JP2000016914A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic excellent in feel of touch and exhibiting stable thickening effect on hydrous cosmetics containing ions or alcohol. SOLUTION: This cosmetic is obtained by formulating spherical crosslinked copolymer resin particles prepared by suspension polymerization between an N-vinylcarboxylic acid amide of the general formula CH=CHNR1COR2 (R1 and R2 are each H or methyl), a water-soluble vinyl compound other than the above vinyl compound and a crosslinking agent in a non-aqueous solvent substantially insoluble for the water-soluble vinyl compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic containing a novel gelling agent. More specifically, the present invention relates to a cosmetic composition which exhibits a stable thickening effect on water-containing cosmetic compositions containing ions and alcohols in particular and is excellent in feel by blending N-vinylcarboxylic acid amide-based spherical crosslinked copolymer resin particles. .

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 3-223304 describes an invention relating to N-vinylcarboxylic acid amide-based crosslinked copolymer particles polymerized in an aqueous system and the use thereof (including cosmetics). It is shown that a carboxylic acid amide-based polymer has water absorbency and is a water-absorbent resin having an affinity for a polar organic solvent.

[0003]

However, the above-mentioned cross-linked copolymer is specifically one which is pulverized by polymerization and then pulverized after polymerization. Since it is a fixed form, it is not always satisfactory in terms of the feel and the like of the blended cosmetic when the specific use of the cosmetic is considered. Further, when a resin typified by a cross-linked polyacrylic acid type or a cross-linked polyacrylamide resin, which has conventionally been frequently used as a thickening gelling agent, is used, since both are cross-linked polymers of a polymer electrolyte resin, However, although it shows a high viscosity for water containing no electrolyte, it has the drawback that the thickening effect is extremely reduced for aqueous liquids containing a large amount of organic or inorganic ions and aqueous liquids containing alcohol and the like. Had.

[0004]

Means for Solving the Problems The present inventors have studied the combination of various copolymerization components and the polymerization method for N-vinylcarboxylic acid amide-based crosslinked copolymer particles. The shape of the crosslinked copolymer resin particles obtained by suspending and polymerizing a water-soluble vinyl compound other than amide and N-vinylcarboxylic acid amide in a non-aqueous solvent in which the water-soluble vinyl compound is substantially insoluble is spherical, It has been found that the properties of the ingredients are excellent.
Here, the excellent properties refer to the stability of the compounded preparation and the excellent feel of the compounded preparation.

That is, the first invention relates to a compound represented by the general formula CH ₂
= CHNR ₁ COR ₂ (wherein R ₁ R ₂ is the same or different and represents hydrogen or a methyl group) and a water-soluble vinyl compound other than that represented by the above general formula. And a water-soluble vinyl compound, wherein the water-soluble vinyl compound is suspended in a substantially insoluble non-aqueous solvent and polymerized and crosslinked to form spherical crosslinked copolymer resin particles.

A second aspect of the present invention has an ability to hold 5000 to 80000 parts by weight of pure water per 100 parts by weight.
An N-vinylcarboxylic acid amide represented by the general formula CH ₂ ＣＨCHNR ₁ COR ₂ (wherein R ₁ R ₂ is the same or different and represents hydrogen or a methyl group) and a water-soluble vinyl other than the above general formula The above-mentioned cosmetic is characterized in that spherical crosslinked copolymer resin particles with a compound are blended.

A third aspect of the present invention relates to a compound represented by the general formula CH ₂ ＣＨCHNR
₁ COR ₂ (wherein R ₁ and R ₂ are the same or different and represent hydrogen or a methyl group) and a spherical form of a water-soluble vinyl compound other than the above-mentioned general formula. A dispersion solution in which crosslinked copolymer resin particles are dispersed in a non-aqueous solvent, wherein the resin particles 1
The ratio of the non-aqueous solvent to 100 parts by weight is 5 to 30 parts by weight, and the resin particles contain 10 to 400 parts by weight of water per 100 parts by weight. A cosmetic comprising a polymer resin particle dispersion.

In a fourth aspect of the present invention, when the amounts of the N-vinylcarboxylic acid amide (a) and the water-soluble vinyl compound (b) are expressed in parts by weight, the following formula (1) is satisfied. The above-mentioned cosmetic is characterized in that: 0.3 ≦ (a) / {(a) + (b)} ≦ 0.95 Equation (1)

A fifth aspect of the present invention is to provide an N-vinylcarboxylic acid amide-based spherical crosslinked copolymer resin particle having an average particle diameter of 0.5 to 0.5.
In the above-mentioned cosmetic, the thickness is 100 μm.

A sixth aspect of the present invention is the above-mentioned cosmetic, wherein the N-vinylcarboxylic acid amide is N-vinylacetamide.

