JP2006257053A - Cosmetic for eyelash - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic for eyelashes, applicable without forming undissolved lumps, easily imparting the eyelashes with beautiful curl-up effect and high curl-retention and having high water resistance. <P>SOLUTION: The cosmetic for eyelashes contains (A) a polymer containing a methacrylic acid monomer as a constitutional unit in a manner totally or partly neutralized with ammonia and having a glass transition temperature (Tg) of ≥80°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides eyelash makeup with high water resistance that does not cause lumps when applied, gives eyelashes a beautiful curl-up effect and a high curl retention effect, and does not cause bleeding on the eyelids even after a long time has passed since makeup. Regarding fees.

The eyelash cosmetic has a cosmetic effect that curls the eyelashes and makes the eyelashes thicker and longer in order to make the eye area clearer and more attractive. With regard to curling in particular, the curling up effect is an important performance that is highly demanded since the consumer can recognize the makeup effect (making eyelashes appear long and thick) only after curling the eyelashes.
However, mascara with high curl-up effect is characterized by curling the eyelashes with a buller and then applying mascara solution to the eyelashes before the curled eyelashes are lowered by gravity and hardening the eyelashes with the mascara film curled. have. For this reason, the mascara liquid has a high quick-drying property, is likely to cause lumps during application, and the beauty of the finished product is often impaired despite the time required.
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 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 adhere to keratin fibers and causes shrinkage exceeding 1% of the stratum corneum and a high-hardness wax. providing.
Patent Documents 2 to 5 disclose 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.

JP-A-11-255619 JP 2003-55136 A JP 2003-55156 A JP 2003-55157 A JP 2003-55158 A

However, the mascara of Patent Document 1 has a problem that it is easy to generate lumps when used and the finish is not sufficient, and the curled eyelashes turn downward over time. Moreover, in the techniques of Patent Documents 2 to 5, there is still a problem that the curl-up effect is not sufficient, and lumps are likely to occur during use, and the finish is not sufficient.
Furthermore, in these mascaras, a part of the mascara may peel off from the eyelashes and adhere to the eyelids during use, thereby generating a black blur on the eyelids.
The object of the present invention is to provide a beautiful curl-up effect and a high curl-retaining effect on the eyelashes without causing lumps when applied, and make-up breakage. The object of the present invention is to provide a cosmetic for eyelashes with a small amount of water, that is, high water resistance.

  The present invention comprises a polymer having a methacrylic acid monomer unit (monomer (a)) as a structural unit, and having a glass transition point (Tg) of 80 ° C. or higher, wherein all or part of the methacrylic acid monomer unit is neutralized with ammonia. The present invention provides a cosmetic for eyelashes characterized by containing (A).

  The cosmetic for eyelashes of the present invention has high water resistance and does not cause lumps when applied, easily imparts a beautiful curl-up effect to the eyelashes, and does not cause bleeding on the eyelids even after a long time has passed since makeup. Fees can be provided.

  The cosmetic for eyelashes of the present invention is a cosmetic for eyelashes comprising a polymer (A) containing a methacrylic acid monomer unit (monomer (a)) as a constituent unit.

[Polymer (A)]
The polymer (A) according to the present invention is one in which all or part of the contained methacrylic acid monomer unit (monomer (a)) is neutralized, and has high water resistance by using ammonia as a neutralizing agent. There is a feature that can be obtained. This prevents the polymer from cracking even in the presence of moisture, so the applied mascara peels off from the eyelashes and adheres to the eyelid, and has a high water resistance that prevents makeup from collapsing such as bleeding on the eyelid. Mascara can be provided.
As a neutralization degree, 0.01-0.5 are preferable and 0.02-0.3 are more preferable. The methacrylic acid monomer unit is not particularly limited in any stage of neutralization, and can be neutralized at any stage of the monomer before polymerization or after polymerization.

