JP2001187710A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic which has excellent adhesivity and persistence of cosmetic active ingredients to hair and skin and give the good sense of use. SOLUTION: This cosmetic contains hydrogel particles carrying the active ingredients of the cosmetic, wherein the hydrogel particles are collapsed by a physical force to release the active ingredients of the cosmetic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hair shampoo,
The present invention relates to cosmetics such as conditioners, body shampoos, showers, facial cleansers and bath foams.

[0002]

2. Description of the Related Art Conventionally, a cosmetic active ingredient (hereinafter referred to as "active ingredient") is blended with a rinse-off type cosmetic such as a hair shampoo, a body shampoo, a conditioner, etc. to efficiently apply to the skin and hair. There was a problem with attaching. The reasons are (1) the problem that the active ingredients are easily washed off even if they are to be attached to the skin or hair, or (2) the stability of the active ingredients in cosmetics is poor, and This is because there was a problem of causing sedimentation, separation and the like.

Japanese Patent Application Laid-Open No. 9-249522 discloses that a composition using a hydrogel can improve the feeling of use and the like, but it is a satisfactory level in terms of the stability of active ingredients in cosmetics. Was not.

Japanese Patent Application Laid-Open No. 9-249522 discloses that
Cosmetics using agar or gelatin have been proposed, but hydrogel in this case is a method of gelling the entire cosmetic, and the amount of gel-like substance used is large and there is a problem in the release of active ingredients. there were. Moreover, in this case, since it is presumed that the gel-like substance is used for leave-on cosmetics, there is a problem that the feeling of use is impaired by the gel-like substance remaining on the hair and skin of the user.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cosmetic and / or cosmetic composition having excellent adhesion and persistence to hair and skin,
Another object of the present invention is to provide a cosmetic having a good feeling of use.

[0006]

The present invention relates to a cosmetic containing hydrogel particles carrying an active ingredient for cosmetics, wherein the hydrogel particles are broken down by physical force and the active ingredient for cosmetics is released. Provide cosmetics. Here, the cosmetic active ingredient refers to an ingredient that remains on the surface of the human body and causes a cosmetic user to exhibit the desired effect of the cosmetic.

Here, the hydrogel is a gel having water as a dispersion liquid.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the cosmetic of the present invention, as a polymer forming hydrogel particles, extraction of seaweed such as agar, κ-carrageenan, ι-carrageenan, λ-carrageenan, furcelleran, alginate, propylene glycol alginate, etc. Mucinous substances such as guar gum, locust bean gum, tamarind seed polysaccharide, tara gum, and cassia gum; mucilage of plant fruits such as pectin and arabinogalactan; xanthan gum, scleroglucan, pullulan, dextran, juran gum, curdlan Viscous waste substances such as microorganisms; animal proteins such as gelatin, albumin and casein; plant proteins such as soybean protein and wheat protein; cellulose such as carboxymethylcellulose, methylcellulose and microcrystalline cellulose and derivatives thereof; starch and starch phosphate Ester, starch and its derivatives such as starch glycolate and the like. These are 1
Used as a mixture of more than one species. As a polymer that forms brittle gel particles that are easily physically disintegrated, κ-carrageenan, agar, and juran gum are preferable.

As active ingredients, sunscreens, skin protectants, oils, humectants, antiperspirants, detergents, perfumes, coloring agents for cosmetics, antibacterial agents, bactericides, feel improvers, foam stabilizers and the like. And mixtures thereof.

Examples of the sunscreen include benzophenone compounds, dibenzoylmethane derivatives and thinner derivatives, and inorganic compounds such as titanium oxide and zinc oxide. The amount of these components is 1 to 50% by weight (hereinafter simply referred to as%), particularly 2 to 3% by weight in the hydrogel particles.
0% is preferred.

[0011] The skin protective agent is formulated for the purpose of preventing skin roughness by softening and smoothing the skin. For example, liquid oils and fats such as paraffin, ester, higher alcohol and glyceride;
Styrene-based, ether-based, ester-based, and silicone-based polymer emulsions or suspensions may be used.
The content of these is preferably 1 to 60%, particularly preferably 2 to 40%, of the hydrogel particles.

