JP4222608B2 - Amorphous particle powder and solid powder cosmetic comprising the amorphous particle powder - Google Patents

Description

  The present invention relates to an irregularly shaped particle powder for use in a solid powder cosmetic such as a foundation or a funeral, and the solid powder cosmetic.

  In solid powder cosmetics such as foundations and funny ones, it is desired that the skin powder not only give a soft feel to the skin but also stretch well on the skin surface and obtain a smooth feeling of use.

Conventionally, in view of such problems, it has been disclosed to obtain a cosmetic material having excellent elasticity and softness by blending true spherical particle powder made of a crosslinked polyacrylate (Patent Document 1).
Japanese Patent Laid-Open No. 11-343225

In addition, an inorganic powder having an average particle diameter of 1/10000 to 1/100 of the resin particles is adhered to the surface of the resin particles to the cross-linked acrylic ester resin particles, and excellent feel (elongation, smoothness) In addition, those having a soft feeling) (Patent Document 2), and organic resin fine particles having an average particle diameter of 1/1000 to 1/5 of the resin particles are also added to the cross-linked acrylic ester resin particles. Has been disclosed (Patent Document 3) in which adhesion to the skin is improved by attaching to the surface of the skin.
According to the prior arts described in Patent Documents 2 and 3, it is said that excellent effects can be achieved in terms of smoothness and elongation by the soft tactile sensation of the resin particles themselves and the rolling effect that is characteristic of spherical particles.
JP 2000-186017 A JP 2000-302624 A

On the other hand, an external preparation using non-spherical resin particles formed of two curved surfaces or one curved surface and one flat surface is also disclosed as another conventional technique (Patent Document 4), which contains spherical particles. It is known that an external preparation having excellent adhesion and adhesiveness can be obtained by eliminating the poor grip and the feeling of use and the like, and having appropriate elongation and covering power.
JP 2001-278746 A

However, according to the prior arts described in Patent Documents 1 to 3, when a large amount of solid powder cosmetic is used, the surface of the cosmetic is cracked when the molded solid powder cosmetic is impacted by dropping or the like. There is a problem that is likely to occur.
Also, in the case of the prior art described in Patent Document 4 in which the particle shape is simply non-spherical, when the cosmetic is impacted by dropping or the like, the surface of the cosmetic is cracked in the same manner as the spherical particles. There is a problem that is likely to occur.

  Accordingly, the present invention provides a so-called resistance to resistance that is less prone to cracking when the product is dropped, in addition to the improvement effect of the soft feeling and the adhesion to the skin that the cross-linked polyacrylate has. An object is to provide a solid powder cosmetic having impact properties.

  In order to solve the above problems, the present invention provides a polymer particle obtained by polymerizing a polymer mixture and a monomer mixture containing 10 to 40% by weight of a crosslinkable monomer and an acrylate monomer. A coating layer for coating, and by combining a plurality of the polymer particles through the coating layer, the sphericity is 0.6 to 0.8, and the average particle size is 5 to 30 μm. An amorphous particle powder is provided.

  According to the amorphous particle powder having such a configuration, since the cross-linked polyacrylic ester resin is used as the coating layer for coating the polymerizable particles, the particles have a soft touch. In addition, since a plurality of polymer particles are coalesced and formed into an indeterminate shape having a sphericity of 0.6 to 0.8 and an average particle diameter of 5 to 30 μm, it is compared with conventional particles. Thus, the impact resistance after producing the solid powder cosmetic is improved.

  Moreover, this invention provides the amorphous particle powder of Claim 1 whose weight ratio of the said polymer particle and the said coating layer is 95: 5-70: 30.

  If the weight ratio of the polymer particles to the coating layer is less than 95: 5, that is, the ratio of the coating layer is less than 5% by weight, the soft feel due to the acrylic acid ester is hardly exhibited, which is not preferable. Further, when the weight ratio of the polymer particles to the coating layer exceeds 70:30, that is, when the ratio of the coating layer exceeds 30% by weight, coarse particles are easily generated, and the solid powder cosmetic. This is not preferable because the presence of the particles can be easily felt when blended into the composition.

  Furthermore, the present invention provides a solid powder cosmetic comprising the amorphous particle powder.

  According to the solid powder cosmetic having such a configuration, due to the action of the irregular-shaped particle powder, the soft feeling and adhesion are excellent, and the impact resistance after the production of the solid powder cosmetic is improved as compared with the spherical particles. Will be.

  According to the present invention, in addition to the effect of improving the feeling of use such as the excellent soft feeling and adhesion to the skin of the cross-linked polyacrylic acid ester, the impact resistance is less likely to cause cracking even when the product is dropped. It is possible to provide a solid powder cosmetic having

Hereinafter, the irregular shaped particle powder and the solid powder cosmetic according to the present invention will be described in detail.
First, the irregular shaped particle powder of the present invention will be described based on an embodiment of the production method.

