JP2000302624A - Acrylic acid ester-based resin particle and external preparation containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain acrylic acid ester-based resin particles giving excellent touch (smoothness, a soft feel and spread) and effect (good adherence to the skin), and to obtain an external preparation containing the resin particles. SOLUTION: The acrylic acid ester-based resin particles comprise crosslinked (meth)acrylic acid ester-based resin particles having an average particle diameter of 0.5-100 μm and a compressive strength of 0.05-0.6 kgf/mm2 in an amount of 100 pts.wt. and organic resin fine particles having an average particle diameter of 1/1000 to 1/5 time the average particle diameter of the resin particles in an amount of 3-40 pts.wt., and adhering the organic resin fine particles to the surfaces of the resin particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to acrylate resin particles and an external preparation containing the same. More specifically, the present invention relates to an acrylic acid which imparts an extremely excellent feel (smoothness, softness, elongation) and an effect (good skin adhesion, wrinkle concealing effect) especially when used in an external preparation. The present invention relates to an ester-based resin particle and an external preparation containing the same. The resin particles of the present invention can be suitably used for external agents such as cosmetics and external medicines, and additives for paints and molding compositions.

[0002]

2. Description of the Related Art Cosmetics containing cosmetic powder include:
Makeup cosmetics such as foundation, white powder, blusher, eye shadow, etc., body cosmetics such as body powder and baby powder, lotions such as pre-shave lotion, body lotion and after-shave lotion are commercially available.

[0003] In cosmetics containing these cosmetic powders, nylon particles and polymethyl methacrylate particles are used for the purpose of imparting functions such as improvement of elongation on the skin, improvement of feel and wrinkle hiding effect. And resin particles such as crosslinked polystyrene particles, silicon particles, urethane particles and polyethylene particles, and inorganic particles such as silica particles.

[0004]

However, polymethyl methacrylate particles, cross-linked polystyrene particles, and silica particles are satisfactory in terms of excellent elongation, but on the other hand, have a soft touch and a smooth touch. Was not able to be given, and it was insufficient.

[0005] Further, nylon particles and silicon particles can give a smooth feel, but are insufficient in that they give a soft feel.

[0006] On the other hand, soft particles such as urethane particles and polyethylene particles are smaller than nylon particles, polymethyl methacrylate particles, cross-linked polystyrene particles and silica particles.
It is possible to give soft feel to cosmetics,
It was insufficient in providing smoothness.

[0007] Accordingly, there has hitherto not been any resin particles that are satisfactory in imparting elongation, smoothness and softness to cosmetics. Further, in the field of external medicines in the form of creams, ointments, emulsions and lotions, it is desired to impart elongation, smoothness and softness to the external medicines.

[0008]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that crosslinked (meth) acrylate-based resin particles having a specific average particle size and compressive strength have been obtained. When resin particles containing organic resin particles with a specific average particle diameter attached to the surface of the external preparation are applied to the surface, not only excellent feel (elongation, smoothness, softness) but also surprisingly excellent skin The present invention was found to have an adhesive property and a wrinkle concealing effect, and completed the present invention. Furthermore, they have found that the resin particles are also useful as additives for paints and molding compositions.

Thus, according to the present invention, the average particle size is 0.5 to 100 μm, and the compressive strength is 0.05 to 0.6 kg.
100 parts by weight of crosslinked (meth) acrylate-based resin particles (hereinafter simply referred to as resin particles) having an average particle diameter of 1/1000 to 1/5 of the resin particles having an f / mm ² of An acrylic acid ester-based resin particle (hereinafter, also referred to as a compounding agent) comprising 3 to 40 parts by weight and comprising organic resin fine particles adhered to the surface of the resin particle is provided.

Further, according to the present invention, the above-mentioned compounding agent is used in an amount of 1 to 6
An external preparation characterized by containing 0% by weight is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The resin particles used in the acrylate resin particles of the present invention are 0.05 to 0.6 kgf.
/ Mm ² .

When the compressive strength is less than 0.05 kgf / mm ² , the feeling of the resin particles is not felt, and
When included in paints and molding compositions (hereinafter referred to as inclusion target), its feel (elongation, smoothness, softness)
Is not preferred because it cannot be improved. on the other hand,
If it exceeds 0.60 kgf / mm ² , on the contrary, the feel of the resin particles is felt, but the feel is close to that of conventional resin particles, and sufficient soft feeling, smoothness, and elongation can be imparted to the contained object. It is not preferable because it cannot be done.