The oil may be volatile or non-volatile, such as hydrocarbon oil, ester oil, vegetable oil,
Liquid oils such as low-viscosity silicone oils and volatile silicone oils, solid paraffin, petrolatum, ceramide, ethylene glycol difatty acid esters (fatty acids having 12 to 3 carbon atoms)
6) and solid to semi-solid fats and oils such as dialkyl ethers (having 12 to 36 carbon atoms); silicones can also be used. The silicones may be those having a silanol skeleton, for example, methylpolysiloxane,
Modified silicones such as methylphenylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methylhydrogenpolysiloxane, highly polymerized methylpolysiloxane, silicone resin, silicone rubber, silicone beads, amino-modified silicone, and alkyl-modified silicone No. The amount of these compounds is 1 to 60%, especially 2 to 40% in the hydrogel particles.
% Is preferred.

Examples of the humectant include glycerin, glycol, sorbitol, dipropylene glycol, polyethylene glycol and the like. The content of these is preferably 1 to 60%, particularly preferably 2 to 40%, in the hydrogel particles.

Examples of the antiperspirant include aluminum hydroxychloride, tannic acid, zinc sulfate, zinc oxide and the like. These blending amounts are 1 to 60 in the hydrogel particles.
%, Particularly preferably 2 to 40%.

Examples of the detergent include anionic surfactants such as sodium stearate, calcium stearate, ammonium stearate, zinc laurate, zinc palmitate and sodium monoalkyl phosphate; and nonionic surfactants such as sorbitan fatty acid esters. No. These blending amounts are in the hydrogel particles,
It is preferably 1 to 60%, particularly preferably 2 to 40%.

Examples of the coloring agent for cosmetics include water-insoluble pigments, oil-soluble dyes, vat dyes and lake dyes. As pigments, for example, carbon black, talc,
Inorganic pigments such as kaolin, mica, mica titanium, red iron oxide, bismuth oxychloride, magnesium silicate, and titanium oxide; red 202, red 204, red 205, red 206, red 219, red 228, red 404
No., yellow 205, yellow 401, orange 401
And organic pigments such as Blue No. 404, and oil-soluble dyes such as Red No. 505, Red No. 501 and Red No. 2
No. 25, Yellow No. 404, Yellow No. 405, Yellow No. 204,
Orange No. 403, Blue No. 403, Green No. 202, Purple No. 201, etc., and examples of vat dyes include Red No. 226, Blue No. 204, Blue No. 201,
Examples of the lake dye include, for example, various acid dyes which are raked with aluminum or barium. One or more such colorants can be used, and the hydrogel particles preferably contain 1 to 60%, particularly 2 to 40%. In addition, various methods can be used to improve the fixability. For example, these colorants have a Tg of −
It can be used in the form of a mixture with or supported by a polymer emulsified dispersion having a temperature of 20 ° C. or lower.

As antibacterial agents and bactericides, alcohols such as ethyl alcohol and isopropyl alcohol; phenols such as phenol and orthophenylphenol;
Aldehydes such as formaldehyde and glutaraldehyde; benzoic acid (sodium), carboxylic acids such as zinc 10-undecylenate, octanoic acid; esters such as glycerin fatty acid esters; 2,4,4'-trichloro-
2'-hydroxydiphenyl ether (triclosan)
Ethers such as 2,4,5,6-tetrachloroisophthalonitrile; peroxides such as peracetic acid and ethylene oxide; epoxys; halogens such as polyvinylpyrrolidone iodine and o-chloronaphthalene; -Oxyquinoline, bis (2-pyridylthio-1-oxide)
Pyridine quinolines such as zinc; triazines; isothiazolones such as 5-chloro-2-methyl-4-isothiazolin-3-one (caisson); imidazole thiazoles such as 1,2-benzothiazolone; 4'-
Anilides such as trichlorocarbanilide; biguanides such as chlorhexidine hydrochloride; disulfides such as bis (dimethylthiocarbamoyl) disulfide; thiocarbamates such as ammonium-N-methyldithiocarbamate; alkyldimethylbenzylammonium chloride; cetyl Surfactants such as dimethylbenzylammonium chloride and cetylpyridinium chloride; organic metals such as copper 8-oxyquinoline; and high-molecular-weight antibacterial agents such as chitosan, polylysine, and polyhexamethylene biguanide hydrochloride. These antibacterial agents and bactericides can be used in combination of one or more. The amount of these components is 1 to 60%, particularly 2 to 60% in the hydrogel particles.
40% is preferred.