<First step>
Polymer particles are obtained by mixing a monomer mixture containing a polymerizable monomer and a polymerization initiator with an aqueous solution containing a dispersion stabilizer and subjecting the mixture to suspension polymerization.
In addition, you may add a crosslinkable monomer to the said monomer mixture in the range of 0-0.1 weight part with respect to 100 weight part of polymerizable monomers.
Further, a surfactant may be added during suspension polymerization.
The average particle size of the polymer particles obtained at this time is preferably 2 to 10 μm. If the average particle size is less than 2 μm, it becomes easy to spheroidize together with the monomer added in the second step, and irregularly shaped particles are obtained. Since it becomes difficult, it is not preferable. On the other hand, if the polymer particles obtained in the first step are larger than 10 μm, the average particle diameter of the amorphous particles tends to exceed 30 μm, which is not preferable.

<Second step>
Next, while stirring the dispersion of polymer particles obtained in the first step, an emulsion of a monomer mixture containing a polymerization initiator, a crosslinkable monomer, an acrylate ester monomer, and the like is prepared. In addition, the monomer mixture is absorbed into the polymer particles, and at the same time, a coating layer covering the polymer particles is formed, and a plurality of the polymer particles are bonded together to form irregularly shaped particles.
In the second step, a monomer other than an acrylate ester and a polymerization initiator are added first, and after obtaining amorphous particles by heat polymerization, an emulsion of the monomer mixture may be further added. good.
The emulsion added in the second step is obtained by mixing the monomer mixture and an aqueous solution containing an amount of surfactant exceeding the critical micelle concentration (CMC) and stirring vigorously.
The mixing ratio of the aqueous solution containing the surfactant is suitably about 100 to 500 parts by weight with respect to 100 parts by weight of the polymerizable monomer component.

<Third step>
Furthermore, the amorphous particles as one embodiment of the present invention can be obtained by heat-polymerizing the monomer mixture that forms the coating layer of the irregular particles obtained in the second step.
More specifically, the suspension containing amorphous particles is heated to 50 to 70 ° C., held at the temperature for 1 to 10 hours, and then cooled to polymerize the monomer mixture of the coating layer. Can be completed.
In addition, since the obtained amorphous particles are suspended in an aqueous solution, it is possible to obtain an amorphous particle powder through steps such as filtration, washing, dehydration, and drying as necessary. it can.
If necessary, coarse particles and fine particles may be removed by a standard sieve or a sedimentation method, for example.

In the second step, when the monomer mixture is added to the polymer particles, the monomer mixture is 5 to 100 parts by weight / hour, preferably 10 to 50 parts per 100 parts by weight of the polymer particles. It is good to carry out continuously or intermittently at an addition rate of parts by weight per hour.
When the addition rate of the monomer mixture exceeds 100 parts by weight / hour, it is not preferable because there are not a few crosslinkable monomers and it is easy to polymerize alone. On the other hand, if the addition rate is slower than 5 parts by weight / hour, productivity is lowered, which is not preferable.

  The weight ratio of the polymer particles to the coating layer formed by polymerizing the acrylate monomer (polymer particles: coating layer) is 95: 5 to 70:30, preferably 93: 7 to 80:20, more preferably 92: 8 to 80:20. When the proportion of the polymer particles is less than 70% by weight, coarse particles are likely to be generated during the process of amorphization, and the presence of the particles (ie, uncomfortable feeling on the skin) is felt when blended into a solid powder cosmetic. Since it becomes easy, it is not preferable. On the other hand, when the ratio of the polymer particles exceeds 95% by weight, the ratio of the acrylic ester resin is decreased, and the softness is hardly exhibited, which is not preferable.

  In the present invention, the average particle diameter of the amorphous particles means the volume average particle diameter described later, and the average particle diameter is preferably 5 to 30 μm, more preferably 5 to 20 μm. When the average particle size is smaller than 5 μm, the effect of improving the soft touch is hardly exhibited when the particles are too small, and when the average particle size exceeds 30 μm, the presence of the particles can be sensed.

Examples of the polymerizable monomer that can be used in the first step include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and Alkyl styrenes such as octyl styrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene and chloromethylstyrene; and styrene resins such as nitrostyrene, acetylstyrene and methoxystyrene Body,
Acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, A monomer constituting a methacrylic ester resin such as isobutyl methacrylate, 2-ethylhexyl methacrylate, or lauryl methacrylate can be used.
The said polymerizable monomer can be used individually or in combination of 2 or more types. Furthermore, what copolymerized the said polymerizable monomer with the bifunctional or polyfunctional monomer can also be used.

As the crosslinkable monomer that can be used in the first step, a bifunctional or polyfunctional monomer can be used. For example, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene Glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trihydroxymethylethane triacrylate, 1,1,1-tris (hydroxymethyl) methylethanetri Examples thereof include acrylate and 1,1,1-tris (hydroxymethyl) propane triacrylate.
In the present invention, a self-crosslinking monomer such as acrylic acid methyl ester can also be used as the crosslinkable monomer in the first step.