[0013] The compressive strength mentioned here is measured by Shimadzu Corporation.
It is a value measured by using a micro compression tester HCTM200 manufactured by Toshiba Corporation. That is, when one resin particle is subjected to a compression test at a constant load speed up to a load of 1 gf, a particle diameter of 1
It is a value calculated by the following equation from the load and the particle size at the time of 0% deformation.

Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / ｛π × particle diameter (mm) × particle diameter (m
m)｝ In the present invention, the resin particles are (meth)
It can be obtained by polymerizing an acrylate monomer by aqueous suspension polymerization, emulsion polymerization, seed polymerization or dispersion polymerization. Among these, from the viewpoint that resin particles can be easily obtained, it is preferable to produce by an aqueous suspension polymerization method. The term (meth) acryl is a concept including both acryl and methacryl.

As the (meth) acrylic ester monomer, it is preferable to use an oil-soluble monomer. Furthermore,
It is preferable to use a (meth) acrylic acid ester-based monomer having 1 to 12 carbon atoms in a substituent forming an ester bond with (meth) acrylic acid. Specifically, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,
Examples include acrylates such as lauryl acrylate, methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. . In particular, it is preferable to use an acrylate having 1 to 8 carbon atoms. Further, it is preferable that this acrylate is contained in a proportion of 50 to 95% by weight based on all monomers.

Further, monomers copolymerizable with (meth) acrylic acid ester monomers, for example, other monomers having a vinyl group such as styrene, p-methylstyrene, α-methylstyrene and vinyl acetate May be added as long as the performance of the obtained resin particles is not deteriorated.

Further, the resin particles used in the present invention are used for imparting a desired compressive strength and for containing objects (particularly,
(Cosmetics) in order to give a favorable feel (elongation, smoothness, softness).

In order to obtain crosslinked resin particles, a polymerization reaction is carried out in the presence of a crosslinkable monomer having a plurality of vinyl groups.

Examples of such crosslinkable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and pentadecaethylene. Glycol di (meth) acrylate, pentacontaector ethylene 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, allyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) phthalate (Meth) acrylate monomers such as acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, polyester acrylate, urethane acrylate, divinylbenzene, divinylnaphthalene And aromatic divinyl monomers which are derivatives thereof. These may be used alone or in combination of two or more.

Among these crosslinking agents, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butanediol dimethacrylate, 1,6-
Methacrylate crosslinkers such as hexanediol dimethacrylate, and caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, and polyester acrylate have low skin irritation, and are used for cosmetics and external medicines. Especially suitable for The crosslinking agent is preferably used in an amount of 5 to 50% by weight based on all the monomers.

These monomers and cross-linking agents may be used alone or in combination of two or more.
5 to 0.6 kgf / mm ² , preferably 0.1 to 0.4
Their composition and amount are determined so as to be kgf / mm ² .

Further, a coloring pigment may be contained in the resin particles. By including a color pigment in the resin particles,
It occurred when simply mixing resin particles and color pigments,
Aggregation of the color pigment and uneven color during use due to a significant change in color due to change from dry powder to wet powder can be prevented.

It is preferable to use a coloring pigment which is hardly soluble in a solvent phase and an oil phase used for polymerizing the resin particles.

Examples of the coloring pigment include titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, iron oxide, iron hydroxide, chromium oxide, chromium hydroxide, ultramarine, navy blue, manganese violet, ultramarine purple, titanium black, carbon black, Aluminum powder, mica titanium, bismuth oxychloride, iron oxide treated mica titanium, navy blue treated mica titanium,
Inorganic such as carmine treated mica titanium, silica, calcium carbonate, magnesium carbonate, barium sulfate, barium silicate, calcium silicate, magnesium silicate, calcium phosphate, hydroxyapatite, zeolite, alumina, talc, mica, bentonite, kaolin and sericite Aluminum lakes such as pigments, tartrazine, sunset erotic FCF, brilliant blue FCF, zirconium lake, barium lake, herringdon pink C
And organic pigments such as N, litholrubin BCA, lake red CBA, phthalocyanine blue, and permanent orange. These color pigments may be used alone or in combination.