A powder can be used as an active ingredient of the cosmetic. Examples of such powder include extender pigments, synthetic polymer particles, and natural polymer particles. Examples of the extender include talc, kaolin, sericite, calcium carbonate, magnesium carbonate, magnesium silicate, and silicic anhydride. Synthetic polymer particles include nylon powder, polyethylene powder, polystyrene powder, tetron powder, epoxy resin powder, silicone particles (methyl silicone rubber particles, polymethyl silsesquioxane particles), cross-linked alkali polyacrylate particles, )
Acrylic ester-based particles, polyimide-based particles, and polyurethane-based particles are exemplified. Examples of the natural polymer particles include chitosan particles, starch particles, cellulose particles, silk powder, crystalline cellulose powder, and the like. When these powders remain on the skin or the like, they can function as a touch improver such as improving the smooth feeling. In particular, particles having a hydrophobic surface have improved persistence on skin and hair. Examples of such particles include silicone particles, Teflon particles, particles obtained by dispersion polymerization of styrene and (meth) acrylates using a silicone macromer as a dispersant in a non-aqueous medium, and the above various powders as silicone or fluorine compounds. A composite powder coated with a hydrophobic substance such as a hydrophobizing agent or a hydrophobizing agent is preferably used. The powder is 1 to 5 in the hydrogel particles.
It is preferable to mix 60%, especially 2 to 40%.

Further, a foam stabilizer can be used as an active ingredient of the cosmetic. The foam stabilizer is an agent that strengthens the foam film formed by the surfactant, and includes a water-soluble polymer and a hydrophilic solid. Examples of the water-soluble polymer include nonionic polymers such as methylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyacrylamide, and guar gum; xanthan gum, soda salt of carboxymethylcellulose, soda salt of polyacrylic acid, and soda salt of carboxy-modified polyvinyl alcohol. Anionic polymers such as hydroxypropyltrimethylammonium chloride guar gum, hydroxypropyltrimethylammonium chloride starch and hydroxypropyltrimethylammonium chloride cellulose; amphoteric polymers such as gelatin and keratin partially hydrolyzed products; No. As a hydrophilic solid,
Examples include silica, cellulose powder, and carboxymethylated cellulose powder. The content of these is preferably 1 to 60%, particularly preferably 2 to 40%, in the hydrogel particles.

The average particle size of the hydrogel particles carrying the active ingredient is preferably 100 to 3000 μm,
200 to 3000 μm is more preferred. The average particle size of the hydrogel particles is 100 g using various sieves.
Is wet-classified in water, excess water is removed with a filter paper, the weight is measured, and the weight can be expressed as a weight average particle size (Fluie method).

In the hydrogel particles, the weight ratio [water / polymer] of the water contained therein to the polymer excluding water in the hydrogel particles is preferably 25 to 1
000, more preferably 100-500.

The hydrogel particles carrying the active ingredient of the present invention are broken down by physical force to release the cosmetic active ingredient. Its physical force is 3 × 10 ⁶ N / m ² or less, especially 1
It is preferably from × 10 ⁴ N / m ² to 1 × 10 ⁶ N / m ² from the viewpoint of releasing the cosmetic active ingredient. The relationship between this physical force and the collapse of the hydrogel particles was determined by preparing a gel sheet having the same composition as the hydrogel particles and using a handy compression tester (KES
-G5, manufactured by Kato Tech Co., Ltd.).