The glass transition point (Tg) of the polymer (A) needs to be 80 ° C. or higher, from the viewpoint of improving the curl-up effect and curl retention effect, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly 150 degreeC or more is preferable. Further, the higher the glass transition point (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.
The glass transition point 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 point.
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 composition ratio of the methacrylic acid monomer units in the polymer (A) is preferably 20 to 98% by mass, more preferably 20 to 90% by mass, and further preferably 20 to 80% by mass in order to obtain a sufficient curl-up effect. preferable.
The polymer (A) preferably has a weight average molecular weight (measured by GPC, converted to polyethylene glycol (in the case of water solubility) and polystyrene (in the case of water insolubility)) of 5,000 to 1,000,000, 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, moderate ease of application can be maintained.

The polymer (A) is preferably a film-forming polymer. 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, cracks may occur with drying, and it is not necessary to obtain a single film.
Further, the polymer (A) can be used regardless of its form, even if it is a solution, a water / alcohol mixed solution system, or an emulsion system.

[Monomer (b)]
Furthermore, the polymer (A) preferably has as a structural unit at least one monomer (b) having a solubility in 100 g of water at 20 ° C. of 2 g or less.
The lower the solubility of the monomer (b), the less likely it will be during application and the higher curl retention effect can be obtained.
The glass transition point 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.
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 acrylate, tert-butyl methacrylate, isobornyl acrylate, isobornyl methacrylate (the following general formula (1)), dicyclopentanyl acrylate, methacrylic acid Dicyclopentanyl (the following general formula (2)), styrene, tert-butyl acrylamide, and tert-butyl methacrylamide are preferable from the viewpoint of the curl-up effect, and methyl methacrylate and tert-butyl acrylamide are more preferable.
Monomer (b) may be used alone or in combination of two or more.

[Eyelash cosmetics]
The cosmetic for eyelashes of the present invention contains a polymer (A). In the eyelash cosmetic of the present invention, the content of the polymer (A) is preferably 0.5% by mass or more from the viewpoint of giving good curl, and preferably 60% by mass or less from the viewpoint of easy use in terms of viscosity. In view of the above, 1 to 50% by mass is more preferable, 2 to 40% by mass is more preferable, and 3 to 40% by mass is particularly preferable.

  The cosmetic for eyelashes of the present invention preferably contains a wax in addition to the polymer (A). The wax used here 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.), silicone wax, and the like. 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, 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 cosmetic for eyelashes of the present invention comprises a nonvolatile component composed of the above polymer (A), wax and the like, and the following volatile component (B), but the wax having a penetration of 8 or more is It is preferable to contain in the range of 0.1-20 mass% in a non-volatile component. By containing 0.1% by mass or more, a sufficient curl-up effect of eyelashes can be obtained, and when it is 20% by mass or less, a good finish can be expected.

  The cosmetic for eyelashes of the present invention may contain other film-forming polymer or polymer having no film-forming property in addition to the polymer (A) as long as the object of the present invention is not impaired.

In the present invention, liquid oils and / or polyols and surfactants that are usually used in cosmetics can be blended as other components.
Examples of liquid oils include hydrocarbon oils such as light isoparaffin, liquid isoparaffin, liquid paraffin, and heavy liquid isoparaffin; diisostearyl malate, isotridecyl isononanoate, glyceryl dimyristate, glyceryl diisostearate, myristic acid / isostearic acid Esters and triglycerides such as glyceryl acid, neopentyl glycol dicaprate, castor oil, macadamian nut oil, jojoba oil; silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, dimethylcyclopolysiloxane, and methylhydrogenpolysiloxane Can be mentioned.
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. 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 improving the finish.
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.

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.

Moreover, it is preferable that the cosmetics of this invention contain 30 to less than 80 mass% of volatile components (B) in all the cosmetics.
Here, the volatile component refers to a compound having a vapor pressure of 10 Pa or more at 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 volatile silicone, the volatile thing is mentioned among the linear or cyclic silicone of the following general formula (3) or (4).

（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, dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.
These volatile components may be used alone or in a combination of two or more. Although content of the volatile component in the cosmetics for eyelashes is 30 mass% or more, it is preferable to contain water especially in a volatile component. Furthermore, the blending amount of volatile components other than water is preferably 0.5 to 20% by mass, and it is particularly preferable to use ethanol from the viewpoint of C1 to C4 lower alcohol and ease of handling.

