JP4933873B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic.

  Silicone typified by dimethylpolysiloxane has a water-in-oil emulsified composition for makeup cosmetics, in addition to excellent water repellency, high safety, etc. Oil is widely used as an oil agent. However, dimethylpolysiloxane has a low solubility parameter, low surface tension, low compatibility with conventional oils such as hydrocarbon oils, ester oils, fats and oils, and the occurrence of discharge phenomenon. There were not a few prescription restrictions.

Conventionally, a lipophilic polyoxyalkylene-modified silicone has been used as a surfactant for preparing a water-in-oil emulsion composition containing a large amount of silicone oil.
However, with this surfactant alone, it has been difficult to make an emulsion composition containing a large amount of silicone oil stable over time. For this reason, attempts have been made to mix wax or organically modified clay minerals that are gelling agents (see Patent Documents 1 and 2), but they satisfy the feeling and usability, and are stable over time. It was difficult to obtain a good one. In order to solve these problems, attempts have been made to combine a specific acrylic-silicone graft copolymer and a specific polyoxyalkylene-modified organopolysiloxane surfactant in the oil phase component (patents). Reference 3), dispersibility and usability of pigments, powders, etc. were not sufficient.

In addition, in order to disperse the powder satisfactorily, the constituent component is an organopolysiloxane monomer having a radical polymerizable group and a nitrogen-containing monomer and / or a monomer having a radical polymerizable group and a polyoxyalkylene group. There has been proposed a method of treating the surface of the powder with a polymer (see Patent Document 4).
However, this method only solves the dispersibility of the powder, and there is no disclosure about the emulsifying action of the cosmetic by the polymer.

  On the other hand, the adhesion state of the powder to the skin is greatly influenced by the dosage form and application method of the cosmetic. In particular, since the fluidity of the powder varies greatly depending on the dosage form, the amount and state of adhesion also vary greatly. The surface of the skin is composed of dermis and skin grooves, but liquid foundations that contain a large amount of liquid components are more likely to flow into the skin grooves, so that the powder is more likely to collect in the skin grooves and is more uniform than the powder foundation. A beautiful finish cannot be obtained. Even plate-like powders with high orientation, such as mica and titanium mica, often enter the skin groove and are unlikely to exhibit sufficient effects. This phenomenon tends to be more conspicuous in metal oxide fine particles such as color pigments and ultraviolet shielding agents. Therefore, a device has been devised to improve the adhesion to the dermis by increasing the blending amount of the powder or adjusting the rheological properties of the agent. However, it is difficult to uniformly adhere to the skin and the skin groove, and as a result, it tends to be thick and have a high makeup finish.

JP-A-61-66752 JP-A-61-218509 Japanese Patent No. 3-8432 JP 11-263708 A

  In the water-in-oil emulsified cosmetic, the present invention controls the adhesion of the powder of the skin and the crevice, has high powder adhesion to the skin, provides a uniform and natural beautiful finish, and high makeup The object is to provide a water-in-oil type milk cosmetic having durability and excellent emulsion stability.

（ａは式（ｉ）で表されるモノマーの平均分子量を１０００〜１００００とする数である）
（Ｃ）粉体 ０．１〜５０質量％
（Ｄ）水 ５〜７０質量％
を含有する油中水型乳化化粧料を提供するものである。 The present inventors have found that the above problems can be solved by using a specific organopolysiloxane-containing copolymer as an emulsifier of a water-in-oil emulsion, and have completed the present invention.
That is, the present invention includes the following components (A), (B), (C) and (D):
(A) Oily component containing silicone oil 15 to 70% by mass
(B) A copolymer obtained by polymerizing a monomer represented by the following formula (i) and an N atom-containing radical polymerizable monomer having an SP value of 19 to 24,
Copolymer having a content of the monomer represented by formula (i) of 60 to 96% by mass 0.1 to 20% by mass

(A is a number which makes the average molecular weight of the monomer represented by Formula (i) 1000-10000)
(C) 0.1-50 mass% of powder
(D) Water 5-70 mass%
A water-in-oil emulsified cosmetic containing

  The water-in-oil emulsified cosmetic of the present invention has high powder adhesion to the skin, a uniform and natural beautiful finish is obtained, and is excellent in high makeup sustainability and emulsion stability.

  The oil component of the component (A) used in the present invention contains a silicone oil, and may be a single component consisting only of a silicone oil, or may contain an oil agent other than a silicone oil. Examples of silicone oil include, but are not limited to, volatile and non-volatile liquid oils and those dispersed in a solvent, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, higher fatty acid-modified organopolysiloxane, Higher alcohol-modified organopolysiloxane, fluorine-modified organopolysiloxane and the like can be mentioned, and two or more kinds can be used in combination.