The method for producing the hydrogel particles carrying the active ingredient is as follows. For example, after dispersing a hydrogel-forming polymer in ion-exchanged water and sufficiently dissolving it at the dissolution temperature, the active ingredient is mixed at a temperature equal to or higher than the gelation temperature, and W / O
The dispersion is added to a preparable oil to form a W / O dispersion and then cooled to prepare hydrogel particles. At this time, a polyvalent salt such as calcium lactate can be added for the purpose of improving the gel-forming ability. It is also possible to form a hydrogel having a uniform particle size by using a vibrating nozzle, or to form a multiphase structure in the gel by using a multiple nozzle such as a double nozzle.

The thus-obtained hydrogel particles carrying the active ingredient are mixed with the cosmetic after washing with oil or as it is. In this case, examples of the cosmetic include cosmetics such as a hair shampoo, a conditioner, a body shampoo, a shower agent, a face wash, and a bath foam. Here, the hydrogel particles carrying the active ingredient are preferably incorporated in the cosmetic in an amount of 0.1 to 80%, particularly preferably 1 to 50%.

Such hydrogel particles are blended into cosmetics by the following method. For example, a predetermined amount of hydrogel particles may be added to and mixed with a cosmetic base which has been prepared in advance, or a cosmetic base such as water and an activator may be added to the hydrogel particle dispersion liquid. .

The cosmetic of the present invention further comprises polyacrylic acid salts for preventing floating and sedimentation of the hydrogel particles.
A thickener such as salts of poly (meth) acrylate copolymer of polyacrylate can be blended. Also,
The cosmetic active ingredient can be separately added to the cosmetic.

The cosmetic of the present invention is applied to hair and skin using tools such as hands and sponges and, if necessary, is massaged so that hydrogel particles are easily disintegrated on hair and skin, The active ingredient adheres on top, and the active ingredient remains. Further, in the present invention, the mechanical force generated when the cosmetic is discharged from the container to the outside can be used as the physical force for disintegrating the hydrogel particles. That is, when the cosmetic is discharged from a container such as a pump or a trigger, the hydrogel particles are easily disintegrated by mechanical force, and the cosmetic active ingredient is further discharged by discharging the liquid, slurry, foam or the like. It can be dispersed efficiently.

[0028]

EXAMPLES The percentages in the examples are percentages by weight unless otherwise specified. Example 1 25 g of Red No. 404 (manufactured by Kishi Kasei) was emulgen 150
5 g of water (manufactured by Kao) and 70 g of water, 1 g of agar (manufactured by Ina agar) was added to the dispersion, and the mixture was stirred at 90 ° C. for 2 hours. Triglyceride)) 1000 g of the mixture was dropped with a syringe having a pore diameter of 1 mm under stirring at 30 ° C. Add 20 parts of water to this solution.
Add 00 g, stir well, stir and phase separate to remove the oil layer. The remaining oil is washed several times with aqueous solution of activator emulgen 150 to obtain the final spherical gel. The resulting spherical gel had a red color, and could be easily crushed by crushing with a finger to color the skin. Examination of the residual amount from the chromaticity of the residual liquid shows that 90% or more is fixed on the skin.

Example 2 Red No. 404 and Emulgen 150 of Example 1 were prepared by replacing 20 g of mica titanium, 3 g of decamethylcyclopentasiloxane and 2 g of highly polymerized methylpolysiloxane (KF9011 manufactured by Shin-Etsu Chemical Co., Ltd.). The appearance at this time was a spherical pale yellow body, which when crushed on the skin also precipitated titanium mica, giving a pearly feeling on the skin.

Example 3 Red No. 404 of Example 1 was replaced with titanium oxide (Persol MC).
X: Teica Co., Ltd.). The appearance at this time was a spherical white body. When this body was crushed on the skin, titanium oxide precipitated and remained on the skin, and was effective as a sunscreen.

Example 4 Red No. 404 of Example 1 was prepared in place of dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.). At this time, the appearance was a spherical white body. When the body was crushed on the skin, the silicone remained on the skin, so that the feeling was good and the skin protection effect was enhanced.

