JP2008088085A - Skin-washing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin-washing agent having a good compatibility with cosmetics, excellent in use feeling such as easy rinsing in washing, or without having a sticky feeling or creaking feeling after washing, excellent in cosmetic removal effects and further having a low skin irritation. <P>SOLUTION: This skin-washing agent contains 0.01 to 70 mass% of a block type alkylene oxide derivative expressed by formula (I) [wherein, Y is a residue of removing hydroxy groups from a polyhydric alcohol having 3 to 6 hydroxy groups; (k) is the number of the hydroxy groups of the polyhydric alcohol; EO is oxyethylene group and AO is a 3-6C oxyalkylene group and each of them are added as a block state; and 0≤a×k≤100, 1≤b×k≤100, 0≤c×k≤100, provided that (a+c)×k>1] and 0.1 to 20 mass% of a humectant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a skin cleanser, and particularly to an improvement of a skin cleanser containing a block-type alkylene oxide derivative as an active ingredient.

Conventionally, there are various types of makeup removers such as a lotion type, an emulsion type, and an oil type.
In general, a lotion-type makeup remover contains a mild nonionic surfactant or amphoteric surfactant that does not irritate the skin as a surfactant having a cleaning action. On the other hand, the oil type has a cleaning effect by dissolving and dispersing cosmetics mainly by using a solvent having a solvent action, and the emulsion type mainly by solvent action of oil and moisture. Have gained.
However, recently, cosmetics with good so-called makeup have been developed, which have good adhesion to the skin and are difficult to make up against moisture and sebum. For this reason, even in the makeup remover, for the purpose of improving the cosmetic removal effect, means such as increasing the alcohol and surfactant, blending a surfactant with a high cleaning action and a solvent with a strong dissolving power, etc. Has been taken.

However, with detergents that contain a detergent with a high cleaning action or a solvent with strong dissolving power, the high dissolving power may cause tingling or redness after washing, or increase the irritation of cosmetics used thereafter. There was a problem. Therefore, in order to avoid these problems and realize high detergency, a make-up removal detergent containing cyclic dimethylpolysiloxane has been developed, but there are problems to be solved such as difficulty in washing off.
On the other hand, specific (poly) ethylene glycol dialkyl ether has been reported as an oily base having high safety and good use feeling and skin affinity (see, for example, Patent Document 1). However, even when this (poly) ethylene glycol dialkyl ether was blended, a product that was sufficiently satisfactory in terms of make-cleaning properties and rinsing properties could not be obtained.
Furthermore, a skin cleanser containing a specific alkylene oxide derivative that has good safety and usability and is easy to wash away has been reported (for example, see Patent Document 2). However, even when this specific alkylene oxide derivative is blended, problems remain in the squeaky sensation of the skin after washing, which is considered to be derived from the surfactant blended together.

JP-A-10-259112 JP 2003-221310 A

  The present invention has been made in view of the circumstances of the prior art, and an object of the present invention is to provide a skin cleanser excellent in usability and a cosmetic removing effect.

  As a result of diligent research conducted by the present inventors to achieve the above-mentioned object, when a block-type alkylene oxide derivative having a specific structure is blended in the skin cleanser, it is well-familiar with cosmetics and is easy to rinse during washing. The present inventors have found that it is possible to provide a skin cleanser that is excellent in usability such as a feeling of stickiness and squeak after washing, excellent in removing cosmetics, and having low skin irritation, and has completed the present invention. .

（式中、Ｙは３〜６個の水酸基を有する多価アルコールの水酸基を除いた残基、ｋは前記多価アルコールの水酸基数、ＥＯはオキシエチレン基、ＡＯは炭素数３〜６のオキシアルキレン基でそれぞれブロック状に付加されている。ａ×ｋ、ｂ×ｋおよびｃ×ｋはそれぞれオキシエチレン基、炭素数３〜６のオキシアルキレン基、オキシエチレン基の平均付加モル数で、０≦ａ×ｋ≦１００、１≦ｂ×ｋ≦１００、０≦ｃ×ｋ≦１００、ただし（ａ＋ｃ）×ｋ＞１である。オキシエチレン基と炭素数３〜６のオキシアルキレン基の合計に対するオキシエチレン基の割合は、１０〜８０質量％である。Ｒは炭素数１〜４の炭化水素基である。）
前記特定構造のブロック型アルキレンオキシド誘導体の含有量が０.１〜２０質量％であることが好適である。 That is, the skin external preparation of the present invention is characterized by containing 0.01 to 70% by mass of a block-type alkylene oxide derivative represented by the following formula (I) and 0.1 to 20% by mass of a humectant.

(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of the alkylene groups is added in the form of a block, a × k, b × k, and c × k are the average addition moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, respectively. ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, (a + c) × k> 1 with respect to the total of oxyethylene groups and oxyalkylene groups having 3 to 6 carbon atoms (The ratio of the oxyethylene group is 10 to 80% by mass, and R is a hydrocarbon group having 1 to 4 carbon atoms.)
It is preferable that the content of the block-type alkylene oxide derivative having the specific structure is 0.1 to 20% by mass.