In a seventh aspect of the present invention, an N-vinyl carboxylic acid amide-based spherical crosslinked copolymer resin particle has a general formula of CH ₂ ＣＨCH
An N-vinylcarboxylic acid amide represented by NR ₁ COR ₂ (wherein R ₁ and R ₂ are the same or different and each represents hydrogen or a methyl group) and a water-soluble vinyl compound other than those represented by the above general formula The above-mentioned cosmetic is characterized by being obtained by dissolving in water, suspending in a non-aqueous solvent in the presence of an oil-soluble surfactant and a crosslinking agent, and polymerizing and crosslinking.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The N-vinylcarboxylic acid amide used in the present invention is represented by the general formula CH ₂ ＣＨCHNR ₁ COR ₂ (wherein R ₁ and R ₂ are the same or different and represent hydrogen or a methyl group). Use what is shown. Specifically, N
-Vinylformamide, N-vinylacetamide, N-methyl-Nvinylformamide, N-methyl-N-vinylacetamide, and the like, and especially N-vinylacetamide sold by Showa Denko KK has purity, safety, and It is preferable because the obtained copolymer resin has a high affinity for water.

The N represented by the above general formula used in the present invention
The water-soluble vinyl compound other than -vinylcarboxylic acid amide is a water-soluble compound copolymerizable with N-vinylcarboxylic acid amide, and a compound substantially insoluble in the non-aqueous solvent used in the present invention is used. Any monomer can be used as long as it gives excellent performance. Monomers that provide such performance include water-soluble ethylenic groups having groups derived from carboxylic acids or (and) salts thereof, phosphoric acid or (and) salts thereof, sulfonic acids or (and) salts thereof as functional groups. Unsaturated monomers. Specifically, (meth) acrylic acid, maleic acid or a salt thereof, itaconic acid or a salt thereof, vinylsulfonic acid or a salt thereof, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, and 2-acryloylethanesulfonic acid Or an anionic compound such as a salt thereof, 2-acryloylpropanesulfonic acid or a salt thereof, 2-itacloylethanesulfonic acid or a salt thereof, vinylphosphonic acid or a salt thereof, or a (meth) acrylate [2- (meth) acrylic (Meth) acryloyloxyalkyltrialkylammonium salts such as loyloxyethyltrimethylammonium chloride and 2- (meth) acryloyloxyethyltrimethylammonium methosulfate], salts of tertiary nitrogen-containing (meth) acrylates [2] Dimethylaminoethyl (meth) sulfate and 2-diethylaminoethyl acrylate (meth)
Salts of dialkylaminoalkyl (meth) acrylates such as acrylate hydrochloride], quaternary nitrogen-containing (meth)
Acrylamide [(meth) such as 2- (meth) acryloylaminoethyltrimethylammonium sulfate
Acryloylaminoalkyltrialkylammonium salt], tertiary nitrogen-containing (meth) acrylamide salt [2
Dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylamide hydrochloride and 2-dimethylaminoethyl (meth) acrylamide acetate
Examples include cationic compounds such as acrylamide, and nonionic compounds such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, (poly) ethylene glycol mono (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. .

Usually, from the viewpoint of preventing hydrolysis of the N-vinyl compound and eliminating the need for neutralization when using the thickening gelling agent, the aqueous solution in which these vinyl compounds are dissolved is p-type.
When an ionic vinyl compound is used, it is preferable to use it in a form neutralized with a salt so that H becomes near neutral.

That is, (meth) acrylic acid, maleic acid, itaconic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloylethanesulfonic acid, 2-acryloylpropanesulfonic acid, 2-itacloyl When an acid which is acidic in an aqueous solution such as ethanesulfonic acid or vinylphosphonic acid is used, it is preferably used in the form of a salt neutralized with sodium, potassium, amine, ammonium or the like.

In the present invention, when the polymerization ratio between the N-vinylcarboxylic acid amide (a) and the water-soluble vinyl compound (b) is expressed in parts by weight, it is preferable that the following relationship be satisfied. 0.3 ≦ (a) / {(a) + (b)} ≦ 0.95 Within this range, the salt resistance, which is a characteristic of N-vinylcarboxylic acid amide, is improved, and the stability and general-purpose properties of the formulated preparation are improved. There is a merit that the nature is further improved.

In the present invention, spherical cross-linked copolymer resin particles of an N-vinyl carboxylic acid amide and a water-soluble vinyl compound are blended, and the cross-linking agent used in the present invention is N-vinyl carboxylic acid amide or a copolymerizable resin. Any material can be used as long as it can crosslink the polymer,
Examples of the polymerizable crosslinking agent include bisamides such as methylenebisacrylamide and methylenebismethacrylamide; N, N'-1.4butylenebis (N-vinylacetamide) and N, N'-1.6hexylenebis (N Bis (N-vinylacetamide) such as vinylacetamide);
Examples include di- or tri (meth) acrylates of polyols such as ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, polyoxyethylene glycol diacrylate, and glycerin triacrylate, which are soluble in an aqueous solution containing a vinyl compound. It can be used without limitation as long as it is copolymerizable. The amount of crosslinking agent is N-
It is preferably 0.0001 to 1% by weight based on the total amount of the vinyl carboxylic acid amide and the water-soluble vinyl compound.

As the polymerization initiator, a usual water-soluble radical polymerization initiator can be used. Examples of the water-soluble initiator include 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2 ' -Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}
Azo compounds such as dihydride, potassium persulfate, ammonium persulfate, and peroxides such as hydrogen peroxide can be exemplified, and these may be used as a redox initiator in combination with a reducing substance such as a sulfite, or an amine. Is also good. Among them, 2,2′-azobis (2-amidinopropane) hydrochloride,
2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobis ｛2
-A water-soluble azo compound such as [-(1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydride is preferred because the polymerization of N-vinylcarboxylic acid amide proceeds smoothly.