The content of the coloring pigment in the resin particles is preferably from 1 to 70% by weight of the total weight. If the content is 1% by weight or less, the effect of blending the coloring pigment becomes extremely thin, which is not preferable. On the other hand, if the content is 70% by weight or more, in the stage of producing the dispersion before polymerization, the amount of the color pigment relative to the resin monomer is too large, the viscosity of the dispersion becomes extremely high, and the production of the resin particles becomes difficult. It is not preferable.

The method for dispersing the color pigment is not particularly limited, but carboxylic acid, sulfonic acid, sulfate ester, phosphate ester, and phosphonic acid, and salts thereof, and coupling agents such as silane, titanate, and aluminate are used. And then subjecting the surface of the pigment to hydrophobic treatment and then adding the resultant to a polymerization system. The amount of the hydrophobizing agent added to the pigment is preferably 0.1 to 30% by weight.

The apparatus for dispersing the color pigment is not particularly limited as long as it can give a sufficient dispersion energy to the dispersion system. For example, a ball mill, a sand mill, an ultrasonic disperser, a homogenizer and the like can be mentioned.

In forming the resin particles, a polymerization initiator, a dispersant, a surfactant and the like are used as necessary.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoic peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide and the like. Examples thereof include oil-soluble peroxides, oil-soluble azo compounds such as 2,2'-azobisisobutyronitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile).

Examples of the dispersant include poorly water-soluble inorganic salts such as calcium phosphate and magnesium pyrophosphate, and water-soluble polymers such as polyvinyl alcohol, methyl cellulose and polyvinyl pyrrolidone.

Further, examples of the surfactant include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkyl naphthalene sulfonate and alkyl phosphate ester salts, polyoxyethylene alkyl ether, Nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, and glycerin fatty acid ester; amphoteric surfactants such as lauryl dimethylamine oxide And the like.

These dispersants and surfactants may be used alone or in combination of two or more.

The addition amount of the polymerization initiator to the monomer is as follows:
0.1 to 1% by weight, the addition ratio of the dispersant to the monomer is 0.5 to 10% by weight, and when a surfactant is used, 0.01 to 0.2% by weight based on water. Is preferred.

Next, the polymerization reaction is started by mixing the resin monomer phase and a solvent phase (for example, an aqueous phase) and then increasing the temperature while stirring. The polymerization initiation temperature is preferably from 40 to 90 ° C. Then, it is preferable that the polymerization is generally performed for about 1 to 10 hours while maintaining the temperature.

At this time, the average particle size of the resin particles can be appropriately determined by controlling the mixing conditions and the stirring conditions of the monomer and the solvent. The control of the mixing conditions and the stirring conditions is, for example, using a homogenizer, an emulsifying and dispersing machine utilizing a high shear applied to the gap between the rotating blades and the machine wall or the rotating blades, or dispersing using an ultrasonic dispersing device or the like. Alternatively, it can be carried out by pressurizing a monomer aqueous solution through a ceramic microporous membrane and inserting it into a dispersion medium.

As the resin particles, those having an average particle diameter of 0.5 to 100 μm are used. If it is less than 0.5 μm or more than 100 μm, the feel of the contained object is undesirably deteriorated. Further, the average particle diameter referred to herein means a particle diameter measured by a Coulter counter method.

After completion of the polymerization, the dispersing agent is decomposed with an acid or the like, if necessary, and filtered, washed, dried, pulverized and classified to obtain a crosslinked (meth) acrylic ester resin which is the object of the present invention. Particles can be obtained. In addition, the method described in JP-A-3-37201 may be used for producing the crosslinked (meth) acrylate-based resin particles themselves.

The acrylate resin particles of the present invention are obtained by adhering organic resin fine particles having a specific average particle diameter to the surface of the resin particles thus obtained.

The above-mentioned organic resin fine particles prevent the coalescence of the resin particles during the production of the resin particles, and have a good feeling peculiar to the resin particles when blended with the contained object. Used to demonstrate

As the organic resin fine particles, for example, polyamide resin, polyolefin resin, acrylic resin,
Fine particles such as a cellulose resin, a polystyrene resin, a silicon resin, a fluorine resin, and a hydrophobic resin may be used.

Among the above organic resin fine particles, spherical fine particles of silicon-based resin and fluorine-based resin are more preferable because of their excellent water repellency and oil repellency, and particularly excellent touch. Furthermore, these fine particles have an excellent effect to hide wrinkles because of their high adhesion to the skin and high scattering of light rays, although unexpectedly, beyond these effects.