Of these silicone oils, dimethylpolysiloxane and dimethylcyclopolysiloxane are preferable, and volatile silicone is preferably used. The dimethylpolysiloxane has a viscosity at 25 ° C. of 50 mm ² / s or less, preferably 0.5 or more and 10 mm ² / s or less. As the volatile silicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dimethylpolysiloxane having a viscosity at 25 ° C. of 2 mm ² / s or less are preferable. These silicone oils are particularly preferred when applying cosmetics, and the adhesiveness is good because the amount of oil remaining on the skin surface is reduced.

  The content of the silicone oil is preferably 5 to 100% by mass, more preferably 50 to 100% by mass in the component (A). If it is 5% by mass or more, there are advantages such as improving the feeling of use without stretching or stickiness after coating.

  The oil used together with the silicone oil is not particularly limited as long as it is usually used in cosmetics. For example, ester oil such as olive oil, jojoba oil, diglyceride, triglyceride, castor oil; carbonization such as squalane, liquid paraffin, and isoparaffin. Hydrogen oils; liquid oils such as perfluorinated polyethers, perfluorodecalin, perfluorooctane, etc .; solids such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols, etc. A semi-solid oil agent is mentioned. These oil agents can use 1 type (s) or 2 or more types.

  The content of the oil-based component containing the component (A) silicone oil used in the present invention is a water-in-oil emulsified cosmetic from the viewpoint of feeling of use such as pigment dispersibility in oil and elongation when applied to the skin. It is preferable to contain 15 to 70% by mass, more preferably 20 to 60% by mass.

  The component (B) copolymer used in the present invention functions as an emulsifier, has excellent emulsification stability, and allows the powder to adhere uniformly to the skin and the skin groove.

The content of the monomer represented by formula (i), which is a constituent monomer of the component (B) copolymer, has a good affinity for silicone oil, good elongation when the emulsion is stretched on the skin, From the viewpoint of feeling of use such as lack, it is preferably 60% by mass to 96% by mass, and more preferably 70 to 92% by mass.
In addition, the polymer formed by polymerizing the monomer represented by formula (i) and the N atom-containing radical polymerizable monomer having an SP value (solubility parameter) of 19 to 24 may be a block body or a random body. There may be.

  Moreover, the value of a in the formula (i) is a number that makes the average molecular weight of the organopolysiloxane (monomer represented by the formula (i)) 1000 to 10,000 from the viewpoints of emulsifying properties and emulsion stability.

Examples of the N atom-containing radical polymerizable monomer having an SP value of 19 to 24 in the component (B) include N, N-dimethylacrylamide (SP value: 20.7), t-butylacrylamide (SP value: 22.2). ), Acryloylmorpholine (SP value: 21.6), isopropylacrylamide (SP value: 23.2), isopropylmethacrylamide (SP value: 22.2), N, N-diethylacrylamide (SP value: 19.9) N, N-dimethylaminoethyl acrylate (SP value: 21.1), N, N-dimethylaminoethyl methacrylate (SP value: 20.4), N, N-dimethylaminopropyl acrylamide (SP value: 22.3) ), N, N-dimethylaminopropyl methacrylamide (SP value: 21.6), N, N-dimethylmethacrylamide (SP value: 19.8). By setting the SP value to 19 to 24, it is considered that the affinity with water is increased, the emulsification performance is improved, and the function of uniformly attaching to the dermis and the skin groove is excellent.
Furthermore, among the above monomers, the Tg value of the homopolymer is preferably 90 ° C. or lower, and more preferably 0 ° C. or higher and 90 ° C. or lower. By setting the value of Tg to 90 ° C. or lower, and further to 0 ° C. or higher and 90 ° C. or lower, the powder adherence to the skin is increased and the makeup persistence is enhanced. Specific examples include N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, and N, N-dimethylaminopropylacrylamide. Of these, N, N-dimethylacrylamide is particularly preferred.

The glass transition temperature (Tg) 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, it is preferable that the value measured by the temperature program 3 is 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 SP value and the Tg value are preferably measured, but can also be calculated using the Bicerano method in Polymer-Design Tools (DTW Associates, Inc.), a polymer property estimation software.

  The weight average molecular weight of the component (B) copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, from the viewpoint of emulsion stability and usability of the water-in-oil emulsion cosmetic. A weight average molecular weight is obtained by polystyrene conversion by GPC.

The component (B) copolymer has a hydrophilic main chain and a polysiloxane chain in the side chain, so that the dispersibility of the components (A) and (C) can be improved without a cosolvent such as ethanol. It became possible to improve, and the emulsification characteristics also improved.
The component (B) copolymer used in the present invention has an emulsion stability and is 0.1 to 20% by mass, and more preferably 0.5 to 5% from the viewpoint of uniformly adhering the powder to the skin and the skin groove. Mass% is preferred.

The component (C) powder used in the present invention is not particularly limited as long as it is used for ordinary cosmetics. The average particle diameter of the powder is preferably 0.001 to 120 μm, particularly preferably 0.02 to 80 μm. The average particle size is measured with a laser scattering type particle size distribution measuring device (for example, LA-920 type, manufactured by Horiba, Ltd.).
The material may be either an inorganic powder or an organic powder, and includes a pigment. The shape may be any of a spherical shape, a needle shape, a plate shape, and the like. Also, the particle structure is not particularly limited, and any of porous and nonporous materials can be used.

  Inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica Phlogopite, red mica, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, Examples thereof include hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, and boron nitride.

  Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, silk powder, nylon powder, 12 nylon, 6Nylon, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder Body, rice starch, lauroyllysine and the like.

  In addition, as colored pigments, inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, black iron oxide, carbon Inorganic black pigments such as black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine blue, tar dyes , Tar-based pigments raked, natural pigments, natural pigments raked, and composite powders obtained by combining these powders.

  Pearl pigments include titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, etc .; metal powder pigments include aluminum powder, copper powder, stainless steel powder Etc. These powders are preferably surface-treated with silicone or a fluorine compound from the viewpoint of improving makeup sustainability.

  The component (C) powder used in the present invention is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, from the viewpoints of the feeling during use and uniform finish.

  Component (D) of the present invention is water. The water is preferably purified water such as pure water or ion exchange water. By containing water, a refreshing feeling is given at the time of application, and the applicability is improved. Component (D) is preferably included in the total composition in an amount of 5 to 70% by mass.

In the cosmetic of the present invention, one or more water-soluble polymers or water-swellable polymers can be used depending on the purpose.
Examples of the water-soluble polymer or water-swellable polymer include gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), algae Plant polymers such as colloid and locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan and pullulan; animal polymers such as collagen, casein, albumin and gelatin; carboxymethyl starch, methylhydroxypropyl starch Starch polymers such as: methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, cellulose Cellulose polymers such as sodium acid and sodium carboxymethyl cellulose; Alginic acid polymers such as sodium alginate and propylene glycol alginate; Vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymer; Polyoxyethylene polymers and polyoxy Ethylene polyoxypropylene copolymer-based polymers; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; other compatible water-soluble polymers such as polyethyleneimine and cationic polymers; There are synthetic polymers. Also included are film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone.

  In the cosmetic of the present invention, one or more surfactants can be used in order to improve the emulsion stability. Such surfactants include anionic, cationic, nonionic and amphoteric active agents, with nonionic surfactants being preferred.

  Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxy Ethylene cholestanol ether, polyoxyethylene cholesteryl ether, poly Kishiarukiren modified organopolysiloxane, polyoxyalkylene-alkyl co-modified organopolysiloxanes, and the like.

  The cosmetic of the present invention can contain an oil-soluble gelling agent. Examples of oil-soluble gelling agents include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid; dextrin palmitate, dextrin stearate, dextrin 2- Dextrin fatty acid esters such as ethylhexanoic acid palmitic acid ester; sucrose fatty acid esters such as sucrose palmitic acid ester and sucrose stearic acid ester; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol, etc. Organic modified clay minerals such as dimethylbenzyl dodecyl ammonium montmorillonite clay and dimethyl dioctadecyl ammonium montmorillonite clay are also included. These can improve a feeling of use and emulsification stability, and can be contained in an amount of 0.1 to 5% by mass in the entire composition.

  The cosmetic of the present invention can further contain a polyhydric alcohol such as glycerin, butylene glycol, propylene glycol, dibutylene glycol, or polyglycerin. By including the polyhydric alcohol, the emulsification characteristics and the moisturizing effect can be improved, and 1 to 10% by mass can be contained in the entire composition.

  The water-in-oil emulsified cosmetic of the present invention includes, as other components, an ultraviolet absorber, a moisturizer, an antiseptic, an antibacterial agent, an antioxidant, a pH adjuster, a chelating agent, a refreshing agent, an anti-inflammatory agent, and beautifying skin Ingredients, vitamins, amino acids, nucleic acids, hormones and the like can be appropriately blended.

  As the shape of the water-in-oil emulsified cosmetic of the present invention, various forms such as liquid, cream, solid, paste, gel, mousse and the like can be selected. In addition, UV cuts that contain makeup cosmetics such as foundation, makeup base, blusher, eye shadow, mascara, eyeliner, eyebrow, and inorganic ultraviolet shielding powders such as titanium oxide and zinc oxide. An agent or the like is preferable.

(Evaluation methods)
(1) Emulsion storage stability: About 70 g of a water-in-oil emulsion cosmetic of each Example and Comparative Example is filled in a polyethylene container containing 100 ml, and stored at 5 ° C., room temperature (20-25 ° C.), 40 ° C. for 1 month. Thereafter, the stability of each emulsion was judged from the appearance according to the following criteria.
A: No change B: Unevenness occurred on the surface.
Δ: Liquid separation within 1 mm was observed on the surface.
X: Completely separated (1 mm or more).