The amount of the polymerization initiator used is based on the amount of the monomer.
The amount is preferably 0.01 to 1% by weight, and if the amount is too small, it is difficult to start smooth polymerization, and if it exceeds 1% by weight, the polymerization proceeds too quickly to increase the risk, which is not preferable.

The cross-linked copolymer resin particles used in the present invention are:
It is preferable to have the ability to hold 5000 to 80000 parts by weight of pure water per 100 parts by weight. Within this range, there is a characteristic that the gelling ability of the preparation is not insufficient, and characteristics excellent in feel can be obtained. The N-vinylcarboxylic acid amide-based crosslinked copolymer resin particles preferably have an average primary particle diameter in the range of 0.5 to 100 μm, more preferably 0.5 to 20 μm. Within this range, a favorable feel can be imparted when blended in a cosmetic. If the size exceeds 100 μm, there is a problem that the feeling of the preparation slips and the viscosity of the preparation decreases, and the gelation becomes weak.

In the cosmetic of the present invention, the crosslinked copolymer resin particles may be blended in the form of a dispersion solution in which the particles are dispersed in a non-aqueous solvent. In this case, there is a merit that the problem of dust generation does not occur at the time of preparing the solution and the handling property is good as compared with a powdery material. As the non-aqueous solvent or the non-aqueous solvent used at the time of polymerization, those which do not substantially dissolve the polymerizable monomer can be used, and petroleum hydrocarbons are preferable. For example, aliphatic hydrocarbons such as normal hexane, normal heptane, ligroin, liquid paraffin, and isoparaffin; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; dimethylpolysiloxane, phenyl A silicone oil such as methylpolysiloxane may be used according to the purpose, but liquid paraffin, isoparaffin, and silicone oil are preferred from the viewpoint of safety of the final preparation. And even if it is manufactured with another solvent, it is preferable to substitute these solvents.

The amount of the non-aqueous solvent used can be varied over a wide range with respect to the amount of the aqueous monomer solution. However, from the viewpoints of economy and performance of the thickening gelling agent, it is generally advantageous to use a smaller amount of the solvent. is there. However, if the amount is too small, it becomes difficult to remove the heat, and it is necessary to prepare the reaction solution in the reaction tank to such an extent that the reaction solution can be stirred. Therefore, usually, the weight ratio of the aqueous vinyl compound solution to the non-aqueous solvent is suitably between 1: 0.5 to 1: 6, and after polymerization, if necessary, by treatment such as concentration or distillation, if necessary. The ratio of the non-aqueous solvent to 100 parts by weight of the resin particles is preferably 5 to 30 parts by weight, and the resin particles are preferably adjusted to hold 10 to 400 parts by weight of water per 100 parts by weight. Also,
These non-aqueous solvents may be used alone or in combination of two or more.

In the case of producing a dispersion solution in which the crosslinked copolymer resin particles are dispersed in a non-aqueous solvent with the cosmetic of the present invention, it is preferable that the dispersion solution contains a surfactant.

The surfactant used here includes an oil-soluble surfactant. In producing the spherical crosslinked copolymer resin particles, the surfactant is used to stabilize the aqueous solution of N-vinylacetamide and other monomers in a non-aqueous solvent, and is used for reverse phase suspension polymerization. One or two or more selected from sucrose fatty acid esters, sorbitan esters, and polyester-based surfactants are used as dispersants at this time.

As the sucrose fatty acid ester, a sucrose ester whose fatty acid is composed of a saturated or unsaturated fatty acid such as stearic acid, palmitic acid, lauric acid, oleic acid and the like is preferable. The number of the esters can be from 1 to 6 per unit of sucrose. Specific examples of sucrose fatty acid esters include sucrose monostearate, sucrose distearate, sucrose tristearate, sucrose monopalmitate, sucrose dipalmitate, sucrose tripalmitate, sucrose monolaurate, sucrose dilaurate, sucrose trilaurate, sucrose monooleate, and sucrose. Examples thereof include diolate, sucrose triolate, sucrose polystearate, sucrose polypalmitate, sucrose polylaurate, and sucrose polyolate.

As the polyester-based surfactant, one having a hydrophilic part and a hydrophobic part, and any oil-soluble one can be used. Usually, the hydrophilic part is made of polyoxyethylene or polyoxyethylene. Propylene group, a polyester having a hydrocarbon or aromatic hydrocarbon group in the hydrophobic portion, the weight average molecular weight of which is in the range of 2,000 to 10,000 in terms of polystyrene has a solubility in a hydrophobic organic solvent or a degree of suspension polymerization. It is preferably used from the viewpoint of dispersion stability performance.

The sorbitan ester is preferably a sorbitan ester whose fatty acid is composed of a saturated or unsaturated fatty acid such as stearic acid, palmitic acid, lauric acid or oleic acid. The number of the sorbitan ester is 1 to 4 per sorbitan unit. obtain. Specifically, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan trilaurate, sorbitan monooleate Sorbitandiolate, sorbitan triolate and the like.