In the skin cleanser, it is preferable that the AO group of the block-type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.
In the skin cleanser, a in the block-type alkylene oxide derivative represented by the above formula (I) is 0, and the addition order of AO and EO is (AO)-(EO) with respect to Y in the formula. ) Is preferred.
It is preferable that the humectant is one or more selected from dipropylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

  According to the present invention, by blending 0.01 to 70% by mass of a block-type alkylene oxide derivative having a specific structure and 0.1 to 20% by mass of a humectant, familiarity with cosmetics is good, and during washing It is possible to obtain a skin cleanser having excellent usability such as ease of rinsing, feeling of stickiness and squeak after washing, excellent cosmetic removal effect and low skin irritation.

Hereinafter, preferred embodiments of the present invention will be described.
<Block-type alkylene oxide derivative>
The skin external preparation of the present invention contains a block-type alkylene oxide derivative having a specific structure represented by the following formula (I).

In the alkylene oxide derivative represented by the above formula (I), Y is a residue excluding the hydroxyl group of the polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, and 3 to 6 It is. Examples of the compound having 3 to 6 hydroxyl groups include glycerin with k = 3, trimethylolpropane, hexylene glycol, erythritol with k = 4, pentaerythritol, xylitol with k = 5, sorbitol with k = 6 And inositol. The block-type alkylene oxide derivative blended in the skin cleanser according to the present invention has a basic skeleton in which the hydroxyl group is removed from one or a mixture of two or more polyhydric alcohols having 3 to 6 hydroxyl groups. And
In the present invention, Y is more preferably a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 4 hydroxyl groups, that is, it is preferable that 3 ≦ k ≦ 4 is satisfied. When k is 2 or less, the smoothness of the skin after washing tends to be inferior when blended in a skin cleanser, and when k is 7 or more, the skin tends to be sticky after washing.

  EO is an oxyethylene group having 2 carbon atoms. AO is an oxyalkylene group having 3 to 6 carbon atoms, and specific examples include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxy t-butylene group, an oxypentylene group, and an oxyhexylene group. . Preferred are an oxypropylene group and an oxybutylene group, and more preferred is an oxybutylene group.

  b × k is the average added mole number of AO, and 1 ≦ b × k ≦ 100, preferably 3 ≦ b × k ≦ 70. a × k and c × k are average added moles of EO, 0 ≦ a × k ≦ 100, 0 ≦ c × k ≦ 100, preferably 3 ≦ a × k ≦ 70, 3 ≦ c × k ≦ 70. Moreover, the preferable range of the average addition mole number of all the oxyethylene groups in the said formula (I) is 1 <(a + c) * k <= 200, More preferably, it is 6 <= (a + c) * k <= 140. AO becomes a hydrophobic site in the block-type alkylene oxide derivative according to the present invention, and when b × k exceeds 0 or 100, the cosmetic removal effect is low when blended in a skin cleanser, and the skin moisturizing effect after cleansing There is a tendency to be inferior. Further, when a × k or c × k is 0, the cosmetic removal effect that should be expected when blended into a skin cleansing material is not exhibited, and when it exceeds 100, the skin tends to be sticky after washing. .

The ratio of the total EO in the said formula (I) with respect to the sum total of AO and EO in the said formula (I) is 10-80 mass%, More preferably, it is 20-70 mass%. If it is less than 10% by mass, the cosmetic removal effect tends to be inferior. If it is more than 80% by mass, the cosmetic removal effect is low, and the skin feels after washing tends to occur.
The addition form of AO and EO is block-like, and the addition order is (AO)-(EO) order, (EO)-(AO) order, (EO)-( Any of the order of AO)-(EO) may be sufficient. In the present invention, the order of (AO)-(EO) with respect to Y in the formula is particularly preferable. In the order of (AO)-(EO) with respect to Y in the formula, it corresponds to a in the formula being 0.

  R is a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. It is done. In the present invention, a methyl group and an ethyl group are preferable. If the carbon number is greater than 5, the moisturizing effect of the skin after washing tends to be inferior. In the block-type alkylene oxide derivative blended in the skin cleanser according to the present invention, R may be the same or different in one molecule, and the block type having the same R in one molecule. One kind of alkylene oxide derivative or a mixture of two or more kinds having different Rs may be used.

