JP2006008757A - Oil-absorbing swellable polymer particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-absorbing swellable polymer useful for an unevenness-hiding cosmetic which completely hides wrinkles and pores and gives natural appearance and touch or an anti-sebum cosmetic by absorbing sebum, and a cosmetic containing the polymer. <P>SOLUTION: The oil-absorbing swellable polymer particles are obtained by copolymerizing monomer components comprising (A) an alkyl (meth)acrylate having a 18-24C linear or branched alkyl group, (B) a vinyl monomer having a polymerizable unsaturated group copolymerizable with component (A), and (C) a crosslinkable monomer having two or more polymerizable unsaturated groups. The molar ratio of component (A) to component (B) is (A)/(B)=45/55-95/5. The proportion of component (C) is 0.001-5 pts.wt. based on 100 pts.wt. of the sum of components (A) and (B). The polymer particles have an average particle size of 1-40 μm before they are swelled. There is provided a cosmetic containing the oil-absorbing swellable polymer particles. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to swelling oil-absorbing polymer particles that are suitably used in cosmetics for concealing skin irregularities, and cosmetics containing the same.

  Conventionally, there have been many troubles regarding female pores and wrinkles, and various cosmetics for concealing uneven skin have been developed. For example, Patent Document 1 discloses an emulsified cosmetic for concealing wrinkles, characterized by containing a highly polymerized methylpolysiloxane, a volatile oil, and a translucent powder. Concealment is an issue. Patent Document 2 discloses a cosmetic containing a powder, a film-forming agent, a volatile solvent, and having a certain dry skin surface roughness. The finish can make the unevenness of the skin difficult to see. However, although these small wrinkles are hidden, it is difficult to hide even large wrinkles that are most worried by women, for example, having a skin groove of 250 μm or more.

  On the other hand, swelling type oil-absorbing polymer particles that absorb oil and swell at room temperature are being used for recovery of spilled oil and waste oil treatment in factories. Such swelling-type oil-absorbing polymer particles are used for concealing skin irregularities. No attempt has been made so far. For example, Patent Document 3 discloses a swellable oil-absorbing agent composed of a crosslinked polymer mainly composed of an alkyl (meth) acrylate having a linear or branched alkyl group having 10 to 16 carbon atoms. When used in the above, there is a problem that the adhesive strength of the particles is strong, the particles are aggregated, and the feeling of use is deteriorated.

Patent Document 4 discloses a self-swelling oil-absorbing polymer mainly composed of an alkyl (meth) acrylate having a linear or branched alkyl group having 8 to 24 carbon atoms, and Patent Document 5 discloses carbon. A cross-linkable polymer mainly comprising an alkyl (meth) acrylate having a linear or branched alkyl group of 2 to 4 is disclosed. However, it has been difficult for these polymers to absorb cosmetic oils at room temperature and hide skin irregularities.
JP 2000-7551 A JP 2002-179530 A Japanese Patent No. 2813224 JP-A-5-209017 JP 2001-348407 A

  An object of the present invention is to swell the oil-absorbing polymer particles useful for cosmetics for concealing irregularities and absorbing sebum by absorbing wrinkles and pores neatly, and not having an uncomfortable appearance and feel, and sebum. To provide cosmetics to do.

  The present invention has (A) an alkyl (meth) acrylate having a linear or branched alkyl group having 18 to 24 carbon atoms, (B) one polymerizable unsaturated group copolymerizable with the component (A). Polymer particles obtained by copolymerizing a monomer component containing a vinyl monomer and (C) a crosslinkable monomer having two or more polymerizable unsaturated groups, the molar ratio of component (A) and component (B) However, (A) / (B) = 45/55 to 95/5, and the ratio of the component (C) is 0.001 to 100 parts by weight of the total of the components (A) and (B). There are provided 5 parts by weight of a swollen oil-absorbing polymer particle having an average particle diameter of 1 to 40 μm before swelling, and a cosmetic containing the swollen oil-absorbing polymer particle.

  In the present specification, “(meth) acrylate” is a concept including both acrylate and methacrylate.

  The swelling type oil-absorbing polymer particles are particles that swell (increase in volume) by absorbing at least squalane at 25 ° C.

  The swelling oil-absorbing polymer particles of the present invention can not only hide small wrinkles, but also can hide large wrinkles, pores, scars, etc. of 250 μm or more, and can suppress shine by absorbing sebum, It is useful as a concealment cosmetic or a sebum-preventing cosmetic.

