HK1153661B - Oil-in-water type topical agent for skin - Google Patents

Description

Oil-in-water type external preparation for skin

RELATED APPLICATIONS

The present application claims priority from japanese patent application No. 2008-143428 filed on 30/5/2008 and the contents of which are incorporated herein.

Technical Field

The present invention relates to an oil-in-water type external skin preparation which has stringiness and a thick feel, is delicate, has good adaptability to the skin, does not cause stickiness when dried, and has excellent stability of stringiness over time.

Background

In order to improve stability and to obtain a moisturizing effect, various water-soluble polymers are blended in the skin external preparation. Among these water-soluble polymers, substances having stringiness are present to varying degrees. However, since substances having stringiness also have stickiness, attempts have been made to suppress stringiness in skin external preparations containing water-soluble polymers having stringiness.

Polyacrylic acid or a metal salt thereof, which is a water-soluble polymer, can impart a sense of firmness to the skin with a delicate feeling of use by being blended, but it is known that only a small amount of the polyacrylic acid or the metal salt thereof is blended to have stringiness. Further, it is known that this compound is poor in skin adaptability, stickiness on dry condition, and also poor in the stability of stringiness with time.

However, polyacrylic acid or a metal salt thereof is known to be used in a tooth grinding agent (patent document 1), a patch, a denture fixative, and the like, due to its remarkable stringiness and adhesiveness.

Further, as an external preparation containing sodium polyacrylate, a hair cosmetic using a base having stringiness is disclosed (patent document 2). The hair cosmetic contains wax as essential component, and is emulsified with surfactant, so it is sticky when applied to skin external preparation.

Further, an oil-in-water emulsion is disclosed as an external skin preparation containing sodium polyacrylate (patent document 3). The oil-in-water emulsion is characterized by containing substantially no surfactant as an emulsifier, being non-sticky, and being capable of being used easily and uniformly. However, it is difficult to obtain sufficient stringiness and delicate texture in an oil-in-water emulsion obtained from the sodium polyacrylate and a predetermined emulsification aid, and even when stringiness or a thick texture is obtained, there is a problem in the stability of stringiness with time.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open No. 2000-319150

Patent document 2: japanese laid-open patent publication No. 10-45546

Patent document 3: japanese laid-open patent publication No. 6-165932

Disclosure of Invention

Problems to be solved by the invention

Although it is expected that the skin preparation has appropriate stringiness and gives a unique thick and rich feeling (リツチ feeling) when applied to the skin, no attempt has been made to impart stringiness to the skin preparation for external use since stickiness occurs when the skin preparation is dried. Further, even when a water-soluble polymer having stringiness is blended in the skin external preparation as described above, deterioration in usability such as stickiness or deterioration in stability of stringiness with time cannot be avoided.

The present invention has been made in view of the above-described conventional techniques, and an object of the present invention is to provide an oil-in-water type external preparation for skin which is excellent in thick feeling, has stringiness, is suitable for skin, is not sticky even when it is delicate or dry, and has stringiness and stability with time.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that when a specific amount of an alkyl-modified carboxyvinyl polymer is blended in an external preparation for skin having stringiness and a thick feeling, which contains a specific amount of polyacrylic acid or a metal salt thereof, the external preparation for skin is excellent in tenderness and emulsion stability, and when a specific amount of polyethylene glycol within a specific molecular weight range is blended therein, the external preparation for skin having stringiness over time can be obtained, and when an oil-in-water type external preparation for skin is prepared by blending a specific amount of an oil component therein, the external preparation for skin can be used without causing stickiness upon drying, and have completed the present invention.

That is, the oil-in-water type external preparation for skin of the present invention contains the following components (a) to (d), and has stringiness.

(a) Polyacrylic acid or a metal salt thereof 0.01 to 3.0 mass%

(b) 0.01 to 1.0% by mass of an alkyl-modified carboxyvinyl polymer

(c) 1.0 to 10.0 mass% of polyethylene glycol having an average molecular weight of 1000 to 50000 inclusive

(d) Oil content of 0.5 to 20.0 mass%

The oil-in-water type external preparation for skin of the present invention preferably further contains a water-soluble polymer other than the above-mentioned components (a) and (b) as the component (e).

In the oil-in-water type external preparation for skin, the drawing length at a speed of 30cm/min is preferably 20mm to 200 mm.

The component (e) is preferably one or more selected from succinoglucan, polyacrylamide, carboxyvinyl polymer, and xanthan gum.

The oil-in-water type external preparation for skin preferably further contains one or more of a hydrophilic nonionic surfactant and a hydrophilic anionic surfactant as the component (f).

Effects of the invention

By blending (a) 0.01 to 3.0% by mass of polyacrylic acid or a metal salt thereof, (b) 0.01 to 1.0% by mass of an alkyl-modified carboxyvinyl polymer, (c) 1.0 to 10.0% by mass of polyethylene glycol having an average molecular weight of 1000 to 50000, and (d) 0.5 to 20.0% by mass of an oil component, an oil-in-water type external preparation for skin having a stringiness, excellent skin-adaptability, no stickiness on drying, excellent usability, and excellent stability with time of stringiness can be obtained.

Detailed Description

The best mode for carrying out the present invention will be described below.

((a) polyacrylic acid or metal salt thereof)

In the present invention, by blending polyacrylic acid or a metal salt thereof, stringiness is imparted when the cosmetic is taken in the hand or applied to the skin. The oil-in-water type external preparation for skin of the present invention has stringiness by the incorporation of the polyacrylic acid or the metal salt thereof, and can give a unique thick and rich feeling when applied to the skin. The polyacrylic acid or its metal salt to be incorporated in the oil-in-water type external preparation for skin is preferably a sodium salt.