The HLB of these surfactants is appropriately in the range of 1 to 9, and if the HLB is outside this range, the solubility may be reduced, the dispersing ability may be reduced, and a dispersion may not be obtained, or the system may be aggregated. is there. These dispersion stabilizers can be used alone or in combination of two or more.

Among them, in the present invention, HLB is 1 to
Sucrose fatty acid ester No. 5 and a polyester surfactant having an HLB of 5 to 9 are preferred, and particularly, a sucrose ester having an HLB of 1 to 2 and a polyester surfactant having an HLB of 5 to 7 are extremely excellent in stability during polymerization. Since it is effective for a wide range of monomer compositions and requires a small amount of use, it is preferable in that the effect of reducing the cloudiness of the gel thickened by the finally obtained thickening gelling agent is high.

An appropriate amount of the surfactant is usually 0.1 to 15% by weight, preferably 0.1 to 15% by weight, based on the monomer.
1 to 5% by weight. If the amount is too small, the polymerization stability decreases, and stable dispersion droplets in oil are not formed. If the amount is too large, the transparency of the thickened gel is adversely affected.

In the present invention, as a method for obtaining crosslinked copolymer resin particles, an N-vinylcarboxylic acid amide and a water-soluble vinyl compound are dissolved in at least water, and a non-solvent is prepared in the presence of an oil-soluble surfactant and a crosslinking agent. It is preferable to use those obtained by suspending in an aqueous solvent and polymerizing and crosslinking, that is, those obtained by reverse phase suspension polymerization reaction.

An example of the polymerization method is shown below. Usually, a crosslinking agent and a water-soluble radical polymerization initiator are added and dissolved in an aqueous monomer solution, and degassing is performed by introducing an inert gas such as nitrogen.
On the other hand, the surfactant is put in a non-aqueous solvent, and if necessary, slightly heated and dissolved, and an inert gas such as nitrogen is introduced to perform deaeration. The above monomer aqueous solution is added thereto, and the mixture is dispersed using a homogenizer, an emulsifying disperser utilizing a high shear applied to the gap between the rotating blade and the machine wall or the rotating blade, an ultrasonic dispersing machine, or a ceramic microporous membrane. The monomer aqueous solution is pressurized and passed into a dispersion medium, and suspended in spherical fine particles so as to have an average particle diameter of 0.1 to 100 μm.

[0033] The monomer dispersion thus obtained is heated to a predetermined temperature. After the initiation of the polymerization, cooling or heating is appropriately performed depending on the state of heat generation. The polymerization reaction temperature is 3
The temperature is 0 to 100 ° C, preferably 40 to 80 ° C. In order to complete the polymerization reaction, the temperature may be further raised and aging may be performed. After the completion of the reaction, the mixture is cooled to obtain a desired dispersion. After completion of the polymerization, the distillation operation or the like is continued, and the polymer is separated and dried, and then used as a thickening gelling agent for the spherical powder. In the present invention, this dispersion may be used, or powdery crosslinked copolymer resin particles may be used.

[0034] If necessary, a hydrophilic surfactant may be added to form a liquid thickening gelling agent. Here, the addition of the hydrophilic surfactant is for the purpose of promptly inverting the phase from a water-in-oil type to an oil-in-water type when used in an aqueous system, and generally a polyoxyethylene alkyl having an HLB of 10 or more. Nonionic surfactants such as ethers and polyoxyethylene alkylphenol ethers;
Among these, polyoxyethylene lauryl ether and polyoxyethylene nonylphenol ether are preferably used.

The addition amount is 5 parts by weight or less based on the dispersion, usually in the range of 0.5 to 3 parts by weight. Of course, instead of adding the hydrophilic surfactant to the dispersion, it is also possible to directly add the hydrophilic surfactant to the liquid to be thickened.
When a water-in-oil emulsion is desired to be obtained as a cosmetic, it is not necessary to add a hydrophilic surfactant.

In the cosmetic of the present invention, the spherical crosslinked copolymer resin particles and the dispersion thus obtained are used in an amount of 0.1 to 50% by weight as a pure content of the crosslinked copolymer resin particles based on the total amount of the cosmetic. It is preferable to mix them, more preferably 0.5
-20% by weight. In this range, the performance as a gelling agent and a feel-improving agent suitable for the properties of the cosmetic can be exhibited.

In the cosmetic of the present invention, in addition to the above-mentioned spherical crosslinked copolymer particles and dispersions, oils, powders (pigments, pigments, resins), fluorine compounds, resins,
Surfactants, viscosity agents, physiologically active ingredients, preservatives, fragrances, ultraviolet absorbers (including organic and inorganic types, which may correspond to UV-A or B), humectants, salts, solvent,
Components such as antioxidants, chelating agents, neutralizing agents, pH adjusters, insect repellents and the like can be used. Among them, it is particularly preferable to use together with at least one of an ultraviolet absorber and a physiologically active ingredient.