[Monomer component]
The monomer component of the present invention comprises (A) an alkyl (meth) acrylate having a linear or branched alkyl group having 18 to 24 carbon atoms, and (B) one polymerizable unsaturated copolymerizable with the component (A). A vinyl monomer having a group and (C) a crosslinkable monomer having two or more polymerizable unsaturated groups.

  Examples of the component (A) include alkyl (meth) acrylates having a linear or branched alkyl group having 18 to 22 carbon atoms such as stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate. preferable.

  Examples of the component (B) include styrene, alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 16 carbon atoms, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, and (meta ) Α, β-unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, maleic anhydride, chloromethylstyrene, glycidyl (meth) acrylate, (meth) acryloyloxyethyl isocyanate, 3- (trimethoxysilyl) propyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyridine and the like can be mentioned, and these can be copolymerized alone or in combination of two or more.

  In addition, a polysiloxane compound having a radical polymerizable group at one end, such as a compound represented by the general formula (I), a (meth) acrylate having a fluoroalkyl group such as a compound represented by the general formula (II), etc. Can be used.

[Where:
X: A group represented by CH ₂ ═C (R ¹ ) COO—, CH ₂ ═C (R ¹ ) CONR ⁵ — or CH ₂ ═CH—C ₆ H ₄ —. However, R ¹ = H or CH ₃ , R ⁵ = H or C _b H _{2b + 1} (b = 1 to 4 integer)
Y: A group represented by — (CH ₂ O) _c —C _d H _2d — (c = 0 or 1, d = 1 to 10).
Z: represents a group represented by C _e H _{2e + 1} (e = 1 to 4).
a: Number from 3 to 1500. ]

(In the formula, R ¹ is H or CH ₃ , R ² is an alkylene group having 1 to 4 carbon atoms, or — (CH ₂ ) _n N (R ³ ) SO ₂ — (R ³ is an alkyl group having 1 to 4 carbon atoms). Or a hydrogen atom, n represents an integer of 1 to 4. Rf represents a C 1-15 fluoroalkyl group having a perfluoroalkyl group at the terminal.
Among these components (B), styrene and alkyl (meth) acrylates having a linear or branched alkyl group having 1 to 16 carbon atoms are preferred, and alkyl having a linear or branched alkyl group having 1 to 16 carbon atoms. (Meth) acrylate is more preferable, and alkyl (meth) acrylate having a linear or branched alkyl group having 4 to 16 carbon atoms is particularly preferable.

  Specific examples of the component (C) used in the present invention include (1) ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate) Etc.), 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tet (Meth) acrylic acid ester compounds of polyhydric alcohols having two or more (meth) acrylate residues such as la (meth) acrylate and dipentaerythritol hexa (meth) acrylate; (2) N-methylallyl (meth) acrylamide; (Meth) acrylamide compounds such as N-vinyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, and bis (meth) acrylamide acetic acid; (3) divinyl compounds such as divinylbenzene, divinyl ether, and divinylethyleneurea; (4) diallyl phthalate, diallyl malate, diallylamine, triallylamine, triallyl ammonium salt, allyl etherified product of pentaerythritol, allyl etherified product of sucrose having at least two allyl ether units in the molecule, etc. Polyallyl compound; (5) vinyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxy-3-acryloyl (meth) acrylic acid esters of unsaturated alcohols such as propyl (meth) acrylate. Among these components (C), the above (1) and (3) are preferable, and (1) is particularly preferable.

  The molar ratio of the component (A) to the component (B) in the monomer component of the present invention is such that the swelling oil-absorbing polymer particles absorb cosmetic oil at room temperature (25 ° C.), so that (A) / (B) = 45 / 55 to 95/5, preferably 45/55 to 90/10, and more preferably 45/55 to 65/35. When the molar ratio of (A) / (B) is 95/5 or less, the deformability of the particles increases and swelling occurs sufficiently. As a result, the effect of concealing pores and concealing fine wrinkles is remarkably exhibited. Moreover, since oil absorption increases, the shine prevention effect is expressed. Further, when the molar ratio of (A) / (B) is 45/55 or more, it is possible to suppress particle fusion and aggregation during oil absorption.

  The proportion of the component (C) in the monomer component of the present invention is 0.001 to 5 with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of obtaining good swelling and crosslinkability. Parts by weight, preferably 0.1 to 3 parts by weight.