Examples of the polyacrylic acid or a metal salt thereof include: AQUALIC L-YS, AQUALIC L-HL (manufactured by SHOKUBA, Japan), JULIMAR AC-10NP, JULIMAR AC-10P, Aronbis S, and Aronbis SS (manufactured by JAPONIC JASCO Co., Ltd.).

The amount of polyacrylic acid or a metal salt thereof is 0.01 to 3.0% by mass, preferably 0.03 to 2.0% by mass, and more preferably 0.03 to 1.0% by mass. When the amount of polyacrylic acid or a metal salt thereof is too small, the drawability and the thick feeling cannot be sufficiently obtained, and when the amount is too large, the suitability in the course of cloth is deteriorated and stickiness is generated.

Further, the present inventors have studied various polyacrylic acids or metal salts thereof, and as a result, they have found that: regardless of the polyacrylic acids or metal salts thereof, or the amounts thereof to be blended, an oil-in-water type external skin preparation having an excellent feeling of use can be produced when the amount of stringness is in a specific range.

That is, the oil-in-water type external preparation for skin of the present invention preferably has a drawing length of 20mm to 200mm at a speed of 30cm/min, and particularly preferably 20mm to 100 mm. When the drawing length is within this range, a particularly remarkable rich and thick feeling can be obtained when the composition is applied to the skin. When the drawing length is too short, the drawability may not be felt and sufficient thickening may not be obtained.

The wire drawing length at a speed of 30cm/min was measured by adjusting to 30 ℃ to bring a spherical disk having a diameter of about 1cm into uniform light contact with the surface of a flat sample, observing the state of wire drawing when the sample was vertically lowered at a speed of 30cm/min, and measuring the length from the time of contact to the time of wire breakage.

((b) alkyl-modified carboxyvinyl Polymer)

The alkyl-modified carboxyvinyl polymer used in the present invention is more preferably an alkyl methacrylate copolymer having a molecular weight of 50 to 300 million represented by the following general formula (formula 1), but is not particularly limited.

[ solution 1]

(wherein, R in the general formula (formula 1))¹N, n ', m and m' represent an arbitrary number such that n + n '+ m + m' is 40 to 100, and 1 represents an arbitrary number such that the molecular weight is within a predetermined range. )

Specific examples of the alkyl-modified carboxyvinyl polymer include Pemulen TR-1, Pemulen TR-2, and Carbopol 1342(Lubrizol advanced materials, Inc.).

The amount of the alkyl-modified carboxyvinyl polymer blended is 0.01 to 1.0 mass%, preferably 0.03 to 0.5 mass%, more preferably 0.03 to 0.3 mass%. When the amount of the alkyl-modified carboxyvinyl polymer blended is too small, the delicate feeling and emulsion stability are insufficient. When the amount is too large, the skin becomes less adaptive, and stickiness occurs.

The oil-in-water type external skin preparation of the present invention can be prepared into an oil-in-water type external skin preparation having excellent tenderness and emulsion stability by emulsifying the alkyl-modified carboxyvinyl polymer, but emulsification with a surfactant may be used in combination as long as the effects of the present invention are not impaired.

(c) polyethylene glycol having an average molecular weight of 1000 to 50000 inclusive)

The polyethylene glycol used in the present invention is a polyethylene glycol having an average molecular weight of 1000 to 50000. Polyethylene glycol having an average molecular weight of 1000 to 20000 is preferable. When the average molecular weight of polyethylene glycol is too small, the stability with time of stringiness cannot be improved, and when the average molecular weight is too large, the skin-friendly property is deteriorated, and stickiness is caused.

Examples of the polyethylene glycol having an average molecular weight of 1000 to 50000 include: polyethylene glycol 1000, polyethylene glycol 1500, polyethylene glycol 6000, polyethylene glycol 11000, polyethylene glycol 20000 (manufactured by Toho chemical Co., Ltd., manufactured by Nichio oil Co., Ltd.), etc.

The amount of polyethylene glycol having an average molecular weight of 1000 to 50000 is 1.0 to 10.0% by mass, preferably 1.0 to 5.0% by mass. When the amount of polyethylene glycol having an average molecular weight of 1000 to 50000 is too small, the stability of the stringiness with time cannot be improved, and when the amount is too large, the skin-friendly property is deteriorated, and stickiness is caused.

((d) oil component)

The oil component to be blended in the oil phase used in the present invention is an oil agent used in a usual cosmetic emulsion composition. As the oil agent, any of natural animal and vegetable oils and synthetic oils can be used, and specific examples thereof include: liquid, pasty or solid hydrocarbons such as liquid paraffin and squalane, waxes, higher fatty acids, higher alcohols, esters, glycerides, or silicone oils.

Examples of the liquid fat and oil include: linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia seed oil, castor oil, sunflower oil, almond oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, meadowfoam oil, almond oil, rapeseed oil, sesame oil, wheat germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, neatsfoot oil, liver oil, triglycerol, tricaprylin, pentaerythritol tetraoctanoate, triisopalmitate, and the like.

Examples of the solid fat and oil include: cocoa butter, coconut oil, palm kernel oil, beef tallow, mutton tallow, lard, horse tallow, hydrogenated oils, hydrogenated castor oil, wood wax, shea butter, and the like. Examples of the waxes include: beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, chinese insect wax, spermaceti wax, montan wax, white wax (ヌケロウ), lanolin, reduced lanolin, hard lanolin, kapok wax, cane wax, jojoba wax, shellac wax and the like.