Specific examples of the block-type alkylene oxide derivative blended in the skin cleanser according to the present invention include POB (30) POE (30) glyceryl trimethyl ether, POB (30) POE (35) glyceryl trimethyl ether, POB (17 ) POE (28) glyceryl trimethyl ether, POB (27) POE (45) glyceryl trimethyl ether, POB (14) POE (34) glyceryl trimethyl ether, POB (22) POE (55) glyceryl trimethyl ether, POB (19) POE (55) Glyceryl trimethyl ether, POB (40) POE (80) glyceryl trimethyl ether, POB (80) POE (40) glyceryl trimethyl ether, POB (30) POE (30) glyceryl triethyl ether , POB (30) POE (35) glyceryl triethyl ether, POB (14) POE (34) glyceryl triethyl ether, POB (30) POE (30) glyceryl tripropyl ether, POE (30) POP (30) glyceryl triethyl ether, POE (35) POP (40) glyceryl trimethyl ether, POE (41) POP (48) glyceryl trimethyl ether, etc. are mentioned.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and may be abbreviated as follows.

  The block-type alkylene oxide derivative of the present invention can be produced by a known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

  The blending amount of the block-type alkylene oxide derivative is usually 0.01 to 70% by mass, preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass, based on the whole skin cleansing material. If it is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited, and if it exceeds 70% by mass, a sticky feeling after washing may occur.

  Specific examples of the humectant of the present invention include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl- Examples thereof include 12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, and merirot extract. . N-lauroyl-N′-carboxymethyl-N ′-(2-hydroxyethyl) ethylenediamine sodium, N-myristoyl-N′-carboxymethyl-N ′-(2-hydroxyethyl) ethylenediamine sodium, N-palmitoyl-N ′ -Carboxymethyl-N '-(2-hydroxyethyl) ethylenediamine sodium, N-lauroyl-N'-carboxymethyl-N'-(2-hydroxyethyl) ethylenediamine potassium, N-lauroyl-N'-carboxymethyl-N ' -(2-hydroxyethyl) ethylenediamine magnesium and the like. In particular, one or more selected from dipropylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin are preferable.

  In addition to the above-mentioned essential components, the skin cleansing material of the present invention can be blended with components usually used in cosmetics and pharmaceutical cleansing agents, and are produced according to conventional methods. Examples of such components include the following, and are prepared by appropriately blending the following components in addition to the essential components.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene Powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, Iron oxide (Bengara), iron titanate, etc .; Inorganic brown pigments (eg, γ-iron oxide, etc.); Inorganic yellow pigments (eg, yellow iron oxide, loess, etc.); Inorganic black pigments (eg, black oxide) Iron, low-order titanium oxide, etc.); inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, Pearl pigments (eg titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored oxidation) Tan-coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204) No., red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, organic pigments such as red 3 , Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 and Blue No. 1 etc.); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.

  Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

  Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin. , Jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.

  Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.

  Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.

  Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylo Propane, tetra-2-ethylhexanoate pentaerythritol, glycerol tri-2-ethylhexanoate, glycerol trioctanoate, glycerol triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmi Tate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2 -Octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate Le, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.

Moreover, it is also possible to mix | blend various surfactant with the skin cleaning material concerning this invention.
Anionic surfactants include, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE lauryl sulfate triethanolamine, POE sodium lauryl sulfate, etc.); N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, N-myristoyl-N-methyl taurine sodium, coconut oil fatty acid) Methyl tauride sodium, lauryl methyl tauride sodium, etc.); Phosphate ester salts (POE oleyl ether sodium phosphate, POE stearyl ether phosphate, etc.); Sodium 2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkylbenzene sulfonates (for example, sodium lineardodecylbenzenesulfonate, triethanolamine lineardodecylbenzenesulfonate) Higher fatty acid ester sulfate (for example, hydrogenated coconut oil fatty acid sodium glyceryl sulfate, etc.); N-acyl glutamate (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl-L-monoglutamate monosodium, etc.); sulfated oil (eg funnel oil, etc.); POE alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate salt; secondary alcohol sulfate ester salt; higher fatty acid alkylolamide sulfate ester salt; sodium lauroyl monoethanolamide succinate; N -Palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N'-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE alkylamine; Examples include amine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexyl); glycerin polyglycerin fatty acids (for example, mono-cotton oil fatty acid glycerin, mono-erucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (eg, Propylene glycol stearate); hydrogenated castor oil derivatives; glycerol alkyl ethers, and the like.

  Examples of hydrophilic nonionic surfactants include POE sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, POE sorbitan tetraoleate, etc.); POE sorbite fatty acid ester (Eg POE sorbite monolaurate, POE sorbite monooleate, POE sorbite pentaoleate, POE sorbite monostearate, etc.); POE glycerin fatty acid esters (eg POE glycerin monostearate, POE glycerin monoisostearate) POE monooleate such as POE glycerin triisostearate); POE fatty acid esters (for example, POE distearate, POE monodiolate, distearies) POE alkyl ethers (for example, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); Pluronic type (for example, POE / POP alkyl ethers (for example, POE / POP cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, etc.) ); Tetra POE / tetra-POP ethylenediamine condensates (for example, Tetronic, etc.); POE castor oil hydrogenated castor oil derivatives (for example, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, P) OE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE hydrogenated castor oil maleic acid, etc .; POE beeswax lanolin derivatives (eg POE sorbite beeswax etc.); Oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; .