  The cosmetic for eyelashes of the present invention comprises a solution system using a solvent that dissolves the polymer (A) as a volatile component (B), an oil-in-water emulsion system (O / W) using water, and a water-in-oil emulsion. It is provided in the form of a system (W / O) or the like. Among these, an oil-in-water type emulsion system (O / W) is preferable from the viewpoint of improving the curl-up effect.

In addition to the above-mentioned components, the cosmetics for eyelashes of the present invention are blended with 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. can do. Examples include extender pigments, white pigments, organic pigments, organic pigments, and other color pigments, as well as thickeners, UV absorbers, UV scattering agents, moisturizers, antioxidants, fragrances, preservatives, and the like. 1 type (s) or 2 or more types can be mix | blended.
In addition, the cosmetics for eyelashes of this invention can also be used as what is called an eyelash base agent etc. not only what mix | blended the coloring pigment.

  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. Moreover, it can also be used as a so-called eyelash base material or top coat as well as a color pigment-containing one.

  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, use a normal mascara applicator brush, comb applicator, coil applicator or brush, flocky, stick applicator, spatula applicator, etc., or apply repeatedly 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 curl-up effect is obtained.

Production Example 1 (Production of poly (methacrylic acid-methyl methacrylate) ammonium salt)
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 20 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 the addition of the mixture of methacrylic acid and methyl methacrylate was completed, the temperature was raised to 70 ° C. and the mixture was stirred for 6 hours for 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 = 47/53 (mass ratio). The weight average molecular weight measured by GPC was 72000 (polystyrene conversion).
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 2 (Production of poly (methacrylic acid-tert-butylacrylamide) ammonium salt)
In Production Example 1, 270 g of tert-butylacrylamide was used instead of 270 g of methyl methacrylate, and polymerization was carried out in the same manner. The obtained polymer solution was reprecipitated with hexane. 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 112000 (polystyrene conversion).
To a solution obtained by dissolving 15 g of the obtained poly (methacrylic acid-tert-butylacrylamide) 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 3 (Production of poly (methacrylic acid-tert-butylacrylamide) sodium salt)
In Production Example 4, 8.3 ml of 1N sodium hydroxide aqueous solution was used instead of 1N ammonia solution to obtain an aqueous suspension of poly (methacrylic acid-tert-butylacrylamide) sodium salt (degree of neutralization 0.08). ). This polymer aqueous suspension had a pH of 6.0 and a solid content of 20%.
Moreover, it was 215 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 polymer latex)
N-stearoyl-N-methyltaurine sodium (Nikko Chemical Co., Nikkor SMT) 0.6 g and ion-exchanged water 875 g were put into a glass reaction vessel, and after substituting with nitrogen with 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 solution prepared by mixing 80 g of methyl methacrylate, 405 g of butyl acrylate, and 15 g of acrylic acid was added dropwise over 3 hours. 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 device (LA-920, manufactured by Horiba, Ltd.), the particle size of the polymer latex was 0.1 μm. The polymer latex had a pH of 6.5 and a solid content of 50%.

(1) Evaluation of curling up 40 mg of the mascara composition shown in Table 1 is uniformly applied on a line equally divided in the vertical direction of a PET film (Merinex S, manufactured by Teijin Limited) having a length of 5 cm, a width of 2 cm, and a thickness of 75 μm. After applying and drying for 10 hours, the bending angle of the film was measured.

(2) Evaluation of water resistance The mascara composition shown in Table 1 is applied on artificial leather made of polyurethane, dried for 120 minutes, dripped with a few drops of water, and the film oozes or collapses while gently tapping with a finger. Time (seconds) was measured. The measurement was performed 3 times, and the average value was evaluated as water resistance.