Examples of the ester oil include: octanoates such as cetyl octanoate, laurates such as hexyl laurate, myristates such as isopropyl myristate and octyldodecyl myristate, palmitates such as octyl palmitate, stearates such as isocetyl stearate, isostearates such as isopropyl isostearate, isopalmitate such as octyl isopalmitate, oleates such as isodecyl oleate, adipates such as diisopropyl adipate, sebacates such as diethyl sebacate, and malic acid diesters such as diisostearyl malate.

As the hydrocarbon oil, for example: liquid paraffin, hydrogenated polydecene, ceresin, squalane, squalene, pristane, paraffin, isoparaffin, ceresin, vaseline, microcrystalline wax, etc. Examples of silicone oils include: chain siloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

The oil component (d) is preferably one or more selected from squalane, liquid paraffin, hydrogenated polydecene, polydimethylsiloxane, triethylhexanoic acid glyceride, dimethylpolysiloxane, methylphenylpolysiloxane, and decamethylcyclopentasiloxane.

The amount of these oil components is 0.5 to 20.0% by mass in the emulsion composition, and preferably 1.0 to 10.0% by mass in view of usability. When the amount of the oil component is too small, the delicate feeling is impaired, and stickiness occurs when the composition is dried. When the amount of the oil component is too large, the stability becomes problematic or greasy.

The oil-in-water type external preparation for skin of the present invention may contain, in addition to the essential components (a) to (d), the following components which are generally used in external preparations for skin, as required.

(e) a thickening water-soluble polymer other than the components (a) and (b)

The oil-in-water type external preparation for skin of the present invention preferably contains, as the component (e), a thickening water-soluble polymer other than the components (a) and (b). By blending the component (e), usability such as a thick feeling and the like and the stability of the drawability with time can be improved.

Examples of the water-soluble polymer include: plant polymers such as acacia, tragacanth, galactan, locust bean gum, guar gum, karaya gum, carrageenan, xanthan gum, pectin, agar, quince seed, starch (rice, corn, potato, wheat), and seaweed colloid (brown algae extract); microbial polymers such as dextran, succinoglucan, and pullulan; animal polymers such as collagen, casein, albumin, and gelatin; starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch.

Further, there may be mentioned: cellulose polymers such as methyl cellulose, nitrocellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, and cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate.

Further, there may be mentioned: vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymers, polyoxyethylene polyoxypropylene copolymer polymers, acrylic polymers such as polyethylacrylate and polyacrylamide, inorganic water-soluble polymers such as polyethyleneimine, cationic polymers, bentonite, aluminum magnesium silicate, LAPONITE, hectorite and anhydrous silicic acid, PEG-240/decyl tetradecanol polyether (decyltradech) -20/hexamethylene diisocyanate copolymer, (dimethylacrylamide/acryloyldimethyltaurine Na) crosslinked polymer, (Na acrylate/acryloyldimethyltaurine) copolymer, (alkyl acrylate/stearyl alcohol polyether-20) copolymer, and (acryloyldimethyltauryl ammonium/VP) copolymer.

(e) Among these water-soluble polymers as the component, one or more selected from succinoglucan, polyacrylamide, carboxyvinyl polymer, and xanthan gum are preferable.

(e) The amount of the component (B) is 0.01 to 3.0% by mass, preferably 0.03 to 2.0% by mass, more preferably 0.03 to 1.0% by mass.

((f) a hydrophilic nonionic surfactant or a hydrophilic anionic surfactant)

The oil-in-water type external preparation for skin of the present invention preferably further contains a hydrophilic nonionic surfactant or a hydrophilic anionic surfactant as the component (f). The emulsion stability can be further improved by blending a hydrophilic nonionic surfactant or a hydrophilic anionic surfactant.

The hydrophilic nonionic surfactant or the hydrophilic anionic surfactant may be as follows.

Examples of the hydrophilic nonionic surfactant used in the present invention include: polyoxyethylene fatty acid ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene cholesterol ethers, polyoxyethylene phytosterol ethers, polyoxyethylene polyoxypropylene phytosterol ethers, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid glycerides, polyglycerol fatty acid esters, sucrose fatty acid esters, and the like.

Examples of the hydrophilic anionic surfactant used in the present invention include: fatty acid soaps, N-acetyl glutamate, acetyl taurate, acetyl alkyl taurate, higher alkyl sulfate, alkyl ether sulfate, N-acetyl sarcosinate, higher fatty acid amide sulfonate, phosphate, sulfosuccinate, alkylbenzene sulfonate, and the like.

The aqueous phase component used in the present invention may be blended with various water-soluble components generally used in emulsion compositions for external preparations for skin, as required, within an amount and quality range not impairing the effects of the present invention. Examples of the lower alcohol include: ethanol, propanol, isopropanol, and the like.

Examples of the humectant include: polyethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butylene glycol, erythritol, trehalose, hexylene glycol, glycerol, diglycerin, polyglycerol, xylitol, maltitol, maltose, D-mannitol, sorbitol, polyoxyethylene methyl glucitol polyether, polyoxyethylene polyoxypropylene copolymer dimethyl ether, maltose, glucose, fructose, sodium chondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate, sodium lactate, bile acid salt, pyrrolidone carboxylate, glucosamine, cyclodextrin, water-soluble collagen, and the like.

The oil-in-water type external preparation for skin of the present invention may contain, in addition to the above components, powders, oil-soluble ultraviolet absorbers, water-soluble ultraviolet absorbers, metal ion blocking agents, neutralizing agents, pH adjusting agents, antioxidants, antibacterial agents, various drugs, various extracts, and the like.