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

  Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and the like); alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

  Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40,000, 60,000). Etc.); acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide and the like); polyethyleneimine; cationic polymers and the like.

  Examples of the thickener include gum arabic, carrageenan, caraya gum, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, silicate A1Mg (vee gum), Examples thereof include laponite and silicic anhydride.

  Examples of UV absorbers include benzoic acid UV absorbers (eg, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester. N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); anthranilic acid-based UV absorbers (for example, homomenthyl-N-acetyl anthranilate, etc.); Salicylic acid ultraviolet absorbers (for example, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid ultraviolet absorbers (for example, octylcinnamate, ethyl- 4-isopropyl cinnamate, meth -2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxy Cinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenyl Cinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone UV absorbers (for example, 2,4-dihydroxybenzophenone, 2 , 2'-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid salt, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- ( 4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4'-t-butyldiben Irumetan; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, and the like.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
Cypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphoric acid; POP / POE-pentane erythritol ether, polyglycerin and the like.

  Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

  Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol. Is mentioned.

  Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Examples of other components that can be blended include antiseptics (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, capsicum, chimney, red snapper, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonyl acid wallenylamide, nicotine) Acid Gyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.

The dosage form of the skin cleanser of the present invention is arbitrary, and examples thereof include a solution system, a solubilization system, an emulsification system, a powder dispersion system, a water-oil two-layer system, and a water-oil-powder three-layer system.
The skin cleansing agent of the present invention is suitably used for cleaning the skin, particularly for skin after makeup or sunscreen application, and the dosage form preferably takes the form of a gel or cream.

The present invention will be described more specifically with reference to the following examples. In addition, this invention is not limited by this. First, the evaluation method used in the present invention will be described.
First, the formulation of the cosmetics used in the test (sunscreen and strong foundation with coating properties) will be described.

Sunscreen prescription (mass%)
―――――――――――――――――――――――――――――――――――
(1) Methylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 20.0
(3) Trimethylsiloxysilicic acid 2.0
(4) Polyoxyethylene / methylpolysiloxane copolymer 1.0
(5) 1,3-butylene glycol 5.0
(6) Isostearic acid 0.3
(7) Titanium oxide 17.0
(8) Octyl methoxycinnamate 8.0
(9) Clay mineral 0.5
(10) Polyalkyl acrylate 5.0
(11) Trisodium edetate appropriate amount (12) Preservative appropriate amount (13) Fragrance appropriate amount (14) Purified water residue
―――――――――――――――――――――――――――――――――――

Formulation of foundation (mass%)
―――――――――――――――――――――――――――――――――――
(1) Decamethylcyclopentasiloxane 14.0
(2) Octamethylcyclotetrasiloxane 24.0
(3) Siliconized pullulan 15.0
(4) Isostearic acid 1.0
(5) Titanium oxide 5.0
(6) Octyl methoxycinnamate 5.0
(7) Dextrin fatty acid-coated powder 25.0
(8) Alcohol balance (9) Perfume appropriate amount
―――――――――――――――――――――――――――――――――――

About the following evaluation (1)-(5), the thing of the following composition was prepared as a control skin washing | cleaning material, and it used as a reference | standard of evaluation.
Control skin cleansing composition (1) Carboxyvinyl polymer 0.5% by mass
(2) Hydroxyethyl cellulose 0.02
(3) Acrylic acid / alkyl methacrylate copolymer 0.1
(4) Decamethylcyclopentasiloxane 10.0
(5) Liquid paraffin 3.0
(6) POE (10) isostearic acid 5.0
(7) 1,3-butylene glycol 5.0
(8) Potassium hydroxide appropriate amount (9) Fragrance appropriate amount (10) Purified water residue (preparation method)
(1) to (3) and (6) to (8) were uniformly mixed and dissolved in (10), and the oil phase component in which (4) and (5) were mixed therein was stirred and mixed. Furthermore, (9) was added and emulsified with a homomixer to obtain cream cleansing (O / W type).

