Polyacrylic acid-treated black iron oxide; “PA-Black BL-100” (manufactured by Miyoshi Kasei Co., Ltd.), 3% polyacrylic acid-treated black iron oxide (* 19) nylon fiber; Length: 2 mm Thickness: 6.7T (Unitika Ltd.)

  The cosmetic for eyelashes of the present invention is suitably used for making up eyelashes, specifically as a mascara. A good curl-up effect is easily imparted to the eyelashes, no lumps are generated during application, and a high curl retention effect and makeup persistence during use can be imparted.

Claims (8)

Containing 0.5-30 mass% and (B) 0.1-40 mass% of the following component (A) with respect to the cosmetics for whole eyelashes, and also (C) 25 degreeC of 8 or more penetrations A cosmetic for eyelashes comprising a solid oily component and (D) a powder having an average particle diameter of 1 to 20 μm.
(A) Methacrylic acid and / or salt thereof (hereinafter referred to as monomer (a)) and homopolymerized homopolymer have a glass transition temperature (Tg ₂ ) of 80 ° C. or higher and a solubility in 100 g of water at 20 ° C. 2 g or less of the monomer (b) as a structural unit, the content of the monomer (a) is 11 to 98% by mass, and the glass transition temperature (Tg ₁ ) is 150 ° C. with respect to the entire film-forming polymer (A). acrylic walk Rimmer made using N- stearoyl -N- methyl taurate sodium as a is film-forming polymer (B) emulsifier or more, and at least one selected from acetic acid vinyl Lupolen Rimmer and Binirupirorido emission port Rimmer, glass transition Film-forming polymer emulsion having a temperature (Tg ₃ ) of −25 to 15 ° C. The monomer (b) is an alkyl acrylated Tomo Nomar, alkyl methacrylate click relays Tomo Nomar, styrene Nmo Nomar, cosmetic eyelashes of claim 1 is at least one selected from alkyl acrylamide Domo Nomar and alkyl methacrylates amino Domo Nomar Fee.   The cosmetic for eyelashes according to claim 1 or 2, wherein the neutralization degree of the carboxyl group contained in the film-forming polymer (A) is 0.01 to 0.6. Acrylic walk Rimmer of the polymer emulsion (B) is composed of a (meth) acrylic acid or its salts / alkyl (meth) acrylate (alkyl group having a carbon number of 3 or 4) / (meth) acrylate copolymer eyelash cosmetic composition according to claim 1 is an acrylic walk Rimmer being.   The cosmetic for eyelashes according to any one of claims 1 to 4, wherein the amount of the emulsifier used is 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymer in the polymer emulsion.   The cosmetic for eyelashes according to any one of claims 1 to 5, wherein the content of the oil component (C) is 0.1 to 40% by mass with respect to the whole cosmetics for eyelashes.   The cosmetic for eyelashes according to any one of claims 1 to 6, wherein the content of the powder (D) is 0.1 to 20% by mass with respect to the whole cosmetics for eyelashes.   The cosmetic for eyelashes according to any one of claims 1 to 7, which is an oil-in-water emulsion composition containing a lower alcohol having 1 to 4 carbon atoms.