  The crosslinkable monomer in the first step is blended in an amount of 0 to 0.1 parts by weight with respect to 100 parts by weight of the polymerizable monomer. Part or less. If the crosslinkable monomer is added in an amount exceeding 0.1 parts by weight, the amorphous shape may be inhibited when the monomer for forming the coating layer is added.

Examples of the polymerization initiator that can be used in the first step include peroxide- or azo-based oil-soluble polymerization initiators that are usually used for suspension polymerization.
Examples of the peroxide polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl orthochloroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile, 2,2′-azobis (2-methylbutyronitrile), and the like.
These polymerization initiators may be used alone or in combination of two or more. Although the usage-amount of such a polymerization initiator is not specifically limited, Usually, it is 0.01-3 weight part with respect to 100 weight part of total amounts of the said polymerizable monomer and a crosslinkable monomer.

  Examples of the dispersion stabilizer that can be used in the first step include water-soluble polymer compounds such as polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, and sodium polyacrylate, tricalcium phosphate, magnesium hydroxide, magnesium pyrophosphate, barium sulfate, and the like. The slightly water-soluble inorganic salt is preferable, but the water-insoluble inorganic salt is preferable because it can be easily removed from the surface of the particles obtained after the polymerization, and the particle size distribution of the polymer particles to be formed can be narrowed. Although the usage-amount of a dispersion stabilizer is not specifically limited, Usually, what is necessary is just to set it as the ratio of 0.1-20 weight part per 100 weight part of polymer particles finally obtained.

  The surfactant that can be used in the first step is not particularly limited. For example, anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, laurylamine acetate, lauryltrimethylammonium chloride, and the like. And nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers. Although the usage-amount is not specifically limited, Usually, 0.005-0.3 weight part is preferable with respect to 100 weight part of water as a reaction solvent.

  When polymer particles are produced in the first step, a water-soluble polymerization inhibitor such as sodium nitrite or hydroquinone may be added to the reaction system as other additives as necessary.

On the other hand, as an acrylate monomer used in the second step, a monomer polymer having a glass transition temperature (Tg) of 20 ° C. (293 K) or less is used alone, or two or more kinds thereof. Can be used in combination.
Examples of such acrylate monomers include, for example, methyl acrylate (Tg = 0 to 3 ° C. of polymer), ethyl acrylate (Tg = −23 to −29 ° C.), n-butyl acrylate (Tg = -56 to -70 ° C), isobutyl acrylate (Tg = -24 ° C), 2-ethylhexyl acrylate (Tg = -70 ° C), and the like.

The crosslinkable monomer used in the second step is not particularly limited as long as it has a plurality of vinyl groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate phthalate, caprolactone Dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, polyester acrylate, urethane acrylate and other (meth) acrylate monomers, divinylbenzene, divinylnaphthalene and the like Examples thereof include aromatic divinyl monomers that are derivatives.
Among them, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, (Meth) acrylic acid ester monomers such as 6-hexanediol di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, polyester acrylate, etc. Is preferable in that it has low skin irritation and is easy to handle. These crosslinkable monomers can be used alone or in combination of two or more.
A crosslinkable monomer is mix | blended so that 10-40 weight% may occupy in the monomer mixture which forms a coating layer. When the crosslinkable monomer is less than 10% by weight, the irregularly shaped particle powder obtained after drying tends to coalesce, which is not preferable. On the other hand, if the crosslinkable monomer exceeds 40% by weight, the coating layer becomes hard and the soft feel is impaired, which is not preferable.

As the polymerization initiator used in the second step, an oil-soluble peroxide-based or azo-based one used for usual suspension polymerization can be used. Examples of the peroxide polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl orthochloroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile, 2,2′-azobis (2-methylbutyronitrile), etc. These oil-soluble polymerization initiators may be used alone or in combination of two or more.
Although the usage-amount of this polymerization initiator is not specifically limited, Usually, what is necessary is just to be 0.01-3 weight% with respect to a monomer.

Examples of the surfactant used in the second step include anionic surfactants such as sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene lauryl ether sulfate, and sodium dioctyl sulfosuccinate. Is mentioned.
These surfactants are used by mixing in an aqueous solution so as to have a concentration equal to or higher than the critical micelle concentration. The critical micelle concentration (CMC) of the sodium dodecylbenzenesulfonate is 0.08%, and the critical micelle concentration (CMC) of sodium lauryl sulfate is 0.23%.

  For example, as shown in the photograph of FIG. 1 (an electron micrograph of the amorphous particle powder obtained in Example 1 described later), the amorphous particle powder obtained by such a production method has a polymer particle as a nucleus. It is coated with a coating layer composed of a cross-linked acrylic ester resin, and many of them are particles that are joined by about 2 to 5 through the coating layer, and the sphericity of the whole powder is 0.6 to 0.8. , An amorphous particle powder having an average particle diameter of 5 to 30 μm.