"Evaluation (1): Ease of compatibility between skin cleanser and cosmetics"
A sunscreen and a strong film foundation were overcoated, and after 2 hours, the face was washed with a sample, and an actual use test was conducted by 10 professional panelists to determine whether the skin cleanser and cosmetics are compatible. . Have the students score based on the following scoring standards. Here, the score determination is performed by setting the familiarity between the control skin cleanser and the cosmetic as 0. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: It was recognized that it was very familiar compared to the control skin cleanser.
+2: Acknowledgment was better than control skin cleanser.
+1: Permitted to be somewhat familiar with the control skin cleanser.
0: Neither can be said.
-1: Not so familiar as compared to the control skin cleanser.
-2: Not compatible with the control skin cleanser.
-3: Not compatible with the control skin cleanser.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

"Evaluation (2): Ease of rinsing skin cleanser"
A sunscreen and a strong coating foundation were repeatedly applied, and after 2 hours, the face was washed with the sample, and an actual use test was conducted by 10 professional panelists to determine whether the skin cleansing agent was easily rinsed. Have the students score based on the following scoring standards. Here, the score is determined by setting the ease of rinsing the control skin cleansing material to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: It was recognized that it was much easier to rinse than the control skin cleanser.
+2: Easier to rinse than control skin cleanser.
+1: It was recognized that it was easy to use compared with the control skin cleanser.
0: Neither can be said.
-1: Not easy to rinse as compared with the control skin cleanser.
-2: It is not easy to rinse as compared with the control skin cleanser.
-3: Not easily rinsed as compared with the control skin cleanser.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

“Evaluation (3): No stickiness after cleaning”
A sunscreen and a strong coating foundation were repeatedly applied, and after 2 hours, the face was washed with a sample, and the presence or absence of stickiness after washing was tested by 10 professional panelists. Have the students score based on the following scoring standards. Here, the score determination is carried out with zero stickiness after use of the control skin cleanser. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: It was recognized that the skin was not very sticky after cleaning compared to the control skin cleanser.
+2: Not sticky after washing as compared to the control skin cleanser.
+1: Slightly non-sticky after cleaning compared to the control skin cleanser.
0: Neither can be said.
-1: Slightly sticky after cleaning compared to control skin cleanser.
-2: Sticky after washing compared to the control skin cleanser.
-3: Very sticky after washing compared to control skin cleanser.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

"Evaluation (4): squeak after cleaning"
A sunscreen and a strong coating foundation were repeatedly applied, and after 2 hours, the face was washed with a sample, and an actual use test was conducted by 10 professional panelists for the presence or absence of squeak after washing. Have the students score based on the following scoring standards. Here, the score is determined with the squeaky feeling of the control skin cleansing material set to zero. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring criteria +3: It was recognized that the skin was not very hard after cleaning compared to the control skin cleanser.
+2: It was recognized that there was no scratch after cleaning compared to the control skin cleanser.
+1: Recognized that it does not burn slightly after washing compared to the control skin cleanser.
0: Neither can be said.
-1: Slightly creaked after cleaning compared to control skin cleanser.
-2: Squeaks after washing compared to the control skin cleanser.
-3: Very squeaky after cleaning compared to the control skin cleanser.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

"Evaluation (5): Cosmetic removal effect"
A sunscreen and a strong coating foundation were overcoated, and after 2 hours, the face was washed with a sample, and 10 professional panelists conducted an actual use test for the presence or absence of the cosmetic removal effect after washing. Have the students score based on the following scoring standards. Here, the score determination is carried out with the effect of removing the control skin cleanser as 0. In addition, the average value which divided the sum total of the score by each panel by the panel number of persons was calculated, and it was set as the evaluation result according to the following evaluation criteria.
Scoring standard +3: It was recognized that the effect of removing cosmetics was very high after washing compared to the control skin cleanser.
+2: It was recognized that the cosmetic removal effect after washing was higher than that of the control skin cleanser.
+1: It was recognized that the effect of removing cosmetics was slightly higher after cleaning than the control skin cleanser.
0: Neither can be said.
-1: It was recognized that the effect of removing cosmetics was slightly lower after cleaning than the control skin cleanser.
-2: It was recognized that the effect of removing the cosmetic after washing was lower than that of the control skin cleanser.
-3: It was recognized that the cosmetic removal effect was very low after washing compared with the control skin cleanser.
Evaluation criteria A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

"Evaluation (6): Skin irritation test"
A 24-hour occlusion patch test was performed on the inner side of the upper arm of 10 subjects, and then the average value was calculated according to the following scoring criteria. The evaluation criteria are as follows.
Scoring standard 0 point: No abnormality is recognized.
1 point: Slight redness was observed.
2 points: Redness was observed.
3 points: Redness and papules were observed.
Evaluation criteria A: The average value of 10 panelists is less than 0.15 points.
B: The average value of 10 panelists is 0.15 or more and less than 0.2.
C: The average value of 10 panelists is 0.2 or more and less than 0.3.
D: The average value of 10 panelists is 0.3 points or more

  The present inventors actually prepared a skin cleansing agent and evaluated it using the following basic composition for testing in which various alkylene oxide derivatives were blended. In addition, the face washing by the cleansing charge of the following basic composition was performed by rinsing the cleansing charge directly on the face and then rinsing with water.