[Method for producing swelling oil-absorbing polymer particles]
The swelling oil-absorbing polymer particles of the present invention are synthesized by a suspension polymerization method, a dispersion polymerization method or the like. In the case of suspension polymerization, it is necessary to disperse the oil phase containing the monomer component in the aqueous phase. For dispersion, a disperser such as a homogenizer, a high-pressure homogenizer, an ultrasonic disperser, a line mixer, a homomixer, or a milder is used.

  Dispersing and emulsifying agents for suspension polymerization include anionic surfactants such as sodium lauryl sulfate, sodium cetyl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium fatty acid, sodium alkyl (methyl) taurine, and other cationic Low molecular surfactants such as surfactants and nonionic surfactants; polymer dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, hydroxypropyl cellulose, gelatin, starch, carboxymethyl cellulose, polyvinyl alkyl ether; barium sulfate And poorly water-soluble inorganic salts such as potassium sulfate, barium carbonate, calcium carbonate, magnesium carbonate and calcium phosphate.

  The polymerization initiator used in the present invention is determined according to the reaction system, but is a peroxide-based initiator, an organic or inorganic peracid or a salt thereof, an azobis compound alone or in combination with a reducing agent. Things.

  For example, t-butyl peroxide, t-amyl peroxide, cumyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), benzoylisobutyryl peroxide, lauroyl peroxide (LPO), t-butyl hydro Peroxide, cyclohexyl hydroperoxide, tetralin hydroperoxide, t-butyl peracetate, t-butyl perbenzoate, bis (2-ethylhexyl peroxydicarbonate), 2,2'-azobisisobutyronitrile (AIBN) 2,2'-azobisisovaleronitrile, 2,2'-azobis (2-methylbutyronitrile), phenylazotriphenylmethane, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2, , '-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, perhydrochloride Examples thereof include sodium sulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, a combination of a persulfate and a tertiary amine such as triethylamine, triethanolamine, and dimethylaniline.

  The amount of the polymerization initiator used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight as the total of the components (A) and (B).

[Swelling oil-absorbing polymer particles]
The average particle diameter of the swelling type oil-absorbing polymer particles of the present invention is 1 to 40 μm in median diameter before swelling, and 5 to 30 μm in terms of median diameter before swelling, from the viewpoint of expressing a good skin unevenness concealing effect and obtaining a good feeling of use. Is preferred.

  The median diameter can be measured in a volume reference mode using a particle size measuring device such as a laser diffraction / scattering particle size distribution measuring device manufactured by HORIBA.

  The swelling oil-absorbing polymer particles of the present invention are particles that swell by absorbing at least squalane at 25 ° C., but particles having a swelling ratio defined below of 1.30 times or more are preferred. The upper limit is not particularly limited, but is preferably 5 times or less, more preferably 3 times or less from the viewpoint of maintaining particle strength.

Swelling ratio = r1 / r2
Here, r1 represents the average particle diameter of the polymer particles 3 minutes after absorbing squalane at 25 ° C., and r2 represents the average particle diameter of the polymer particles before squalane absorption, and was determined by the following measurement method.

<Swelling ratio measurement method>
In a 25 ° C. measurement chamber, a double-sided tape is affixed on a slide glass, and swelling oil-absorbing polymer particles are fixed in a primary particle state thereon. Using a ultra deep depth measurement microscope VK-8510 manufactured by Keyence Corporation, 10 or more particles near the median diameter are selected, and the diameter of the particles before swelling is measured. Next, one drop of squalane is dropped on the swelling oil-absorbing polymer particles in the observation field using a micro syringe. After 3 minutes, measure the diameter of the same particle as previously measured (excess amount of squalane is wiped off with a tissue).

  As the oil agent for swelling the swelling type oil-absorbing polymer particles of the present invention, hydrocarbon oils such as squalene, squalane and oleic acid are preferred. Further, sebum components (such as glycerin ester and cholesterol) and cosmetic ester oil (such as isopropyl palmitate and isopropyl myristate) may be mixed with the hydrocarbon oil.

[Cosmetics]
The swelling type oil-absorbing polymer particles of the present invention can be suitably blended in a cosmetic for concealing uneven parts, a sebum-preventing cosmetic, and the like. Specifically, makeup cosmetics such as foundation, blusher, eye shadow, mascara, eyeliner, eyebrow, lipstick and the like, and base cosmetics are preferable. The content of the swelling oil-absorbing polymer particles in the cosmetic is preferably 1 to 60% by weight, more preferably 1 to 40% by weight.