Example 5 1 g of agar (manufactured by Ina Agar) was added to 100 g of water, and stirred at 90 ° C. for 2 hours. An aqueous solution of agar was prepared, and 5 g of polymer particles (polymer A), 9 g of decamethylcyclopentasiloxane, A mixed liquid of 1 g of polymerized methylpolysiloxane (KF9011 manufactured by Shin-Etsu Chemical Co., Ltd.) was added with stirring at 60 ° C. or higher to prepare a mixed dispersion. This dispersion is dropped with a syringe having a pore diameter of 1 mm while stirring 1000 g of coconard (Kao Oil) at 30 ° C. Add water 2 to this solution
Add 000 g, stir well, stir and phase-separate to remove the oil layer, and wash the remaining oil with an Emulgen 150 aqueous solution several times to obtain the final spherical gel. The obtained spherical gel has white spherical spots inside, and is easily crushed by crushing with a finger, and the polymer A remains on the skin.

Production Example of Polymer Particle A After purging with nitrogen a 500 mL four-necked flask equipped with a cooler, a thermometer, and a stirrer, 276.9 g of n-hexane, 90 g of toluene, and a polysiloxane compound having a methacryloxy group at one end were used. (Sisla Plane F manufactured by Chisso Corporation)
M-0725 (registered trademark), number average molecular weight 10,000) 1.5
8 g was charged and the temperature was raised to 70 ° C. 39.50 g of methyl methacrylate (MMA), 13.17 g of styrene and 1.06 g of lauroyl peroxide were added and reacted at 70 ° C. for 12 hours. The reaction system was initially homogeneous, but turned pale white about 10 minutes after the initiator was charged, and then became a white emulsion. After cooling the reaction solution, it was diluted with 200 g of n-hexane,
Solid-liquid separation was performed by centrifugation. The remaining liquid is n-hexane 30
After redispersing at 0 g, the washing step of centrifugation was performed twice, and vacuum drying was performed in a dryer at 50 ° C. to obtain white particles.
0 g was obtained. The obtained polymer particles were monodisperse particles having a diameter of 1.5 μm.

Example 6 1 g of agar (manufactured by Ina agar) and mica titanium (FLAMENCO STAIN VIOLET, manufactured by Engel hard, USA) in 100 g of water
0.35 g was added, and the mixture was stirred at 90 ° C. for 2 hours to prepare an agar aqueous solution (Q). Separately, 5 g of polymer particles (polymer A) and 9 g of decamethylcyclopentasiloxane
And highly polymerized methylpolysiloxane (Shin-Etsu Chemical Co., Ltd.)
(KF9011), 1 g of a mixed solution (R) was prepared. These solutions are mixed with 1000 g of Coconado (Kao Oil) 30
Using a double nozzle (outer nozzle hole diameter 2 mm, inner nozzle hole diameter 1 mm) under stirring at ℃, the solution (Q) was injected from the outer nozzle.
The mixed solution (R) is dropped at a flow rate of 0.5 mL / min from the inner nozzle at a flow rate of 5 mL / min. Add 200 ml of water to this solution.
Add 0 g, stir well, stir and phase separate to remove the oil layer, and wash the remaining oil with several times an aqueous solution of Emulgen 150 to obtain the final spherical gel. The obtained spherical gel had a core-shell structure and exhibited a pearl-like color.
It is easily crushed by crushing with a finger, and the polymer A remains on the skin.

Example 7 The spherical gel containing titanium oxide obtained in Example 3 was crushed while being discharged from a pump having an outlet diameter of 250 μm, and when rubbed on the skin, the titanium oxide remained on the skin. It was effective as a sunscreen.

Example 8 In Example 1, carboxymethylated cellulose (carboxymethylation degree = 0.4, Nippon Paper Industries Co., Ltd.) was used in place of red 404, emulgen 150 and water.
5 g) and 5 g of common salt were dispersed in 9 g of water, and the same operation as in Example 1 was carried out to prepare a cosmetic. The appearance at this time is a spherical white body, it becomes a fine and fine foam,
It was effective as a foam stabilizer.