Examples of the oil include volatile and non-volatile oils, solvents and resins which are usually used in cosmetics. Liquids, pastes and solids at room temperature may be used, but liquids excellent in handling are preferable. Examples of oils include, for example, higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyl dodecanol; fatty acids such as isostearic acid, undecylenic acid, oleic acid; glycerin, sorbitol, ethylene glycol,
Polyhydric alcohols such as propylene glycol and polyethylene glycol; myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyldecyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, oxystearin Esters such as octyl acid; hydrocarbons such as liquid paraffin, vaseline, and squalane; waxes such as lanolin, reduced lanolin, and carnauba wax; mink oil, cocoa butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, and olive oil And the like; ethylene, α-olefin, cooligomer and the like.

Examples of other types of oils include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, and fluoroalkyl.
Polyoxyalkylene co-modified organopolysiloxane,
Alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone, amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, silicone compounds such as silicone RTV rubber, perfluoropolyether, Pitch fluoride,
Fluorine compounds such as fluorocarbon and fluoroalcohol are exemplified.

Examples of powders include Red No. 104, Red 2
Dyes such as No. 01, Yellow No. 4, Blue No. 1, Black No. 401,
Lake pigments such as yellow No. 4 Al lake and yellow No. 203 Ba lake; nylon powder, silk powder, urethane powder, Teflon powder, silicone powder,
Polymers such as polymethyl methacrylate powder, cellulose powder, silicone elastomer spherical powder, and polyethylene powder; colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine blue, navy blue; zinc oxide Pigments such as talc, mica, sericite, kaolin, and barium sulfate; pearl pigments such as mica titanium; barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate Metal salts such as; inorganic powders such as silica and alumina; bentonite;
Smectite, boron nitride, and fine particle powders such as fine particle titanium oxide and fine particle zinc oxide. The shape of these powders (spherical, rod, needle, plate, irregular, scaly,
The size is not particularly limited.

These powders and the crosslinked copolymer resin particles used in the present invention may be subjected to conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium Coating agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc. I do not care.

When among these powders, elastomers such as silicone elastomer spherical powder, polyethylene powder, polypropylene powder, Teflon powder, silicone rubber, urethane powder and the like are used, since the aging stability and feel of the product are further improved. preferable. In particular, it is preferable to use a combination of a silicone elastomer spherical powder and an ester oil or a combination of a silicone elastomer spherical powder and a silicone oil (including volatile and non-volatile). Examples of the silicone elastomer spherical powder include Trefil-E series manufactured by Dow Corning Toray Silicone Co., Ltd.

Examples of the physiologically active ingredient include substances which give some physiological activity to the skin when applied to the skin. For example, whitening ingredients, anti-inflammatory agents, anti-aging agents, UV protection agents, slimming agents, tightening agents, antioxidants, hair growth agents, hair restorers, moisturizers, blood circulation promoters, antibacterial agents, bactericides, desiccants, Cooling sensation, warming sensation, vitamins, amino acids, wound healing promoters, stimulants, analgesics, cell activators, enzyme components, and the like. Among them, natural plant extract components, seaweed extract components, and crude drug components are particularly preferable. In the present invention, it is preferable to mix one or more of these physiologically active ingredients.

Examples of these components include, for example, ashitaba extract, avocado extract, amacha extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo extract, fennel extract, turmeric extract, oolong tea extract, Age extract, Echinashi leaf extract, Japanese gourd extract, Oubaku extract, Ouren extract, Barley extract, St. John's wort extract, Red rosacea extract, Dutch mustard extract, Orange extract, Seawater dried product, Seaweed extract, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolysis Silk, chamomile extract, carrot extract, sagebrush extract, licorice extract, calcade extract, syllium extract, kiwi extract, kina extract, cucumber extract, guanosine,
Gardenia extract, Kumazasa extract, Clara extract, Walnut extract, Grapefruit extract, Clematis extract, Chlorella extract, Mulberry extract, Gentian extract,
Black tea extract, yeast extract, burdock extract, rice bran extract, rice germ oil, comfrey extract, collagen,
Cowberry extract, Saishin extract, Psychoextract, Saitai extract, Salvia extract, Sabonso extract, Sasa extract, Hawthorn extract, Sansho extract, Shiitake extract, Jio extract, Shikon extract, Perilla extract, Shinanoki extract, Shimotsukeiso extract, Peony extract, Shobu root extract , Birch extract, horsetail extract, vegetative extract, hawthorn extract,
Western elderberry extract, Achillea millefolium extract, Common mint extract, Sage extract, Genus mallow extract, Senkyu extract, Assembly extract, Soybean extract, Tissou extract, Thyme extract, Tea extract, Clove extract, Chigaya extract, Chimpanzee extract, Touki extract, Calendula extract, Tonin extract , Spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract, nobara extract, hibiscus extract, bakkumondou extract, parsley extract, honey, hamamelis extract, Parietaria extract, chickpea extract, bisabolol, loquat extract, coltsfoot extract , Fukinotou extract, kukuroyou extract, butcher bloom extract, grape extract, propolis, loofah extract, safflower Vinegar, peppermint extract, lime extract, button extract, hops extract, pine extract, horse chestnut extract, skunk cabbage extract, Sapindus extract, Melissa extract, peach, cornflower extract, eucalyptus extract, saxifrage extract, Yuzuekisu,
Yokuinin extract, mugwort extract, lavender extract,
Examples include apple extract, lettuce extract, lemon extract, astragalus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, and the like.