Examples of the oil-soluble ultraviolet absorber include: cinnamic acid-based ultraviolet absorbers such as p-aminobenzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers such as methyl anthranilate, salicylic acid-based ultraviolet absorbers such as octyl salicylate, phenyl salicylate, and methyl salicylate (homomethyl salicylate), isopropyl p-methoxycinnamate, octyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, glycerol mono-2-ethylhexanoate di-p-methoxycinnamate, and 3, 4, 5-trimethoxycinnamate [ e ] such as 4-bis (trimethylsiloxy) methylsilyl-3-methylbutyl ] -3, 4, 5-trimethoxycinnamate.

Examples of the water-soluble ultraviolet absorber include: benzophenone-based ultraviolet absorbers such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, octyl p-methoxycinnamate, glyceryl octyl di-p-methoxycinnamate, urocanic acid, ethyl urocanic acid, 2-phenyl-5-methylbenzophenoneOxazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 4-tert-butyl-4 ' -methoxybenzoylmethane, and the like.

Examples of the metal ion blocking agent include: sodium edetate, sodium polyphosphate, sodium metaphosphate and the like.

Examples of the neutralizing agent include: 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol, potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate, amino acids, and the like.

Examples of the pH adjuster include: lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, phosphoric acid, and the like. Examples of the antioxidant include: ascorbic acid, alpha-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole, sulfite, pyrosulfite, and the like. Examples of the antibacterial agent include: benzoic acid, salicylic acid, iodine, phenol, sorbic acid, parabens, parachloro-metacresol, hexachlorobenzene, benzalkonium chloride, chlorhexidine hydrochloride, trichlorocarbanilide, phenoxyethanol, parabens, ethyl hexanediol, and the like.

Examples of the various agents include: vitamins such as vitamin a oil, retinol palmitate, inositol, pyridoxine hydrochloride, benzyl nicotinate, nicotinic acid amide, dl- α -tocopherol nicotinate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, vitamin D2 (ergocalciferol), dl- α -tocopherol acetate, pantothenic acid, and biotin; amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, tryptophan, alanine, glycine, and trimethylglycine; anti-inflammatory agents such as allantoin, glycyrrhizic acid, glycyrrhetinic acid, azulene, etc.; whitening agents such as alkoxy salicylic acid, tranexamic acid, linoleic acid, ascorbyl glucoside, ethyl vitamin C, arbutin, etc.; astringents such as zinc oxide and tannic acid; algefacients such as L-menthol and camphor; or iodine, lysozyme chloride, gamma-ferulic acid ester, etc.

Examples of the various extract solutions include: houttuynia cordata extract, phellodendron amurense extract, scutellaria baicalensis extract, coptis chinensis extract, sweet clover extract, sesameseed (Lamium album var. barbatum) extract, licorice extract, peony extract, lycorine extract, luffa extract, saxifrage extract, sophora flavescens extract, fennel extract, rose extract, rehmannia glutinosa extract, lemon extract, curcuma zedoary extract, aloe extract, calamus root extract, eucalyptus extract, equisetum arvense (スギナ) extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, clove extract, raspberry extract, melissa (melissa) extract, ginseng extract, horse chestnut extract, peach leaf extract, mulberry extract, feverfew extract, ginger extract, grapefruit seed extract, witch hazel extract, cornflower extract, lily flower extract, ginseng extract, lily flower extract, lily, Silk (シルク) extract, and the like.

The water-soluble drug may be used in a free state, in the form of an acid or a base, which can be salified, or in the form of an ester thereof, which has a carboxylic acid group. Further, the oil-in-water type external preparation for skin of the present invention may contain, if necessary, a perfume, a coloring matter, material, and the like as long as emulsification stability is not impaired.

The oil-in-water type external preparation for skin of the present invention has stringiness, and preferably has a stringiness of 20mm to 200mm at a speed of 30cm/min. The oil-in-water type external preparation for skin of the present invention can be produced by a conventional method. However, the drawability and the drawability length obtained by the polyacrylic acid (a) or the metal salt thereof may vary depending on physical shearing of a homogenizer or the like. Depending on the amount of each component to be blended, when the preferable drawing length cannot be obtained, the polyacrylic acid (a) or its metal salt may be added and dissolved after the completion of the dissolution or emulsification of the other components.

The oil-in-water external preparation for skin of the present invention preferably has a viscosity of 3000 to 50000 mPas, more preferably 5000 to 30000 mPas immediately after preparation.

The form of the oil-in-water type external preparation for skin of the present invention, that is, the dosage form, can be variously employed without limitation, and specific examples thereof include: liquid, emulsion or cream products such as cosmetic liquid, emulsion, cream, daily emulsion, foundation (makeup base), liquid foundation, eyeliner, mascara, hair spray, etc., and cosmetic liquid is particularly preferable.

Examples

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto. The amount of the additive represents mass% unless otherwise specified.

Before the description of the examples, the evaluation method of the test used in the present invention will be described.

Evaluation (1): drawability

The presence or absence of stringiness when the sample immediately after preparation was applied to the skin was evaluated based on the following evaluation method.

Evaluation method

O: has wire-drawing property.

X: has no stringiness.

Evaluation (2): thick sensation

The thick feeling when the sample immediately after preparation was applied to the skin was evaluated by 20 functional tests specified for judgment. The scoring criteria are as follows.

Scoring benchmark

And 5, dividing: it is very thick.

And 4, dividing: slightly thick.

And 3, dividing: and (4) common.

And 2, dividing: slightly less thick.

1 minute: it had no thick feeling at all.

Evaluation (3): tender feeling

The tenderness of the sample immediately after preparation when applied to the skin was evaluated by 20 functional tests specified for evaluation. The scoring criteria are as follows.

Scoring benchmark

And 5, dividing: is very delicate.

And 4, dividing: slightly delicate.

And 3, dividing: and (4) common.

And 2, dividing: is not delicate slightly.