Basic composition for testing (1) Carboxyvinyl polymer 0.5% by mass
(2) Hydroxyethyl cellulose 0.02
(3) Acrylic acid / alkyl methacrylate copolymer 0.1
(4) Decamethylcyclopentasiloxane 10.0
(5) Liquid paraffin 3.0
(6) Alkylene oxide derivatives
(7) Moisturizer
(8) Potassium hydroxide appropriate amount (9) Fragrance appropriate amount (10) Purified water residue (preparation method)
(1) to (3) and (6) to (8) were uniformly mixed and dissolved in (10), and the oil phase component in which (4) and (5) were mixed therein was stirred and mixed. Furthermore, (9) was added and emulsified with a homomixer to obtain cream cleansing (O / W type).

The present inventors examined various skin cleansing agents containing various alkylene oxide derivatives. The results are shown in Tables 1-3.
In addition, the block type alkylene oxide derivative in the following table | surface shall have a structure of the following formula | equation (II). For example, when a + c + e = 30 and b + d + f = 30, they are expressed as (BO) ₃₀ (EO) ₃₀ .

In Test Examples 1 to 10 in Table 1 above, 5% by mass of 1,3-butylene glycol is blended as a humectant.
As a control, even if the conventionally used surfactant POE (10) isostearic acid is blended for detergency (control), the stickiness after washing and the skin irritation are not satisfactory.
When the structure of the blended alkylene oxide derivative is composed of only the oxyethylene part or only the oxybutylene part (Test Examples 7 and 8), these substances do not function as surfactants, so that they are easily compatible with cosmetics. The ease of rinsing during washing and the effect of removing cosmetics are very poor.

Further, in Test Example 9 in which an alkylene oxide derivative having hydrogen at its terminal was blended, the stickiness after washing and evaluation of skin irritation were inferior. In addition, when a random type alkylene oxide derivative is blended (Test Example 10), the function as a surfactant is inferior, so that the compatibility with cosmetics, ease of rinsing during washing, and cosmetic removal effects are not satisfactory. There wasn't.
On the other hand, in the test example which mix | blended various block type alkylene oxide derivatives mix | blended with Test Examples 1-6, it was excellent in any evaluation of (1)-(6).

As is clear from the above results, when a block-type alkylene oxide derivative having a specific structure is blended into a skin cleanser, it is well-familiar with cosmetics and is easy to rinse during cleaning, and does not feel sticky or squeaky after cleaning. It is possible to obtain a skin cleanser having excellent usability such as excellent cosmetic removal effect and low skin irritation.
Next, the moisturizing agent blended in the skin cleanser was examined. The results are shown in Table 2 below.

In the case where no block-type alkylene oxide derivative having a specific structure was blended (Test Example 14), it was confirmed that the rinsing ease during washing, the squeaky feeling after washing, and the skin irritation were inferior. Further, when no humectant such as propylene glycol or glycerin was added (Test Example 15), it was confirmed that the squeaky feeling after washing was not particularly good.
On the other hand, when the block type alkylene oxide derivative having a specific structure blended in Test Examples 11 to 13 and the humectant were combined, the evaluation was excellent in any of (1) to (6).
Next, Table 3 below shows the results of studying suitable blending amounts of the block-type alkylene oxide derivative having a specific structure in the skin cleanser.

  From the results of Table 3 above, the blending amount of the block-type alkylene oxide derivative having a specific structure is recognized from about 0.1% by mass, but particularly noticeable is 1.0% by mass or more. However, when it becomes 20.0% by mass or more, a sticky feeling after washing starts to occur to some extent, and the blending up to about 10% by mass is particularly preferable. Therefore, the blending amount of the block-type alkylene oxide derivative having a specific structure is preferably 0.1 to 20.0% by mass.

Hereinafter, a part of synthesis examples of various alkylene oxide derivatives blended in the skin cleansing material of the above test example will be shown.
<Synthesis Example 1>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) trimethylglyceryl ether (block type alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Then, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.
Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 49, the alkylene oxide derivative 1 had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.008. An atom is converted to a methyl group.

<Synthesis Example 2>
Synthesis of polyoxyethylene (57 mol) trimethylglyceryl ether (alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then stirred at 140 ° C. The catalyst was completely dissolved. Next, 2508 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and an alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 66, and the alkylene oxide derivative 1 had a hydroxyl value of 0.60.009, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was almost completely hydrogen atoms. Has been converted to a methyl group.

<Synthesis Example 3>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) glyceryl ether (block type alkylene oxide derivative) 92 g of glycerol and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Thereafter, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.

<Synthesis Example 4>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) tributyl glyceryl ether (block-type alkylene oxide derivative) 92 g of glycerol and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Then, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2160 g of butylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, after charging 800 g of potassium hydroxide and replacing the inside with dry nitrogen, 1200 g of butyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid and adjusted to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a block-type alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 50, the alkylene oxide derivative 1 had a hydroxyl value of 1.5, and the ratio of the number of hydrogen atoms to the number of terminal butyl groups was 0.03, indicating that hydrogen was almost completely removed. Atoms are converted to butyl groups.