Since the resin particles used in the present invention have a low compressive strength, they can be adhered to the surface of the resin particles by adding and mixing a specific amount of organic resin fine particles having a specific average particle size. It is possible to exhibit extremely good performance while making use of the unique feel possessed by.
There is no deterioration in the feel that is observed when organic resin fine particles are added to and mixed with particles having high compressive strength.

The average particle diameter of the organic resin fine particles is preferably 1/1000 to 1/5 of the resin particles.
It is preferably 1/500 to 1/10. When the average particle diameter is less than 1/1000 or exceeds 1/100,
The effect of preventing the coalescence of the resin particles is reduced, and it is not preferable because good feel (elongation, smoothness, soft feeling) and adhesion to the skin cannot be obtained when blended with the contained object. More specifically, the average particle size of the organic resin fine particles is preferably 0.1 to 10 μm.

The average particle diameter referred to herein means an average particle diameter measured by a Coulter method or a laser diffraction method.

These organic resin fine particles can be easily adhered by adding them during suspension polymerization of the resin particles, washing and filtration, and before or during drying. Also,
Addition after drying is preferable because the organic resin fine particles can be more firmly attached. Furthermore, in each step,
It is also possible to adhere more firmly by mixing for a short time with a usual powder mixer, for example, a Henschel mixer, a ribbon blender or the like. In this case, the peripheral speed of a mixer such as an automatic mortar or a ball mill having a strong mixing and compressing operation or a stirring blade such as a hybridizer is set to 50.
A strong mixer exceeding m / s is not preferred because the resin particles are deformed and coalesced, and it is difficult to obtain the target acrylate-based resin particles.

The amount of the organic resin fine particles varies depending on the ratio of the surface area of the resin particles, but is added in an amount of 3 to 40 parts by weight based on 100 parts by weight of the resin particles. If the addition amount is outside this range, coalescence of the resin particles may occur, or the feel when blended with the contained object may be deteriorated. A more preferred amount is 10 to 30 parts by weight.

Further, if the inorganic fine particles are attached beforehand in the drying step of the resin particles or the like before the organic resin fine particles are attached, the coalescence of the resin particles is prevented, and the organic resin fine particles are attached very efficiently. Is possible,
The performance can be further improved.

As the inorganic fine particles, both hydrophobic and hydrophilic ones can be used. Examples include silica, alumina, titania, zirconia, ceria, iron oxide, zinc oxide and the like. Among these inorganic fine particles, fine particles obtained by subjecting the surface of hydrophilic inorganic fine particles to a hydrophobic treatment are particularly preferable.

As a method of the hydrophobic treatment, there is a method of treating hydrophilic inorganic fine particles with a surface treating agent having a hydrophilic group and a hydrophobic group. Specifically, coupling agents such as silane coupling agents and titanate coupling agents, silicone oils and silicone resins such as dimethylpolysiloxane and methylhydrogenpolysiloxane, surfactants having a hydrophobic group and a hydrophilic group, and acrylic based agents Resins, amino acids,
A method of performing a surface treatment with lecithin or the like under wet or dry conditions can be used.

In particular, hydrophobic colloidal silica is particularly preferred because it efficiently adheres to the resin particles and exhibits good performance.

The average particle diameter of the inorganic fine particles is 1
/ 1000 to 1/100, more preferably 1/2000 to 1/200.
If the average particle diameter is less than 1/10000 or more than 1/100, the effect of preventing coalescence of the resin particles is reduced,
In particular, it is not preferable because a good feel cannot be obtained when it is blended in cosmetics. More specifically, the average particle diameter of the inorganic fine particles is preferably 5 to 50 nm.
Here, the average particle size means a value calculated by an electron microscope observation method.

These inorganic fine particles can be added to any one of a polymerization step, a filtration step, a drying step, a pulverization step, and a classification step of resin particles, or a plurality of steps. In particular, it is preferable to add in the drying step and the pulverizing step.

The inorganic fine particles are preferably added in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the resin particles.
It is more preferable to add 5 to 4 parts by weight. If the addition amount is outside the above range, coalescence of the resin particles occurs, and the feel when blended with the contained object is unfavorably deteriorated.

The thus-obtained acrylate resin particles of the present invention can be further treated with a surface treating agent such as an oil agent, a silicon compound or a fluorine compound. Water-repellency and oil-repellency can be enhanced by surface treatment of the resin particles. Therefore, especially when it is blended in a cosmetic, it is possible to provide a cosmetic which is hardly wetted by water, sweat, sebum, etc. even after being adhered to the skin, and which does not easily lose its makeup even when used for a long time.