(2) Feeling of use (no stickiness): 15 expert panelists applied the water-in-oil emulsified cosmetics of each Example and Comparative Example to the face, and evaluated the non-stickiness according to the following criteria, and the average Judged from the point.
Bad ... Score 1
Slightly bad Score 2
Normal ... Score 3
Somewhat good score 4
Good ... Score 5

(3) Covering power: A water-in-oil emulsified cosmetic was applied to the face in the same manner as in (2) No stickiness, evaluated according to the following criteria, and judged from the average score. The covering power means the degree to which the uneven color or color of the background before application is hidden.
Cover power is low ... Score 1
Cover power is slightly low. Score 2
Normal ... Score 3
Cover power is slightly high. Score 4
Cover power is high ... Score 5

(4) Evaluation of degree of drop of pearl pigment into skin groove: (2) Water-in-oil emulsified cosmetic is applied to the face in the same manner as in the case of no stickiness, and a digital microscope (manufactured by Keyence Corporation: VXH- In 500), the coating film was observed at a magnification of 500 times, and the amount of the interference pearl pigment that had fallen into the skin groove was evaluated according to the following criteria, and the average point was determined.
There is a lot of amount falling in the skin groove ... Score 1
Slightly larger amount in the skin groove score 2
About half of the skin has fallen. Score 3
Slightly less amount in the skin groove. Score 4
The amount falling in the skin groove is small. Score 5

(5) Pearly feeling (color development of pearl pigment (purple pearl)): (2) A water-in-oil emulsified cosmetic is applied to the face by the same method as that described above, and the average is evaluated according to the following criteria. Judged from the point.
Low color development ... Score 1
Color development is slightly low. Score 2
Normal .... Score 3
Color development is slightly high. Score 4
High color development ... Score 5

(6) Persistence of makeup: 15 professional panelists apply a water-in-oil emulsified cosmetic of each example and comparative example in a fixed amount: 120 to 140 mg (0.35 to 0.40 mg / cm ² ) on the face for 5 hours After the lapse, the finished evaluation was evaluated according to the following criteria and judged from the average score.
The makeup is broken ... Score 1
The makeup is broken ... Score 2
The makeup is broken a little ... Score 3
Almost no makeup collapse ... Score 4
No makeup collapse ... Score 5

Production Example 1 Synthesis of Copolymer (1) of Component (B) 140 g of dimethylpolysiloxypropyl methacrylate (Chisso Corporation “FM0711” molecular weight 1000), N, N-dimethylacrylamide (Kojin Co., Ltd. “DMAA”) 60 g and 200 g of methyl ethyl ketone are placed in a beaker and mixed, and then 2.0 g of 2,2-azobis-2,4-dimethylvaleronitrile (Wako Pure Chemical Industries, Ltd. “V-65”) is added and dissolved uniformly. did. 10% by mass of the obtained mixed monomer solution was charged into a glass four-necked flask equipped with a reflux condenser, a dropping funnel, a stirrer, and a thermometer and purged with nitrogen.
Next, after heating to 70 ° C., the remaining 90% by mass of the mixed monomer solution was added dropwise over 2 hours, and 2,2-azobis-2,4-dimethylvaleronitrile (Wako Pure Chemical Industries, Ltd. “V- 65 ") and a solution consisting of 0.4 g and 20 g of methyl ethyl ketone were added dropwise over 5 minutes. Thereafter, the polymerization was completed by further heating at 70 ° C. for 2 hours. A volatile component was distilled off by heating under reduced pressure to obtain a copolymer of component (B). The monomer composition in the copolymer almost coincided with the charged composition (weight average molecular weight 650,000). (Content of monomer represented by formula (i): 70% by mass)

Production Example 2 Synthesis of Component (B) Copolymer (2) In the same manner as in Production Example 1, 160 g of FM0711 used in Production Example 1 and 40 g of N, N-dimethylacrylamide were prepared. The monomer composition in the copolymer (2) obtained from the polymer (2) almost coincided with the charged composition (weight average molecular weight 61,000). (Content of monomer represented by formula (i): 80% by mass)

Production Example 3 Synthesis of Component (B) Copolymer (3) 176 g of FM0711 used in Production Example 1 and 24 g of N, N-dimethylacrylamide were charged, and in the same manner as in Production Example 1, A polymer (3) was obtained. The monomer composition in the copolymer (3) almost coincided with the charged composition (weight average molecular weight 63,000). (Content of monomer represented by formula (i): 88% by mass)

Production Example 4 Synthesis of Component (B) Copolymer (4) 184 g of FM0711 used in Production Example 1 and 16 g of N, N-dimethylacrylamide were charged, and in the same manner as in Production Example 1, A polymer (4) was obtained. The monomer composition in the copolymer (4) almost coincided with the charged composition (weight average molecular weight 40,000). (Content of monomer represented by formula (i): 92% by mass)

Production Example 5 Synthesis of Component (B) Copolymer (5) In place of FM0711 used in Production Example 1, 160 g of dimethylpolysiloxypropyl methacrylate (Chisso Corporation “FM0721” molecular weight 5000), N, N— 40 g of dimethylacrylamide was charged, and a copolymer (5) of component (B) was obtained in the same manner as in Production Example 1. The monomer composition in the copolymer (5) almost coincided with the charged composition (weight average molecular weight 74,000). (Content of monomer represented by formula (i): 80% by mass)