Further, sugars such as glucose, mixed isomerized sugar, trehalose, sulfated trehalose, pullulan and maltose; deoxyribonucleic acid, mucopolysaccharide, sodium hyaluronate, chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolysis Biopolymers such as eggshell membranes; amino acids, sodium lactate, urea,
Moisturizing components such as sodium pyrrolidonecarboxylate, betaine and whey; oily components such as sphingolipids, ceramides, cholesterol, cholesterol derivatives and phospholipids; ε-aminocaproic acid, glycyrrhizic acid, β-glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, etc. Anti-inflammatory agents; vitamins A, B ₂ , B
₆ , C, D, E, calcium pantothenate, biotin,
Vitamins such as nicotinamide, vitamin C ester; active ingredients such as allantoin, diisopropylamine dichloroacetate, 4-aminomethylcyclohexanecarboxylic acid; antioxidants such as tocopherol, carotenoid, flavonoid, tannin, lignan, saponin, α- Cell activators such as hydroxy acids and β-hydroxy acids; blood circulation promoters such as γ-oryzanol and vitamin E derivatives; wound healing agents such as retinol and retinol derivatives; arbutin, kojic acid, placenta extract, sulfur, ellagic acid, and linole Whitening agents such as acid, tranexamic acid, glutathione; cepharanthin, licorice extract,
Pepper tincture, hinokitiol, garlic iodide extract, pyridoxine hydrochloride, dl-α-tocopherol,
Dl-α-tocopherol acetate, nicotinic acid, nicotinic acid derivatives, calcium pantothenate, D-pantothenyl alcohol, acetyl pantothenyl ethyl ether, biotin, allantoin, isopropylmethylphenol, estradiol, ethinylesteradiol, capronium chloride, benzalco chloride , Diphenhydramine hydrochloride, tacanal, camphor, salicylic acid, vanillyl amide nonylate, vanillyl nonanoate, pyrocton olamine, glyceryl pentadecanoate, l-menthol, mononitroguaiacol, resorcinol, γ-aminobutyric acid, benzethonium chloride, mexiletine hydrochloride, auxin , Female hormones, cantaris tincture, cyclosporine, zinc pyrithione, hydrocortisone, minoxidil, monostearin And a hair restorer such as acid polyoxyethylene sorbitan, peppermint oil and Sasanishiki extract.

Examples of the solvent include purified water, cyclic silicone, ethanol, light liquid isoparaffin, lower alcohol, ethers, LPG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, volatile linear silicone, next-generation Freon, etc. Is mentioned.

As the surfactant, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant can be used.

Examples of the tackifier and resin include sodium polyacrylate, cellulose ether, calcium alginate, carboxyvinyl polymer, ethylene / acrylic acid copolymer, vinylpyrrolidone-based polymer, vinyl alcohol / vinylpyrrolidone copolymer, nitrogen Substituted acrylamide polymer, polyacrylamide, cationic polymer such as cationized guar gum, dimethylacrylammonium polymer, acrylic acid methacrylate acrylic copolymer, POE / POP copolymer, polyvinyl alcohol, pullulan, agar, gelatin, tamarind seed Polysaccharides, xanthan gum, carrageenan, high methoxyl pectin, low methoxyl pectin, guar gum, gum arabic, crystalline cellulose, arabinogalactan, karaya gum, tragacanth Arm, alginic acid, albumin, casein, curdlan, gellan gum, dextran, cellulose, polyethyleneimine, highly polymerized polyethylene glycol, cationized silicone polymer, synthetic latex, and the like.

Examples of the ultraviolet absorber include inorganic and organic types. Among the inorganic types, fine particle titanium oxide and fine particle zinc oxide are listed.
For example, 2-ethylhexyl paramethoxycinnamate, 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,
2'-dihydroxy-4-methoxybenzophenone, p
-Methoxyhydrocinnamic acid diethanolamine salt, paraaminobenzoic acid (hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3- Diphenyl acrylate, octyl dimethyl PABA, octyl methoxycinnamate, octyl salicylate, 2-phenyl-benzimidazole-5-sulfate, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine , 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, 4- (3,4-dimethoxyphenylmethylene ) 2-Ethylhexyl 2,5-dioxo-1-imidazolidinepropionate, polymer derivatives thereof, and silane derivatives. Furthermore, those in which these absorbents, preferably 4-tert-butyl-4'-methoxydibenzoylmethane are sealed in a polymer, can also be preferably used.

The cosmetics of the present invention include, for example, makeup cosmetics such as foundation, white powder, eyeshadow, eyeliner, eyebrow, cheek, lipstick, nail color; emulsions, creams, lotions, calamine lotions, sunscreens , Suntan, aftershave lotion, preshave lotion, pack fee,
Basic cosmetics such as cleansing ingredients, facial cleansers, anti-acne cosmetics, and essences; hair cosmetics such as shampoos, rinses, conditioners, hair colors, hair tonics, and setting agents; body powders, deodorants, depilatory, soaps, body shampoos Bath salts, hand soaps, perfumes and the like.

The dosage form of the cosmetic of the present invention is a two-layer
Conventionally known dosage forms such as a water-in-oil emulsion, an oil-in-water emulsion, a gel, a spray, a mousse, an oil, a solid, a powder, and a sheet can be used.