The oil agent is not particularly restricted but includes, for example, hydrocarbon oils such as liquid paraffin, squalane, petrolatum, paraffin wax, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearin Acids, linoleic acid, lanolin fatty acids, higher fatty acids such as synthetic fatty acids, glyceryl trioctanoate, propylene glycol dicaprate, 2-
Ester oils such as cetyl ethylhexanoate and isocetyl stearate, waxes such as beeswax, spermaceti, lanolin, carnauba wax, candelilla wax, linseed oil, cottonseed oil, castor oil, egg yolk oil, oils such as coconut oil, stearic acid A method for treating an oil agent such as a metal soap such as zinc and zinc laurate, and a higher alcohol such as cetyl alcohol, stearyl alcohol, and oleyl alcohol is not particularly limited. For example, a method in which an oil agent is added to acrylate resin particles and a mixer is used Drying method in which the oil is coated by stirring, etc., or dissolving the oil in an appropriate solvent such as ethanol, propanol, ethyl acetate, hexane, etc., adding acrylate resin particles to the mixture, mixing and stirring, and then removing the solvent under reduced pressure Or coating oil by heat removal It is possible to use an expression method, or the like.

Examples of the silicone compound include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acryl-silicone-based graft polymer, and organic silicone resin partially crosslinked organopolysiloxane polymer.

The method of treating the silicone compound is not particularly limited. For example, the above-mentioned dry method and wet method can be used. If necessary, a baking treatment may be performed, and in the case of a reactive silicone compound, a reaction catalyst or the like may be appropriately added.

Examples of the fluorine compound include perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, and polymers having a perfluoro group.

The method for treating the fluorine compound is not particularly limited, and for example, the above-mentioned dry method and wet method can be used. If necessary, a baking treatment may be performed, and in the case of a fluorine compound having reactivity, a reaction catalyst or the like may be appropriately added.

These surface treatment agents can be used alone or in combination of two or more. The addition amount of these surface treatment agents varies depending on the particle size of the acrylate resin particles, but is 0.01 to 50% by weight, particularly 0.1 to 10% by weight, based on the acrylate resin particles.
% By weight is preferred. If the amount of the surface treatment agent is less than 0.01% by weight, sufficient water and oil repellency cannot be obtained,
If the amount exceeds 50% by weight, a remarkable effect increase in proportion to the increase in the added amount is not recognized or aggregation is caused, which is not preferable.

The acrylate-based resin particles of the present invention thus obtained are used as a compounding agent in an amount of 1 to 60% by weight.
The external preparation of the present invention can be obtained by containing the compound in the range described above. Here, the external preparation includes cosmetics and external medicines. The method for incorporating the compound into the external preparation is not particularly limited, and any known method can be used.

As cosmetics, washing cosmetics such as soap, body shampoo, face wash cream, scrub face wash, etc.,
Lotion, cream, milky lotion, packs, whitenings, foundation, lipstick, lip balm, blush, eyebrows cosmetics, nail polish, shampoo, hair dye, hair coloring, aromatic cosmetics, toothpaste, bath agent, antiperspirant And sunscreen products, suntan products, body cosmetics such as body powder and baby powder, shaving creams, lotions such as pre-shave lotions, after-shave lotions and body lotions. However, as long as the effects of the present invention are recognized, the present invention is not limited to the above cosmetics.

The external medicine is not particularly limited as long as it is applied to the skin. Specific examples include pharmaceutical creams, ointments, pharmaceutical emulsions, and pharmaceutical lotions.

If the amount is less than 1% by weight, the amount of the resin particles is too small, and the effect of the addition is not clearly recognized. On the other hand, if it exceeds 60% by weight, even if the addition amount is further increased, a remarkable effect enhancement corresponding to the increase in the addition amount is not recognized, which is not preferable. A more preferred amount is 3 to 40% by weight.

In addition, as long as the effects of the present invention are not impaired,
Components generally used in external preparations can be blended according to the purpose. As such a component, for example,
Water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, humectants, surfactants, high molecular compounds, coloring material raw materials, fragrances, preservatives / disinfectants, oxidation Inhibitors, ultraviolet absorbers, and special compounding ingredients.