In the present invention, the average particle diameter of the amorphous particle powder means a volume average particle diameter measured by a Coulter counter method.
The Coulter counter method is a method of measuring the particle diameter by an electric resistance method called the Coulter principle. Specifically, this method is based on placing an electrode on both sides of the aperture (pore) of the aperture tube in the electrolyte and passing a current to suspend the particles to be measured in the electrolyte, followed by electrolysis with a manometer from inside the aperture tube. When the liquid is sucked and passes through the aperture, the electrolyte corresponding to the particle volume is replaced, and resistance is generated between both electrodes, but this resistance change is proportional to the volume of the particle passing through the aperture. This is a method of obtaining the volume average particle diameter of the particle diameter by detecting and calculating.
Specifically, according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited, calibration was performed using an aperture having a diameter of 100 μm and measurement was performed. More specifically, a particle size measuring apparatus composed of Coulter Multisizer II and Sampling Stand IIA (manufactured by Beckman Coulter, Inc.) is used, and 0.1 g of particles is added to 10 ml of 0.1% nonionic surfactant solution. Preliminarily disperse using a touch mixer and ultrasonic wave inside, and drop it with a dropper while gently stirring in a beaker filled with ISOTON II (manufactured by Beckman Coulter, Inc .: measurement electrolyte) equipped with the main body, After adjusting the concentration meter reading on the main unit screen to around 10%, input the aperture size, Current, Gain, and Polarity into the Multisizer II main unit according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited. The measurement was performed. During the measurement, the beaker was gently stirred to the extent that no bubbles were introduced, and the measurement was completed when 100,000 particles were measured.

In the present invention, the sphericity of the irregular-shaped particle powder is determined by calculating the ratio of the shortest diameter / longest diameter based on the image data of the particles, and the average of the ratios of the shortest diameter / longest diameter obtained for 500 or more particles. Value.
Specifically, an image of the particle is obtained, and the ratio of the shortest diameter / longest diameter is obtained by reading the longest diameter and the shortest diameter of the particles from the image data, and 500 or more particles are obtained for one type of irregularly shaped particle powder. The average value of the ratio of the shortest diameter / longest diameter of the particles is calculated to obtain the sphericity of the irregular shaped particle powder. Therefore, the closer the sphericity is to 1, the more the powder is made of particles closer to a sphere.
As a method for obtaining image data of particles, for example, when particles pass through apertures (pores) of the aperture tube used when measuring the average particle diameter, a multi-image analyzer (manufactured by Beckman Coulter, Inc.) is used. A method of acquiring image data for each particle can be employed.

  Examples of the solid powder cosmetic containing the amorphous particles of the present invention include fungi, foundations, lipsticks, lip balms, blushers, eyebrow cosmetics, nail polish and the like. The content of the irregularly shaped particle powder in the solid powder cosmetic is preferably about 0.5 to 50% by weight, more preferably 1.0 to 20% by weight. When the content of the amorphous particle powder is less than 0.5% by weight, the effect is not clearly recognized. Conversely, even when the content is more than 50% by weight, the effect is commensurate with the increased amount. Is not preferable because it is not recognized.

  The amorphous particle powder of the present invention may be previously treated with a surface treatment agent such as an oil agent, a silicone compound and a fluorine compound, an organic powder, an inorganic powder or the like before being used in a solid powder cosmetic.

As the oil agent, any oil agent can be used as long as it is usually used for external preparations. For example, liquid oil such as liquid paraffin, squalane, petrolatum, paraffin wax, lauric acid, myristic acid, palmitic acid, stearic acid, olein Acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, synthetic fatty acids and higher fatty acids, glyceryl trioctanoate, propylene glycol dicaprate, cetyl ethyl hexanoate, isocetyl stearate, beeswax, Waxes such as whale wax, lanolin, carnauba wax, candelilla wax, oilseed such as linseed oil, cottonseed oil, castor oil, egg yolk oil, coconut oil, metal soaps such as zinc stearate and zinc laurate, cetyl alcohol stearyl alcohol, Oleil Arco Higher alcohols such as Le like.
The method of treating the amorphous particle powder with an oil agent is not particularly limited. For example, a dry method in which an oil agent is added to the amorphous particle powder and the oil agent is coated by stirring with a mixer or the like, or the oil agent is ethanol, propanol, It is possible to use a wet method or the like that coats an oil agent by heating and dissolving in a suitable solvent such as ethyl acetate, hexane, etc., adding amorphous particles to it, mixing and stirring, and then removing the solvent under reduced pressure or removing it by heating. it can.

Any silicone compound may be used as long as it is usually used for external preparations. For example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acrylic-silicone graft polymer, and organic silicone resin partially crosslinked. Type organopolysiloxane polymer.
The method for treating the amorphous particle powder with the silicone compound is not particularly limited, and for example, the dry method or the wet method described above can be used. In addition, if necessary, a baking treatment may be performed, or in the case of a reactive silicone compound, a reaction catalyst or the like may be added as appropriate.