(3) Evaluation of makeup collapse (evaluation of water resistance)
<Disintegration of makeup>
About evaluation of water resistance, in addition to the evaluation of (2), evaluation of makeup collapse was performed.
The mascara composition of Table 1 was applied to the eyelashes, and the state of the lower eyelid after 7 hours was visually evaluated by nine professional panelists based on the following criteria. The evaluation with the largest number of instructors was taken as the evaluation of makeup collapse.
○: Not black at all △: Black but inconspicuous ×: Black

Examples 1-4 and Comparative Examples 1-3
A mascara composition was prepared by uniformly stirring and mixing the components having the composition shown in Table 1. The viscosity of each composition was in the range of 100 to 2000 Pa · s at 25 ° C.
About the mascara composition of Examples 1-4 and Comparative Examples 1-3, evaluation of the curl-up effect, water resistance, and makeup collapse was implemented according to said method. The results are shown in Table 1.

The mascara compositions of Examples 1 to 4 of the present invention had a sufficient curl-up effect and high water resistance, excellent water resistance, and almost no makeup collapse. In Example 1, the water resistance was particularly high.
When Examples 2 and 3 and Comparative Examples 1 and 2 having different neutralizing bases are compared, the water resistance is remarkably improved without impairing the curl-up effect in ammonia neutralization (Example).

[note]
(* 1) Poly (methacrylic acid-methyl methacrylate) ammonium salt produced in Production Example 1 (* 2) Poly (methacrylic acid-tert-butylacrylamide) ammonium salt produced in Production Example 2 (* 3) Production Example 3 Poly (methacrylic acid-tert-butylacrylamide) sodium salt (* 4) extremely hydrogenated jojoba oil manufactured by Koseki Kogyo Co., Ltd., penetration 1
(* 5) Paraffin wax; “HNP-9” (Nippon Seiki Co., Ltd.), penetration 7
(* 6) Refined candelilla wax; “SR2” (Mitsuba Trading Co., Ltd., penetration 1-2)
(* 7) Stearic acid; “Purified stearic acid 700V” (manufactured by Kao Corporation)
(* 8) Polyvinyl alcohol; “GOHSENOL EG-30” (manufactured by Nippon Synthetic Chemical Co., Ltd.)
(* 9) Polyacrylic acid-treated black iron oxide; “PA-Black BL-100” (manufactured by Miyoshi Kasei Co., Ltd.), 3% polyacrylic acid-treated black iron oxide (* 10) The polymer latex produced in Production Example 4 (* 11) Nylon fiber; Length: 2mm, Thickness: 6.7T (Unitika Ltd.)

The cosmetic for eyelashes of the present invention is suitably used for making up eyelashes, specifically as a mascara. No lumps are generated at the time of application, the eyelashes can be easily given a beautiful curl-up effect and a high curl retention effect, and can have high water resistance that does not cause bleeding on the eyelids even after a long time has passed since makeup.

Claims (6)

  A polymer containing a methacrylic acid monomer unit (hereinafter referred to as monomer (a)) as a structural unit, and having a glass transition point (Tg) of 80 ° C. or higher, wherein all or part of the methacrylic acid monomer unit is neutralized with ammonia. A cosmetic for eyelashes comprising A).   The cosmetic for eyelashes according to claim 1, wherein the proportion of the monomer (a) contained in the polymer (A) is 20 to 98% by mass.   The eyelash cosmetic according to claim 1 or 2, wherein the polymer (A) further comprises a monomer (b) having a solubility in 100 g of water at 20 ° C of 2 g or less as a constituent unit.   The cosmetic for eyelashes according to claim 3, wherein the monomer (b) is at least one selected from alkyl acrylate monomers, alkyl methacrylate monomers, styrene monomers, alkyl acrylamide monomers and alkyl methacrylamide monomers.   Monomer (b) is methyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, styrene, tert-butyl acrylamide The eyelash cosmetic according to claim 3, wherein the cosmetic is one or more selected from tert-butylmethacrylamide. The eyelash cosmetic according to any one of claims 1 to 5, wherein the polymer (A) is contained in an amount of 0.5 to 60% by mass in the eyelash cosmetic.