1 minute: is not delicate at all.

Evaluation (4): degree of non-stickiness

The samples immediately after preparation were applied to the skin and evaluated for stickiness when dry by 20 sensory tests with a special judgment. The scoring criteria are as follows.

Scoring benchmark

And 5, dividing: it is not sticky at all.

And 4, dividing: slightly tack-free.

And 3, dividing: and (4) common.

And 2, dividing: slightly sticky.

1 minute: it is very sticky.

Evaluation (5): stability of drawability over time

The drawing length (a) of the sample immediately after the preparation and the drawing length (B) of the sample after 1-month storage in a 50 ℃ thermostatic bath were measured, and the stability with time of the drawability was evaluated based on the following evaluation method.

Evaluation method

Very good: (B) 0.8 or more

O: (B) 0.6 or more and less than 0.8

And (delta): (B) 0.4 or more and less than 0.6

X: (B) (A) < 0.4

The sample immediately after preparation was also evaluated as X when the drawn wire length was less than 20 mm.

Evaluation (6): length of wire drawing

The sample immediately after the preparation was adjusted to 30 ℃ so that a spherical disk made of stainless steel having a diameter of about 1cm was uniformly brought into light contact with the surface of the flat sample, and the state of drawing was observed when the sample was vertically lowered at a speed of 30cm/min, and the length at which the wire broke was measured.

Evaluation (7): viscosity of the oil

The sample immediately after the preparation was measured using a VDA type viscometer (Zhipu \12471; \12473 テム, DIGITALVISMETRON VDA) using a spindle No.3 or No.4 at 12rpm for 1 minute.

Evaluation (8): adaptability to skin

The suitability for the skin when the sample immediately after preparation was applied to the skin was evaluated by 20 functional tests specified for judgment. The scoring criteria are as follows.

Scoring benchmark

And 5, dividing: has good adaptability to skin.

And 4, dividing: the adaptability to the skin was slightly good.

And 3, dividing: and (4) common.

And 2, dividing: the adaptability to the skin is slightly poor.

1 minute: the adaptability to the skin is slightly poor.

First, the present inventors produced samples prepared by blending various components as water-soluble polymers and having blending compositions shown in table 1 below.

Then, each sample was evaluated for the evaluation item (1) by the above evaluation method, and the measurement and evaluation for (5) were performed by the above method. Further, each sample was evaluated for the evaluation items (2) to (4) by the above-mentioned evaluation criteria by the special evaluation, and the total score was evaluated based on the below-mentioned special evaluation method. The results are shown in Table 1.

Special evaluation method

Very good: the total score is more than 80.

O: the total score is more than 60 points and less than 80 points.

And (delta): the total score is more than 40 points and less than 60 points.

X: the total score is less than 40.

[ Table 1]

	1-1	1-2	1-3	1-4
					Polyacrylamide sodium salt	1	-	-	-
Hyaluronic acid	-	1	-	-
					Xanthan gum	-	-	1	-
Glycerol	-	-	-	1
					Water (W)	99	99	99	99
(1) Drawability	○	○	○	×
					(2) Thick sensation	◎	○	○	×
(3) Tender feeling	○	△	△	○
					(4) Degree of non-stickiness	△	△	×	◎
(5) Stability of drawability over time	×	○	○	×

In test example 1-1 in which sodium polyacrylate, which is a water-soluble polymer, was blended, the sample had stringiness, had a very remarkable thick and tender feel, but was slightly sticky and had poor stability of stringiness over time.

In test example 1-2 in which hyaluronic acid was blended, the sample had stringiness and the stability of thick feeling and stringiness was slightly excellent with time, but the sample was slightly inferior in tenderness and non-stickiness.

In test examples 1 to 3 in which xanthan gum was blended, the sample had stringiness and the stability of thick feel and stringiness was slightly excellent with time, but the sample was slightly inferior in tenderness and very sticky.

In test examples 1 to 4 in which glycerin was added, the sample was not sticky at all and slightly excellent in delicate texture, but did not have stringiness and did not feel thick.

As is clear from the above, when polyacrylic acid or a metal salt thereof is blended as a water-soluble polymer, not only stringiness but also a remarkably thick feeling can be obtained as compared with a composition blended with another water-soluble polymer. However, it is found that there is a problem in the stability of the stringiness with time while a slight stickiness is felt.

Next, the types of other components necessary for blending polyacrylic acid or a metal salt thereof to obtain a very excellent thick feeling and for obtaining a composition which is delicate, non-sticky and stable in stringiness with time were investigated.

The present inventors prepared samples having the formulation shown in Table 2 below. The test examples 2-1 to 2-4 were produced by a conventional method. In addition, for test examples 2-5 to 2-9, an oil-in-water type external skin preparation (cosmetic liquid) was produced by the following production method.

Method for preparing cosmetic liquid

After preparing the aqueous phase other than sodium polyacrylate, the oil phase was slowly added to the aqueous phase. After completion of emulsification of the other components, sodium polyacrylate was added and dissolved, and the mixture was stirred by a homogenizer.

The present inventors evaluated the evaluation items (2) to (4) on the above-mentioned evaluation criteria by a special evaluation for each sample, and evaluated the total score based on the above-mentioned special evaluation method. Further, each sample was measured and evaluated for the evaluation item (5) by the above-described method. The results are shown in Table 2.

[ Table 2]

In addition, the method is as follows: aronbis S (manufactured by pure Japan pharmaceutical Co., Ltd.)

In addition, 2: pemulen TR-2(Lubrizol Advanced Materials, Inc. Co., Ltd.)

In test example 2-1 in which an alkyl-modified carboxyvinyl polymer and polyethylene glycol were blended with sodium polyacrylate, the sample had an excellent thick feel and also the stringiness was stable with time, but the sample had a slightly poor tenderness and non-stickiness.