  The fluorine compound may be any compound as long as it is usually blended in an external preparation, and examples thereof include perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, and polymers having a perfluoro group. . A method for treating the amorphous particle powder with the fluorine compound is not particularly limited, and for example, the dry method or the wet method described above can be used. In addition, if necessary, a baking treatment may be performed, or in the case of a reactive silicone compound, a reaction catalyst or the like may be added as appropriate.

  Examples of the organic powder include gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, casein and other natural polymer compounds, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, Semi-synthetic polymer compounds such as ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, Nylon particles, polymethyl methacrylate particles, cross-linked polystyrene particles, silicon particles, urethane particles, polyester Ren particles include resin particles such as fluorine particles.

  Examples of the inorganic powder include iron oxide, ultramarine blue, salmon, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, and silicic acid. Examples thereof include aluminum, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, hydroxyapatite, and ceramic powder.

  These organic powders and inorganic powders may be subjected to surface treatment in advance. As the surface treatment method, a known surface treatment technique as described above can be used.

  Furthermore, if it is a range which does not impair the effect of this invention, the normal additive generally used for the external preparation can be mix | blended according to the objective. Examples of such components include water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymer compounds, and coloring materials. Examples include raw materials, fragrances, antiseptic / bactericides, antioxidants, ultraviolet absorbers, and other special ingredients.

  Oils and waxes include avocado oil, almond oil, olive oil, cacao oil, beef tallow, sesame oil, wheat germ oil, safflower oil, shea butter, turtle oil, persimmon oil, persic oil, castor oil, grape oil, macadamia nut oil , Mink oil, egg yolk oil, owl, palm oil, rosehip oil, hydrogenated oil, silicone oil, orange luffy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like. Examples of hydrocarbons include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane and the like.

  Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acid. Higher alcohols include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyl decanol, isostearyl alcohol, jojoba alcohol, decyltetradecane And the like.

  Examples of sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like.

  Fatty acid esters include ethyl linoleate, isopropyl myristate, lanolin fatty acid isopropyl, hexyl laurate, myristyl myristate, cetyl myristate, octyldodecyl myristate, decyl oleate, octyldodecyl oleate, hexyldecyl dimethyloctanoate, isooctane Cetyl acid, decyl palmitate, glyceryl trimyristate, glycerin tri (capryl / capric acid), propylene glycol dioleate, glyceryl triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate, isostearic acid Examples thereof include cyclic alcohol fatty acid esters such as cholesteryl and cholesteryl 12-hydroxystearate.

  Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc undecylenate and the like.

  Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylit, maltitol and the like.

  Surfactants include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, cationic surfactants such as amine salts and quaternary ammonium salts, betaines Type, amino acid type, imidazoline type, amphoteric surfactant such as lecithin, nonionic surfactant such as fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate Can be mentioned.

  Examples of the polymer compound include gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, casein and other natural polymer compounds, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropylcellulose, crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles , Polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, polyethylene Child, synthetic polymer compounds such as resin particles of the silica particles and the like.

  Color material raw materials include iron oxide, ultramarine, conger, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, Barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, hydroxyapatite, ceramic powder and other inorganic pigments, azo, nitro, nitroso, xanthene And tar dyes such as quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.

  Note that powder materials such as powder materials and color material materials of the polymer compound that have been surface-treated in advance can be used. As a surface treatment method, known surface treatment techniques can be used, for example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. Fluorine compound treatment with perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether and polymer having perfluoroalkyl group, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. Silane coupling agent treatment with isopropyl triisostearoyl titanate, Titanium coupling agent treatment with isopropyl tris (dioctylpyrophosphate) titanate, metal soap treatment, acylgluta Amino treatment with phosphate and the like, lecithin treatment with hydrogenated egg yolk lecithin, collagen treatment, polyethylene process, moisture retention treatment, an inorganic compound treatment, and processing methods such as mechanochemical treatment.

  Examples of the fragrance include anisaldehyde, benzyl acetate, geraniol and the like. Examples of the antiseptic / bactericidal agent include methylparapen, ethylparapen, propylparapen, benzalkonium, and benzethonium.

  Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like. Ultraviolet absorbers include inorganic absorbents such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle iron oxide, fine particle zirconium oxide, benzoic acid-based, paraaminobenzoic acid-based, anthranilic acid-based, salicylic acid-based And organic absorbents such as cinnamic acid, benzophenone and dibenzoylmethane.

  Special blending ingredients include, for example, hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, Skin astringents such as aluminum sulfate / potassium sulfate, allantochlorohydroxyalumonium, zinc paraphenolsulfonate, zinc sulfate, cantalis tincture, pepper tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid Examples include hair growth promoters such as glycerides, vitamin E, estrogens, and photosensitizers, and whitening agents such as phosphoric acid-L-magnesium ascorbate.