[0052]

The present invention will be described in detail below with reference to examples and comparative examples. In addition, evaluation methods for various properties of the cosmetics used in Examples and Comparative Examples are described below.

Stability Evaluation The cosmetics filled in the container were stored at room temperature and 40 ° C. for 1 month and 3 days.
In the third month, visual observation was made to see if there was any abnormality in the appearance. It was determined that the stability of the emulsion was secured when there was no abnormality such as separation.

Tactile evaluation Ten expert panelists (however, panelists may be duplicated depending on the item) evaluate each item according to the evaluation criteria shown in Table 1, and evaluate the total score of all panelists. And Therefore, the higher the score, the higher the evaluation. (Score: 50 points)

[0055]

[Table 1]

Production Example 1 100 g of isoparaffin in a 500 ml beaker
And 1 g of a polyester-based surfactant (Hypermer B246 manufactured by ICI Japan Co., Ltd., HLB value 5 to 6) were mixed, and nitrogen replacement was sufficiently performed to adjust an oil phase. Separately 50
N-vinylacetamide 70 in a 0 ml beaker
g, 30 g of sodium acrylate, 0.2 g of methylenebisacrylamide as a cross-linking agent, and 0.2 g of a water-soluble azo polymerization initiator as a polymerization initiator are dissolved in 100 g of ion-exchanged water. An aqueous solution of the body was prepared, and a monomer dispersion was prepared by a conventional method. mixer,
500 connected with thermometer, reflux condenser and nitrogen inlet tube
The whole amount of the prepared monomer dispersion was charged into a milliliter four-neck separable flask, and the monomer dispersion was heated under a nitrogen atmosphere to initiate polymerization. After holding for about 8 hours, the mixture was cooled to obtain a water-in-oil polymer dispersion. At this time, the polymer was spherical and the average particle diameter was 2.0 μm. The polymer dispersion after polymerization was distilled to remove water, separated by filtration from isoparaffin, and dried to obtain a spherical powdery thickener. The water absorption retention capacity of this polymer powder is
It was 40,000 parts by weight based on 100 parts by weight of the polymer.

Production Example 2 150 g of cyclohexane in a 500 ml beaker
And sucrose fatty acid ester-based oil-soluble surfactant (DK Ester F-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 1.0)
1 g was heated and mixed, and nitrogen replacement was sufficiently performed to adjust an oil phase. Separately, in a 500 ml beaker, 50 g of N-vinylacetamide, 50 g of methacryloyloxytrimethylammonium chloride, 0.01 g of methylenebisacrylamide as a cross-linking agent, 2,2 g of a polymerization initiator
2'-azobis [2- (2-imidazolin-2-yl)
Propane] 0.2 g of dihydride in 10 parts of ion-exchanged water
The resulting solution was dissolved in 0 g, and similarly replaced with nitrogen sufficiently to prepare an aqueous monomer solution. Under a nitrogen atmosphere, a monomer dispersion was prepared by an ordinary method. A 500 ml four-neck separable flask connected to a stirrer, thermometer, reflux condenser and nitrogen inlet tube was charged with the entire amount of the prepared monomer dispersion, and heated to 40 ° C. under a nitrogen atmosphere to start polymerization. did. About 8
After holding for a time, the mixture was cooled to obtain a dispersion of N-vinylcarboxylic acid amide-based crosslinked resin particles. During the polymerization, the reaction system was stable throughout, and no reaction scale was observed on the inner wall of the flask. After adding and mixing 10 g of isoparaffin to the obtained solution, cyclohexane was removed by distillation,
To 100 g of the dispersion, 2 g of polyoxyethylene lauryl ether of HLB 12.1 was added as a phase inversion reagent to obtain a dispersion, thereby obtaining a liquid thickener. The water absorption retention capacity of this dispersion was 50,000 parts by weight based on 100 parts by weight of the polymer. In addition, the measuring method of the ability to hold water was implemented by the following method. Transfer 0.5 g of the dispersion into a centrifuge tube,
After drying under reduced pressure at 0 ° C. for 10 hours, the resin amount (a) was measured. Next, gently pour distilled water into the centrifuge tube and leave it overnight.
The mixture was centrifuged at 1500 rpm for 10 minutes in a centrifuge. After the separation, the supernatant was removed, and the weight (b) was measured and calculated by the following equation. Water holding power (parts by weight) = [ba / a] × 100

For the purpose of evaluating the salt resistance of the production examples, the effect of thickening the aqueous alcohol solution and the salt water of each production example was confirmed. Table 2 shows the results. In addition, the test is a viscosity (unit: cps) when 1% by weight of each of the production examples is added to each solution.

[0059]

[Table 2]

From the results shown in Table 2, it was confirmed that all of the production examples of the present invention had a thickening effect on an aqueous alcohol solution and salt water. A cosmetic was produced by blending the thus-obtained production examples.

Example 1 A sunscreen gel was obtained according to the following formulation. The unit of the following compounding amount is% by weight.

[0062]

[Table 3]

The components A and B were homogenized at room temperature. Component C was uniformly dissolved at 75 ° C., and then cooled to room temperature.
The component C was added while stirring the component A, and when the mixture became homogeneous, the component B was added and emulsified. When the mixture was homogenized, the mixture was filled in a container to obtain a product.