Oils and waxes include avocado oil, almond oil, olive oil, cocoa butter, beef tallow, sesame fat, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, macadamia Nut oil, mink oil, egg yolk oil, mokuro, coconut oil, rosehip oil, hydrogenated oil, silicone oil, orange roughy oil,
Carnauba wax, candelilla wax, whale wax, jojoba oil,
Montan wax, beeswax, lanolin and the like.

Examples of the hydrocarbon include liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane and the like.

The higher fatty acids 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 acids.

As higher alcohols, lauryl alcohol, cetyl alcohol, cetostearyl alcohol,
Stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol,
Isostearyl alcohol, jojoba alcohol, decyltetradecanol and the like can be mentioned.

Sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like.

Examples of fatty acid esters include ethyl linoleate, isopropyl myristate, isopropyl lanolin fatty acid, hexyl laurate, myristyl myristate, cetyl myristate, octyl dodecyl myristate, decyl oleate, octyl dodecyl oleate,
Hexyldecyl dimethyloctanoate, cetyl isooctanoate, decyl palmitate, glycerin trimyristate, glycerin tri (caprylate / caprate), propylene glycol dioleate, glycerin triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, apple And cyclic alcohol fatty acid esters such as diisostearyl acid, cholesteryl isostearate, 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, xylitol, maltitol and the like. .

Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, and cationic surfactants such as amine salts and quaternary ammonium salts. Agents, betaine type, amino acid type, imidazoline type, amphoteric surfactant such as lecithin, fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate, etc. Surfactants.

As the high molecular compound, gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, irismos, quince seed, gelatin,
Shellac, rosin, natural polymer compounds such as casein, sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose,
Semi-synthetic polymer compounds such as 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 And synthetic polymer compounds such as resin particles such as polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, and polyethylene particles.

As a coloring material, iron oxide, ultramarine, navy blue,
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, inorganic pigments such as ceramic powder, azo, nitro, nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenyl Examples include tar dyes such as methane, phthalocyanine, and pyrene.

Here, the powdery raw material such as the above-mentioned polymer compound and coloring material raw material may be subjected to a surface treatment in advance. As the surface treatment method, a conventionally known surface treatment technique can be used. For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc., perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether And fluorine compound treatment with a polymer having a perfluoroalkyl group, 3-methacryloxypropyltrimethoxysilane, silane coupling agent treatment with 3-glycidoxypropyltrimethoxysilane, etc., isopropyl triisostearoyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanium coupling agent treatment with titanate, etc., metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin treatment with hydrogenated egg yolk lecithin, etc., collagen treatment, polyethylene treatment, moisturizing treatment, inorganic compound treatment,
Processing methods such as mechanochemical processing are exemplified.

Examples of the flavor include natural flavors such as lavender oil, peppermint oil, and lime oil, and synthetic flavors such as ethylphenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate.

As the antiseptic / bactericide, methyl parapen,
Ethyl parapen, propyl parapen, benzalkonium, benzethonium and the like can be mentioned.

Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like.

Examples of the ultraviolet absorber include inorganic absorbers such as fine titanium oxide, fine zinc oxide, fine cerium oxide, fine iron oxide, fine zirconium oxide, benzoic acid, paraaminobenzoic acid, anthranilic acid, and the like.
Organic absorbents such as salicylic acid, cinnamic acid, benzophenone, and dibenzoylmethane may be used.

The special compounding ingredients include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone, etc.
Vitamins such as vitamin A, vitamin B, vitamin C and vitamin E, skin astringents such as citric acid, tartaric acid, lactic acid, aluminum chloride, aluminum potassium potassium sulfate, allantochlorohydroxy aluminum, zinc paraphenol sulfonate, zinc sulfate, etc. , Tincture tincture, pepper tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid glyceride, vitamin E, estrogen, photoreceptor and other hair growth promoters, magnesium phosphate-L-ascorbate, And a whitening agent such as kojic acid.

The molding composition is not particularly limited. For example, the molding composition includes a polyester resin, a polyamide resin, an acrylic resin, a polycarbonate resin, a polyolefin resin, and the like, and the compounding agent is added for the purpose of imparting impact resistance.

In the molding composition, the compounding agent is 1-6.
Preferably, it is contained at 0% by weight.

The paint is not particularly limited. For example, paint is acrylic, polyester-based resin,
It is composed of solvents such as water, alcohols, acetates, and aromatic hydrocarbons.

The compounding agent is contained in the paint in an amount of 1 to 60% by weight.
Preferably, it is included.