Comparative Examples 1 to 6 Preparations were made by removing the hydrogel-forming polymer from the substances of Examples 1 to 6.

Comparative Example 7 A hydrogel-forming polymer was prepared from the substance of Example 8 to remove the hydrogel-forming polymer, and was subjected to washing evaluation. Fine bubbles were obtained, but the foaming amount was insufficient and the performance was not satisfactory. .

<Confirmation of Hydrogel Particles> The particles of Examples 1 to 6 were confirmed to be hydrogel particles containing an active ingredient by an optical microscope (5 times) and visual observation.
The average particle size was measured by the sieve method. Table 1 shows the results.

<Evaluation of stability> Potassium laurate 10
%, Potassium myristate 10%, cationized cellulose (K-60 H-60) 0.5%, Amphitol 20N
(Lauryl dimethylamine oxide solution) To a mixture of 3% of glycerin, 3% of purified water and 73.5% of purified water, 5% of an active ingredient except for the hydrogel-forming polymer was added to the samples of Examples and Comparative Examples. Was evaluated based on the change in viscosity and the uniformity during use. The stability over time was evaluated after storage at a constant temperature of 40 ° C. for one month, and the rank was determined according to the following criteria. ：: when the viscosity change is less than ± 10% compared to the initial value and when the content of the active ingredient is less than ± 10% when 10 g of the blended liquid is taken out of the container. ×: when the viscosity change is ± 10% or more compared to the initial value. When the content of the active ingredient is 10% or more when 10 g of the compounded liquid is taken out of the container, the evaluation results are shown in Table 1.

<Skin Fixing Property> The component blended as an active ingredient for cosmetics was applied to the skin, and the percentage of fixation was calculated by the weight of the non-fixing raw material. That is, about 10 cm x 10
5 g of the mixture was added to the pig skin of cm and spread with a finger evenly 50 times in a circle on the pig skin, washed with 500 mL of ion-exchanged water, and washed at 40 ° C / 6.7 KPa. After drying for 24 hours, the weight was measured, and only the mixture containing no active ingredient was calculated as a blank. Table 1 shows the evaluation results.

[0042]

[Table 1]

[0043]

According to the present invention, it is possible to provide a cosmetic composition which is excellent in the adhesiveness and persistence of the cosmetic active ingredient to hair and skin and has a good feeling upon use.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideaki Kubo 1334 Minato, Wakayama City, Wakayama Prefecture Inside Kao Corporation Research Laboratory (72) Inventor Chitoshi Shigeno 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Laboratory F-term (reference) 4C083 AB051 AB242 AB332 AB432 AC422 AD152 AD172 AD211 AD212 AD272 AD351 AD371 AD431 BB11 BB21 BB41 BB48 BB51 CC01 CC02 CC19 DD41 EE12 EE17

Claims (7)

[Claims] 1. A cosmetic comprising hydrogel particles carrying an active ingredient for cosmetics, wherein the hydrogel particles are broken down by physical force to release the active ingredient for cosmetics. 2. The hydrogel particles have an average particle size of 100 to 100.
The cosmetic according to claim 1, which has a size of 3000 µm. 3. The cosmetic according to claim 1, wherein the hydrogel particles are disintegrated by a physical force of 3 × 10 ⁶ N / m ² or less. 4. The cosmetic according to claim 1, wherein the hydrogel particles are formed of at least one selected from carrageenan, agar, duran gum, xanthan gum, gelatin and pectin. 5. The cosmetic active ingredient comprises a sunscreen, a skin protectant, an oil agent, a humectant, an antiperspirant, a detergent, a fragrance, a coloring agent for cosmetics, an antibacterial agent, a bactericide, a feel improving agent, and a foam. The cosmetic according to any one of claims 1 to 4, wherein the cosmetic is at least one selected from stabilizers. 6. The cosmetic according to claim 1, wherein the physical force for disintegrating the hydrogel particles is a mechanical force generated when the cosmetic is discharged from the container to the outside. 7. The cosmetic according to claim 1, wherein the cosmetic is a rinse-off cosmetic.