Comparative Example 1 A product was obtained in the same manner as in Example 1 except that carboxyvinyl polymer was used in place of the crosslinked copolymer resin particles (Production Example 1) of Example 1 and neutralized with sodium hydroxide. .

Example 2 A foundation was prepared according to the following formulation.

[0066]

[Table 4]

The components A and B are separately mixed at 80 ° C. While stirring, the component B was mixed with the component A, allowed to cool, and filled in a container to obtain a product.

Comparative Example 2 The same procedures as in Example 2 were carried out except that polymethyl methacrylate spherical resin beads (average particle diameter: 3 μm) were used instead of the crosslinked copolymer resin particle dispersion (Production Example 2) used in Example 2. To get the product.

Comparative Example 3 In place of the crosslinked copolymer resin particles (Preparation Example 2) used in Example 2, an irregular-shaped poly N-vinylacetamide polymer powder (particle diameter: 0.5 to 10 μm) was used. A product was obtained in the same manner as in Example 2 except for the above.

Tables 5 and 6 show the evaluation results for the examples and comparative examples.

[0071]

[Table 5]

[0072]

[Table 6]

From the results in Tables 5 and 6, it can be seen that this example is excellent in stability and feel. Regarding the feel of this example, the panelists pointed out that a specific feeling of smoothness was felt during application. In this example, no abnormalities on the skin were observed after use. Further, in this example, a thickening effect was recognized by adding a crosslinked copolymer resin, but in Comparative Example 2, no thickening effect was recognized. Furthermore, when the sunscreen agent of Example 1 was used as a makeup base material and the foundation was applied from above, the durability of the foundation was slightly improved, and the makeup paste was good, and it was suitable as a base material. understood.

[0074]

As described above, by blending N-vinyl carboxylic acid amide-based crosslinked copolymer resin particles, a stable thickening effect can be exhibited especially for water-containing cosmetics containing ions and alcohols. Clearly, the feel of the formulation is very good.

Continued on the front page F term (reference) 4C083 AA112 AA122 AB212 AC022 AC072 AC102 AC122 AC242 AC342 AC422 AC542 AD091 AD092 AD152 AD162 AD512 BB21 BB48 BB60 CC12 CC19 EE01 EE06 FF01

Claims (7)

[Claims] 1. An N-vinylcarboxylic acid amide represented by the general formula CH ₂ ＣＨCHNR ₁ COR ₂ (wherein R ₁ R ₂ is the same or different and represents hydrogen or a methyl group) and a compound represented by the above general formula. A water-soluble vinyl compound other than the water-soluble vinyl compound and a crosslinking agent, characterized in that the water-soluble vinyl compound is suspended in a substantially insoluble non-aqueous solvent and polymerized and crosslinked to obtain spherical crosslinked copolymer resin particles. Cosmetics. 2. 500 to 8 pure water per 100 parts by weight.
General formula CH ₂ = with the ability to hold 0000 parts by weight
CHNR ₁ COR ₂ (wherein R ₁ R ₂ is the same or different,
2. A spherical cross-linked copolymer resin particle of an N-vinyl carboxylic acid amide represented by hydrogen or a methyl group) and a water-soluble vinyl compound other than the above-mentioned general formula is blended. Cosmetics. 3. An N-vinylcarboxylic acid amide represented by the general formula CH ₂ ＣＨCHNR ₁ COR ₂ (wherein R ₁ and R ₂ are the same or different and represent hydrogen or a methyl group), and Spherical cross-linked copolymer resin particles with a water-soluble vinyl compound other than those represented, is a dispersion solution obtained by dispersing in a non-aqueous solvent, the ratio of the non-aqueous solvent to 100 parts by weight of the resin particles is 5 to 30 parts by weight Wherein the resin particles contain 10 to 400 parts by weight of water per 100 parts by weight of the N-vinyl carboxylic acid amide-based crosslinked copolymer resin particle dispersion. Characterized cosmetics. 4. The N-vinylcarboxylic acid amide (a)
The cosmetic according to any one of claims 1 to 3, wherein, when the amount of the water-soluble vinyl compound (b) and the water-soluble vinyl compound (b) is represented by parts by weight, the following formula (1) is satisfied. . 0.3 ≦ (a) / {(a) + (b)} ≦ 0.95 Equation (1) 5. The cosmetic according to claim 1, wherein the N-vinylcarboxylic acid amide-based spherical crosslinked copolymer resin particles have an average particle size of 0.5 to 100 μm. . 6. The cosmetic according to claim 1, wherein the N-vinylcarboxylic acid amide is N-vinylacetamide. 7. The N-vinyl carboxylic acid amide-based spherical crosslinked copolymer resin particles having the general formula CH ₂ ＝ CHNR ₁ COR ₂
(Wherein R ₁ and R ₂ are the same or different and represent hydrogen or a methyl group) and a water-soluble vinyl compound other than the above-mentioned general formula is dissolved in at least water. 7. It is obtained by suspending in a non-aqueous solvent and polymerizing and crosslinking in the presence of an oil-soluble surfactant and a crosslinking agent.
The cosmetic according to item.