Production Example 6 Synthesis of Copolymer (6) of Component (B) Instead of FM0711 used in Production Example 1, 180 g of dimethylpolysiloxypropyl methacrylate (Chisso Corporation “FM0725” molecular weight 10000), N, N— 20 g of dimethylacrylamide was charged, and a copolymer (6) of component (B) was obtained in the same manner as in Production Example 1. The monomer composition in the copolymer (6) almost coincided with the charged composition (weight average molecular weight 60,000). (Content of monomer represented by formula (i): 90% by mass)

Production Comparative Example 1
110 g of FM0711 used in Production Example 1 and 90 g of N, N-dimethylacrylamide were charged, and a copolymer (7) was obtained in the same manner as in Production Example 1. The monomer composition in the copolymer (7) almost coincided with the charged composition (weight average molecular weight 56,000). (Content of monomer represented by formula (i): 55% by mass)

Production Comparative Example 2
194 g of FM0711 used in Production Example 1 and 6 g of N, N-dimethylacrylamide were charged, and a copolymer (8) was obtained in the same manner as in Production Example 1. The monomer composition in the copolymer (8) almost coincided with the charged composition (weight average molecular weight 38,000). (Content of monomer represented by formula (i): 97% by mass)

Examples 1-6 and Comparative Examples 1-6
A water-in-oil emulsion composition (foundation) having the composition shown in Table 1 was produced by the following method and evaluated by the above evaluation method. The results are shown in Table 1.
(Production method) The oil phase components (1) to (16) were mixed. Separately, the powders of components (21) to (25) were pulverized and mixed with a pulverizer, added to the oil phase component, and stirred to disperse the powder. Components (17) to (20) were mixed to form an aqueous phase component, and the aqueous phase component was slowly added dropwise to the oil phase in which the powder was dispersed while stirring. The mixture was further emulsified by stirring with a homomixer for 10 minutes. Next, the mixture was defoamed and filled in a polyethylene container to prepare each water-in-oil emulsified cosmetic.

  As is apparent from the results in Table 1, the water-in-oil emulsified cosmetics (foundations) of Examples 1 to 6 containing the (B) copolymer of the present invention were more stable than Comparative Examples 1 to 6. It has been demonstrated that it has excellent properties, non-stickiness, covering power, low degree of pearl pigment drop into the skin groove, color development of pearl pigment, and very good makeup. The high covering power and high color development of the pearl pigment means that the foundation of this example allows more blended powders to adhere to the skin than the comparative example, and further increases the orientation of the pearl pigment in the skin. It is suggested that

Example 7: Creamy lipstick (component) Mass (%)
1. Palmitic acid / 2-ethylhexanoic acid dextrin (Note 1) 9.0
2. Glyceryl triisooctanoate 22.0
3. Bentonite 1.0
4). Acrylamide-modified silicone (Production Example 3) 1.5
5. Decamethylcyclopentasiloxane 38.0
6.1,3-Butylene glycol 5.0
7). Sodium chloride 0.5
8). Purified water 10.0
9. Color pigment (average particle size 0.1 to 0.3 μm) 3.0
10. Mica titanium (average particle size: 8μm) 10.0
(Note 1) Palmitic acid / 2-ethylhexanoic acid dextrin: Leopard TT (Chiba Flour Milling Co., Ltd.)
(Production method)
A: Component 1, a part of component 2, and components 3 to 5 are mixed and dissolved.
B: Component 9 is mixed with the remainder of component 2 and dispersed with a roller.
C: Add B and component 10 to A and mix uniformly.
D: Components 6 to 8 are mixed and heated.
E: D is added to C and emulsified.
The lipstick obtained as described above is a W / O type cream lipstick with excellent makeup sustainability, light spreading, no stickiness and oiliness, and the color development of pearl pigment. I found it expensive.

Example 8: Eyeliner (component) Mass (%)
1. Octamethylcyclotetrasiloxane 53.5
2. Acrylamide-modified silicone (Production Example 4) 3.0
3. Silicone network resin (Note 2) 15.0
4). Dimethyl distearyl ammonium hectorite 3.0
5. Silicone-treated black iron oxide (average particle size: 0.3 μm) (Note 3) 10.0
6.1,3-Butylene glycol 5.0
7). Sodium sulfate 0.5
8). Preservative appropriate amount 9. Perfume Trace amount 10. Purified water Balance (Note 2) Silicone network resin: 50% -decamethylpentasiloxane solution of silicone network compound having a [Me ₃ SiO _1/2 ] / [SiO ₂ ] ratio of 0.8: KF-7312J (Shin-Etsu Chemical Co., Ltd.) (stock))
(Note 3) Silicone-treated black iron oxide: Heat treated after adding 2% methylhydrogenpolysiloxane to black iron oxide (manufacturing method)
A: Components 1 to 4 are mixed, and component 5 is added and mixed and dispersed uniformly.
B: Components 6 to 8 and 10 are mixed.
C: B was gradually added to A to emulsify, and then component 9 was added to obtain an eyeliner.
The eyeliner obtained as described above is light and easy to draw, has a refreshing feeling and is refreshing and non-sticky, has no change over time and temperature, and has excellent usability and stability. It was found that both water resistance and sweat resistance were excellent, and the makeup lasting was very good.