[0087]

Embodiments of the present invention will be described below. Note that the present invention is not limited to the following embodiments.・ Manufacture of acrylate resin particles

Example 1 Oil phase Ethyl acrylate 90 parts by weight 1,6-hexanediol dimethacrylate 10 parts by weight 0.5 parts by weight benzoyl peroxide Aqueous phase Deionized water 400 parts by weight Polyvinyl alcohol (degree of saponification 85%) 8 Parts by weight Sodium lauryl sulfate 0.04 parts by weight Spherical silicon resin fine particles 20 parts by weight (Tospearl 105 manufactured by Toshiba Silicon Corporation, average particle size 0.5 μm)

After dispersing the above oil phase in the aqueous phase using a tabletop type TK homomixer manufactured by Tokushu Kika Co., Ltd. (rotation speed: 6000 rpm), this dispersion was put into a polymerization vessel equipped with a stirrer and a thermometer. Stirring was continued for 10 hours to complete the suspension polymerization. After cooling, the suspension was filtered and washed to obtain spherical resin particles having a compressive strength of 0.15 kgf / mm ² and an average particle size of 8.3 μm when a load of 1 gf was applied. The dehydrated cake after filtration and washing is put in a rotary vacuum dryer equipped with stirring blades, and after adding spherical silicon resin fine particles, the mixture is dried while stirring at a peripheral speed of 3 m / s, and then classified to classify an acrylic ester of the present invention. Resin particles were obtained. Scanning electron micrographs confirmed that silicon resin fine particles had adhered to the resin particle surfaces.

Example 2 After a polymerization reaction was carried out under the same conditions as in Example 1 to obtain resin particles, the dehydrated cake was put into a rotary vacuum dryer equipped with stirring blades.
One part by weight of hydrophobized colloidal silica (R-812 manufactured by Nippon Aerosil Co., Ltd.) was added, and dried while stirring at a peripheral speed of 3 m / s. After drying, it was confirmed by an electron micrograph that colloidal silica had adhered to the particle surface. Further, 20 parts by weight of silicon resin fine particles (Tospearl 105 manufactured by Toshiba Silicon Co., Ltd.) were added, and the mixture was gently mixed at a peripheral speed of 5 m / s to obtain acrylate resin particles of the present invention. Scanning electron micrographs confirmed that silicon resin fine particles were further attached to the surface of the resin particles to which colloidal silica was attached.

Example 3 The acrylate resin particles of the present invention were prepared in the same manner as in Example 1 except that the silicon resin fine particles were changed to PMMA resin fine particles (Sekisui Chemical Co., Ltd., particle size: 0.5 μm). Obtained. Scanning electron microscopy confirmed that PMMA resin fine particles were attached to the surface of the crosslinked acrylic acid ester particles.

Example 4 Example 1 was repeated except that the silicon resin particles were changed to fluororesin particles (Sekisui Chemical Co., Ltd., particle size 1.0 μm).
Was obtained in the same manner as described above. Scanning electron microscopy confirmed that fluororesin microparticles had adhered to the crosslinked acrylic acid ester particle surfaces.

Comparative Example 1 Silicon resin fine particles were prepared by using PMMA having an average particle diameter of 20 μm.
Acrylic ester-based resin particles were obtained in the same manner as in Example 1, except that the resin particles were changed to resin fine particles (manufactured by Sekisui Plastics Co., Ltd.).

Comparative Example 2 Acrylic ester resin particles were produced in the same manner as in Example 1 except that the amount of the silicon resin fine particles was changed to 60 parts by weight, but no uniform particles were obtained.

Comparative Example 3 Acrylic ester resin particles were obtained in the same manner as in Example 1 except that the amount of the silicon resin fine particles was changed to 1 part by weight.・ Preparation of external preparation (1) Manufacture of powder foundation

Example 5 Acrylic ester resin particles of the present invention (Example 1) 15 parts by weight Talc 21 parts by weight Muscovite 51 parts by weight Red iron oxide 0.6 parts by weight Yellow iron oxide 1 part by weight Black iron oxide 0 0.1 part by weight Cetyl 2-ethylhexanoate 10 parts by weight Sorbitan sesquioleate 1 part by weight Preservatives 0.2 parts by weight Fragrance 0.1 parts by weight

The acrylate resin particles of the present invention,
Talc, muscovite, red iron oxide, yellow iron oxide, and black iron oxide are mixed with a Henschel mixer, and a mixture obtained by mixing and dissolving cetyl 2-ethylhexanoate, sorbitan sesquioleate, and a preservative is added. Mixed.