  Furthermore, in cosmetics, other components used as usual raw materials for cosmetics, such as white pigments (titanium oxide, etc.), extender pigments (mica, talc, sericite, barium sulfate, etc.), color pigments (bengala, Yellow iron oxide, black iron oxide, yellow 401, red 226, encapsulated colored pigment, organic dye, pearl pigment, natural mineral, organic powder, oil (petrol, paraffin, lanolin, ceresin, olive oil, jojoba oil, Castor oil, squalane, liquid paraffin, ester oil, diglyceride, triglyceride, silicone oil, perfluoropolyether and other fluorine oils, fluorine-modified silicone oil, ester oils such as isopropyl myristate), UV protection agent, gelling agent , Waxes (microcrystalline wax, higher fatty acids, higher alcohols, etc.・ Semi-solid oil, etc.), metal soap, surfactant, moisturizer, antiseptic, fragrance, thickener, antioxidant, bactericidal agent, antiperspirant, whitening agent, astringent, emollient, pH buffer Various other additives can be appropriately selected and blended.

  Examples of the humectant include glycerin, 1,3-butylene glycol, sorbitol and the like. Further, the cosmetic contains a lower alcohol having 1 to 3 carbon atoms such as ethanol and isopropyl alcohol; a solvent such as water accelerates the drying property of the agent and gives a refreshing feel. Further, the swelling type oil-absorbing polymer particles It is also possible to adjust the swelling of the resin.

  The cosmetics of the present invention are solid cosmetics, wax cosmetics, emulsified (O / W, W / O) cosmetics, oily cosmetics, spray cosmetics, stick cosmetics, gel cosmetics, aqueous cosmetics, etc. Can be used in product form.

Example 1
In a beaker, 2000 g of water and 7.5 g of polyvinyl alcohol (EG-30, manufactured by Nippon Gosei Co., Ltd.) were added and mixed and dissolved. In another beaker, 350 g (1.034 mol) of stearyl methacrylate, 150 g (0.590 mol) of lauryl methacrylate, 5 g of ethylene glycol dimethacrylate, and 20 g of lauroyl peroxide were added and stirred. After dissolving the lauroyl peroxide, it was mixed with the aforementioned aqueous polyvinyl alcohol solution and emulsified with a line mixer (emulsified particle size 21 μm). The emulsion was put into a 5 L reaction vessel, and dissolved oxygen was removed with nitrogen gas. Then, the emulsion was heated to 70 ° C., polymerized for 5 hours, and further polymerized at 80 ° C. for 4 hours. After cooling, stationary separation and decantation were performed to obtain a particle slurry having a solid content of 60% (yield 97%). The slurry was dried to obtain polymer particles.

Example 2
In a beaker, 2100 g of water and 300 g of 5% polyvinyl alcohol (EG-30, manufactured by Nihon Gosei Co., Ltd.) aqueous solution were added and mixed. In another beaker, 420 g (1.240 mol) of stearyl methacrylate, 180 g (1.404 mol) of butyl acrylate, 6 g of ethylene glycol dimethacrylate, and 12 g of lauroyl peroxide were stirred. After dissolving the lauroyl peroxide, it was mixed with the aforementioned aqueous polyvinyl alcohol solution and emulsified with a line mixer (emulsified particle size 13 μm). The emulsified liquid was put into a 3 L reaction vessel, and dissolved oxygen was removed with nitrogen gas, and then the emulsified liquid was heated to 70 ° C. and polymerization was continued for 6 hours. After cooling, stationary separation and decantation were performed to obtain a particle slurry having a solid content of 60% (yield 97%). The slurry was dried to obtain polymer particles.

Example 3
In a beaker, 2100 g of water and 300 g of 5% polyvinyl alcohol (EG-30, manufactured by Nihon Gosei Co., Ltd.) aqueous solution were added and mixed. In another beaker, 540 g (1.595 mol) of stearyl methacrylate, 60 g (0.468 mol) of butyl acrylate, 6 g of ethylene glycol dimethacrylate, and 12 g of lauroyl peroxide were stirred. After dissolving lauroyl peroxide, it was mixed with the aqueous polyvinyl alcohol solution described above and emulsified with a line mixer (emulsified particle size 10 μm). The emulsified liquid was put into a 3 L reaction vessel, and dissolved oxygen was removed with nitrogen gas, and then the emulsified liquid was heated to 70 ° C. and polymerization was continued for 6 hours. After cooling, stationary separation and decantation were performed to obtain a particle slurry having a solid content of 60% (yield 97%). The slurry was dried to obtain polymer particles.