(Example 1)
<First step> 2900 g of water, 90 g of tricalcium phosphate, 1 g of sodium dodecyl sulfate, 999 g of styrene, 1 g of divinylbenzene and 9 g of benzoyl peroxide are put into a 5 liter autoclave equipped with a stirrer. Dispersed with a TK-homomixer manufactured by Co., Ltd. into droplets of about 6 μm. Subsequently, the suspension polymerization was continued under a nitrogen stream at 70 ° C. for 8 hours to obtain polymer particles. The average particle diameter of the polymer particles was 5.8 μm.
<Second step> 22 g of butyl acrylate, 8 g of ethylene glycol dimethacrylate, and 0.3 g of benzoyl peroxide are put into 30 g of water in which 0.15 g of sodium lauryl sulfate is dissolved, and this monomer mixture is mixed with an ultrasonic homogenizer. The oil droplets were dispersed to a particle size of about 2 μm or less.
Further, 320 g of the aqueous dispersion medium of the polymer particles obtained in the first step was taken into a separable flask having a capacity of 500 cc, and the dispersion of the monomer mixture was continuously added to the flask at 50 ° C. for 5 minutes. The weight ratio of polymer particles: coating layer was 73:27.
<Third Step> After completion of the dropping, the temperature was raised to 65 ° C. and polymerized for 5 hours. Thereafter, the temperature was raised to 90 ° C., and the reaction was further continued for 3 hours. Then, after cooling and adding hydrochloric acid to dissolve the tricalcium phosphate, it was washed with water, dehydrated, and dried in an oven at 60 ° C. for 1 day.
The average particle diameter of the amorphous particle powder obtained as described above was 8.9 μm, and the sphericity was 0.76. In addition, the electron micrograph of the obtained amorphous particle powder is shown in FIG.

(Example 2)
Amorphous particle powder was obtained in the same manner as in Example 1 except that the polymerization was performed without adding divinylbenzene, which is a crosslinkable monomer, in the production of the polymer particles in the first step. The obtained amorphous particle powder had an average particle size of 9.2 μm and a sphericity of 0.70.

(Example 3)
In the second step, amorphous particle powder was obtained in the same manner as in Example 1 except that the proportion of the crosslinkable monomer in the monomer mixture was 40% by weight. The obtained amorphous particle powder had an average particle size of 8.6 μm and a sphericity of 0.78.

(Example 4)
In the second step, amorphous particle powder was obtained in the same manner as in Example 1 except that the ratio of the crosslinkable monomer in the monomer mixture was changed to 12% by weight. The obtained amorphous particle powder had a volume average particle diameter of 9.0 μm and a sphericity of 0.76.

(Example 5)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the weight ratio of the polymer particles to the coating layer was 95: 5 when adding the emulsion of the monomer mixture. . The obtained amorphous particle powder had an average particle size of 6.3 μm and a sphericity of 0.79.

(Example 6)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the weight ratio of polymer particles: coating layer was set to 70:30 when the emulsion of the monomer mixture was added. . The obtained amorphous particle powder had a volume average particle diameter of 10.2 μm and a sphericity of 0.74.

(Example 7)
In the production of the polymer particles in the first step, the amorphous particle powder was prepared in the same manner as in Example 1 except that the polymerizable monomer was 999 g of methyl methacrylate and the crosslinkable monomer was 1 g of ethylene glycol dimethacrylate. Obtained. The obtained amorphous particle powder had a volume average particle diameter of 8.8 μm and a sphericity of 0.75.

(Example 8)
In the production of polymer particles in the first step, the polymerizable monomer is 999 g of methyl methacrylate, the crosslinkable monomer is 1 g of ethylene glycol dimethacrylate, and the acrylic ester monomer of the emulsion in the second step. Was obtained in the same manner as in Example 1 except that 17 g of butyl acrylate, 2 g of 2-ethylhexyl acrylate, 3 g of methyl acrylate, and 8 g of ethylene glycol dimethacrylate as the crosslinkable monomer were obtained. The obtained amorphous particle powder had an average particle size of 9.0 μm and a sphericity of 0.77.

Example 9
In the production of polymer particles in the first step, the polymerizable monomer is 999.5 g of butyl acrylate, the crosslinkable monomer is 0.5 g of ethylene glycol dimethacrylate, and the acrylate ester in the second step is a single amount. An amorphous particle powder was obtained in the same manner as in Example 1 except that the body was changed to 13 g of butyl acrylate, 2 g of 2-ethylhexyl acrylate, 3 g of methyl acrylate, and 12 g of ethylene glycol dimethacrylate. The obtained amorphous particle powder had an average particle size of 9.3 μm and a sphericity of 0.79.

(Comparative Example 1)
Example 1 except that polymer particles were produced in the first step by polymerizing with a composition of 2850 g water, 80 g tricalcium phosphate, 1.2 g sodium dodecyl sulfate, 996 g styrene, 4 g divinylbenzene and 5 g benzoyl peroxide. In the same manner, an amorphous particle powder was obtained. The obtained amorphous particle powder had an average particle size of 5.5 μm and a sphericity of 0.92. In addition, the electron micrograph of the obtained amorphous particle powder is shown in FIG.

(Comparative Example 2)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the weight ratio of polymer particles: coating layer was 97: 3 when adding the emulsion of the monomer mixture. . The obtained amorphous particle powder had an average particle size of 5.8 μm and a sphericity of 0.90.