<Synthesis Example 5>
Synthesis of polyoxybutylene (30 mol) polyoxyethylene (30 mol) glyceryl ether (random alkylene oxide derivative) 92 g of glycerin and 18 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave was replaced with dry nitrogen. Thereafter, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 2160 g of butylene oxide and 1320 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 400 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 300 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to adjust to pH 6 to 7, and treated at a reduced pressure of -0.088 MPa (gauge pressure) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and a random alkylene oxide derivative was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 47, the resulting random alkylene oxide derivative 5 compound had a hydroxyl value of 0.5, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.011. The hydrogen atom is almost completely converted to a methyl group.

  Although the example of formulation of the skin washing | cleaning material concerning this invention is given to the following, the technical scope of this invention is not limited by these. In addition, the obtained skin cleanser is well-familiar with cosmetics, and is excellent in ease of rinsing during washing, excellent in usability such as stickiness after washing, no squeaky feeling, excellent in cosmetic removal results, Low skin irritation was confirmed.

（式（III）中、ａ＋ｃ＋ｅ＝３０、ｂ＋ｄ＋ｆ＝３５であり、ＢＯはオキシブチレン基、ＥＯはオキシエチレン基を示す。）
（８）水酸化カリウム 適 量
（９）アルコール ５．０
（１０）防腐剤 適 量
（１１）デカメチルシクロペンタシロキサン １８．０
（１２）メチルポリシロキサン ３．０
（１３）香料 適 量
（１４）精製水 残 余
（製法及び評価）
（１４）に（１）〜（８）を加え攪拌溶解し、これを水相部とした。その後（９）に（１０）を溶解させたものを水相部に加え、更に（１１）〜（１３）を加えて、乳化機で乳化してメーククレンジングジェルを得た。得られたメーククレンジングジェルを直接なじませた後、水で洗い流したところ、該クレンジングジェルは化粧料とのなじみが良く、洗浄中のすすぎやすさ、洗浄後のべたつき感・きしみ感のなさ等の使用性に優れ、化粧料除去効果に優れ、さらに低皮膚刺激性であることが認められた。 The formulation examples are shown below.
Formulation Example 1: Makeup Cleansing Gel (1) Hydroxyethylcellulose 0.1% by mass
(2) Carboxyvinyl polymer 0.4
(3) Acrylic acid / alkyl methacrylate copolymer 0.2
(4) Trisodium edetate appropriate amount (5) Palm oil fatty acid methyl taurine sodium 0.1
(6) Polyethylene glycol monoisostearate 0.5
(7) POB (30) POE (35) Trimethylglyceryl ether (block) 5.0

(In formula (III), a + c + e = 30 and b + d + f = 35, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(8) Potassium hydroxide appropriate amount (9) Alcohol 5.0
(10) Preservative appropriate amount (11) Decamethylcyclopentasiloxane 18.0
(12) Methylpolysiloxane 3.0
(13) Appropriate perfume (14) Residual water residue (Production method and evaluation)
(1) to (8) were added to (14) and dissolved by stirring to obtain an aqueous phase part. Then, (10) dissolved in (9) was added to the aqueous phase, and (11) to (13) were further added and emulsified with an emulsifier to obtain a make-up cleansing gel. After directly blending the obtained make-up cleansing gel and washing with water, the cleansing gel is well-familiar with cosmetics, such as ease of rinsing during washing, feeling of stickiness and creaking after washing, etc. It was confirmed that it was excellent in usability, excellent in removing cosmetics, and low in skin irritation.

Formulation Example 2: Makeup Cleansing Gel (1) Hydroxyethylcellulose 0.05% by mass
(2) Carboxyvinyl polymer 0.45
(3) Acrylic acid / alkyl methacrylate copolymer 0.1
(4) Trisodium edetate appropriate amount (5) Palm oil fatty acid methyl taurine sodium 0.01
(6) POB (32) POE (52) Trimethylglyceryl ether (block) 7.0
(In formula (III), a + c + e = 32 and b + d + f = 52, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(7) Sodium polyaspartate solution (8) Chamomile extract (9) Potassium hydroxide (10) Alcohol 5.0
(11) Polyoxyethylene hydrogenated castor oil 0.1
(12) Preservative appropriate amount (13) Decamethylcyclopentasiloxane 18.0
(14) Methylpolysiloxane 3.0
(15) Appropriate amount of fragrance (16) Residual water residue (Production method and evaluation)
(1) to (9) were added to (16) and dissolved by stirring, and this was used as the aqueous phase. Then, (11) to (12) dissolved in (10) was added to the aqueous phase part, (13) to (15) were further added, and the mixture was emulsified with an emulsifier to obtain a make-up cleansing gel. After directly blending the obtained make-up cleansing gel and washing with water, the cleansing gel is well-familiar with cosmetics, such as ease of rinsing during washing, feeling of stickiness and creaking after washing, etc. It was confirmed that it was excellent in usability, excellent in removing cosmetics, and low in skin irritation.