[0098] A fragrance was added to the mixture, mixed, then pulverized and passed through a sieve. This was compression-molded on a metal plate to obtain a powder foundation.・ Preparation of cosmetic emulsion

Example 6 Acrylic ester resin particles of the present invention (Example 1) 10.0 parts by weight Stearic acid 2.5 parts by weight Cetyl alcohol 1.5 parts by weight Vaseline 5.0 parts by weight Liquid paraffin 10.0 Parts by weight Polyethylene (10 mol) monooleate 2.0 parts by weight Polyethylene glycol 1500 3.0 parts by weight Triethanolamine 1.0 part by weight Purified water 64.5 parts by weight Fragrance 0.5 part by weight Preservatives appropriate amount

First, stearic acid, cetyl alcohol,
Vaseline, liquid paraffin, and polyethylene monooleate are heated and dissolved, and the acrylate resin particles of the present invention are added and mixed, and the temperature is kept at 70 ° C. (oil phase). In addition, polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C (aqueous phase). Add the oil phase to the water phase, pre-emulsify, then homogenize uniformly with a homomixer, and after emulsification, stir 30
By cooling to ℃, a cosmetic emulsion was obtained.

Comparative Example 4 A cosmetic emulsion was obtained in exactly the same manner as in Example 6, except that the acrylate resin particles of Comparative Example 1 were used instead of the acrylate resin particles used in Example 6. .

Comparative Example 5 A cosmetic emulsion was obtained in exactly the same manner as in Example 6, except that the acrylate resin particles of Comparative Example 3 were used instead of the acrylate resin particles used in Example 6. .

A sensory test was conducted by 10 panelists on the acrylate resin particles of Examples 1 to 4 and Comparative Examples 1 and 3, and the external preparations of Examples 5 and 6 and Comparative Examples 4 and 5. As the evaluation items in this test, a rough feeling, a soft feeling, adhesion to the skin, and a wrinkle concealing effect were selected.
A grading was performed. However, the roughness was evaluated according to the criteria in parentheses.

1... Bad (very rough) 2... Somewhat bad (rough) 3... Normal (somewhat rough) 4... Somewhat good (almost no roughness) 5... Good (no roughness at all) This sensory test Table 1 shows the results. In addition, the numerical value in a table | surface is an average value of the test result of ten persons.

[0105]

[Table 1]

As described above, the acrylate-based resin particles of the present invention are not only excellent in elongation, smoothness and softness, but also excellent in adhesion to skin and wrinkle concealing effect. It was found that the external preparation to which the system resin particles were added also had those excellent properties.

[0107]

As described above, external preparations, paints and moldings obtained by adding acrylate resin particles obtained by adhering or adhering a specific organic resin powder to the surface of crosslinked organic resin particles having a specific compressive strength according to the present invention. The composition for use has an unprecedented excellent feel (elongation, smoothness, soft feeling).
In particular, when added to an external preparation, in addition to the above-mentioned feel, the external preparation gives excellent adhesion to the skin and a wrinkle concealing effect,
A new external preparation having excellent performance which has never been obtained before can be obtained. Therefore, the acrylate resin particles of the present invention can be expected to be applied to a wide range of contained objects.

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Claims (5)

[Claims] 1. 100 parts by weight of crosslinked (meth) acrylate resin particles having an average particle diameter of 0.5 to 100 μm and a compressive strength of 0.05 to 0.6 kgf / mm ² , / 3 to 40 parts by weight of organic resin fine particles having an average particle diameter of / 1000 to 1/5, wherein the organic resin fine particles adhere to the surface of the resin particles. 2. The crosslinked (meth) acrylate resin particles have inorganic fine particles adhered to the surface thereof, and the inorganic fine particles are 1/1000 to 1/100 of the resin particles.
Having an average particle size of 0.1 wt.
2. The resin particles according to claim 1, wherein the resin particles are attached at a ratio of from 0.5 to 5 parts by weight. 3. The resin particles according to claim 2, wherein the inorganic fine particles are inorganic fine particles subjected to a hydrophobic treatment. 4. The method according to claim 1, wherein the organic resin fine particles are silicon-based resin or fluorine-based resin fine particles.
4. Resin particles according to any one of the above. 5. An external preparation comprising 1 to 60% by weight of the acrylate resin particles according to any one of claims 1 to 4.