(Comparative Example 3)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the weight ratio of the polymer particles to the coating layer was 60:40 when adding the emulsion of the monomer mixture. . The obtained amorphous particle powder had an average particle size of 13.5 μm and a sphericity of 0.88.

(Comparative Example 4)
An amorphous particle powder was obtained in the same manner as in Example 1 except that the average particle size of the polymer particles produced in the first step was changed to 22 μm. The obtained amorphous particle powder had an average particle size of 35 μm and a sphericity of 0.85.

(Comparative Example 5)
An amorphous particle powder was obtained in the same manner as in Example 1 except that the average particle size of the polymer particles produced in the first step was 1.5 μm. The obtained amorphous particle powder had an average particle size of 3.8 μm and a sphericity of 0.78.

(Comparative Example 6)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the ratio of the crosslinkable monomer in the monomer mixture was 9% by weight. The obtained amorphous particle powder had an average particle size of 9.2 μm and a sphericity of 0.72.
The obtained particles were not only inferior in sensory evaluation and impact resistance, as described later, but also the particles were too soft, resulting in coalescence of particles after drying and poor handling properties.

(Comparative Example 7)
In the second step, an amorphous particle powder was obtained in the same manner as in Example 1 except that the proportion of the crosslinkable monomer in the monomer mixture was 50% by weight. The obtained amorphous particle powder had an average particle size of 8.8 μm and a sphericity of 0.79.

(Comparative Example 8)
Using a special machine-made desktop TK homomixer (rotation speed: 6000 rpm), the oil phase (ethyl acrylate 90 parts by weight, 1,6-hexanediol dimethacrylate 10 parts by weight, benzoyl peroxide 0.5 parts by weight) After being dispersed in an aqueous phase (400 parts by weight of deionized water, 8 parts by weight of polyvinyl alcohol having a saponification degree of 85%, 0.04 parts by weight of sodium lauryl sulfate), the dispersion is placed in a polymerization vessel equipped with a stirrer and a thermometer. The suspension polymerization was completed by continuing stirring at 70 ° C. for 10 hours. After cooling, the suspension was filtered and washed to obtain spherical resin particles having an average particle size of 8.3 μm. The dehydrated cake after filtration and washing is placed in a rotary vacuum dryer equipped with a stirring blade, and after adding spherical silicon resin fine particles (TOSpearl 105 manufactured by Toshiba Silicon Corporation, average particle size 0.5 μm), stirring is performed at a peripheral speed of 3 m / s. After drying, classification was performed to obtain a particle powder in which silicon resin particles adhered to the surface of the crosslinked acrylic ester. The average particle size was 8.5 μm, and the sphericity was 0.93.

(Comparative Example 9)
A dispersion medium in which 20 g of magnesium pyrophosphate was produced by metathesis method was added to 200 g of water in a 500 ml separable flask, and 0.25 g of sodium lauryl sulfate was dissolved therein. Separately from this, a monomer composition obtained by uniformly mixing and dissolving 80 g of styrene, 20 g of dimethylpolysiloxane (viscosity 1000 cSt (25 ° C.)) and 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile). Was added to the above dispersion medium. This mixture was finely dispersed at 10,000 rpm for about 10 seconds using a homomixer (ULTRA TURRAX T-25 manufactured by IKA). The flask was equipped with a stirring blade, a thermometer and a condenser, and placed in a 60 ° C. water bath. After sufficiently replacing the inside of the flask with nitrogen gas, heating was continued at a stirring speed of 200 rpm for 10 hours to carry out a polymerization reaction. After confirming that the polymerization reaction was completed, the reaction solution was cooled, and hydrochloric acid was added until the pH of the slurry was about 2, to decompose the dispersant. The particles were suction filtered through a Buchner funnel with filter paper and washed with 1.2 liters of ion exchange water to remove the dispersant. The dehydrated cake after suction filtration was dried and then dispersed in cyclohexane, and suction filtration was repeated several times to obtain resin particles.
When the resin particles are observed with an electron microscope, unlike a particle shape formed by coalescing a plurality of polymer particles serving as nuclei as in the present invention, one convex curved surface and one concave curved surface are both. The particle shape appeared in the same direction across the boundary line. The obtained particle powder had an average particle size of 8.2 μm and a sphericity of 0.66.

(1) Evaluation of amorphous particles (A) Average particle diameter The average particle diameter of the powders obtained in Examples and Comparative Examples is the Coulter counter method using the above-mentioned Coulter Multisizer II (manufactured by Beckman Coulter, Inc.). Asked.
(B) Sphericity The sphericity of the powders obtained in the examples and comparative examples was determined by image analysis using the above-mentioned multi-image analyzer (manufactured by Beckman Coulter) etc. It calculated | required as an average value of the ratio of the longest diameter.
(C) Coefficient of friction of particles The coefficient of friction of particles was measured as an index for evaluating the difficulty of rolling particles (the rolling effect is small). The coefficient of friction when the surface of artificial skin (Beaulux Bio Skin Plate) with a cosmetic puff applied with a fine particle is rubbed at a constant speed with an indenter is used as a friction tester (made by Kato Tech, KES-SE) was used to determine the average coefficient of friction (MIU) in an environment with an air temperature of 20 ° C. and a relative humidity of 65%.
The average coefficient of friction (MIU) represents the slip property of the surface, and the smaller the value, the easier the particles to roll.