Example 9: Eye shadow (component) Mass (%)
1. Decamethylcyclopentasiloxane 15.0
2. Dimethylpolysiloxane (6 mm ² / s (25 ° C.)) 10.0
3. Acrylamide-modified silicone (Production Example 4) 2.0
4). PEG (10) lauryl ether 0.5
5. Silicone-treated chromium oxide (average particle size: 2.5 μm) (Note 4) 6.2
6). Silicone treated ultramarine (average particle size: 0.3 to 2.0 μm) (Note 4) 4.0
7). Silicone-treated mica titanium (average particle size: 8 μm) (Note 4) 6.0
8). Sodium chloride 2.0
9. Propylene glycol 8.0
10. Preservative appropriate amount11. Fragrance 12 Purified water Balance (Note 4) Silicone treatment; 3% methyl hydrogen polysiloxane added to the powder and then heat-treated (production method)
A: Components 1 to 4 are mixed, and components 5 to 7 are added and dispersed uniformly.
B: Components 8 to 10 and 12 are uniformly dissolved.
C: Under stirring, B was gradually added to A to emulsify, and component 11 was added to obtain an eye shadow.
The eye shadow obtained as described above has a light spread, no oiliness or powderiness, freshness, refreshing feeling and moisturization, water resistance, water repellency, sweat resistance Good and long-lasting, hard to break makeup, excellent stability with no change over time and temperature, high color development of pearls, excellent use feeling, makeup sustainability and finish It was.

Example 10: Sun cut cream (component) Mass (%)
1. Decamethylcyclopentasiloxane 17.5
2. Acrylic silicone resin / decamethylcyclopentasiloxane 12.0
(Note 5)
3. Glyceryl triisooctanoate 5.0
4). Octyl paramethoxycinnamate 6.0
5. Cross-linked polyether-modified silicone (Note 6) 5.0
6). Acrylamide-modified silicone (Production Example 2) 1.0
7). Lipophilicized zinc oxide (average particle size: 0.1 to 0.3 μm) 20.0
8). Sodium chloride 0.5
9. 1,3-Butylene glycol 2.0
10. Preservative appropriate amount11. Fragrance 12 Purified water Balance (Note 5) Acrylic silicone resin / Decamethylcyclopentasiloxane: KP545 (Shin-Etsu Chemical Co., Ltd.)
(Note 6) Crosslinked polyether-modified silicone: KSG210 (Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Add component 2 to a part of component 1 to make it uniform, add component 7 and disperse with a bead mill.
B: The remainder of component 1 and 3-6 are mixed and mixed uniformly.
C: Components 8 to 10 and 12 are mixed and dissolved.
D: C was added to B to emulsify, and A and component 11 were added to obtain a sun cut cream.
The suncut cream obtained as described above has no stickiness, spreads lightly, has good adhesion, has a good fit, has a glossy finish, and has a very long lasting makeup. Also found to be very stable.

Example 11: Suncut emulsion (component) Mass (%)
1. Decamethylcyclopentasiloxane 3.0
2. Dimethylpolysiloxane (6 mm ² / s (25 ° C.)) 5.0
3. Glyceryl triisooctanoate 5.0
4). Acrylamide-modified silicone (Production Example 1) 1.0
5. Cross-linked polyether-modified silicone (Note 7) 3.0
6). Titanium oxide / decamethylcyclopentasiloxane dispersion (Note 8) 25.0
7). Zinc oxide / decamethylcyclopentasiloxane dispersion (Note 9) 35.0
8). Dipropylene glycol 3.0
9. Sodium citrate 0.5
10. Preservative appropriate amount11. Fragrance 12 Purified water balance (Note 7) Crosslinked polyether-modified silicone: KSG-210 (Shin-Etsu Chemical Co., Ltd.)
(Note 8) Titanium oxide / decamethylcyclopentasiloxane dispersion: SPD-T5 (Shin-Etsu Chemical Co., Ltd.) Titanium oxide average particle size: 0.01 to 0.05 μm
(Note 9) Zinc oxide / decamethylcyclopentasiloxane dispersion: SPD-Z5 (Shin-Etsu Chemical Co., Ltd.) Zinc oxide average particle size: 0.02 μm
(Production method)
A: Components 1 to 5 are mixed and mixed uniformly.
B: Components 8 to 10 and 12 are mixed and dissolved.
C: B was added to A to emulsify, and components 6, 7 and 11 were added to obtain a suncut emulsion.
The suncut emulsion obtained as described above has no stickiness, spreads lightly, has good adhesion, has a good fit, has a glossy finish, and has a very long lasting makeup. Also found to be very stable.