Formulation Example 3: Body shampoo (1) Hydroxypropyl methylcellulose 0.1% by mass
(2) Glycerin 10.0
(3) Dipropylene glycol 5.0
(4) Triethanolamine laurate 12.0
(5) Lauryldimethylaminoacetic acid betaine 5.0
(6) Palm fatty acid diethanolamide 3.0
(7) POB (17) POE (28) Trimethylglyceryl ether (block) 5.0
(In formula (III), a + c + e = 17 and b + d + f = 28, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(8) Kamimora extract appropriate amount (9) edetate trisodium appropriate amount (10) preservative appropriate amount (11) colorant appropriate amount (12) perfume appropriate amount (13) purified water residue (production method and evaluation)
(1) was added to (13) and dispersed by stirring, and then heated to 70 ° C., and (2) to (12) were added and dissolved by stirring. Thereafter, it was cooled using a heat exchanger to obtain a body shampoo. The obtained body shampoo was foamed with water, and then washed away with water. The body shampoo was well-suited with cosmetics, easy to rinse during washing, and not sticky or squeaky after washing. It was recognized that the cosmetics were excellent in usability, the cosmetic removal effect and the low skin irritation.

Formulation Example 4: Machine-kneaded soap (1) Sodium soap Residue (2) Potassium soap 5.0% by mass
(3) Sodium chloride 0.3
(4) Glycerin 0.5
(5) Lauric acid 5.0
(6) POB (41) POE (48) Trimethylglyceryl ether (block) 3.0
(In formula (III), a + c + e = 41, b + d + f = 48, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(7) Coloring agent appropriate amount (8) Trisodium edetate appropriate amount (9) Fragrance appropriate amount (Manufacturing method and evaluation)
(1) to (9) were heated and mixed at 60 ° C., and this liquid was poured into a frame, cooled and solidified to obtain a mechanically kneaded soap. The soap obtained was foamed with water, and then washed away with water. The soap was well-familiar with cosmetics, and it was easy to rinse during washing, and was not sticky or squeaky after washing. It was confirmed that it was excellent in usability, excellent in removing cosmetics, and low in skin irritation.

Formulation Example 5: Makeup Cleansing Gel (1) Hydroxyethylcellulose 0.1% by mass
(2) Carboxyvinyl polymer 0.3
(3) Acrylic acid / alkyl methacrylate copolymer 0.3
(4) Trisodium edetate appropriate amount (5) Polyethylene glycol monoisostearate 0.5
(6) POB (14) POE (34) Trimethylglyceryl ether (block) 3.0
(In formula (III), a + c + e = 14, b + d + f = 34, BO represents an oxybutylene group, and EO represents an oxyethylene group.)
(7) Potassium hydroxide appropriate amount (8) Alcohol 5.0
(9) POE hydrogenated castor oil 0.3
(10) Preservative appropriate amount (11) Decamethylcyclopentasiloxane 10.0
(12) Methylpolysiloxane 10.0
(13) Appropriate perfume (14) Residual water residue (Production method and evaluation)
(1) to (7) were added to (14) and dissolved by stirring to obtain an aqueous phase. Thereafter, (9) to (10) dissolved in (8) was added to the aqueous phase part, and (11) to (13) were further added, followed by emulsification with an emulsifier to obtain a make-up cleansing gel. After directly blending the obtained make-up cleansing gel and washing with water, the cleansing gel is well-familiar with cosmetics, such as ease of rinsing during washing, feeling of stickiness and creaking after washing, etc. It was confirmed that it was excellent in usability, excellent in removing cosmetics, and low in skin irritation.

Claims (5)

A skin cleanser comprising 0.01 to 70% by mass of a block-type alkylene oxide derivative represented by the following formula (I) and 0.1 to 20% by mass of a humectant.

(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of the alkylene groups is added in the form of a block, a × k, b × k, and c × k are the average addition moles of oxyethylene group, oxyalkylene group having 3 to 6 carbon atoms, and oxyethylene group, respectively. ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, (a + c) × k> 1 with respect to the total of oxyethylene groups and oxyalkylene groups having 3 to 6 carbon atoms (The ratio of the oxyethylene group is 10 to 80% by mass, and R is a hydrocarbon group having 1 to 4 carbon atoms.)   The skin cleanser according to claim 1, wherein the content of the block type alkylene oxide derivative represented by the formula (I) is 0.1 to 20% by mass.   The skin cleansing composition according to claim 1 or 2, wherein the AO group of the block type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.   The skin cleanser according to any one of claims 1 to 3, wherein a of the block-type alkylene oxide derivative represented by the formula (I) is 0, and the addition order of AO and EO is relative to Y in the formula And (AO)-(EO). The skin cleanser according to any one of claims 1 to 4, wherein the humectant is one or more selected from dipropylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin. Skin cleanser.