(2) Evaluation by solid powder cosmetic (powder foundation) A powder foundation was prepared by blending the irregular shaped particle powders prepared in Examples and Comparative Examples, and an impact resistance test and a sensory test by 10 panelists were performed.
Preparation of solid powder cosmetic (powder foundation) Prescription irregular shaped powder 15 parts by weight Talc 21 parts by weight Mica mica 51 parts by weight Red iron oxide 0.6 parts by weight Yellow iron oxide 1 part by weight Black iron oxide 0.1 part by weight 2 -Cetyl ethylhexanoate 10 parts by weight Sorbitan sesquioleate 1 part by weight Preservative 0.2 part by weight Fragrance 0.1 part by weight
Preparation procedure of solid powder cosmetics Based on the above formulation, resin particles, talc, muscovite, red iron oxide, yellow iron oxide, black iron oxide are mixed with a Henschel mixer, and this is mixed with cetyl 2-ethylhexanoate, sorbitan A sesquioleate and preservative mixed and dissolved were added and mixed uniformly.
After adding perfume and mixing, pulverize and pass through a 100 mesh screen, weigh 7g and fill it into an aluminum dish with an outer diameter of 58mm, an inner diameter of 57mm, a depth of 4.5mm, and a weight of 3.63g. Then, using a hydraulic hand press, uniaxial pressure was applied for 1 minute at a pressure of 120 kg / cm 2 to obtain a solid powder cosmetic (powder foundation).

Evaluation method of solid powder cosmetics The solid powder cosmetics prepared as described above were evaluated by performing sensory evaluation on usability and impact resistance tests of the solid powder cosmetics.
(A) Sensory evaluation method of feeling of use Regarding the prepared solid powder cosmetics, the feeling of softness (feeling of feeling felt when stretching to the face using a puff), the feeling of close contact with the skin, and the presence of particles with respect to the prepared solid powder cosmetics. A sensory test on roughness was performed. About evaluation of each item, it was set as the average value of 10 persons when 5-step evaluation was performed on the following criteria. In addition, the average value of each item was a value obtained by rounding off the second decimal place of the arithmetic average.
1 ... Bad 2 ... Somewhat bad 3 ... Normal 4 ... Somewhat good 5 ... Good And, for sensory evaluation, the average value of each item is totaled, and the score is 11 or more, and the score is Those less than 11 were judged as x. The perfect score is 15 points. However, if at least one of the three items had an average value of 1.9 or less, it was marked as x.
○ …… Total 11 or more × …… Total 11 or less.

(B) Evaluation method of impact resistance Six solid powder cosmetics filled in an aluminum dish as described above are prepared for each Example and each Comparative Example, and the bottom of the aluminum dish is directed downward to 50 cm. Free fall from a height onto a concrete floor. This dropping operation was repeated for each test piece until cracks and cracks occurred on the cake surface, and the number of drops required for cracks and cracks occurring on the cake surface was determined. Then, this test was performed on all six test pieces for each example and comparative example, and an arithmetic average of four measured values excluding the maximum value and the minimum value was obtained. The larger the value, the higher the impact resistance, and the ability to withstand two or more drops was regarded as a pass criterion.

(C) Comprehensive evaluation The judgment of the sensory evaluation result regarding usability was "good", and the thing which endured two or more drops in the impact resistance test was "good".
The results are shown in Table 1.

  As shown in Table 1, when the amorphous particle powder of the example of the present invention is used, it has a feeling of use (soft feeling, adhesion feeling, graininess) which is an advantage when the cross-linked polyacrylate is used. And it turns out that the solid powder cosmetics excellent in the impact resistance which are hard to produce a crack also when dropped are obtained.

  The irregularly shaped particle powder of the present invention can be used as a solid powder cosmetic such as a funny product, foundation, lipstick, lip balm, blusher, eyebrow cosmetics, nail polish, and paint.

4 is an electron micrograph of the irregular shaped particle powder of Example 1. FIG. The electron micrograph of the irregular-shaped particle powder of the comparative example 1.

Claims (3)

  A coating layer that is formed by polymerizing a polymer mixture and a monomer mixture containing 10 to 40% by weight of a crosslinkable monomer and an acrylate monomer, and coats the polymerizable particle; Amorphous particle powder characterized by having a sphericity of 0.6 to 0.8 and an average particle diameter of 5 to 30 μm by fusing together a plurality of the polymer particles via .   The amorphous particle powder according to claim 1, wherein a weight ratio of the polymer particles to the coating layer is 95: 5 to 70:30.   A solid powder cosmetic comprising the irregular shaped particle powder according to claim 1.