Example 12: W / O type makeup base (component) Mass (%)
1. Cross-linked polyether-modified silicone (Note 11) 5.0
2. Cross-linked dimethylpolysiloxane (Note 12) 1.0
3. Acrylamide-modified silicone (Production Example 4) 0.5
4). Dimethylpolysiloxane (6 mm ² / s (25 ° C.)) 6.0
5. Dimethylpolysiloxane (20 mm ² / s (25 ° C.)) 2.0
6). Decamethylcyclopentasiloxane 3.0
7). Titanium oxide / cyclopentasiloxane dispersion (Note 13) 10.0
8). Dipropylene glycol 5.0
9. Sodium citrate 0.2
10. Methyl cellulose (2% aqueous solution) (Note 14) 2.5
11. Ethanol 3.0
12 Preservative appropriate amount13. Fragrance 14 Purified water balance (Note 11) Cross-linked polyether-modified silicone: KSG-210 (Shin-Etsu Chemical Co., Ltd.)
(Note 12) Cross-linked dimethylpolysiloxane: KSG-15 (Shin-Etsu Chemical Co., Ltd.)
(Note 13) Titanium oxide / cyclopentasiloxane dispersion: SPD-T5 (Shin-Etsu Chemical Co., Ltd.) Titanium oxide average particle size: 0.01 to 0.05 μm
(Note 14) Methyl cellulose: Metroles 65-SH4000 (Shin-Etsu Chemical Co., Ltd.) (Production method)
A: Components 1 to 7 are heated and mixed.
B: Components 8 to 14 are mixed and dissolved, and added to A and emulsified with stirring.
The makeup base obtained as described above is oily, non-sticky, lightly spreads, has a fresh and refreshing usability, has a good feeling of adhesion, has a good fit, and is glossy. It was found that this was an excellent W / O-type makeup base having a certain finish and having a UV protection effect and good makeup.

Example 13: Cream foundation (component) Mass (%)
1. Cross-linked polyether-modified silicone 5.0
2. Acrylamide-modified silicone (Production Example 2) 0.5
3. Glyceryl trioctanoate 4.0
4). Dimethylpolysiloxane (6 mm ² / s (25 ° C.)) 5.0
5. Decamethylcyclopentasiloxane 6.0
6). Phenyl-modified hybrid silicone composite powder (Note 15) 2.5
7). Pigment 8.0
8). Acrylic silicone resin (Note 16) 5.0
9. Dipropylene glycol 5.0
10. Sodium citrate 0.2
11. Preservative appropriate amount 12. Fragrance 13 Purified water Balance (Note 15) Phenyl-modified hybrid silicone composite powder: KSP-300 (Shin-Etsu Chemical Co., Ltd.) Average particle size: 5.0 μm
(Note 16) Acrylic silicone resin: KP-575 (Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 6 are heated and mixed.
B: Components 9 to 13 are mixed and dissolved, and added to A and emulsified with stirring.
C: Components 7 to 8 are mixed and added to B to make it uniform.
The cream foundation obtained as described above was found to be a cream foundation that has no stickiness, light spread, light adhesion, good cushioning, and a matte finish.

Example 14: W / O type UV cut cream (component) Mass (%)
1. Silicone-treated zinc oxide (average particle size: 0.1 to 0.3 μm) 20.0
2. Acrylate / dimethyl silicone copolymer (Note 17) 12.0
3. Decamethylcyclopentasiloxane 20.0
4). Glyceryl trioctanoate 3.0
5. Cross-linked polyether-modified silicone (Note 18) 7.0
6). Polyether-modified silicone (Note 19) 1.0
7). Alkyl / polyether co-modified silicone (Note 20) 0.5
8). Acrylamide-modified silicone (Production Example 4) 0.5
9. Octyl methoxycinnamate 6.0
10. Sodium citrate 0.2
11. Dipropylene glycol 3.0
12 Preservative appropriate amount13. Fragrance 14 Purified water Balance (Note 17) Acrylate / dimethyl silicone copolymer: KP-545 (Shin-Etsu Chemical Co., Ltd.)
(Note 18) Crosslinked polyether-modified silicone: KSG-210 (Shin-Etsu Chemical Co., Ltd.)
(Note 19) Polyether-modified silicone: KF-6017 (trade name) (Shin-Etsu Chemical Co., Ltd.)
(Note 20) Alkyl / polyether co-modified silicone: KF-6026 (trade name) (Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: A part of component 3 and 4 to 9 are heated and mixed.
B: Components 10 to 12 and 14 are mixed and added to A and emulsified with stirring.
C: The remaining components 1, 2 and 3 are mixed and dispersed, and component 13 is added to B to make it uniform.
The UV cut cream obtained as described above is light and refreshing, has no stickiness or oily feeling, is transparent, has a good makeup, has no change over time and temperature, and is extremely easy to use and stable. It was a W / O type UV cut cream excellent in