In test example 2-2 in which an alkyl-modified carboxyvinyl polymer and dextrin were blended with sodium polyacrylate, the sample had an excellent thick feel, but the sample had a slightly poor long-term stability of delicate feel and stringiness, and was very sticky.

In test examples 2 to 3 in which a carboxyvinyl polymer and polyethylene glycol were blended with sodium polyacrylate, the sample had an excellent thick feel, and the stringiness was slightly stable over time, but the sample was slightly less tender and very sticky.

In test examples 2 to 4 in which a carboxyvinyl polymer and dextrin were blended with sodium polyacrylate, the sample had an excellent thick feel, but the samples were slightly inferior in stability with time in tenderness and stringiness and very sticky.

In addition, in test example 2-5, which was prepared as an oil-in-water type external skin preparation by blending an oil component in test example 2-1, the sample had an excellent thick feel, and also had very excellent usability such as a delicate feel and a non-stickiness at the time of drying, and the stringiness was stable with time.

In test example 2-6, in which the oil component was mixed in test example 2-2 to prepare an oil-in-water type external preparation for skin, the sample had an excellent thick feel, an excellent moist feel, and a slightly excellent degree of non-stickiness, but the stability of stringiness with time was slightly poor.

In test examples 2 to 7, which were prepared into oil-in-water type external skin preparations by blending oil components in test examples 2 to 3, the samples had excellent thickening feeling and stringiness was somewhat stable over time, but the usability such as tenderness and non-stickiness was somewhat inferior.

In test examples 2 to 8, which were prepared into oil-in-water type external skin preparations by blending oil components in test examples 2 to 4, the samples had excellent thick feeling, but usability such as delicate feeling and non-stickiness was not required, and stringiness was slightly unstable with time.

In addition, in test examples 2 to 9 in which sodium polyacrylate was blended in an oil-in-water type external skin preparation, the sample had an excellent thick feel, but the degree of non-stickiness was slightly poor, and the long-term stability of the tenderness and stringiness was poor.

As is clear from the above, by blending (b) an alkyl-modified carboxyvinyl polymer and (c) polyethylene glycol with (a) polyacrylic acid or a metal salt thereof and further blending (d) an oil component to produce an oil-in-water type external skin preparation, it is possible to obtain an external skin preparation which has stringiness and a very excellent thick feeling, and which is tender, non-sticky and stable in stringiness over time.

The amounts of the components (a) to (d) and other components in the oil-in-water type external skin preparation containing the components (a) to (d) were examined in detail.

The present inventors prepared samples having the formulation shown in tables 3 and 4 below, and produced an oil-in-water type external skin preparation (cosmetic liquid) based on the following production method.

Method for preparing cosmetic liquid

< test examples 3-1 to 3-11, and 4-1 to 4-6>

Cosmetic liquids having compositions shown in tables 3 and 4 below were prepared by a conventional method (a method of preparing an aqueous phase and then slowly adding an oil phase to the aqueous phase). Among them, the drawn wire length obtained from sodium polyacrylate is easily shortened by physical shearing by a homogenizer or the like. Therefore, the preferable drawing length is adjusted by adding and dissolving the other components after the completion of the dissolution and emulsification, and stirring the mixture by a homogenizer.

< test examples 4 to 7>

Cosmetic liquids having compositions of test examples 4 to 7 shown in Table 4 below were prepared by the above-described conventional method.

The present inventors evaluated the evaluation items (3), (4), and (8) on the above-mentioned evaluation criteria by a special evaluation for each sample, and evaluated the total score by the above-mentioned special evaluation method. Further, the evaluation item (5) was measured by the above-described method, and the evaluation items (6) and (7) were measured by the above-described evaluation method. The results are shown in tables 3 and 4.

[ Table 3]

[ Table 4]

In test examples 3-1 to 3-11, which are appropriately blended with polyacrylic acid or a metal salt thereof, an alkyl-modified carboxyvinyl polymer, and any of polyethylene glycols having average molecular weights of 1500, 6000, and 20000, the sample had an appropriate viscosity and a long stringy length, and was excellent in usability such as a delicate feeling, skin suitability, and non-stickiness, and also had a stable stringiness with time.

However, in test example 4-1 in which no polyacrylic acid or a metal salt thereof was blended, although the degree of suitability for skin and non-stickiness were excellent, the drawn yarn length was poor and the delicate feeling was slightly poor.

Further, in test example 4-2 in which an alkyl-modified carboxyvinyl polymer was blended, although the drawability was long, the drawability was inferior in stability with time, and a significant problem was caused in terms of usability.

Further, in test examples 4-3 in which no polyethylene glycol was blended, although the workability was good, the drawability was slightly inferior with time.

Further, in test examples 4 to 4 in which polyethylene glycol having an average molecular weight of 400 was blended, although the workability was excellent, the stability of the drawability with time was slightly inferior.

In addition, in test examples 4 to 5 in which a high-polymeric polyethylene glycol having an average molecular weight of 200000 was blended, although the drawability was very stable over time, a significant problem occurred in terms of usability.

In addition, in test examples 4 to 6 in which polyacrylic acid or a metal salt thereof, an alkyl-modified carboxyvinyl polymer, and polyethylene glycol having an average molecular weight of 6000 were blended, but no oil component was blended, the sample could not form an oil-in-water type external skin preparation, and although the skin preparation was excellent in the suitability for skin and the stability with time of stringiness, the sample was slightly poor in tenderness and did not become sticky.