Comparative Example 1
In a beaker, 175 g of water and 25 g of 5% polyvinyl alcohol (217E, manufactured by Kuraray Co., Ltd.) aqueous solution were added and mixed. In another beaker, 50 g of stearyl methacrylate, 0.5 g of ethylene glycol dimethacrylate, and 1 g of lauroyl peroxide were added and stirred. After dissolving lauroyl peroxide, it was mixed with the above-mentioned aqueous polyvinyl alcohol solution and emulsified with a line mixer (emulsified particle size 19 μm). The emulsion was put into a 500 mL reaction vessel, and dissolved oxygen was removed with nitrogen gas, and then the emulsion was heated to 70 ° C., polymerized for 6 hours, and further polymerized at 80 ° C. for 3 hours. After cooling, stationary separation and decantation were performed to obtain a particle slurry having a solid content of 60% (yield 97%). The slurry was dried to obtain polymer particles.

Comparative Example 2
Synthesis was performed by changing the monomer of Comparative Example 1 from stearyl methacrylate to lauryl methacrylate, but the particles were fused / aggregated, and evaluation was impossible.

  Table 1 summarizes the monomer blend ratios of Examples 1 to 3 and Comparative Examples 1 and 2, the average particle diameters of the obtained polymer particles before and 3 minutes after absorption of squalane, and the swelling ratio.

Formulation Examples 1-3
To 100 g of the polymer particle slurry having a solid content of 60% obtained in Examples 1 and 2 or Comparative Example 1, 12 g of ethanol was added and stirred. Next, 7.5 g of a previously prepared carbopol gel (gel obtained by dispersing 1.134 g of carbopol 980 (manufactured by Goodrich) in ion-exchanged water 118.44 g) was added over 15 minutes with stirring. . Finally, 0.028 g of potassium hydroxide was added and stirred for 1 hour to prepare an aqueous cosmetic composition having the following composition. This cosmetic was applied to the face of one panelist, and the pore concealing effect and the shine-inhibiting effect were examined. The results are shown in Table 2.

<Aqueous cosmetic composition>
Polymer particles (Examples 1 and 2 or Comparative Example 1) 60 g (solid content)
Ethanol 12g
Thickener (Goodrich Carbopol 980) 0.071g
pH adjuster (potassium hydroxide) 0.028g
47.4g of water

Formulation Examples 4-6
To 45.8 g of the polymer particle slurry having a solid content of 60% in Examples 1-2 or Comparative Example 1, 12.5 g of an acrylic emulsion having a solid content of 55% (manufactured by Nippon SC Co., Ltd., Yodosol GH41) was added dropwise with stirring. added. Next, after adding 6.9 g of porous polystyrene (particle size 10 μm) and adding a balanced amount of ion-exchanged water, stirring was continued for 30 minutes to obtain an aqueous cosmetic having the following composition. This cosmetic was applied to small wrinkles in the eyes of one panelist, and then a drop of squalane was dropped on the small wrinkles to examine the effect of hiding the small wrinkles. The results are shown in Table 3.

<Aqueous cosmetic composition>
Polymer particles (Examples 1-2 or Comparative Example 1) 37.6 g (solid content)
Acrylic emulsion with a solid content of 55% 6.9 g (solid content)
(Yodosol GH41 manufactured by NSC Japan)
Porous polystyrene (particle size 10 μm) 6.9 g
58.6g of water

Claims (5)

  (A) an alkyl (meth) acrylate having a linear or branched alkyl group having 18 to 24 carbon atoms, (B) a vinyl monomer having one polymerizable unsaturated group copolymerizable with the component (A), and ( C) Polymer particles obtained by copolymerizing a monomer component containing a crosslinkable monomer having two or more polymerizable unsaturated groups, wherein the molar ratio of the component (A) and the component (B) is (A ) / (B) = 45/55 to 95/5, and the ratio of the component (C) is 0.001 to 5 parts by weight with respect to the total of 100 parts by weight of the component (A) and the component (B). Swelled oil-absorbing polymer particles having an average particle diameter before swelling of 1 to 40 μm.   The swelling oil-absorbing polymer particles according to claim 1, wherein the component (B) is an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 16 carbon atoms.   The swollen type oil-absorbing polymer particle according to claim 1 or 2, wherein the polymer particle is a particle having an average particle size 3 minutes after absorption of squalane at 25 ° C of 1.30 times or more of the average particle size before absorption.   The swelling oil-absorbing polymer particles according to any one of claims 1 to 3, which are for cosmetics. Cosmetics containing swelling type oil-absorbing polymer particles according to any one of claims 1 to 4.