Example 15: W / O type UV cut emulsion (component) Mass (%)
1. Dimethylpolysiloxane (6 mm ² / s (25 ° C.)) 5.0
2. Glyceryl trioctanoate 2.0
3. Cross-linked polyglycerin-modified silicone (Note 21) 6.0
4). Polyglycerin-modified silicone (Note 22) 0.5
5. Acrylamide-modified silicone (Production Example 1) 0.5
6). Titanium oxide / decamethylcyclopentasiloxane dispersion (Note 23) 30.0
7). Zinc oxide / decamethylcyclopentasiloxane dispersion (Note 24) 30.0
8). Dipropylene glycol 3.0
9. Sodium citrate 0.2
10. Preservative appropriate amount11. Fragrance 12 Purified water balance (Note 21) Crosslinked polyglycerin-modified silicone: KSG-710 (Shin-Etsu Chemical Co., Ltd.)
(Note 22) Polyglycerin-modified silicone: KF-6104 (trade name) (Shin-Etsu Chemical Co., Ltd.)
(Note 23) Titanium oxide / decamethylcyclopentasiloxane dispersion: SPD-T5 (Shin-Etsu Chemical Co., Ltd.) Titanium oxide average particle size: 0.01 to 0.05 μm
(Note 24) Zinc oxide / decamethylcyclopentasiloxane dispersion: SPD-Z5 (Shin-Etsu Chemical Co., Ltd.) Zinc oxide average particle size: 0.02 μm
(Production method)
A: Components 1 to 5 are heated and mixed.
B: Components 8 to 10 and 12 are mixed and dissolved, and added to A and emulsified with stirring.
C: Components 6, 7, and 11 are added to B to make it uniform.
The UV-cut emulsion obtained as described above is light and refreshing, has no stickiness or oily feeling, is transparent, has a good makeup, has no change over time and temperature, and is very easy to use and stable. W / O type UV cut emulsion excellent in

Example 16: Cream eye shadow (component) Mass (%)
1. Acrylate / dimethyl silicone copolymer (Note 25) 10.0
2. Acrylate / dimethyl silicone copolymer (Note 26) 2.0
3. Acrylamide-modified silicone (Production Example 3) 0.3
4). Polyglycerin-modified silicone (Note 27) 1.5
5. Decamethylcyclopentasiloxane 20.0
6). Organically modified clay mineral (Note 28) 1.2
7). Cetyl isooctanoate 3.0
8). Polyamide 3.0
9. Talc (average particle size: 13 μm) 4.0
10. Acrylic silicone resin (Note 29) treated pigment (average particle size: 0.5 μm) 20.0
11. Ethanol 5.0
12 Purified water 30.0
(Note 25) Acrylate / dimethyl silicone copolymer: KP-545 (Shin-Etsu Chemical Co., Ltd.)
(Note 26) Acrylate / dimethyl silicone copolymer: KP-561P (Shin-Etsu Chemical Co., Ltd.)
(Note 27) Polyglycerin-modified silicone: KF-6105 (Shin-Etsu Chemical Co., Ltd.)
(Note 28) Organically modified clay mineral: Benton 38 (NL Industry)
(Note 29) Acrylic silicone resin: KP-574 (Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 10 were mixed.
B: Components 10 to 11 were mixed and then mixed uniformly with A.
The eye shadow obtained as described above has no stickiness, spreads lightly, has excellent adhesion, has a good fit, has a glossy finish, and has a moist and durable makeup. It was confirmed that there was.

  The water-in-oil emulsified cosmetic of the present invention is very excellent in high emulsification stability, light use feeling without stickiness, powder adhesion, etc., and further in cosmetic sustainability. Is preferred.

Claims (4)

The following components (A), (B), (C) and (D):
(A) Oily component containing silicone oil 15 to 70% by mass
(B) a monomer represented by the following formula (i) , N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, and N, A copolymer obtained by polymerizing an N atom-containing radical polymerizable monomer selected from N-dimethylaminopropylacrylamide, wherein the content of the monomer represented by the formula (i) is 60 to 96% by mass Coal 0.1-20% by mass

(A is a number which makes the average molecular weight of the monomer represented by Formula (i) 1000-10000)
(C) 0.1-50 mass% of powder
(D) Water 5-70 mass%
Water-in-oil emulsified cosmetic containing   The water-in-oil emulsified cosmetic according to claim 1, wherein the component (B) copolymer has a weight average molecular weight of 5,000 to 200,000. The water-in-oil emulsified cosmetic according to claim 1 or 2 , wherein the N atom-containing radical polymerizable monomer constituting the component (B) copolymer is N, N-dimethylacrylamide. The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the content of the monomer represented by the formula (i) in the component (B) copolymer is 70 to 92% by mass.