In addition, in test examples 4-7 in which sodium polyacrylate, an alkyl-modified carboxyvinyl polymer, and polyethylene glycol having an average molecular weight of 6000 were blended with the same components as in test example 3-2, but sodium polyacrylate was not added after completion of emulsification, although the composition was excellent in the sense of tenderness, the suitability for skin, and the degree of non-stickiness, the yarn length was poor, and the thick feeling was very poor.

The present inventors have studied in more detail and, as a result, have found that: the oil-in-water type external preparation for skin of the present invention has an appropriate stringiness, and is excellent in long-term stability of usability and stringiness when (a) polyacrylic acid or a metal salt thereof is blended in an amount of 0.01 to 3.0% by mass, (b) an alkyl-modified carboxyvinyl polymer is blended in an amount of 0.01 to 1.0% by mass, (c) polyethylene glycol has an average molecular weight of 1000 to 50000 and a blended amount of 1.0 to 10.0% by mass, and (d) an oil is blended in an amount of 0.5 to 20.0% by mass.

The following examples are formulations of the oil-in-water type external preparation for skin of the present invention. It goes without saying that the present invention is not limited to these formulation examples but is specified by the scope of the claims. The obtained oil-in-water type skin external preparation has good stringiness and thick feeling, excellent stability of stringiness with time, good adaptability to skin, and no stickiness when dried.

Formulation example 1 cosmetic liquid

Sodium polyacrylate 0.3% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.1

Polyethylene glycol 15003.0

Cetyl octanoate 1.0

Decamethylcyclopentasiloxane 2.0

Squalane 2.0

Pentaerythritol Tetraoctanoate 1.0

Polyacrylamide 0.1

(acrylic acid Na/acryloyldimethyltaurine) copolymer 0.1

Sodium stearyl methyl taurate 0.1

Ethanol 5.0

Glycerol 6.0

1, 3-butanediol 5.0

PEG/PPG-17/4 dimethyl Ether 5.0

Tranexamic acid methylamide hydrochloride 2.0

Dipotassium glycyrrhizinate 0.05

Tocopheryl acetate 0.2

Xanthan gum 0.1

Silica 2.0

Polyethylene powder 1.0

Proper amount of sodium metaphosphate

Proper amount of potassium hydroxide

Proper amount of citric acid

Proper amount of sodium citrate

Proper amount of iron oxide yellow

Proper amount of phenoxyethanol

Proper amount of perfume

Pure water surplus

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 2 cosmetic liquid

Sodium polyacrylate 0.1% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.1

Polyethylene glycol 10002.0

Polyethylene glycol 200001.0

Decamethylcyclopentasiloxane 2.0

Lauroyl glutamic acid di (phytosterol/octyl dodecyl) 0.5

Ethanol 5.0

Glycerol 2.0

PEG/PPG-14/7 dimethyl Ether 10.0

Sodium hyaluronate 0.3

Ethyl vitamin C2.0

Salicylic acid 0.5

Dipotassium glycyrrhizinate 0.01

Nicotinic acid amides 3.0

Proper amount of sodium metaphosphate

Proper amount of potassium hydroxide

Proper amount of citric acid

Proper amount of sodium citrate

Proper amount of phenoxyethanol

Proper amount of perfume

Pure water surplus

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 3 emulsion

Sodium polyacrylate 0.8% by mass

(C10-C30) acrylic acid-methacrylic acid copolymer in electric field of 30.3

Polyethylene glycol 110004.0

Triethylhexanoic acid glyceride 5.0

Xanthan gum 0.3

(dimethylacrylamide/acryloyldimethyl taurine Na)

Crosslinked Polymer 0.8

Polyoxyethylene hydrogenated castor oil 1.0

Polyoxyethylene phytosterol ether 0.3

Dipropylene glycol 10.0

Maltitol 2.0

Sorbitol 4.0

Xylitol 0.5

Proper amount of sodium metaphosphate

Proper amount of potassium hydroxide

Proper amount of phenoxyethanol

Pure water surplus

And (2) in color: pemulen TR-1(Lubrizol Advanced Materials, Inc. Co., Ltd.)

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 4 cream

Sodium polyacrylate 0.1% by mass

The (C10-C30) acrylic acid-methacrylic acid copolymer is in a color of 40.1

Polyethylene glycol 60002.0

Agar 1.0

Hydrogenated polyisobutene 2.0

Decamethylcyclopentasiloxane 5.0

Tridecyl isononanoate 1.0

Batyl alcohol 2.0

Vaseline 1.0

(Acryloyldimethyltaurinate/VP) copolymer 1.5

POE (30) behenyl ether 3.0

Sorbitan monooleate 0.5

Myristyl myristate 1.5

1, 3-butanediol 3.0

Glycerol 2.0

Ethyl vitamin C0.5

Ascorbic acid magnesium phosphate ester 0.5

Proper amount of potassium hydroxide

Proper amount of citric acid

Proper amount of sodium citrate

Proper amount of methyl p-hydroxybenzoate

Proper amount of perfume

Pure water surplus

In addition, 4: carbopol 1342(Lubrizol Advanced Materials, Inc. Co., Ltd.)

(production method)

Heating after preparing the water phase, slowly adding the heated oil phase into the water phase, emulsifying by a homogenizer, and dissolving sodium polyacrylate.

Formulation example 5Daily emulsion

Sodium polyacrylate 0.05% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.4

Polyethylene glycol 10005.0

Myristyl myristate 3.0

2-Ethylhexanoic acid-2-ethylhexyl ester 2.0

Polydimethylsiloxane 2.0

0.5 parts of Vaseline

Behenyl alcohol 2.0

Carboxyvinyl Polymer 0.5

Isostearic acid PEG (40) glyceride 1.2

Stearic sorbitan ester 0.3

Stearic acid 0.5

Diglycerin 10.0

1, 3-butanediol 1.0

Erythritol 2.0

Octyl p-methoxycinnamate 6.0

2.0 of di-p-methoxy cinnamic acid glyceride octyl ester

4-tert-butyl-4' -methoxydibenzoylmethane 1.0

4-Methoxysalicylic acid potassium salt 2.0

Proper amount of sodium hydroxide

Proper amount of methyl p-hydroxybenzoate

Proper amount of perfume

Pure water surplus

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 6 foundation

Sodium polyacrylate 0.2% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.3

Polyethylene glycol 15004.0

Dimethylpolysiloxane 2.0

Decamethylcyclopentasiloxane 5.0

Behenyl alcohol 0.5

Batyl alcohol 0.3

Isostearic acid polyoxyethylene glyceride 0.3

Dipropylene glycol 5.0

1, 3-butanediol 3.0

Tocopheryl acetate 0.1

Titanium oxide-red lead-coated mica 0.3

Mica titanium 0.3

Porous spherical cellulose powder 0.5

Proper amount of sodium metaphosphate

Proper amount of potassium hydroxide

Proper amount of methyl p-hydroxybenzoate

Proper amount of perfume

Pure water surplus

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 7Liquid foundation

Sodium polyacrylate 0.3% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.3

Polyethylene glycol 200003.0

Dimethylpolysiloxane 6.0

Behenyl alcohol 0.3

Batyl alcohol 0.7

1, 3-butanediol 3.0

Isostearic acid 1.4

Stearic acid 1.0

Behenic acid 0.7

Cetyl ethylhexanoate 2.0

Polyoxyethylene glyceryl monostearate 2.0

Self-emulsifying glyceryl monostearate 0.5

Mica titanium coated with iron oxide yellow 2.0

Titanium oxide 4.0

Talc 0.5

Kaolin 3.0

Synthetic phlogopite 0.1

Cross-linking type Silicone powder 0.3

Anhydrous silicic acid 5.0

Tocopheryl acetate 0.1

Hyaluronic acid sodium salt 0.1

Proper amount of p-hydroxybenzoate

2-ethylhexyl p-methoxycinnamate 1.0

Proper amount of red lead

Proper amount of iron oxide yellow

Proper amount of iron oxide black

Proper amount of triethanolamine

Proper amount of methyl p-hydroxybenzoate

Proper amount of perfume

Pure water surplus

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 8 mascara

1.0% by mass of sodium polyacrylate

(C10-C30) acrylic acid/methacrylic acid copolymer 0.2

Polyethylene glycol 110001.0

Decamethylcyclopentasiloxane 2.0

Xanthan gum 1.0

Sodium carboxymethylcellulose 1.0

Polyoxyethylene hydrogenated castor oil 0.2

Ethanol 10.0

Glycerol 1.0

Anhydrous silicic acid 1.0

Iron lead coated mica titanium (pearling agent) 8.0

Iron oxide black 1.0

Proper amount of sodium metaphosphate

Proper amount of sodium hydroxide

Proper amount of p-hydroxybenzoate

Proper amount of phenoxyethanol

Proper amount of perfume

Pure water balance

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Formulation example 9Hair spray

Sodium polyacrylate 0.5% by mass

(C10-C30) acrylic acid/methacrylic acid copolymer 0.5

Polyethylene glycol 15005.0

Liquid Paraffin 1.0

Dimethylpolysiloxane 1.0

High polymerized methyl polysiloxane 4.0

Hydroxypropyl cellulose 0.4

Ethyl cellulose 0.3

Polyvinylpyrrolidone 0.5

Fatty acid polyoxyethylene glyceride 0.2

1, 3-butanediol 5.0

Ethanol 20.0

Proper amount of edetate sodium

Proper amount of 2-amino-2-methyl-1, 3-propanediol

Proper amount of methyl p-hydroxybenzoate

Proper amount of perfume

Pure water balance

(production method)

After the preparation of the aqueous phase, the oil phase was slowly added to the aqueous phase, and the sodium polyacrylate was dissolved after emulsification with a homogenizer.

Claims (5)

1. An oil-in-water type external preparation for skin, which comprises the following components (a) to (d) and has a stringiness, wherein the wire-drawing length at a speed of 30cm/min is 20mm to 200mm,

(a) 0.03 to 2.0 mass% of sodium polyacrylate

(b) (C10-C30) 0.01 to 1.0% by mass of an acrylic acid/methacrylic acid copolymer

(c) 1.0 to 10.0 mass% of polyethylene glycol having an average molecular weight of 1000 to 20000

(d) Oil content is 0.5 to 20.0 mass%.

2. The oil-in-water-type external preparation for skin of claim 1, further comprising a water-soluble polymer other than the above-mentioned components (a) and (b) as component (e).

3. The oil-in-water-type external preparation for skin as claimed in claim 2, wherein the component (e) is one or more selected from succinoglucan, polyacrylamide, carboxyvinyl polymer and xanthan gum.

4. The oil-in-water-type external skin preparation according to any one of claims 1 to 3, further comprising one or more of a hydrophilic nonionic surfactant and a hydrophilic anionic surfactant as the component (f).

5. A method for producing an oil-in-water type external preparation for skin comprising the following components (a) to (d),

slowly adding the oil phase into the water phase, emulsifying, adding and dissolving component (a),

(a) 0.03 to 2.0 mass% of sodium polyacrylate

(b) (C10-C30) 0.01 to 1.0% by mass of an acrylic acid/methacrylic acid copolymer

(c) 1.0 to 10.0 mass% of polyethylene glycol having an average molecular weight of 1000 to 20000

(d) Oil content is 0.5 to 20.0 mass%.